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    • 专利摘要:
    catalyst article for use in an internal combustion engine and methods of treating engine exhaust and for manufacturing a catalyst article. catalyst articles comprising palladium and related method of preparation and use are described. A catalyst article is disclosed which comprises a first catalytic layer formed on a substrate, wherein the first catalytic layer formed on a substrate, wherein the first catalytic layer comprises palladium impregnated on a ceria-free platinum-impregnated oxygen storage component. a refractory metal oxide; and a second catalytic layer formed on the first catalytic layer comprising platinum and rhodium impregnated onto a ceria-containing oxygen storage component. The palladium component of the catalyst article is present in a higher proportion to the other metal components of the platinum group. Catalyst articles provide improved conversion of carbon monoxide into exhaust gases, particularly under rich engine operating conditions.
    公开号:BR112012022487B1
    申请号:R112012022487
    申请日:2011-03-04
    公开日:2018-09-25
    发明作者:Alive Keshavaraja；P Galligan Michael；Harrison Tran Pascaline；Liu Xinsheng；Liu Ye
    申请人:Basf Corp；
    IPC主号:
    专利说明:

    (54) Title: CATALYST ARTICLE FOR USE IN AN INTERNAL COMBUSTION ENGINE AND METHODS OF TREATING EXHAUST ENGINES AND MANUFACTURING A CATALYST ARTICLE.
    (51) Int.CI .: B01J 23/63; B01J 35/02; B01J 37/02; B01D 53/94 (30) Unionist Priority: 3/2/2011 US 13/038784, 3/5/2010 US 61/310922 (73) Holder (s): BASF CORPORATION (72) Inventor (s): XINSHENG LIU; YE LIU; PASCALINE HARRISON TRAN; KESHAVARAJA ALIVE; MICHAEL P. GALLIGAN (85) National Phase Start Date: 09/05/2012 “CATALYST ARTICLE FOR USE IN AN INTERNAL COMBUSTION ENGINE AND METHODS OF TREATING EXHAUST ENGINES AND MANUFACTURING A CATALYST ARTICLE”
    TECHNICAL FIELD
    This invention relates to articles of catalyst useful for the treatment of gas streams containing hydrocarbons, carbon monoxide and nitrogen oxides; methods of using catalyst articles for the treatment of gas streams and methods for producing catalyst articles. More particularly, the present invention provides catalyst articles and methods for treating the exhaust produced by internal combustion engines, including carbureted motorcycle engines.
    FUNDAMENTALS
    Exhaust gases from internal combustion engines contain pollutants, such as hydrocarbons, carbon monoxide and nitrogen oxides (NO X ) that dirty the air. Emission standards for contaminants from unburned hydrocarbons, carbon monoxide and nitrogen oxide have been established by several governments and must be met by older vehicles, as well as new ones. In order to meet these standards, catalytic converters that contain a three-way catalyst (TWC) can be located in the exhaust gas line of internal combustion engines. The use of exhaust gas catalysts has contributed to a significant improvement in air quality. TWC is the most commonly used catalyst and provides the three functions of oxidation of carbon monoxide (CO), oxidation of unburned hydrocarbons (HC's) and the reduction of NOx to N 2 . TWCs typically use one or more platinum group metals (PGM) to simultaneously oxidize CO and HC and reduce NOx compounds. The most common catalytic components of a TWC are platinum (Pt), rhodium (Rh) and palladium (Pd) .
    TWC catalysts perform best when the engine operates over or close to stoichiometric conditions (air / fuel ratio, λ = 1). In actual use, however, the motors must operate on either side of λ = 1 at various stages during the operating cycle. For example, in enriched operating conditions such as during acceleration, the exhaust gas composition is reducing and it is more difficult to carry out oxidation reactions on the catalyst surface. For this reason, TWC’s have been developed to incorporate a component that stores oxygen during depleted portions of the operating cycle and releases oxygen during enriched portions of the operating cycle. This component is ceria-based in most commercial TWC’s. Unfortunately, when the ceria is doped with precious metal catalysts, it tends to lose its surface area when exposed to high temperatures, for example, 800 ° C, or above, and the overall performance of the catalyst is degraded. Therefore, TWC’s that use mixed ceria-zirconia oxides as the oxygen storage component have been developed, since mixed oxides are more stable for loss of surface area than ceria individually. TWC catalysts are generally formulated as wash coating compositions containing supports, oxygen storage components and PGMs. These catalysts are designed to be effective over a specific range of operating conditions that are both impoverished and enriched compared to stoichiometric conditions.
    The platinum group metals in the TWC catalysts (eg platinum, palladium, rhodium, rhenium and iridium) are typically arranged in a raised surface area, refractory metal oxide support, for example, an alumina coating in the elevated surface, or in an oxygen storage component. The support is made of a suitable carrier or substrate, such as a substrate that comprises a honeycomb-like structure of refractory metal or ceramic, or refractory particles such as spheres or small extruded segments, of a suitable refractory material. The TWC catalyst substrate can also be a wire mesh, typically a metal wire mesh, which is particularly useful in small engines.
    Refractory metal oxides, such as alumina, bulk ceria, zirconia, alpha alumina and other materials can be used as supports for the catalytic components of a catalyst article. Alumina support materials, also referred to as alumina gamma or activated alumina, typically exhibit a BET surface area in excess of 60 square meters per gram (m 2 / g), often up to about 200 m 2 / g or more . Such activated alumina is generally a mixture of gamma and delta alumina phases, but can also contain substantial amounts of eta, kappa and theta phases of alumina, although many of the other refractory metal oxide supports suffer from the disadvantage of having a surface area. considerably less BET than activated alumina, the disadvantage of which tends to be offset by a longer durability of the resulting catalyst. The oxygen storage components, as discussed above, can also be used as supports for the TWC PGM components.
    In a running engine, the temperatures of the exhaust gases can reach 1000 ° C, and such high temperatures cause the support material to suffer thermal degradation caused by a phase transition with accompanying volume shrinkage, especially in the presence of steam, in which the catalytic metal becomes clogged in the shrunk support medium with a loss of exposed catalyst surface area and a corresponding decrease in catalytic activity. Alumina supports can be stabilized against such thermal degradation, using materials such as zirconia, titanium oxide, alkaline earth metal oxides, such as barium, calcium or strontium or rare earth metal oxides, such as cerium , lanthanum and mixtures of two or more oxides of rare earth metals.
    The stability of the automotive catalyst is tested in the laboratory by exposing the catalyst to accelerated aging under laboratory conditions in different atmospheres. These test protocols mimic the operating conditions of the engine, including high temperatures and depleted / enriched exhaust gas disturbances. Such tests typically include high temperatures, in the presence or absence of water. Two types of accelerated aging protocols are steam / air (oxidative hydrothermal aging, simulating impoverished operating conditions) or aging in an atmosphere of nitrogen, argon or hydrogen (inert aging simulating enriched operating conditions). Although tests on both catalyst aging conditions provide better reproduction of catalyst performance in actual use in the engine environment, more attention in the field has been given to the development of catalysts that survive under high steam / air aging conditions temperature. Little has been done to resolve the catalyst's stability through rich high temperature aging. Current catalyst technology exhibits significant catalyst deactivation under enriched aging conditions, especially when exposed in sequence to both steam / air protocols and enriched aging protocols at elevated temperatures.
    In a carbureted motorcycle engine, wide ranges of air to fuel ratios are often found as a result of loss of control by the carburetor. An emission control catalyst is therefore required to function in this wide range of environments and often loses CO conversion activity under enriched aging conditions. Thus, there is a need for a catalyst article containing TWC with improved CO conversion stability and performance after hydrothermal aging, particularly in enriched engine operating conditions. The catalysts of the present invention address this need. It is known that the conversion of CO under enriched conditions is carried out through two oxidation reactions: (CO + '/ 2 O 2 = CO 2 ) and gas-water displacement (WGS) (CO + H 2 O = CO 2 + H 2 ). It has now been found that hydrothermal aging processes are more detrimental to the WGS reaction than to the oxidation reaction and that maintaining good PGM dispersion under these conditions is essential for WGS activity. The inventive catalysts described herein exhibit improved PGM dispersion after hydrothermal aging and provide improved catalyst performance.
    SUMMARY
    One embodiment of the present invention is directed to a catalyst article and methods of preparation and use. In one aspect, a first catalytic layer is formed on a support substrate, wherein the first catalytic layer comprises palladium impregnated with a ceria-free oxygen storage component. The exempt oxygen storage component. ceria can be a composite of zirconia and a rare earth metal oxide other than ceria, for example, praseodymia, neodymia or lanthania. The first catalytic layer may also comprise platinum and / or palladium impregnated on a metal oxide support. A second catalytic layer is formed on top of the first catalytic layer, where the second catalytic layer comprises platinum and rhodium impregnated on an OSC support with a high content of cerium. The second catalytic layer is free of palladium and substantially free of refractory metal oxides. In one embodiment, the catalyst article exhibits improved CO conversion stability and performance over known TWC catalyst articles, particularly under enriched operating conditions. The substrate of the catalyst article can typically be a honeycomb-like structure. The catalyst article may further comprise an optional chemical etching coating layer formed on a substrate, wherein the chemical etching coating layer comprises a refractory metal oxide and has a surface that is substantially uniform.
    In another aspect of the invention, the catalyst article is optionally made by coating on a substrate a chemical etching coating layer comprising a refractory metal oxide in an acidic sol, drying the chemical etching coating layer to obtain a surface substantially uniform, depositing a first catalytic layer on the chemical etching coating layer by coating a paste on the chemical etching coating layer (if present) or on the substrate (if the chemical etching coating layer is not present) , the paste comprising 1) a ceria-free oxygen storage component impregnated with palladium and 2) platinum impregnated in a refractory metal oxide support, and drying of the first catalytic layer. A portion of the palladium in the first catalytic layer can also be impregnated on the refractory metal oxide support. The ceria-free oxygen storage component of the first catalytic layer may be a composite of zirconia and a rare earth metal oxide other than ceria, for example, praseodymia, neodymia or lanthania. A second catalytic layer is deposited on the first catalytic layer by coating a paste on the first catalytic layer, the paste comprising platinum and rhodium impregnated in a ceria OSC, which is substantially free of refractory metal oxides, in which the OSC has a high content of cerium.
    The catalyst articles of the present invention are particularly useful for the treatment of exhaust gases produced by internal combustion engines, such as carburized motorcycle engines, where depleted / enriched fluctuations in operating conditions produce high variations in exhaust contaminants that must be removed. In particular, articles of conventional catalysts are subject to a rapid loss of activity for the conversion of CO under enriched conditions. The catalyst articles of the present invention exhibit substantially less deterioration in CO conversion compared to the performance of the fresh catalyst under such operating conditions.
    DESCRIPTION OF THE DRAWINGS
    Fig. 1 is a bar graph showing the relative contributions of WSC and oxidation reactions to the conversion of CO with the aging of the catalyst.
    Fig. 2A and Fig. 2B are bar graphs comparing PGM surface available after depleted and enriched aging for CSOs containing varying amounts.
    Fig. 3 is a graph of the efficiency of CO conversion for the inventive catalysts, under enriched and depleted operating conditions.
    Fig. 4 is a graph of HC conversion efficiency for inventive catalysts under enriched and depleted operating conditions.
    DETAILED DESCRIPTION
    The present invention relates to catalyst articles, catalyst article components, methods of using catalyst articles and methods of producing catalyst articles, generally referred to as a three-way conversion catalyst and which has the ability to simultaneously catalyze the oxidation of hydrocarbons and carbon monoxide and the reduction of nitrogen oxides. The catalyst article according to an embodiment of the invention comprises at least two layers of washing coating. It has been found that substantially improved performance in enriched operating conditions is achieved by providing two layers containing catalysts on a substrate, wherein the first catalytic layer comprises a high level of palladium in relation to platinum and rhodium in the catalyst article. In the first catalytic layer, the palladium component is supported in a ceria-free oxygen storage component. A portion of the palladium can also be supported on a deficient metal oxide. The platinum component of the first catalytic layer is supported by a refractory metal oxide, however, a portion of the platinum component can also be supported on the ceria-free oxygen storage component. The second catalytic layer is substantially free of refractory metal oxides, such as zirconia and alumina, and substantially free of non-ceria rare earth oxides and comprises platinum and rhodium supported on an oxygen storage component having a high cerium content.
    As used here, the term high cerium content with reference to an oxygen storage component means that the OSC contains ceria (CeO 2 ) in an amount by weight between about 45% to about 100%, for example, about 60% to about 100%, about 80% to 100%, about 90% to about 100% or about 100%. The ceria-containing OSC may contain additional components, such as non-ceria rare earth oxides or refractory metal oxides such as alumina or zirconia. Such additional components will typically be present in amounts less than about 55% by weight of the OSC containing ceria, but in general should not represent more than about 5 to 40% by weight of OSC. In one aspect of the invention, the support containing ceria for platinum and rhodium in the second catalytic layer is pure ceria, also called mass ceria. In an additional aspect, the supports for platinum and rhodium in the second catalytic layer are pure ceria and Zr-doped alumina, where the amount of alumina in the second catalytic layer is less than or equal to about 15% by weight of the second layer catalytic.
    As used herein, the term ceria-free oxygen storage component or ceria-free OSC ”refers to an OSC that contains less than 1% ceria, preferably less than 0.5% ceria and more preferably essentially 0% ceria. Examples of non-ceria CSOs include zirconia-praseodymia, zirconia-neodymia, zirconia-listria and zirconia-lanthania.
    As used herein, the term substantially free of refractory metal oxides and their equivalents in relation to an OSC means that refractory metal oxides conventionally used to stabilize CSOs are present in the OSC in amounts of no more than about 50% in weight, for example, about 20% to 50%, about 5% to 30%, about 0% to 10%, about 0% to 5% or are essentially absent.
    As used herein, the term substantially free of non-ceria rare earth oxides or their equivalents in relation to an OSC means that ceria represents the majority of rare earth oxides present in the OSC. If other rare earth oxides are present, they are in an amount of no more than about 10% by weight, for example, about 5% to 10%, or about 5% are essentially absent. Non-ceria rare earth oxides include lanthanum, praseodymia and neodymia, the total of which is not more than about 10% by weight of the catalytic layer.
    As used herein, the term palladium-high, with reference to a catalyst article or a layer of a catalyst article, the palladium content by weight in the article or the layer is greater than the weight content of non-palladium PGM components in the article or layer. Preferably, the palladium content is higher than each of the non-palladium PGM components. Most preferably, the palladium content is higher than the total content of all non-palladium PGM components. In one aspect, the palladium content can be 3 to 10 times higher than the total non-palladium PGM content of the catalytic layer or catalyst article. Typically, the total PGM content of the catalyst article is 30 to 100 g / ft 3 , (1059.44 to 3531.47 g / m 3 ) 50 to 80 g / ft 3 (1765.73 to 2825.17 g / m 3 ), or about 75 g / ft 3 (2648.6 g / m 3 ).
    As used herein, the term palladium-free with reference to a catalyst article layer or a catalyst article composition means that no palladium is added to the layer or composition. However, trace amounts of residual palladium may be present in the layer or composition as a contaminant of other ingredients included in the composition or layer. Such trace amounts are included in the term palladium-free and normally do not constitute more than 0.5%, preferably less than 0.5% and more preferably 0% of the layer or composition by weight.
    As used herein, the term substantially uniform with respect to a layer of the catalyst article means the surface of the layer that is free of defects over at least about 90% of the total surface area. The substantially uniform surface does not present more than about 10% of the total surface area of the layer of cracks, cracks or flaking of the surface of the layer.
    As used herein, the term support with respect to a catalytic layer refers to a material that receives platinum group metals, stabilizers, promoters, binders, and the like through association, dispersion, impregnation or other suitable methods . Examples of supports include, but are not limited to, refractory metal oxides, high surface area refractory metal oxides and materials containing oxygen storage components. Refractory metal oxide supports with a high surface area include activated compounds selected from the group consisting of alumina, aluminazirconia, alumina-ceria-zirconia, lanthania-alumina, lanthania-zirconia-alumina, alumina-baria, baria lantana- alumina, baria lanthania-neodymia alumina and alumina-ceria. Examples of materials containing oxygen storage components include, but are not limited to, ceriazirconia, ceria-zirconia-lanthania, zirconia-praseodymia, yttria-zirconia, zirconia-mimia and zirconia-lanthania. In certain embodiments, the support comprises bulk rare earth metal oxide, such as bulk ceria with a nominal 100% rare earth metal content (i.e., purity> 99%).
    As used herein, the term oxygen storage component (OSC) refers to a material that has a state of multivalence and can react actively with oxidants such as oxygen or nitrous oxide under oxidizing conditions, or with reducers such as monoxide carbon (CO) or hydrogen, under reduction conditions. Examples of oxygen storage components include ceria and praseodymy. The distribution of an OSC to a layer can be achieved through the use of, for example, mixed oxides. For example, ceria can be distributed by a mixed cerium and zirconium oxide, a mixed cerium, zirconium, neodymium oxide and / or a mixed cerium, zirconium, lanthanum, and praseodymium oxide. In another example, praseodymium can be distributed by a mixed oxide of praseodymium and zirconium, and / or a mixed oxide of praseodymium, cerium, lanthanum, yttrium, zirconium, and neodymium.
    As used herein, the term impregnated means that a solution containing platinum group metal is placed in pores of a support. In detailed embodiments, the impregnation of the metals in the platinum group is achieved through incipient moisture, in which a diluted volume of metal in the platinum group is approximately equal to the pore volume of the support bodies. The incipient moisture impregnation generally leads to a substantially uniform distribution of the precursor solution through the support pore system.
    As used here, the component in connection with a platinum group metal means any compound, complex, or the like that, upon calcination, or its use, decomposes or converts to a catalytically active form of the platinum group metal , usually metal or metal oxide. Water-soluble compounds or water-dispersible compounds or metal component complexes can be used as long as the liquid medium used to impregnate or deposit the metal component on the refractory oxide metal support particles does not react with the metal or its compound or its complexes or other components that may be present in the catalyst composition and is capable of being removed from the metal component by volatilization or decomposition upon heating and / or applying a vacuum. In some cases, the completion of liquid removal cannot occur until the catalyst is put into use and subjected to the high temperatures encountered during operation. Generally, both from the point of view of economic and environmental aspects, aqueous solutions of soluble compounds or complexes of metals of the platinum group are used. For example, suitable compounds include palladium nitrate. During the calcination step, or at least during the initial use phase of the compounds, these compounds are converted into a catalytically active form of the metal or a composite thereof.
    In a first aspect, the catalyst article of the present invention is a palladium-rich article, comprising: a first catalytic layer on a suitable substrate, the first catalytic layer comprising a high level of palladium. All the palladium components present in the catalyst article are contained in the first catalytic layer. A portion of the palladium component in the first catalytic layer can be supported on a refractory metal oxide support, preferably a support of high refractory metal oxide surface area. The remaining portion of the palladium component in the first catalytic layer is supported in a ceria-free oxygen storage component, preferably zirconia doped with praseodymia, lanthania, neodymia, yttria or a mixture thereof. Alternatively, all palladium can be supported on the ceria-free oxygen storage component. The first catalytic layer may further comprise a platinum component supported on a refractory metal oxide, which may be a support containing alumina. The first catalytic layer is coated with a second catalytic layer comprising a rhodium component and a platinum component supported on a ceria containing oxygen storage component. The second catalytic layer is free of palladium and substantially free of a non-ceria oxygen storage component.
    In an additional aspect, the OSC of the first catalytic layer is a praseodymy-zirconia composite, a yttria-zirconia composite, a neodymium-zirconia composite or a lanthania-zirconia composite in which the composite's rare earth component represents about 1 to 40% by weight. In the second catalytic layer the composite may comprise bulk ceria or ceria in a composite with small amounts of zirconia, lanthania, neodymia or praseodymia. The compound can be prepared using methods known in the art, including coprecipitation, sun gels and the mixing of rare earth metal oxide with zirconia. The presence of a rare earth metal oxide in such composites typically gives improved thermal stability to the zirconia component.
    Another aspect of the invention provides that the palladium component of the catalyst article is present, in weight, in higher amounts than in either or both of the platinum component and the rhodium component. The ratio of platinum to palladium to rhodium (Pt / Pd / Rh), by weight, can be 0.5 to 5/2 to 80 / 0.1 to 5, 1 to 3/5 to 40 / 0.25 to 2 or about 2/9/1, respectively. That is, in a specific embodiment, the palladium content of the catalyst article is about 4 to 5 times the platinum content and about 8 to 10 times the rhodium content.
    Other aspects of the invention provide that the second catalytic layer comprises a cerium OSC with a high cerium content. Platinum and rhodium components are supported in ceria OSC. In one or more modalities, the ceria OSC comprises ceria en masse (providing essentially 100% cerium). Alternatively, the high cerium CSO may comprise about 55 to 65% ceria, about 2 to 4% lanthania, about 6 to 8% praseodymia and about 25 to 35% zirconia or about 40 at 50% ceria, about 4 to 5% neodymia and about 45 to 50% zirconia. The second catalytic layer is free of palladium, substantially free of non-ceria OSC and substantially free of refractory metal oxides, as defined above. The rhodium and platinum components are fully supported in the cerium OSC.
    Other aspects of the present invention provide methods for treating a gas comprising hydrocarbons, carbon monoxide and nitrogen oxides, the method comprising: contacting the gas in a gasoline engine exhaust stream with a catalytic material on a substrate, the catalytic material comprising the two catalytic layers described herein, with or without an optional chemical etching coating layer underlying the first catalytic layer, such that hydrocarbon, carbon monoxide and NOx in the exhaust stream are reduced. In particular, CO in the exhaust stream is substantially reduced by the catalyst articles of the invention, after enriched aging compared to catalyst articles in which the second catalytic layer has a lower cerium content (typically present as an oxide composite). refractory metal with ceria) and includes oxides of refractory metals such as supports for platinum and rhodium.
    One aspect of the present invention provides a catalyst article comprising: a catalytic material on a substrate, the catalytic material comprising the two catalytic layers described herein and the catalyst article which further comprises a chemical etching coating layer between the substrate and the first catalytic layer . The chemical etching coating layer comprises a high surface area of refractory metal oxide and is preferably prepared in such a way that the surface is substantially uniform. A substantially uniform surface over the chemical etching coating provides improved bonding of the first catalytic layer to the substrate and is particularly advantageous when the catalyst article is used in high vibration environments, such as small engines. A quick and complete drying of the chemical etching coating facilitates the production of a substantially uniform surface and can be achieved by drying the layer at lower temperatures with air movement. The complete drying of the chemical etching coating also contributes to obtaining a uniform distribution of the palladium component in the first catalytic layer.
    In one embodiment, a significant improvement in reducing CO emissions from a carb gasoline engine, such as a motorcycle engine, can be achieved using the catalyst articles of the present invention. Improvement in hydrocarbon conversion can also be achieved. NOx conversion performance is usually comparable to known catalyst articles, however, NOx reduction is of less interest in motorcycle applications than CO reduction. The catalyst articles of the present invention exhibit substantially better CO conversion performance under enriched engine operating conditions, as is normally the case with small carbureted engines.
    In detailed aspects, the ceria-free oxygen storage component is typically present in the first catalytic layer in an amount of 10 to 60%, 30 to 50% or 40 to 50% by weight of the components of the first catalytic layer. The oxygen storage component with ceria in the second catalytic layer is typically present in an amount of 20 to 100%, 40 to 100%, 60 to 100% or 80 to 100% by weight of the components of the second catalytic layer.
    One or more modalities that provide the PGM components are present in an amount of about 10 to 150 g / ft 3 (353.14 to
    5297.2 g / m 3 ), about 20 to 100 g / ft 3 (706.29 to 3531.47 g / m 3 ) or about 40 to 80 g / ft 3 (1412.59 to 2825.17 g / m 3 ) In a specific embodiment, the PGM components are present in an amount of about 45 g / ft 3 (1558.16 g / m 3 ), 60 g / ft 3 (2118.88 g / m 3 ) or 75 g / ft 3 (2648.8 g / m 3 ) in the catalyst article. It should be understood that the content of each PGM in the catalyst article, and therefore its relative weight ratios, can be varied to achieve the desired total PGM content. It is generally preferred that palladium is present in higher amounts than platinum and rhodium to reduce the cost, however, this is not necessary for the function of the catalyst article. Typically, platinum is present at 1 to 90 g / ft 3 (35.31 to
    3178.32 g / m 3 ), palladium is present at 1 to 90 g / ft s (35.31 to 3178.32 g / m 3 ) and rhodium is present at 1 to 30 g / ft 3 (35.31 at 1059.44 g / m 3 ). In a specific embodiment, platinum is present in 2 to 20 g / ft 3 (70.63 to 706.29 g / m 3 ), palladium is present in 20 to 70 g / ft 3 (706.29 to 2472.03 g / m 3 ) and rhodium is present in 1 to 10 g / ft 3 (35.31 to 353.14 g / m 3 ). In other specific embodiments, the total PGM is 45 g / ft 3 (1589.16 g / m 3 ), 60 g / ft 3 (2118.88 g / m 3 ) or 75 g / ft 3 (2648.8 g / m 3 ), optionally, with a Pt / Pd / Rh ratio of 2/9/1.
    A detailed embodiment provides two catalytic layers on the substrate. The first catalytic layer is a palladium-rich layer coated on the substrate and comprises palladium impregnated with zirconia doped with praseodymia and alumina, and platinum impregnated with alumina. The first catalytic layer is coated on the substrate, and calcined. A second catalytic layer is coated over the first catalytic layer and comprises rhodium and platinum impregnated in a mass OSC-ceria. The second catalytic layer is also calcined.
    A second detailed embodiment provides three layers on the substrate. The first layer coated on the substrate is a chemical etching coating layer comprising a refractory metal oxide such as gamma alumina. The chemical etching coating layer is coated and dried on the substrate in such a way that its surface is substantially uniform, that is, substantially free of defects such as cracks, cracks and flaking. The first catalytic layer comprises a ceria-free OSC support, for example, praseodymy doped zirconia, and a high refractory metal oxide surface area such as alumina range impregnated with palladium and palladium / platinum, respectively. A second catalytic layer coated on the first catalytic layer comprises platinum and / or rhodium, but does not contain palladium. The second catalytic layer comprises rhodium and platinum impregnated in an OSC support, such as ceria, which is substantially free of refractory metal oxides, such as zirconia and alumina, and substantially free of non-ceria CSOs, such as lanthania, praseodymia and neodymia. The weight ratio of platinum / palladium / rhodium is typically 0.5 to 5/2 to 80/0, 1 to 5, 1 to 3/5 to 40 / 0.25 to 2 or about 2/9/1 .
    In another aspect, a method is provided for the treatment of a gas that comprises hydrocarbons, carbon monoxide and nitrogen oxides, the method comprising: contacting the gas in a gasoline engine exhaust stream with a catalytic material on a substrate , the catalytic material comprising two catalytic layers as described herein. Optionally, the catalytic material may further comprise a chemical etching coating layer as described herein coated on the substrate prior to depositing the first catalytic layer. In a further aspect, the first catalytic layer of the catalytic material is coated on a chemical etching coating comprising a high refractory metal oxide surface area, where the chemical etching coating surface is substantially uniform. According to the invention, this method is effective for removing significantly more CO from exhaust gases under enriched engine operating conditions than catalytic materials where the cerium content of the second catalytic layer is lower and significant amounts of oxides refractory metals and / or non-ceria CSOs are present. The improved reduction in hydrocarbons can also be performed under enriched engine operating conditions using the catalyst materials of the present invention.
    An additional aspect provides a method for making a catalyst article, the method comprising: optionally forming a chemical etching coating on a substrate by coating a refractory metal oxide, preferably a high surface area of refractory metal oxide , on the substrate. The coating can be carried out by any of the coating methods known in the art, such as dipping or manual airbrushing. The chemical etching coating is subsequently dried using heat and air, preferably selecting the temperature and air flow in such a way that a substantially uniform chemical etching coating surface is formed. The drying temperature can be in the range of about 60 to 140 ° C. A smooth to moderate air flow is maintained throughout the substrate, while drying the chemical etching coating, as can be provided by a conventional fan. The chemical etching coating layer is then calcined, typically at 490 to 550 ° C for 1 to 2 hours. The first catalytic layer is coated over the chemical etching coating.
    The first layer of catalytic coating is carried out by deposition on the chemical etching coating or directly on the substrate of a palladium-rich catalytic material comprising palladium impregnated in a rare earth-doped zirconia support and platinum impregnated in a support of refractory metal oxide. The OSC rare earth component in the first catalytic layer can have 1 to 40% by weight of the composite. The first catalytic layer is then dried and calcined, usually at 490 to 550 ° C for 1 to 2 hours. A second catalytic layer is coated over the first catalytic layer. The second catalytic layer comprises platinum and rhodium supported in a cerium OSC, where the cerium OSC support has a high ceria content and is substantially free of refractory metal oxides, and substantially free of non-ceria CSOs. The second catalytic layer is palladium-free. The OSC containing cerium in the second catalytic layer can be, for example, ceria by mass (100% CeO 2 ) or a ceria composite with refractory metal oxides and / or non-ceria CSOs as long as the ceria content of the material is at least about 40%, at least about 45% or at least about 60% by weight. The PGM content ratio of the catalyst article is typically about 0.5 to 5/5 to 15 / 0.1 to 5.1 to 3/5 to 40 / 0.25 to 2 or about 2/9/1 by weight (Pt / Pd / Rh).
    Details of the components of a catalyst article according to the invention are provided below.
    The Substrate
    According to one or more embodiments, the substrate can be any of the materials normally used for the preparation of TWC catalysts and will preferably comprise a metal or ceramic structure. Any suitable substrate can be employed, such as a monolithic substrate of the type having a plurality of parallel, thin gas flow passages that extend through it from an inlet or outlet face of the substrate, such that the passages are open for the flow of fluid through them. The passages, which are essentially straight pathways from their fluid inlet to their fluid outlet, are defined by walls on which the catalytic material is coated as a wash coat 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 have any shape and size of suitable cross-section such as trapezoidal, rectangular, square, sinusoidal, hexagonal, oval, circular, etc. Such structures can contain about 60 to about 600 or more gas inlet openings (i.e., cells) per square inch of cross section.
    The ceramic substrate can be made of any suitable refractory material, for example, cordierite, cordierite-α alumina, silicon nitride, zirconium mullite, spodumene, silica-magnesia alumina, zirconium silicate, silimanite, magnesium silicates, zirconium, petalite, a-alumina, aluminosilicates and the like.
    The substrates useful for the layered catalyst composites of the present invention can also be of a metallic nature and be composed of one or more metals or metal alloys. Metal substrates can be used in various forms, such as corrugated sheet, metal plate, wire mesh or 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 may contain one or more of nickel, chromium and / or aluminum, and the total amount of these metals may advantageously comprise at least 15% by weight of the alloy, for example, 10 to 25% by weight of chromium, 3 to 8% by weight of aluminum and up to 20% by weight of nickel. The alloys can also contain small amounts or traces of one or more other metals, such as copper, manganese, vanadium, titanium and the like. The surface of the metal substrates can be oxidized at elevated temperatures, for example, 1000 ° C and higher, to improve the corrosion resistance of the alloy, by forming an oxide layer on the substrate surface. Such oxidation induced by high temperature can potentiate the adhesion of the support of refractory metal oxide and component of promoting metals in a catalytic way to the substrate.
    Catalytic Materials
    The catalytic materials of the present invention are formed in two layers. The composition for each catalytic layer is prepared as a suspension of the PGM component and this paste is used to form the layers on the substrate. Materials can be easily prepared by processes well known in the prior art. A representative process is presented below. As used herein, the wash coating has its usual significance in the art of a thin, adherent coating of a catalytic or other material applied to a substrate support material, such as a honeycomb or mesh substrate component of wire, which is sufficiently porous to allow passage through the gas stream to be treated.
    To obtain a layer of a specific wash coating, the finely divided particles of an oxide surface of high refractory metal such as gamma alumina, or an OSC, such as praseodymy-zirconia, are suspended in a suitable vehicle, for example , Water. The substrate can then be immersed one or more times in the paste or the paste can be coated on the substrate in such a way that the desired charge of the metal oxide or OSC will be deposited on the substrate, for example, about 0.5 to about from 2.5 g / in 3 (about 0.03 to 0.15 g / cm 3 ) about a by dipping. To incorporate components such as platinum group metals (for example, palladium, rhodium, platinum and / or combinations thereof), stabilizers and / or promoters, such components can be incorporated into the paste as a mixture of compounds or complexes soluble in water or water dispersible. Then, the coated substrate is calcined by heating, for example, at 500 to 600 ° C for about 1 to about 3 hours. Typically, the PGM component is used in the form of a compound or complex to achieve dispersion of the component on the deficient metal oxide support. A suitable method of preparing any catalytic layer of the catalyst article of the present invention is to prepare a mixture of a solution of a metal component of the desired platinum group and at least one support, such as a refractory metal oxide support, of area raised, finely divided surface, for example, alumina coated with zirconia or gamma-alumina, which is sufficiently dry to absorb substantially all of the solution to form a wet solid which is then combined with water to form a coating paste. In one or more embodiments, the slurry is acidic, having, for example, a pH of about 2 to less than about 7. The pH of the slurry can be reduced by adding an appropriate amount of an inorganic acid or organic to the mixture. Combinations of both can be used when compatibility of raw materials and acid is considered. Inorganic acids include, but are not limited to, nitric acid. Organic acids include, but are not limited to, acetic, propionic, oxalic, malonic, succinic, glutamic, adipic, maleic, fumaric, phthalic, tartaric, citric and the like. Thereafter, if desired, water-soluble or water-dispersible compounds from oxygen storage components, for example, cerium-zirconia composites, a stabilizer, for example, barium acetate, and a promoter, for example, nitrate lanthanum, can be added to the suspension. The metal components of the platinum group can also be impregnated in the oxygen storage component, for example, zirconia doped with praseodymia or ceria-zirconia, in a similar way, prior to addition to the paste.
    In one embodiment, the paste is then crushed to reduce the size of the support particles. The crushing can be carried out in a ball mill or other similar equipment, and the solids content of the paste can be, for example, about 20 to 60% by weight, more particularly, about 30 to 40% by weight.
    Additional layers can be prepared and deposited on the first catalytic layer in the same manner as described above for the deposition of the first catalytic layer.
    Before describing several exemplary embodiments of the invention, it should be understood that the invention is not limited to the details of construction or process of the steps defined in the description that follows. The invention is capable of other modalities and is practiced in several ways. The following non-limiting examples serve to illustrate certain embodiments of the present invention.
    Example 1: Effect of Aging Conditions on the Water-Gas Displacement Reaction
    The effect of hydrothermal aging on the water-gas displacement reaction (WGS) was evaluated as follows: the catalyst (Reference Catalyst A, 40 g / ft 3 (1412.59 g / m 3 ), 2/4 / 1) was subjected to a wash coating on a metallic substrate (1 in diameter and 2 in length, 300 cpsi), then it was tested in a laboratory reactor of 70,000 l / h, 450 ° C. The gas composition was as follows: - 5.4% CO, ~ 10% CO 2 C 3 H6 plus C 3 H 8 (in the ratio of 2) -360 ppm and NO -500 ppm. The air and N 2 flows were controlled for lambda = 0.94 The test was carried out both in wet conditions (H 2 O -6%) and in dry conditions, with no H 2 O in the feed.
    The results are shown in Fig. 1, which shows an insignificant decrease in CO conversion after aging attributable to a reduction in the oxidation reaction. In contrast, the reduction in CO conversion due to the reduction in WGS was substantially greater, and was reduced from more than 60% to less than 40% conversion. It is concluded that the WGS is important for the efficient conversion of CO under enriched conditions and that the maintenance of the WGS reaction activity contributes to the improved stability and durability of the catalyst after aging.
    Example 2: Effect of Cerium Content on the PGM Surface
    Available
    CSOs with ceria containing varying amounts of ceria in relation to non-ceria refractory metal oxide components were impregnated with each of 0.5% platinum, 0.25% rhodium and 0.5% platinum / 0 platinum / 0 , 25% rhodium. OSC support compositions are shown in Table 1.
    TABLE
    Support# CeO 2 LaO 3 Pr 6 O „ Nd 2 O 3 ZrO 2 A1 2 O 3 #1 100% ... ... ... ... ... #2 59.9% 3.1% 7% ... 30% ... # 3 45.6% ... ... 4.8% 49.6% ... # 4 ... ... ... ... 18.2% 81.8% # 5 ... 3% ... ... 20% 77%
    For the evaluation of PGM available on the metal surface, CO chemisorption, followed by diffuse reflectance FT-IR (DRIFTS) was used. A sample of the catalyst was initially loaded into the sample container of a peak diffuse reflectance chamber on a spectrometer
    Varian FTS-7000 equipped with an MCT detector and then reduced with 7% H 2 , in argon (flow rate: 40cm 3 / min) at 400 ° C for 1h. After cooling to 30 ° C in an argon atmosphere, the DRIFT spectrum was collected with a spectral resolution of 2 cm ' 1 . Thereafter, 1% CO in argon was introduced at 40 cm 3 / min into the sample chamber and spectra were collected until equilibrium was reached. Spectral differences were obtained by taking the ratio of the CO adsorption spectrum to the spectrum before introducing CO. The bands in the spectrum corresponding to the chemo-vivid CO on the metal surface of PGM were integrated and the intensity of the band was taken as a measure of PGM available on the metal surface.
    The results are shown in Fig. 2A and Fig. 2B, which demonstrates that the PGM surface available after enriched aging is substantially higher for catalysts containing 45.6% to 100% ceria. In addition, the bulk ceria support had substantially greater available PGM surface after depleted aging compared to supports that were ceria composites or that did not contain any ceria.
    Example 3: Catalyst Performance Test
    Aged
    Catalyst preparation - A cylindrical metallic honeycomb substrate was used as a vehicle. The carrier had a diameter of 1.57 inches (3.99 centimeters), a length of 3.54 inches (8.99 centimeters) and a total volume of 6.9 cubic inches (114.54 cubic centimeters). Three catalysts according to the invention and a catalyst for use as a control were prepared. The total precious metal content of the inventive catalysts was 45 g / ft 3 (1589.16 g / m 3 ), 60 g / ft 3 ( 2118.88 g / m 3 ) or 75 g / ft 3 (2648.8 g / m 3 ). The catalyst controls had a total precious metal content of 100 g / ft 3 (3531.47 g / m 3 ). The precious metal component consisted of palladium, platinum and rhodium in a ratio of 2/9/1, respectively, in each catalyst. The metal carrier was pre-treated at 930 ° C for 6 hours to form a thin layer of alumina on the surface.
    A first catalytic layer in the form of an aqueous solution was applied to the carrier surface. The paste used for the first catalytic layer of the 75 g / ft 3 catalyst (2648.8 g / m 3 ) consisted of a content of approximately 40% solids, the aqueous solution containing 228 g of alumina, 228 g of doped zirconia with Pr, 30 g of barium hydroxide, 12.4 g of Pd impregnated with alumina and zirconia doped with Pr as a solution of Pd nitrate and 0.27 g of Pt impregnated as a solution of Pt nitrate. two remaining inventive catalysts were adjusted to obtain the desired catalyst load and ratio. The paste for the first catalytic layer of the control catalyst consisted of 226g of alumina, 226g of Zirconia doped with Pr-, 16.34g of Pd impregnated with alumina and zirconia doped with Pr- as Pd nitrate solution and 0.36 g of Pt impregnated as Pt nitrate solution. The coated carriers were then calcined at 550 ° C for 1 hour to obtain a dry wash coating at approximately 1.64 g / in 3 (0.10 g / cm 3 ).
    An upper layer (i.e., the second catalytic layer), in the form of an aqueous solution, was then applied to the support surface already coated with the first catalytic layer. The aqueous suspension used for the top coating of the 75 g / ft 3 (2648.8 g / m 3 ) catalyst (Catalyst 3) contained 2.87 g of platinum impregnated as a solution of platinum nitrate el, 59 g of rhodium impregnated as a solution of rhodium nitrate by a planetary mixture in 418 g of the oxygen storage component (bulk mass) and 66 g of alumina doped with Zr. The pastes for the two remaining inventive catalysts were adjusted to obtain the desired catalyst loading and ratio (Catalyst 1 - 45 g / ft 3 (1589.16 g / m 3 ); Catalyst 2-60 g / ft 3 (2118, 88 g / m 3 )). The slurry for the second catalytic layer of the control catalyst (Control - 100 g / ft 3 (3531.47 g / m 3 )) consisted of 208 g of Zr doped alumina, 283 g of oxygen storage component (powder containing Ce -Zr-Nd), 3.28 g of Pt impregnated with Zr doped alumina and an oxygen storage component as a solution of Pt el nitrate, 82g Rh impregnated with Zr doped alumina and an oxygen storage component as a rhodium nitrate solution. The resulting carriers were then calcined at 550 ° C for 1 hour to obtain a dry wash coating at approximately 1.33 g / in 3 (0.08 g / cm 3 ).
    Performance Tests
    The samples were evaluated in the aforementioned laboratory reactor at 40,000 space velocity with a gas composition as follows: CO ~ 0.5 to 5.6%; CO 2 ~ 10%, HC (Cl) ~ 1350ppm (C 3 H 6 / C 3 H 8 = 2); NO ~ 400 ppm ;. H 2 O ~ 6 to 7%. Lambda varied with CO / O 2 to correspond with enriched (lambda ~ 0.93) and impoverished (lambda ~ 1.04) conditions. Steam aging was carried out at 950 ° C, 10% H 2 O in air for 4 hours.
    The results are shown in Fig. 3 and Fig. 4. Catalysts containing an OSC support with 100% ceria in the second catalytic layer provided significantly improved CO conversion at lambda <1 (where CO emissions are typically increased ) compared to the control catalyst having zirconia-coated alumina supports and ceria / zirconia composite oxide for platinum and rhodium in the second catalytic layer. The total conversion of hydrocarbons was also improved at lambda <1 using the catalysts of the present invention. For CO and THC, the conversion efficiency increased with increasing PGM load. The conversion of NOx for the inventive catalysts (data not shown) was equivalent to the control catalyst through the entire lambda scan and gave about 100% conversion to lambda <1.
    权利要求:
    Claims (3)
    [1]
    1/5
    Ó) ’ll
    120%
    OBSJSAUOO
    6% H2O Fresh 0% H2O Fresh 6% H2O Aged 0% H2OEnvelhacida
    1. Catalyst article for use in an internal combustion engine, characterized by the fact that it comprises a first catalytic layer formed on a substrate, 5 in which the first catalytic layer comprises palladium impregnated with an oxygen storage component free of ceria and platinum impregnated with a refractory metal oxide, and a second palladium-free catalytic layer formed on the first catalytic layer, the second catalytic layer comprising 10 platinum and rhodium impregnated with a cerium-containing oxygen storage component, in which the oxygen containing ceria contains refractory metal oxides in amounts not exceeding 50% by weight, and rare earth oxides without ceria in an amount not exceeding 10% by weight; and
    15 in which the catalyst article is effective in reducing carbon monoxide in the exhaust gas from the internal combustion engine.
    [2]
    2/5
    SUPPORT
    2. Article according to claim 1, characterized by the fact that palladium in the first catalytic layer is impregnated with zirconia-praseodymia and the platinum in the first catalytic layer is impregnated
    20 with alumina, or where the palladium in the first catalytic layer is impregnated with zirconia-praseodymia and the first catalytic layer of platinum and palladium on alumina.
    3. Article according to claim 1, characterized by the fact that the oxygen storage component of the second layer
    25 catalytic contains 40% to 100% ceria.
    4. Article according to claim 1, characterized in that it comprises a total of 20-100 g / ft 3 (706.29 - 3531.47 g / m 3 ) of platinum group metal.
    5. Article according to claim 4, characterized by the
    Petition 870180056652, of 06/29/2018, p. 9/13 fact that it comprises 1-90 g / ft 3 (35.31 - 3178.31 g / m 3 ) of platinum, 1-90 g / ft 3 (35.31 - 3178.31 g / m 3) of palladium and 1-30 g / ft3 (35.31 - 1059.44 g / m3) rhodium.
    6. Article according to claim 1, characterized by the fact that it has a platinum / palladium / rhodium ratio of 0.5-5 / 2-80 / 0.1-5, by weight, respectively, or a ratio platinum / palladium / rhodium of 1-3 / 540 / 0.25-2 by weight, respectively.
    7. Method of treating engine exhaust, comprising hydrocarbons, carbon monoxide and nitrogen oxides, characterized
    10 for the fact that it understands:
    contacting the exhaust with a catalyst article, as defined in claim 1, wherein the catalyst article comprises a first catalytic layer coated on a substrate, the first layer comprising palladium impregnated with a storage component
    15 of ceria-free oxygen and platinum impregnated with a refractory metal oxide, and;
    a second palladium-free catalytic layer formed on the first catalytic layer, the second layer comprising platinum and rhodium impregnated with an oxygen storage component
    20 containing ceria, where the oxygen storage component containing ceria contains refractory metal oxides in amounts not exceeding 50% by weight, and rare earth oxides without ceria in an amount not exceeding 10% by weight,
    25 where the method is effective in reducing exhaust carbon monoxide.
    8. Method according to claim 7, characterized by the fact that the exhaust is contacted with a catalyst article comprising a) palladium impregnated with zirconia doped with praseodymy and platinum
    Petition 870180056652, of 06/29/2018, p. 10/13 impregnated with alumina in the first catalytic layer, and b) platinum and rhodium impregnated with ceria by volume in the second layer.
    9. Method according to claim 8, characterized in that the ratio of platinum / palladium / rhodium is 0.5-5 / 2-80 / 0.1-5 by weight,
    5 respectively.
    Method according to claim 9, characterized in that the exhaust is contacted with a catalyst article comprising a total of 20-100 g / ft 3 (706.29 - 3531.47 g / m 3 ) of metal platinum group.
    10
    Method according to claim 10, characterized in that the exhaust is contacted with a catalyst article comprising 1-90 g / ft 3 (35.31 - 3178.31 g / m3) of platinum, 1-90 g / ft 3 (35.31 3178.31 g / m 3 ) of palladium and 1-30 gf (35.31 - 1059.44 g / m3) of rhodium.
    12. Method of making a catalyst article, as defined
    15 in claim 1, characterized by the fact that it comprises:
    forming a first layer on a substrate by depositing a slurry on the substrate, the slurry comprising palladium impregnated with a ceria-free oxygen storage component and platinum impregnated with a refractory metal oxide;
    20 dry the first layer;
    form a second palladium-free layer on the first layer by depositing a slurry on the first layer, the slurry comprising platinum and rhodium impregnated with an oxygen storage component containing ceria,
    25 wherein the ceria containing oxygen storage component contains refractory metal oxides in amounts not exceeding 50% by weight and rare earth oxides without ceria in an amount not exceeding 10% by weight, and drying the second layer.
    Petition 870180056652, of 06/29/2018, p. 11/13
    13. Method according to claim 12, characterized in that a total of 20-100 g / ft 3 (706.29 - 3531.47 g / m 3 ) of platinum group metals is formed on the catalyst article .
    14. Method according to claim 13, characterized by the fact that 1-90 g / fl 3 (35.31 - 3178.31 g / m3) of platinum, 1-90 g / fl 3 (35.31
    - 3178.31 g / m3) palladium and 1-30 g / fl 3 (35.31 to 1059.44 g / m3) of rhodium are formed on catalyst article.
    15. Method according to claim 14, characterized by the fact that platinum, palladium and rhodium are deposited on the article
    10 catalyst, in a ratio of 0.5-5 / 2-80 / 0.1-5 by weight, respectively.
    16. Article according to claim 1, characterized by the fact that it comprises a total of 40-80 g / ft3 (1412.59 - 2825.17 g / m3) of platinum group metal.
    Petition 870180056652, of 06/29/2018, p. 12/13
    [3]
    3/5
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    同族专利:
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    CA2792084C|2018-11-27|
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    法律状态:
    2018-04-03| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2018-07-31| B09A| Decision: intention to grant|
    2018-09-25| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 04/03/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US31092210P| true| 2010-03-05|2010-03-05|
    US13/038,784|US8828343B2|2010-03-05|2011-03-02|Carbon monoxide conversion catalyst|
    PCT/US2011/027120|WO2011109676A2|2010-03-05|2011-03-04|Carbon monoxide conversion catalyst|
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