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    • 专利摘要:
    CATALYTIC SYSTEM OF THREE MODES HAVING THE AMOUNT A SINGLE LAYER CATALYST. The present invention relates to a three-way layered catalytic system being separated into a front and a rear part having the ability to simultaneously catalyze the oxidation of hydrocarbons and carbon monoxide and the reduction of nitrogen oxides. A catalytic composite is provided which comprises a single catalytic front layer and two rear catalytic layers together with a substrate, wherein the single front layer and the rear bottom layers comprise a Pd component, the top rear layer comprises a Rh component and the rear bottom layer is substantially sits from an oxygen storage component (OSC).
    公开号:BR112013012564B1
    申请号:R112013012564-0
    申请日:2011-11-21
    公开日:2021-01-05
    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:

    TECHNICAL FIELD
    [001] The present invention relates to layered catalysts used for the treatment of gas streams containing hydrocarbons, carbon monoxide and nitrogen oxides. More specifically, this invention is directed to a three-way conversion catalyst (TWC) having a single layer catalyst upstream and multiple layer catalysts downstream. BACKGROUND AND PREVIOUS TECHNIQUE
    [002] Current TWC catalysts are used to control mobile emissions from Otto engines. The technology is well developed with a reduction in emission capacities of> 99% with respect to CO2 (hydrocarbons) and NOx (nitrogen oxides) after heating to operating temperatures of more than 250 ° C. Typical TWC catalyst configurations consist of a single block or multiple block system in the vehicle's exhaust line. If more than one catalyst is used, the catalysts can be located in a single converter, inserted together, or separated by a space defined as in separate converters. A common model for large, cooled motors is to have one converter in a closed hot (DC) position coupled with the second converter in the bottom (UB) location of the chiller. Since almost all mobile emission control systems are passive in nature, the time to warm up to the operating temperature of the catalyst is important as described in EP 1900416, which is reliable and which is incorporated here in this patent application by reference in its entirety.
    [003] Thus, CC catalyst designs almost always consist of features that favor rapid heating such as light, small area substrates (low thermal inertia), high cell density (mass transfer and improved heat) and a charge of high platinum metal group (PGM; for example, platinum, palladium, rhodium, rhenium, ruthenium and iridium). On the other hand, UB catalysts can be of larger volumes and of low cell density (lower pressure drop) and more often contain a lower PGM load. For small vehicles that operate at a high RPM only one convert is typically used, almost always located in the CC position. A disadvantage of locating the catalyst near the crankshaft is the increase in thermal degradation, and the faster loss of activity, especially under conditions of high load / high speed which results in loss of the support surface area or pore volume and the quick sintering of PGM.
    [004] Modern TWC catalysts use a variety of strategies to limit or slow down thermal degradation such as supports high stable surface area alumina for PGMs, the addition of promoters and stabilizers and advanced oxygen storage components (OSCs) ) that both increase performance and degrade at a slower speed (see, for example, US5672557, which deserves credit and which is incorporated here, in this patent application by reference in its entirety).
    [005] In technique, certain design strategies have been used to balance performance with associated costs. These strategies include selecting the type and distribution of PGM, volume of the substrate, stratification of WC and composition of the various layers of WC.
    [006] An important feature of the design with respect to TWC technologies consists of the proper separation and configuration of both components of the PGM and the washable lining (WC) both in separate WC layers and / or in separate blocks if systems are used multiple blocks. Modern TWC catalysts, however, have one or more toilet layers, the most common being 2-layer systems. For example, EP1541220, US5981427, WO09012348, WO08097702, W09535152, US7022646, US5593647, which are reliable and are incorporated herein, in this patent application, by reference in their entirety.
    [007] For PGM, the most common strategy is to locate the Rh and optionally the Pt component at the top of the 2nd layer of the toilet with the Pd located preferably at the bottom or in the 1st layer of the toilet (see, for example, US5593647). Separation of both WC and PGM components can also be achieved for single blocks by zoning whereby the front zone or the back zone or section of a WC layer can consist of different support components or components different PGM or more commonly different concentrations of a given PGM such as Pd. An advantage with regard to the separation of PGMs into layers or zones, is that more optimum supports and promoters for each of the PGMs can be used in such a way as to maximize total performance.
    [008] Before the present invention, researchers were attracted to various configurations of WC compositions that were taught how to re-present the preferred configuration for the best performance. Thus, with respect to two-layer UB catalysts, Rh is invariably located in the top layer (2nd layer) with optionally the Pt also present while the Pd is located in the 1st layer or the bottom layer (see, for example, US5593647 ). Also, both the top layers (2nd layer) and the bottom layer (1st layer) ideally contain a high surface area refractive oxide support, such as a gamma, gamma / theta / delta alumina with another addition of promoters. , stabilizers and a component of adequate oxygen storage (OSC). This WC project is described in detail by Sung et al. (US6087298) and Hu et al. (US6497851) included here, in this patent application for reference purposes. Both Sung et al., And Hu et al., Also describe preferred WC compositions and configurations for the CC catalysts or zones at the inlets of the exhaust gas flow. Thus, with respect to the CC entrance or entrance zone (front), the WC design is preferably free of an OSC and consists of a support area of high refractory oxide surface, such as a range or theta / delta alumina with suitable additives and stabilizers. On the other hand, it is preferably that the catalyst, zone or catalyst UB at the rear, has an OSC present in the top and bottom layers. These and other characteristics are described, for example, by Hu et al., And the references cited in them.
    [009] Within the field of TWC catalysts, new technologies and toilet configurations and systems are necessary to satisfy the increasingly stringent emission standards and the need to reduce the catalyst deactivation speed and achieve an increasing performance in loads PGM drops. SUMMARY OF THE INVENTION
    [0010] This invention relates to TWC catalysts that have different WC compositions with respect to their relative 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 block or front zone (upstream) and one block or rear zone (downstream). The block or rear zone comprises at least two layers, in which a CSO is absent in the 1st (lowest) catalytic layer. In some embodiments, one or more blocks can be placed between the blocks and zones at the front and rear. In some modalities, the zones or blocks are located in a single converter supported together or separated by a defined space. In some embodiments, the blocks are located in separate converters. In some embodiments, two or more separate converters are provided and at least one convert contains a back zone or block with at least two layers and the absence of OSC in the 1st catalytic layer. In some embodiments that comprise more than one separate converter, the further downstream converter contains a rear zone or block with at least two layers and the absence of OSC in the 1st catalytic layer.
    [0011] In some embodiments, the invention is directed to a catalytic composite for the purification of exhaust gases from a combustion engine operating substantially under stoichiometric conditions that comprise a sequence and in order: a single catalytic layer in front of a substrate; and a double back layer on a substrate having a 1st catalytic layer (lower), and a 2nd catalytic layer (above); wherein the 2nd catalytic layer comprises a compound of a platinum group metal (PMG) such as rhodium; and wherein the single front catalytic layer and the 1st catalytic layer comprise another platinum group metal (PMG), such as palladium; and wherein the 1st catalytic layer is substantially free of an oxygen storage component (OSC).
    [0012] With reference to the 1st and 2nd catalytic layers, no limitations are being placed on the location of the layer in view of the direction of the exhaust flow. The locations of the layers in view of the exhaust flow are preferably described as the front (upstream) and rear (downstream) layers. The 1st catalytic layer is deposited on a substrate with a bottom layer already deposited on a substrate to form a lower coating. A 2nd catalytic layer is deposited on and having physical contact with the 1st catalytic layer to form the top coat.
    [0013] In other words, the front zone or block (upstream) that comes into contact with the exhaust gas first is the one closest to the engine, The rear zone or block (downstream) is one that comes into contact with the exhaust gas after contact with a previous zone or block. The rear zone or block may have a (1a) bottom catalytic layer and a (2a) top catalytic layer. The front and rear zones or blocks can be in the same converter and can be touching each other or be separated by a distance, for example, about an inch or more. Alternatively, the front and rear zones or blocks can be in separate converters that can be separated by a greater distance, for example, from 30.48 to 182.88 cm (1 to 6 feet).
    [0014] The phrase "substantially free of an oxygen storage component (OSC)" refers to having a very small amount, preferably no CSOs in, for example, a certain layer. A very low amount of CSOs 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.
    [0015] In one embodiment, an exhaust treatment system is provided that comprises a catalyst composite. The exhaust treatment system may further comprise one or more exhaust treatment devices selected from the group consisting of particulate gas filter (GTP) interceptors HC and NOx absorption catalysts.
    [0016] In some embodiments, the present invention provides methods for the treatment of exhaust gases comprising, by contacting a gas stream composed of hydrocarbons, carbon monoxide and nitrogen oxides with a layered catalyst composite or a treatment system of exhaust as described here, in this patent application, in which the catalytic material employed is effective to substantially oxidize both carbon monoxide and hydrocarbons and reduce nitrogen oxides. In some embodiments, the temperature of the exhaust gas at the catalyst inlet can vary from room temperature to as high as 1100 ° C, however the typical catalyst operating temperatures by design fall in the range of about 300 - 900 ° Ç.
    [0017] Both the general description preceding the detailed description which follows are by way of example only and explanatory and are intended to provide a further explanation of the invention as claimed. The accompanying drawings are included to provide a greater understanding of the invention and are incorporated and form part of this specification, illustrate various modalities of the invention, and together with the description serve to explain the principles of the invention. BRIEF DESCRIPTION OF THE DRAWINGS
    [0018] The present invention would be further understood with reference to the drawings, in which:
    [0019] Figs. 1a and 1b are examples of washable coating layer configurations.
    [0020] Fig. 2 are examples of forming washable coating layers and configuration of the present invention in which the first layer of the rear zone or block does not have the OSC.
    [0021] Fig. 3 is a comparison of THC performance with respect to a conventional catalyst configuration for a catalyst system made in accordance with the present invention. Aging = 50 hours of thermal aging in 4 modes; Vehicle = 2005 MY, BIN 5, 2,2l / 4 cylinders with fuel injection in sequence. Front block: 10.56 centimeters (4.16 ") in circumference x 7.62 centimeters (3") in length; 4.24 c MPa (600 cpsi) / 4.3 mill; Volume = 263.2 square centimeters (40.8 square inches); Pd + Rh = 27 g / 6.45 square centimeters (1 square foot); > 0: 12.5: 1; Rear block: 10.56 centimeters (4.16 ") in circumference x 7.62 centimeters (3") in length; 2.86 cMPa (400 cpsi) / 4 mill; Volume = 263.2 square centimeters (40.8 square inches); Pd + Rh = 3 g / 6.45 square centimeters (1 square foot); @ 0: 2: 1.
    [0022] Fig. 4 is a comparison of NOx performance for a conventional catalyst configuration with respect to a catalyst system made in accordance with the present invention. Aging = 50 hours of thermal aging in 4 modes; Vehicle = 2005 MY, BIN 5, 2,2l / 4 cylinders with fuel injection in sequence. Front block: 10.56 centimeters (4.16 ") in circumference x 7.62 centimeters (3") in length; 4.24 c MPa (600 cpsi) / 4.3 mill; Volume = 263.2 square centimeters (40.8 square inches); Pd + Rh = 27 g / 6.45 square centimeters (1 square foot); > 0: 12.5: 1; Rear block: 10.56 centimeters (4.16 ") in circumference x 7.62 centimeters (3") in length; 2.86 cMPa (400 cpsi) / 4 mill; Volume = 263.2 square centimeters (40.8 square inches); Pd + Rh = 3 g // 6.45 square centimeters (1 square foot); @ 0: 2: 1. DETAILED DESCRIPTION OF THE INVENTION
    [0023] The present invention is directed to a three-way conversion catalyst (TWC) and the compositions and locations of the catalyst layers with respect to the direction of the exhaust gas flow. Specifically, the TWC catalysts according to the present invention comprise at least one block or front zone (upstream) and one block or rear zone (downstream), wherein the block or the rear zone comprises at least two layers, in which an OSC is not present in the 1st (lowest) catalytic layer. As described here, in this patent application, the TWC catalysts according to the present invention provide great performance advantages that are not expected based on the teachings and best practice in the art prior to the present invention.
    [0024] The present invention relates to a layered catalyst composite of the type generally referred to as a three-way conversion catalyst (TWC) having 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 either by using different zones on a substrate or by using separate blocks being located in a single converter, supported together or separated by a defined space as in separate converters.
    [0025] In some embodiments, the charge of the platinum group metal (PMG) of the catalytic layers is about 0.001 - 20.00% by weight. In some embodiments, each layer of the catalytic layers may comprise a different composition. In some embodiments, each layer has a load of about 6.45 square centimeters (1 square foot). In some embodiments, each layer has a PGM charge from about 0.01% by weight to about 20.00% by weight of the layer. In some embodiments, each of the respective layers is deposited in a PGM charge of about 0.02 - 15% by weight.
    [0026] In some embodiments, the catalytic composite refers to a PGM content of the layers which are as follows: Single catalytic front layer - 0.01 - about 12% by weight of the layer; 1st catalytic layer - 0.1 - about 6.0% by weight of the layer; 2nd catalytic layer - 0.01 about 2.0% by weight of the layer.
    [0027] The 2nd catalytic layer always comprises rhodium as a PGM can also include other PGMs. Rh is preferably in the 2nd catalytic layer as the reduction of NOx based on the reaction 2CO + 2NO ^ N2 + 2CO2 is more efficient at intermediate temperatures in the range of 300 - 600 ° C. In some embodiments, the amount of rhodium in a layer is about 0.01 - 1.0% by weight, preferably 0.02 - 0.5% by weight and most preferably 0.05 - 0, 25% by weight.
    [0028] The single front catalytic layer and the 1st catalytic layer always comprise palladium as a PGM but can also also comprise other PGMs. In a preferred embodiment, the single front catalytic layer and the 1st catalytic layer comprise palladium such as PGM. Palladium is specifically effective for the oxidation of HC and is almost always concentrated in the leading or front block in such a way as to initiate HC reduction as early as possible. This increases as the concentration of HC emitted from the engine is higher in the initial stages of vehicle operation in contrast to the Nox that is emitted largely after the vehicle is warmed up. In some embodiments, the amount of palladium in that layer is about 0.1 - 15% by weight, preferably about 0.1 - 110% and most preferably about 0.5 - 5.0% by weight. Weight.
    [0029] As already indicated it can be advantageous to have Pt present as the PGM in the layers, especially in the 2nd catalytic layer. Pt has the advantage of being specifically effective for the difficult oxidation of HC (of saturated HC) and can advantageously form alloys with Rh. Under stoichiometric / rich / lean exhaust gas conditions the alloy surface is rich in Rh which protects this PGM from negative interactions with the support. In some embodiments, an amount of a platinum group metal is up to about 4% by weight of the layer.
    [0030] In some embodiments the amount of platinum in a layer is about 0.05 - m5% by weight, preferably about 0.1 - 2.0% by weight, and most preferably about 0 , 3 - 1.0% by weight. In some embodiments, the platinum content of the layers is as follows: single front catalytic layer - about 0.05 - 5% by weight of the layer, preferably about 0.1 - 2.0%, and most preferably about 0.5 - 1.0%; 2nd catalytic layer - about 0.025 - 2.5% by weight of the layer, preferably about 0.1 - 2.0% and most preferably about 0.3 - 1.0%.
    [0031] The reference to OSC (oxygen storage component) refers to an entity that has a multiple valence and that can react actively with oxidants such as oxygen or nitrogen oxides under oxidation conditions or that reacts with reagents such as carbon monoxide (CO), hydrocarbons (HC) or hydrogen under reducing conditions. Suitable oxygen storage components may include one or more oxides from 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 them. Examples of suitable oxygen storage components include ceria, praseodymia or combinations thereof.
    [0032] The supply of an OSC to the layer can be achieved through the use of, for example, mixed oxides. For example, cerium can be supplied through 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, praseodymia can be supplied through 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 herein, in this patent application by reference in its entirety.
    [0033] OSC can be present in up to about 80% by weight of the layer, preferably about 20 - 70%, and most preferably in about 30 - 60 ". The content of ceria or praseodymia in the range of about 3 - 98%, preferably about 10 - 60%, more preferably about 20 - 40% by weight of the OSC. Suitable oxygen storage components may include one or more oxides of one or more rare earth or transition metal 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 them.
    [0034] In some embodiments, the composite catalyst according to the invention comprises an oxygen storage component (OSC) content by weight of the layer as follows: single front catalytic layer - about 10 - 80% by weight of the layer layer, preferably about 20 - 70%, and most preferably about 30 - 60%; 2nd catalytic layer - about 10 - 80% by weight of the layer, preferably about 20 - 70% and most preferably about 30 - 60%.
    [0035] In some embodiments, the catalyst composite also comprises exhaust treatment materials selected from the group consisting of hydrocarbon storage components, NOx storage components insofar as the chain design has a specific applicability for treatment exhaust systems that comprise HC retainers and / or NOx absorption features. Current HC retainer designs use a subcoat (UC - see later) consisting of HC retaining materials including certain zeolites with a one- or two-layer TWC topcoat (OC), as described in Japanese Patents JP7124468 and JP7124467 and US7442346 which are incorporated herein in this patent application by reference. Optimal performance is achieved with respect to projects in which the 1st catalytic layer does not contain OSC and in which the 2nd catalytic layer does not contain an OSC as described in the present invention with respect to an optimal configuration of the WC composition in the 1st and 2nd layers front and rear technology. In addition, the newest design with respect to the location of the HC retainer is at the rear of the chiller or the location at the bottom of the body (UB) (US7442346) as distinct from the earlier strategies of placing the HC retainer in the OC position (US 5772972; Silver RG, Dou D., Kirby C. W ,, Richmond RP, Balland J., and Dunne S.; SAE 972843 and references therein) again in line with the current configuration of WC layers . For the NOx absorption catalysts, a preferred location of the adsorber is again in the location of the UB cooler with an active TWC also present for both to generate H2 and complete HC / CO combustion during the rich / lean transition.
    [0036] A suitable support according to some embodiments of the present invention is a refractory oxide support. 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, refractory metal oxides with a high surface area, composites containing oxygen storage components, and molecular sieves as are well known in the art. In some embodiments, the support of 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, aluminum silicates, alumina-zirconia , lanthania-alumina, lanthania-zirconia-alumina, barium-alumina, lanthania alumina barium, chromium alumina and cerium alumina. The support can comprise any suitable material, for example, a metal oxide comprising gamma-alumina or gamma-alumina stabilized with a promoter having a specific surface area of about 50 - 350 m2 / g, preferably of about 75 - 250 m2 / g, and most preferably about 100 - 200 m2 / g. In some embodiments, the alumina present in any of the layers optionally comprises zirconia - and lanthania - stabilized alumina (gamma) at a charge of about 5 - 90% by weight of the layer, preferably about 20 - 70%, and most preferably about 30 - 60%. For example, a suitable stabilized alumina may comprise 0.1 - 15% by weight of lanthanum (preferably as a stabilizer), preferably about 0.5 - 10%, and most preferably about 1 - 7%; and / or about 0.5 - 15%, preferably about 0.5 - 10%, and most preferably about 1 - 7% zirconia (preferably as a gamma-alumina stabilizer). In some embodiments, alumina comprises alumina gamma stabilized through barium oxide, neodymia, lanthanum and combinations thereof. The stabilizer charge on a suitable alumina is about 0 - 4% by weight of the support, preferably about 1 - 3%, and most preferably about 2% barium oxide. It is observed that lanthania, zirconia, and neodymia are stabilizers and that, in some modalities, one or more may be in the same load range, that is, lanthanum, zirconia, neodymia or a combination of them may be present at 0, 1 - 15% by weight.
    [0037] In some embodiments, a molecular sieve material can be selected from the group consisting of faujasite, chabazite, silcalite, zeolite X, zeolite Y, ultra-stable zeolite, ofretite, Beta, ferrierite and ZSM / MFI . Specifically, ion-exchanged Beta zeolites can be used, such as Faith / Beta zeolite, or preferably, H / Beta zeolite. Zeolites, preferably Beta zeolites can have a molar ratio of silica / alumina from at least about 25/1 or at least about 50/1, with useful ranges from about 25/1 to 1000 / 1, 50/1 to 500/1 as well as from about 25/1 to 300/1, for example.
    [0038] In some embodiments, the layers provided are the first single on the front and / or the 1st catalytic layer comprising a stabilized alumina, such as gamma-alumina which can be present in an amount in the range of about 10 - 90% by weight of the layer, preferably about 20 - 70%, and most preferably about 30 - 60%; substantially only palladium, which may be present in an amount in the range of about 0.1 - 10% by weight of the layer, preferably about 0.1 - 5.0%, and most preferably about 0.2 - 2.0%.
    [0039] In some embodiments, the 2nd catalytic layer comprises a stabilized alumina, such as a range of stabilized alumina with slant, which may be present in an amount in the range of about 10 - 90% by weight of the layer, preferably about 20 - 70% and most preferably about 30 - 60%; rhodium, which can be present in an amount in the range of about -, - 1 - 1.0% by weight of the layer, preferably about 0.05 - 0.5% and most preferably about 0, 1 - 0.25%.
    [0040] In some embodiments, the 2nd catalytic layer comprises a stabilized alumina, such as a gamma-alumina, which may be present in an amount in the range of about 10 - 90% by weight of the layer, preferably about 20 - 70% and most preferably around 30 - 60%; platinum, which can be present in an amount in the range of up to about 4.0% by weight of the layer, preferably about 0.1 - 2.0% and most preferably about 0.05 - 1% , whereby rhodium can be present in an amount in the range of about 0.01 - 1.0% by weight of the layer, preferably about 0.05 - 0.5% and most preferably about 0.1 - 0.25%.
    [0041] In some embodiments, it may be desirable that a given layer still comprises up to about 40%, preferably about 5 - 30%, and more preferably about 10 - 20% of a stabilizer comprising one or more if non-reducible metal oxides, in which the metal is selected from the group consisting of barium, calcium, magnesium, strontium and mixtures thereof. A layer may also comprise, according to an embodiment, from 0 to 40%, preferably about 5 - 30%, and more preferably about 10 - 30% from one or more promoters comprising one or more rare earths or transition metals selected from the group consisting of lanthanum, praseodymium, yttrium, zirconium, samarium, gadolinium, ytterbium, niobium, neodymium, and mixtures thereof. A layer can also comprise, according to an embodiment, from 0 to about 20%, preferably about 2 - 20% and most preferably about 5 - 10% of one or more binders comprising one or more of Bohemians alumina, zirconia hydroxites or silica suns, and mixtures thereof. A layer can also comprise, according to a mode of 0 to about 20%, preferably about 0 - 12%, more preferably about 0 - 6% of one or more other additives comprising hydrogen sulfide (H2S ), control agents such as nickel, iron, zinc, boron, manganese, strontium and mixtures thereof.
    [0042] Segregated wash coatings that address certain catalytic functionality can be used. The use of at least two layers on a substrate can lead to a more efficient use of, and / or a decrease in the total amount of, for example, metals of the platinum group due to their separation from each other.
    [0043] In some embodiments, the compositions of each layer are adapted to address a specific function of the TWC catalyst. For example, topcoat layers which are substantially free of platinum group metals and which comprise alumina and one or more base metal oxides, are, for example, effective in retaining poisons such as components containing sulfur, nitrogen , magnesium, calcium, zinc and phosphorus. Examples of base metal oxides include, but are not limited to, SrO, La203, Nd203, or BaO.
    [0044] The catalyst composite in its zone mode comprises a substrate comprising a final axial inlet and, a final axial outlet, wall elements having a length that extends between the final axial inlet to the final axial outlet and a plurality of axially closed channels defined by the wall elements; and a front portion of the catalyst composite deposited on the wall element adjacent the final axial inlet and having a length extending less than the length of the wall of the wall elements, wherein the inlet portion of the catalyst composite comprises the single layer of front described above. The catalyst composite also comprises a rear portion adjacent to the final axial outlet and having a length that extends for less than the length of the wall elements, wherein the outlet portion of the catalyst composite comprises the described 1st and 2nd catalytic layers above. For example, the front part of the catalyst composite may comprise (a) a substrate; (b) a single layer deposited on the substrate, the layer comprising palladium deposited on a support and, for example, the rear part of the catalyst composite can comprise (a) a substrate; (b) a 1st catalytic layer deposited on the substrate, the 1st catalytic layer comprising palladium deposited on a support; (c) a 2nd catalytic layer deposited on the 1st catalytic layer, the 2nd catalytic layer comprising rhodium, and optionally platinum, deposited on a support.
    [0045] In some embodiments, the front of the catalyst composite overlaps the rear of the catalyst composite. In some embodiments, the front of the catalyst composite comprises between about 10 - 100%, more preferably about 20 - 60%, and most preferably about 25 - 50% of the total length (such as 1 - 15 cm of total length) of the substrate, such as a honeycomb substrate. In some embodiments, the rear part of the catalyst composite comprises between about 1- - 90%, more preferably about 40 - 80%, and most preferably about 50 - 75% of the total length of the substrate, as well as a substrate the type of hive.
    [0046] In some embodiments, one or more of the catalyst composites of the invention are arranged on a substrate. The substrate can be of any of those materials typically used for the preparation of catalysts, and will preferably comprise a metal or ceramic hive structure. Any suitable substrate can be employed, such as a monolithic substrate of the type that has thin, parallel gas passages that extend there from an inlet or an exit face of the substrate, such as passages that are open to the flow of fluids not through them (referred to as flow hive substrates through it). The passages, which are essentially straight paths from their fluid inlets to their fluid outlets, are defined through walls on which the catalytic material is coated as a wash coating in such a way that the gases flowing through the passages come in contact with the catalytic material. The substrate flow passages are thin-walled channels that can be of any shape and size in cross-section such as trapezoidal, rectangular, square, sinuzoidal, hexagonal, oval, circular, etc. These structures can contain from 60 - 900 or more openings for the entry of gas (ie cells) per square inch of cross section.
    [0047] The substrate can also be a wall flow filter substrate, in which the channels are alternately blocked, allowing a gaseous stream to enter the channels from one direction (inlet direction) to flow through the channel walls. and exit the channels from the other direction (exit direction). A dual oxidation catalyst composition can be coated on the wall flow filter. If this substrate is used, the resulting system will be able to remove particulate matter along with the polluting gases. 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 exhibits a front zone comprising a single front layer deposited on the inlet channels of a wall flow filter, and the rear zone comprising the 1st and 2nd catalytic layers is deposited on is output channels of a wall flow filter.
    [0048] The ceramic substrate can be made of any suitable refractory material, such as cordierite, cordierite-alumina, silica, nitrite, zirconium mullite, spodumene, magnesia silica alumina, zirconium silicate, silimanite, a magnesium silicate , zirconium, petalite, alumina, an aluminum silicate and the like.
    [0049] The substrates useful for the catalyst composite of the present invention can also be of a metallic nature and be composed of one or more metals or metal alloys. The metallic substrate can be used in several formats such as a corrugated sheet or monolithic shape. Metal supports preferably include heat-resistant metals and metal alloys such as titanium and stainless steel as well as other alloys in which iron is a substantial or major component. Such alloys may contain one or more of nickel, chromium, and / or aluminum, and the total amount of these metals can advantageously comprise at least about 15% by weight of the alloy, for example, about 10 - 25% by weight. chromium weight, about 3 - 8 wt% aluminum and up to about 20 wt% nickel. 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 substrates can be oxidized at high temperatures, for example, around 1000 ° C to improve the corrosion resistance of the alloys by forming an oxide layer on the substrate surfaces. This oxidation induced by high temperature can improve the adhesion of the refractory metal oxide support and catalytically promote the metal components of the substrate. In alternative embodiments, one or more catalytic compositions can be deposited on an open cell substrate and foam. Such substrates are well known in the art and are typically formed of refractory ceramics or metallic materials.
    [0050] Based on the prior art, the configuration of the WC compositions of the present invention is not taught or recognized as having a favorable performance or other advantageous characteristics. In fact, the preceding technique teaches specifically against this configuration as outlined in detail in the patent by Hu et al., And references therein. PREPARATION
    [0051] The layered catalytic composite of the present invention can be easily prepared by processes known in the art. See, for example, US 6478874 and EP 0 441 1743 which are incorporated herein, in this patent application by reference in its entirety. A representative process is shown below. In the form used here, in this patent application, the term "wash coating" has its usual meaning in the art of a thin adherent coating of a catalytic material or other material applied to a substrate material, such as a substrate member of the type of hive, which is sufficiently porous to allow the gas stream being treated to pass through.
    [0052] The catalyst composite can be easily prepared in layers on a monolithic substrate. For a first layer of a specific wash coating, finely divided particles of a high-surface refractory metal oxide such as the alumina range are thickly suspended in an appropriate solvent, such as water. The substrate can be immersed one or more times in this slurry or the slurry can be coated on the substrate in such a way that it will be deposited on the substrate in the desired metal oxide load, for example, about 0.5 - 4.0 g / 16.4 centimeters3 (1 inch3). For the incorporation of components such as precious metals (such as, for example, palladium, rhodium, platinum and / or combinations thereof) stabilizers, binders, additives and / or promoters, these components can be incorporated into the slurry as a mixture of compounds or water-soluble or water-dispersible complexes. Then the coated substrate is calcined by heating, for example, to about 300 - 800 ° C for about 1 - 3 hours. Typically, when palladium is desired, the palladium component is used in the form of a compound or a complex to achieve a high dispersion of the component on the refractory metal oxide support, such as activated alumina. For the purpose of the present invention, the term "palladium component" means any compound, complex or similar, which on calcination or when it decomposes or otherwise converts to a catalytically active form, usually of metal or of metal oxide. Water-soluble compounds or water-dispersing compounds or complexes of the metal component can be used as long as the liquid medium used to impregnate or to deposit the metal component on the refractory metal oxide particles of the support does not react adversely with the metal or its compounds or complexes or with other components that may be present in the catalytic composite and that is capable of being removed from the metal component through volatilization or decomposition when heating and / or applying a vacuum. In some cases, complete removal of the liquid may not happen until the catalyst is put into use and subjected to the high temperatures encountered during operation. In general, both from the point of view of economic and environmental aspects, aqueous solutions of compounds or soluble complexes of precious metals are used. For example, suitable compounds are palladium nitrates or rhodium nitrates. During the calcination stage, or at least during the initial phase of using the composite, these compounds are converted into a catalytically active form of the metal or a compound thereof.
    [0053] Before describing various embodiments of the invention by way of example, it should be understood that the invention is not limited to the details of construction or process steps shown in the description that follows. The invention is capable of other modalities and can be practiced in several ways. SINGLE LAYER FRONT MODALITIES.
    [0054] According to some modalities, the single front layer that is deposited on occasion, that is when and adhered to the substrate comprises palladium deposited on a support. A suitable support is a high surface area refractory metal oxide support. In a specific embodiment, the load of the first layer on the substrate is between about 0.2 - 4.0 g / 16.4 centimeters3 (1 inch3). Examples of high surface area refractory metal oxides include, but are not limited to, alumina, silica, titania and zirconia and mixtures thereof. Refractory metal oxide may consist of, or contain a mixed oxide such as silica-alumina, aluminum silicates, which may be amorphous or crystalline, alumina-zirconia, alumina-lanthan, alumina-lanthanum-neodymia, alumina-chromium , alumina, alumina and the like. A refractory metal oxide as an example comprises gamma-alumina having a specific surface area of about 50 - 350 m2 / g and which is present in a load of about 10 - 90% by weight of the wash coating. This layer will typically have oxygen storage components in the range of about 10 - 90% by weight with a ceria content ranging from about 3 - 98% by weight of the layer material.
    [0055] Examples of palladium filler in the single front layer include up to about 15% by weight, alternatively between about 0.05 - 5% by weight of palladium and between up to about 0.6 Rh by weight, alternatively between about 0.01 - 0.15% rhodium by weight. This layer can also contain up to about 40% of stabilizers / promoters / binders / additives. Suitable stabilizers include one or more of non-reducing 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 of barium and / or strontium. Suitable promoters include one or more of non-reducible oxides, or rare earths or transition metals selected from the group consisting of lanthanum, neodymium, praseodymium, yttrium, zirconium, samarium, gadolinium, dysprosium, ytterbium, niobium and mixtures of the same. 2-LAYER MODALITIES
    [0056] The top layer or the 2nd catalytic layer of a 2-layer catalyst: the 2nd catalytic layer, which is deposited on, that is, deposited on and adhered to the first back layer, comprises rhodium or rhodium and platinum deposited on a high surface area refractory metal oxide and / or an oxygen storage component that can be any of those mentioned above with respect to the front catalytic layer 1. The 2nd catalytic layer will be present at a charge of about 1 - 2.5 g / inch3, alternatively between about 1 - 1.6 g / inch3, and will have substantially an amount of oxygen storage components in a charge of about 10 - 90% by weight of the layer. The oxygen storage components can be ceria, which contains a ceria / zirconia composite with the ceria varying from about 3 - 98% by weight percent. Preferably, about 5 - 55% ceria is in the composite. The 2nd catalytic layer can also comprise gamma-alumina or stabilized gamma-alumina which has a specific surface area of about 50 - 350 m2 / g and which is present in a load of about 10 - 90% by weight of the layer.
    [0057] In some embodiments, rhodium and platinum will be present in the 2nd catalytic layer at a charge of about 0.001 - 6.0% by weight, alternatively about 0.005 - 1.0% by weight of rhodium and about 0 .01 - 5.0% by weight, preferably about 0.1 - 1.0% by weight of platinum. The 2nd catalytic layer can also contain about 0 - 40% by weight of a promoter or more promoters. Suitable promoters include one or more of base metal oxides in which the metal is selected from the group consisting of barium, calcium, magnesium, strontium, one or more rare earths and transition metals selected from the group consisting of zirconium, lanthanum, praseodymium, yttrium, samarium, gadolinium, dysprosium, ytterbium, niobium, neodymium and mixtures thereof. CATALYTIC LAYER MODALITIES
    [0058] According to some modalities, the first catalytic layer that is deposited on, that is, coated on and adhered to the substrate, comprises palladium deposited on a support. A suitable support can be a high surface area refractory metal oxide. In a specific embodiment, the load of the first layer on the substrate is between about 0.2 - 2.6 g /, 16, 4 centimeters3 (1 inch3). Examples of high surface area refractory metal oxides include, but are not limited to, a high surface area refractory metal oxide such as alumina, silica, titania, and zirconia and mixtures thereof. Refractory metal oxide may consist of or comprise a mixed oxide such as silica-alumina, aluminum silicates which may be amorphous or crystalline, alumina-zirconia, alumina-lanthania-neodymia, alumina-chromium, alumina- barium, and the like. An example refractory metal oxide comprises gamma-alumina which has a specific surface area of about 50 - 350 m2 / g and which is present in a charge of about 10 - 90% by weight of the layer. The first layer that is applied to the rear area is free from oxygen storage materials that comprise ceria.
    [0059] Examples of palladium loading in the first layer include up to about 15% by weight, alternatively between about 0.05 - 10% by weight of palladium. This layer can also contain up to about 40% by weight of stabilizers / promoters / binders / additives. Suitable stabilizers include one or more of 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 of non-reducible oxides or you will have rare or transition metals selected from the group consisting of zirconium, lanthanum, praseodymium, yttrium, samarium, gadolinium, dysprosium, ytterbium, niobium, neodymium and mixtures thereof .
    [0060] The first catalytic layer is deposited in exactly the same way as the single front layer, except with respect to not substantially comprising OSC. Examples:
    [0061] This invention will be illustrated by the following examples and descriptions.
    [0062] The following examples are intended to illustrate, but not to limit the invention. MANUFACTURE OF THE 1 LAYER CATALYST PRECEDENT
    [0063] The preparation of washing and coating coatings has already been described in US7041622, Column 9, Lines 20 - 40; Column 10, lines 1 - 15, which is incorporated here, in this patent application by reference in its entirety. The catalyst of the 1 layer of the front or zone consists of two alumines stabilized in a 1: 1 ratio, one with 4% by weight of lanthanum oxide, and the other with 3% by weight of lanthanum oxide; barium sulfate and an oxygen storage material of mixed oxides with a composition of 50% Zr02 + Hf02 / 40% Ce02 / 5% Pr6On and 5% La203. The slurry was prepared as follows: nitric acid was added to water at 1% by weight based on the total solids in the slurry. BaSO4 was then added with stirring followed by the OSC. The slurry was stirred for 15 minutes and then the alumines were added with stirring for 30 minutes. The slurry was then ground (using a Sweco type mill) such that the d50 was 4.5 - 5.5 microns; the d90 was 17 - 21 microns and 100% passed was less than 65 microns (ie 100% of the particles were less than n65 micrometers in size). The slurry was then weighed and the LOI (loss of ignition) measured at 540 ° C to determine the total content of calcined solids. Based on this value, the Pd and Rh weights were calculated. Rh was first added to the thick solution like Rh nitrate by slowly adding it dropwise over 30 minutes. The Pd nitrate solution was then added to the slurry again dropwise over a period of 30 minutes while stirring. After the addition of Rh and Pd, the specific gravity of the thick suspension was in the range of 1.49 to 1.52. The parts were coated by immersing one end of a honeycomb ceramic monolith into the thick wash coating suspension, followed by inserting the thick suspension into the channels using a vacuum. The part was then removed from the thick suspension and the channels were cleaned by applying a vacuum to the other end of the part. The wash coating load was controlled by varying the specific gravity, and other coating parameters such as the vacuum time and the amount of slurry carried into the channels. After the application of the wash coating, the parts were calcined at 540 ° C for 2 hours.
    [0064] After calcination, the front layer 1 catalyst composition was as follows: 40 g / l of alumina stabilized with 4% lanthanum 40 g / l of alumina stabilized with 3% lanthanum 80 g / l of oxygen storage material 13 g / l barium sulfate 2 g / foot3 rhodium; and 25 g / ft3 of palladium. MANUFACTURE OF THE 1st CATALYTIC LAYER OF THE REAR CONVENTIONAL REFERENCE CATALYST.
    [0065] The catalytic layer of the zone consisted of two alumines stabilized in a 1: 1 ratio, one with 4% by weight of lanthanum oxide and the other with 3% by weight of lanthanum oxide; barium sulfate and a mixed oxygen storage oxygen material with a composition of 50% Zr02 + Hf02, 40% Ce02, 5% Pr5Ou and 5% La203. The preparation of the slurry and coating was carried out as described above for the front layer 1 catalyst. After calcination at 540 ° C for 2 hours the composition of the 1st catalytic layer was as follows: 25 g / l of alumina stabilized with 4% lanthanum 25 g / l of alumina stabilized with 3% lanthanum 50 g / l of oxygen storage material 8 g / l barium sulfate 2 g / ft3 palladium. MANUFACTURE OF THE 2nd REAR CATALYTIC LAYER OF THE CONVENTIONAL REFERENCE CATALYST
    [0066] The 2nd catalytic layer of the zone consisted of two alumines stabilized in a 1: 2 ratio, one with 4% by weight of lanthanum oxide and the other with 3% by weight of lanthanum oxide; barium sulfate and a mixed oxygen storage oxygen material with a composition of 58% Zr02 + Hf02, 32% Ce02, 8% Y203 and 2% La203 by weight. The preparation of the slurry and coating was carried out as described above for the front layer 1 catalyst. After calcination at 540 ° C for 2 hours the composition of the 1st catalytic layer was as follows: 30 g / l of alumina stabilized with 4% lanthanum 15 g / l of alumina stabilized with 3% lanthanum 68 g / l of oxygen storage material 8.5 g / l barium sulfate 1.0 g / ft3 rhodium. MANUFACTURE OF THE 2nd REAR CATALYTIC LAYER OF THE CATALYST ACCORDING TO THE INVENTION.
    [0067] The composition and manufacture of the 2nd catalytic layer was identical with the conventional reference catalyst. MANUFACTURE OF THE REAR CATALYTIC LAYER OF THE CATALYST ACCORDING TO THE INVENTION.
    [0068] The composition of the rear catalytic layer consisted of alumina stabilized with 3% by weight of lanthanum oxide and barium oxide. The preparation of the slurry and the coating were carried out as described above for the front layer I catalyst. After calcination at 540 ° C for 2 hours, the composition of the catalytic layer was as follows: ii0.0 c / l of alumina stabilized with lanthanum i0.0 g / l of barium oxide; and 2.0 g / ft3 of palladium.
    [0069] Aging consisted of 50 or 100 hours of an aging protocol in 4 modes. The cycle consisted of four modes within a 60 second period. The first mode consisted of a stoichiometric cruise, followed by a rich condition, a rich condition with a secondary air injection and finally a stoichiometric condition with a secondary air injection. Mode 1 lasted 40 seconds with a catalyst injection T bed (thermocouple placed 1 ° from the catalyst injection face) of 904 ± 2 ° C. Mode 2 lasted for 6 seconds with an inlet CO concentration of 2.0 ± 0.1%. Method 3 lasted for 10 seconds with a catalyst inlet T bed of 980 ° C ± 2 ° C; 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 O2 concentration of 2.5 ± 1.0 vol%. Mode 4 lasted for 4 seconds with a stoichiometric composition of exhaust gas from an engine outlet and a secondary air injection to give an O2 concentration of 4.5 ± 0.1% vol. on the catalyst road. The engine used for aging was a 7.4L V-8 equipped with a multi-port sequential fuel injection.
    [0070] The performance results are summarized in Figures 3 and 4 in which it is observed that the catalyst design of the present invention shows clear advantages over THC and NOx in Phases 2 and 3 of the FTP test.
    [0071] To the degree necessary to understand or complete the description of the present invention, all publications and patent applications mentioned here, in this patent application are expressly incorporated by reference here, in this patent application, to the same degree as if each were individually incorporated in that way.
    [0072] Having thus described the exemplary modalities of the present invention, it should be noted by those skilled in the art that the descriptions within it are by way of example only and that various other alternatives and adaptations, and modifications can be made within the scope of the present invention. Consequently, the present invention is not limited to the specific modalities such as those illustrated here, in this patent application, but is only limited by the claims that follow.
    权利要求:
    Claims (12)
    [0001]
    1. Catalytic composite characterized by the fact that it is for the purification of exhaust gases from a combustion engine substantially operating under stoichiometric conditions, comprising in sequence and in order: a single catalytic layer facing on a substrate; and a double back layer on a substrate, having a 1st catalytic layer (lower) and a 2nd catalytic layer (upper); wherein the 2nd catalytic layer comprises rhodium as a platinum group metal; and wherein the single front catalytic layer and the 1st catalytic layer comprise palladium as a compound of the platinum metal group; wherein the 1st catalytic layer comprises less than 1% of an oxygen storage component (OSC) by weight of the layer; and where the single front catalytic layer forms a front zone and the double back layer forms a rear zone in which the catalytic composite is a single block system or the single front catalytic layer is located in a front block and the The double back layer is located in a rear block in which the catalytic composite is a multiple block system, and in which the contents of the oxygen storage components (OSC) by weight of the layer are as follows: Single front catalytic layer: 10 to 80% by weight of the layer; and 2nd catalytic layer: 10 to 80% by weight of the layer.
    [0002]
    2. Catalytic composite according to claim 1, characterized by the fact that the PGM contents of the layers are as follows: Single front catalytic layer: 0.01 to 12.0% by weight of the layer; 1st catalytic layer: 0.05 to 6.0% by weight of the layer; and 2nd catalytic layer: 0.01 to 2% by weight of the layer.
    [0003]
    3. Catalytic composite according to claim 2, characterized by the fact that the single front catalytic layer and the 1st catalytic layer comprise only palladium such as PGM.
    [0004]
    4. Catalytic composite according to claim 1, characterized in that the 2nd catalytic layer further comprises platinum as the metal of the platinum group.
    [0005]
    5. Catalytic composite according to claim 4, characterized by the fact that the content of platinum in the layers is as follows: single catalytic layer from the front: 0.05 to 12.0% by weight of the layer; and 2nd catalytic layer: 0.01 to 5.0% by weight of the layer.
    [0006]
    6. Catalytic composite according to claim 1, characterized by the fact that it also comprises exhaust treatment materials selected from the group consisting of hydrocarbon storage and NOx storage catalysts in which the HC storage layers and of NOx are located as a coating WC layer underneath the substrate for the formation of the front zone or the front block and / or the rear zone or the rear block.
    [0007]
    7. Catalytic composite according to claim 1, characterized by the fact that it also comprises exhaust treatment materials selected from the group consisting of hydrocarbon and NOx storage catalysts in which the HC and NOx storage layer it is located as the top or full-layer WC layer for forming the front zone or the front block and / or the rear zone or the rear block.
    [0008]
    Catalytic composite according to claim 1, characterized in that the catalytic composite comprises an axial inlet end, an axial outlet end, wall elements having a length extending between the axial inlet end and the axial outlet end, and a plurality of axially closed channels defined through the wall elements; and wherein the single front catalytic layer is deposited on the wall elements adjacent the axial inlet end and having a length that extends for less than the length of the wall elements for forming the front zone; and the 1st and 2nd catalytic layers of the rear double layer are deposited on the wall element adjacent the axial outlet end and having a length that extends for less than the length of the wall elements for forming the rear zone.
    [0009]
    9. Catalytic composite according to claim 1, characterized by the fact that the single front layer is deposited on the entrance channels of a wall flow filter for the formation of the front zone and the 1st and 2nd catalytic layers are deposited in the inlet channels and / or in the outlet channels of the wall flow filter to form the rear zone.
    [0010]
    10. Exhaust treatment system characterized by the fact that it is for the purification of exhaust gases from a combustion engine operating substantially under stoichiometric conditions comprising a catalytic composite, as defined in claim 1.
    [0011]
    11. Exhaust treatment system according to claim 10, characterized by the fact that it also comprises one or more devices for the treatment of exhaust selected from the group consisting of particulate gasoline filter, device for storage of NOx and device for HC storage.
    [0012]
    12. Method for the treatment of exhaust gases from a combustion engine operating substantially under stoichiometric conditions, characterized by the fact that the method comprises: contacting a gas stream comprising hydrocarbons, carbon monoxide and nitrogen oxides with a catalytic composite as defined in claim 1, wherein the catalytic composite is effective for substantially and simultaneously oxidizing carbon monoxide and hydrocarbons and reducing nitrogen oxides.
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    同族专利:
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    KR101913662B1|2018-11-01|
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    WO2012069404A1|2012-05-31|
    CN103201019A|2013-07-10|
    JP2014509241A|2014-04-17|
    EP2643077B1|2019-03-20|
    BR112013012564A2|2016-08-30|
    EP2643077A1|2013-10-02|
    US20120128557A1|2012-05-24|
    US20130287660A1|2013-10-31|
    RU2013128389A|2014-12-27|
    KR20130131343A|2013-12-03|
    JP5841160B2|2016-01-13|
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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]|
    2019-06-04| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2020-04-14| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2020-10-20| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-01-05| B16A| Patent or certificate of addition of invention granted|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
    US12/951,301|US8557204B2|2010-11-22|2010-11-22|Three-way catalyst having an upstream single-layer catalyst|
    US12/951,301|2010-11-22|
    PCT/EP2011/070539|WO2012069404A1|2010-11-22|2011-11-21|Three-way catalytic system having an upstream single -layer catalyst|
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