FRESH OXIDATION CATALYST FOR TREATING AN EXHAUST GAS, EXHAUST SYSTEM FOR A DIESEL ENGINE, VEHICLE, A

专利摘要:
OXIDATION CATALYST FOR TREATING AN EXHAUST GAS, EXHAUST SYSTEM FOR A COMBUSTION ENGINE, VEHICLE, METHOD OF TREATING AN EXHAUST GAS, USE OF AN OXIDATION CATALYST, AND, METHOD OF PREPARING A CATALYST OF OXIDATION. An oxidation catalyst for the treatment of an exhaust gas produced by a combustion engine, wherein the oxidation catalyst comprises a substrate and a catalyst layer, wherein the catalyst layer comprises: a first support material; a first noble metal; and a second noble metal; wherein the catalyst layer is arranged on a surface of the substrate, and the catalyst layer has a non-uniform distribution of the first noble metal in a direction perpendicular to the surface of the substrate. The oxidation catalyst can be used to oxidize carbon monoxide (CO), hydrocarbons (HCs), as well as nitrogen oxides (NO) in such an exhaust gas.
公开号:BR112015020505B1
申请号:R112015020505-4
申请日:2014-02-18
公开日:2020-11-24
发明作者:Andrew Francis Chiffey；David Bergeal；John Benjamin Goodwin；Paul Richard Phillips
申请人:Johnson Matthey Public Limited Company；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[001] The invention relates to an oxidation catalyst for the treatment of an exhaust gas from a combustion engine, methods involving the oxidation catalyst and the use of the oxidation catalyst. The invention also relates to a method for preparing the oxidation catalyst. The invention also relates to an exhaust system or a vehicle comprising the oxidation catalyst. BACKGROUND OF THE INVENTION
[002] Combustion engines produce exhaust gases containing pollutants, such as carbon monoxide (CO), unburned hydrocarbons (HCs), nitrogen oxides (NOX) and particulate matter (PM). Emission standards for pollutants in an exhaust gas produced by a combustion engine, particularly for vehicular engines, are becoming increasingly stringent. There is a need to provide improved catalysts and exhaust systems for the treatment and removal of pollutants in such exhaust gases that are capable of meeting such standards and are cost-effective.
[003] Exhaust gas from gasoline and diesel engines is commonly treated with a catalyst that is capable of oxidizing (i) carbon monoxide (CO) to carbon dioxide (CO2) and (ii) hydrocarbons (HCs) to water (H2O) and carbon dioxide (CO2). Three-way catalysts (TWCS) are typically employed to treat the exhaust gas of a gasoline engine, which is capable of reducing nitrogen oxides (NOX) to nitrogen (N2), water (H2O) and carbon dioxide ( CO2), in addition to performing oxidation reactions (i) and (ii). The exhaust gas of a compression ignition engine, such as a diesel engine, is typically treated with an oxidation catalyst (usually called a diesel oxidation catalyst (DOC)) that performs oxidation reactions (i) and (ii). Some diesel oxidation catalysts are also capable of oxidizing nitrogen monoxide (NO) to nitrogen dioxide (NO2), which can facilitate the removal of NOX by an additional emission control device downstream.
[004] Oxidation catalysts for combustion engines typically contain one or more noble metals. The specific noble metal (s) selected for inclusion in an oxidation catalyst will (will) depend on several factors, such as reactivity to specific pollutants and under different gas conditions. exhaust, cost, durability at high temperatures, chemical compatibility with the support material and any other components of the catalyst and susceptibility to contamination by impurities. For example, platinum (Pt) and palladium (Pd) are each capable of oxidizing carbon monoxide (CO) and hydrocarbons (HCs) in an exhaust gas from a compression ignition engine. Palladium is more susceptible to sulfur contamination in the fuel compared to platinum, but it is generally cheaper than platinum and has a longer thermal durability.
[005] Due to the difference in properties between noble metals, diesel oxidation catalysts have been developed which contain layered arrangements of different noble metals. In such arrangements, the noble metals were arranged in order to optimize their combined reactivity and minimize degradation. For example, WO 2006/056811 describes a diesel oxidation catalyst where the top layer contains palladium and the bottom layer in contact with the substrate contains platinum. Palladium has the lowest CO “off” temperature than platinum. Such an arrangement facilitates the contact between palladium and CO in the exhaust gases, and the heat that is generated can take the platinum in the bottom layer upwards until its "off" temperature.
[006] An alternative approach is to vary the distribution of noble metal within the substrate channels. US 5,043,311 describes a monolithic or honeycomb catalyst composed of an inert ceramic or metallic substrate crossed by parallel flow channels, a layer disposed on top of it and composed of metal oxide promoting catalysis and a catalytically active component supported by metal oxide, in which the concentration of metal oxide promoting catalysis or the catalytically active component increases from the periphery to the central axis of the substrate. The layer composed of the metal oxide promoting catalysis and the catalytically active component that is arranged in each channel have a uniform composition. However, the composition of each layer varies from channel to channel.
[007] Methods for preparing oxidation catalysts with layered arrangements or for preparing catalysts, such as those described in US 5,043,311, have an increased production cost, particularly when compared to single-layer oxidation catalysts wherein the composition of each layer is the same in all channels of the substrate. Also, the method employed for the preparation of multilayer oxidation catalysts is necessarily more complicated and increases the likelihood of production errors.
[008] Therefore, it is desirable to provide an oxidation catalyst arrangement, which offers the advantages of a multilayer catalyst arrangement, but without the increased cost or difficulty of production. SUMMARY OF THE INVENTION
[009] The inventors have surprisingly found that many or all of the benefits associated with multilayer catalysts, particularly multilayer diesel oxidation catalysts, can be achieved with an oxidation catalyst with a non-uniform distribution of at least one noble metal in a vertical direction through the layer containing catalyst.
[0010] The distribution of noble metal in each layer of such multi-layer catalysts is generally uniform. Multilayer catalysts have a plurality of layers in which the concentration of noble metal in one layer is different from the concentration of noble metal in the other layer. This allows for a variation in the noble metal concentration to be obtained as the layers are traversed through their thickness. However, such a catalyst must be prepared by a process involving a plurality of coating steps to form each layer.
[0011] The oxidation catalyst of the invention can be advantageously prepared using the same methodology that is used for the preparation of catalysts having a single layer, while maintaining many or all the advantages of the activity provided by a multilayer catalyst. In particular, the oxidation catalyst of the invention can provide good or improved performance in the conversion of carbon monoxide (CO), hydrocarbons (HCs) and, optionally, also conversion of nitrogen oxides (NOX), by reduction or oxidation. The oxidation catalyst of the invention can have a surprisingly low CO T50.
[0012] The invention provides an oxidation catalyst for the treatment of an exhaust gas from or produced by a combustion engine, wherein the oxidation catalyst comprises a substrate and a catalyst layer, wherein the catalyst layer comprises: a first support material; a first noble metal; and a second noble metal; wherein the catalyst layer is disposed on a substrate surface and has (i.e., the catalyst layer has) a non-uniform distribution of the first noble metal in a direction perpendicular to the substrate surface.
[0013] The invention also relates to an exhaust system for a combustion engine comprising the oxidation catalyst and at least one emission control device. It should be understood that the oxidation catalyst and exhaust system of the invention can be used with stationary combustion engines or mobile combustion engines. However, the oxidation catalyst and exhaust system of the invention are particularly suitable for use with mobile combustion engines.
[0014] Another aspect of the invention relates to a vehicle or apparatus, the vehicle or apparatus of which comprises an internal combustion engine and either the oxidation catalyst of the invention or the exhaust system of the invention.
[0015] The invention also relates to a method of treating an exhaust gas produced by an internal combustion engine, the method of which involves contacting the exhaust gas with an oxidation catalyst, wherein the oxidation catalyst comprises: a substrate and a catalyst layer, wherein the catalyst layer comprises: a first support material; a first noble metal; and a second noble metal; wherein the catalyst layer is disposed on a substrate surface and has (i.e., the catalyst layer has) a non-uniform distribution of the first noble metal in a direction perpendicular to the substrate surface. The method is generally a method of treating carbon monoxide (CO), preferably treating carbon monoxide (CO), hydrocarbons (HCs) and optionally nitrogen oxides (NOX), such as nitrogen oxide (NO), in a exhaust gas from an internal combustion engine.
[0016] An additional aspect of the invention relates to the use of the oxidation catalyst of the invention for the treatment of an exhaust gas produced by an internal combustion engine. The invention generally relates to the use of the oxidation catalyst to oxidize carbon monoxide (CO) in an exhaust gas of an internal combustion engine. In particular, the invention relates to the use of the oxidation catalyst to oxidize carbon monoxide (CO), hydrocarbons (HCs) and optionally nitrogen oxides (NOX), such as nitrogen oxide (NO), in an exhaust gas of an internal combustion engine.
[0017] Another aspect of the invention relates to a method of preparing an oxidation catalyst, the method comprising: (a) providing an aqueous slurry comprising a precursor to the first support material, a first noble metal component and a second noble metal component; (b) applying the aqueous slurry to a substrate to form a coating; and (c) drying and calcining the coating using conditions that allow at least the first noble metal component to flow towards or away from the substrate. BRIEF DESCRIPTION OF THE DRAWINGS
[0018] Figure 1 is an EPMA-WDX (wavelength dispersive electron-X-ray electron microprobe) showing the composition of the catalyst layers in Example 3. The image shows that there is no homogeneous or uniform of platinum and palladium particles in the layer above the black line (the layer that was first coated directly on to the substrate). A non-uniform distribution of palladium particles was obtained in the layer below the black line. The black arrows in the image show that a high concentration of palladium particles was obtained in the vicinity of the exposed surface of the layer.
[0019] Figure 2 is a schematic illustration of a layer according to the invention, which has a uniform or homogeneous distribution of a first noble metal (for example, noble metal 1, as represented by Δ) and a non-uniform distribution ( that is, not homogeneous) of a second noble metal (for example, a noble metal 2, as represented by o).
[0020] Figure 3 is a schematic illustration showing the uniform distribution of two noble metals (for example, noble metal 1, as represented by Δ and noble metal 2, as represented by o) in conventional oxidation catalysts. DETAILED DESCRIPTION OF THE INVENTION
[0021] For the avoidance of doubt, the catalyst described here is called an "oxidation catalyst" because it can oxidize pollutants in an exhaust gas. The activity of the oxidation catalyst is not limited to oxidation reactions, although the oxidation catalyst must be able to oxidize one or more pollutants in exhaust gases during normal use. For example, the oxidation catalyst may additionally be able to carry out a reduction reaction and / or may be able to temporarily store one or more pollutants from the exhaust gases. It is to be understood that the term "oxidation catalyst" includes a "three-way catalyst", such as a three-way catalyst that is typically used for gasoline engines. The oxidation catalysts of the invention are, however, particularly suitable for use with compression ignition engines, especially diesel engines. Thus, it is preferred that the oxidation catalyst is intended for use in the treatment of an exhaust gas produced by a compression ignition engine, or is a diesel oxidation catalyst (DOC).
[0022] It was found that a non-uniform vertical distribution of noble metal can be achieved within a single layer. Thus, the benefits associated with layering to achieve a non-uniform vertical distribution of noble metal through the catalyst layers can be achieved using a single layer or fewer layers.
[0023] In the oxidation catalyst of the invention, the catalyst layer has a non-uniform distribution of the first noble metal in a direction perpendicular to the substrate surface. For the avoidance of doubt, the catalyst layer is a single layer (i.e., the catalyst layer does not comprise a plurality of layers).
[0024] In general, the catalyst layer has a non-uniform distribution of the first noble metal through its thickness (that is, the direction perpendicular to the substrate surface represents the thickness of the catalyst layer).
[0025] Typically, the catalyst layer has a first surface and a second surface. Generally, the first surface is parallel (for example, substantially parallel) to the second surface (i.e., the plane containing the first surface is parallel to the plane containing the second surface). The first surface and the second surface are typically parallel to the substrate surface. Thus, the direction perpendicular to the substrate surface is also perpendicular to the first surface and / or the second surface.
[0026] The perpendicular distance between the first surface and the second surface is generally the thickness of the catalyst layer.
[0027] The first surface can be an exposed surface of the catalyst layer or an additional layer (for example, second layer) can be arranged or supported on the first surface. The first surface is generally on the upper side (i.e., it is the top surface) of the catalyst layer. By exposed, it is meant that the first surface is not completely or substantially covered by another material and, typically, an exhaust gas passing through the catalyst comes into contact with the first surface before the second surface.
[0028] The second surface is not an exposed surface of the catalyst layer. Generally, the second surface is in direct contact with a substrate surface and / or a surface of another layer. Thus, the second surface is generally the underside (i.e., the bottom or bottom surface) of the catalyst layer.
[0029] The quantity of the first noble metal may increase in a direction perpendicular to the surface of the substrate (that is, the quantity of the first noble metal may increase in a direction perpendicular from the first surface to the second surface). The amount of the first noble metal can increase continuously or increase discontinuously, preferably increasing continuously, in a direction perpendicular to the surface of the substrate. Thus, when, for example, the oxidation catalyst comprises a single layer, which is the catalyst layer, then the amount of the first noble metal increases from an exposed surface of the catalyst layer towards the substrate surface.
[0030] The catalyst layer can have a linear or non-linear rate of increase in the amount of the first noble metal in a direction perpendicular to the substrate surface (i.e., a linear or non-linear rate of increase in the amount of the first metal) noble in a perpendicular direction from the first surface to the second surface).
[0031] Typically, at least 60% of the total amount of the first noble metal (for example, the catalyst layer) is distributed between the second surface and a point or plane in the catalyst layer that is in the middle of the path between the first surface and the second surface (for example, 50% of the perpendicular distance between the first surface and the second surface). The plane is typically parallel to the second surface. The reference to “half way between” in this context generally refers to the average half way distance between the first surface and the second surface. It is preferred that at least 70%, more preferably at least 75%, such as at least 80%, even more preferably at least 90%, of the total amount of the first noble metal (for example, the catalyst layer) is distributed among the second surface and a point or plane in the catalyst layer that is in the middle of the path between the first surface and the second surface.
[0032] Generally, at least 60% of the total amount of the first noble metal (for example, the catalyst layer) is distributed between the second surface and a point or plane in the catalyst layer that is 25% of the distance perpendicular to from the second surface to the first surface. The plane is typically parallel to the second surface. It is preferred that at least 70%, more preferably at least 75%, such as at least 80%, even more preferably at least 90%, of the total amount of the first noble metal (for example, the catalyst layer) is distributed among the second surface and a point or plane in the catalyst layer that is 25% of the perpendicular distance from the second surface to the first surface.
[0033] At least 60% of the total amount of the first noble metal (for example, the catalyst layer) can be distributed between the second surface and a point or plane in the catalyst layer that is 10% of the perpendicular distance from the second surface to the first surface. The plane is typically parallel to the second surface. It is preferred that at least 70%, more preferably at least 75%, such as at least 80%, even more preferably at least 90%, of the total amount of the first noble metal (for example, the catalyst layer) is distributed among the second surface and a point or plane in the catalyst layer that is 10% of the perpendicular distance from the second surface to the first surface.
[0034] Alternatively, the quantity of the first noble metal may decrease in a direction perpendicular to the surface of the substrate (that is, the quantity of the first noble metal may decrease from the first surface to the second surface). The amount of the first noble metal can decrease continuously or decrease discontinuously, preferably decreasing continuously, in a direction perpendicular to the surface of the substrate. Thus, when, for example, the oxidation catalyst comprises a single layer, which is the catalyst layer, then the amount of the first noble metal decreases from an exposed surface of the catalyst layer towards the substrate surface.
[0035] The catalyst layer can have a linear or non-linear rate of decrease in the amount of the first noble metal in a direction perpendicular to the surface of the substrate (i.e., a linear or a non-linear rate of decrease in the amount of the first noble metal in a perpendicular direction from the first surface to the second surface).
[0036] Typically, at least 60% of the total amount of the first noble metal (for example, the catalyst layer) is distributed between a first surface and a point or plane in the catalyst layer that is in the middle of the path between the first surface and the second surface (for example, 50% of the perpendicular distance between the first surface and the second surface). The plane is typically parallel to the first surface. The reference to “half way between” in this context generally refers to the distance to the middle half between the first surface and the second surface. It is preferred that at least 70%, more preferably at least 75%, such as at least 80%, even more preferably at least 90%, of the total amount of the first noble metal (for example, the catalyst layer) is distributed between one first surface and a point or plane in the catalyst layer that is in the middle of the path between the first surface and the second surface.
[0037] Generally, at least 60% of the total amount of the first noble metal (for example, the catalyst layer) is distributed between a first surface and a point or plane in the catalyst layer that is 25% of the perpendicular distance from from a first surface to the second surface. The plane is typically parallel to the first surface. It is preferred that at least 70%, more preferably at least 75%, such as at least 80%, even more preferably at least 90%, of the total amount of the first noble metal (for example, the catalyst layer) is distributed between one first surface and a point or plane in the catalyst layer that is 25% of the perpendicular distance from a first surface to the second surface.
[0038] At least 60% of the total amount of the first noble metal (for example, the catalyst layer) can be distributed between the first surface and a point or plane in the catalyst layer that is 10% of the perpendicular distance from a first surface to a second surface. The plane is typically parallel to the first surface. It is preferred that at least 70%, more preferably at least 75%, such as at least 80%, even more preferably at least 90%, of the total amount of the first noble metal (for example, the catalyst layer) is distributed between one first surface and a point or plane in the catalyst layer that is 10% of the perpendicular distance from a first surface to the second surface.
[0039] It is preferred that the quantity of the first noble metal decreases in a direction perpendicular to the substrate surface.
[0040] The non-uniform distribution of the first noble metal in a direction perpendicular to the substrate surface can, in general, be a graduated distribution of the first noble metal. Alternatively, the non-uniform distribution of the first noble metal in a direction perpendicular to the substrate surface can be a stepwise distribution of the first noble metal.
[0041] The catalyst layer can have a uniform horizontal distribution or a non-uniform horizontal distribution of the first noble metal.
[0042] Typically, the distribution of the first noble metal in a direction parallel to the substrate surface (that is, a longitudinal plane) and perpendicular to a central longitudinal axis of the substrate (that is, direction parallel to the entrance end face and / or the exit end face of the substrate) is uniform or non-uniform. It is preferred that the distribution of the first noble metal in a direction parallel to the surface of the substrate and perpendicular to a central longitudinal axis of the substrate is uniform.
[0043] Generally, the distribution of the first noble metal in a direction parallel to the substrate surface (ie, a longitudinal plane) and parallel to a central longitudinal axis of the substrate (ie, direction perpendicular to the entrance end face and / or the exit end face of the substrate) can be uniform or non-uniform. It is preferable that the distribution of the first noble metal in a direction parallel to the surface of the substrate and parallel to a central longitudinal axis of the substrate is uniform.
[0044] In general, the first noble metal can be selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium, platinum, silver and gold. It is preferred that the first noble metal is selected from the group consisting of rhodium, palladium, platinum and gold. Most preferably, the first noble metal is selected from the group consisting of palladium, platinum and gold. The first noble metal can be palladium. The first noble metal can be platinum. The first noble metal may be gold. Even more preferably, the first noble metal is palladium.
[0045] Generally, the catalyst layer comprises a total amount of the first noble metal of 0.5 to 15% by weight (for example, 11.5 to 14% by weight or 12 to 15% by weight), preferably 1 to 10% by weight, more preferably 2 to 9% by weight (for example, 3 to 8% by weight), as 4 to 7% by weight (for example, 5 to 6% by weight).
[0046] The first noble metal is typically in particulate form. Thus, the catalyst layer comprises particles of a first noble metal, and in which the catalyst layer has a non-uniform distribution of particles of the first noble metal in a direction perpendicular to the substrate surface.
[0047] When the first noble metal is in particulate form, then typically the particles of the first noble metal have a D90 of <40 nm, more preferably <30 nm, and even more preferably <20 nm.
[0048] Typically, the catalyst layer comprises a first noble metal in an amount of 5 to 300 g / 0.0283 m3, more preferably 10 to 250 g / 0.0283 m3, such as 25 to 200 g / 0.0283 m3 , even more preferably 35 to 175 g / 0.0283 m3, and even more preferably 50 to 150 g / 0.0283 m3 (e.g., 75 to 125 g / 0.0283 m3). For example, the catalyst layer may comprise the first noble metal in an amount of 110 to 300 g / 0.0283 m3, preferably 125 to 275 g / 0.0283 m3, such as 150 to 250 g / 0.0283 m3, plus preferably 175 to 200 g / 0.0283 m3. In some cases, a relatively high charge of a first noble metal, particularly when the first noble metal is palladium, is beneficial (for example, for CO oxidation activity).
[0049] The first support material typically comprises or consists essentially of refractory oxide selected from the group consisting of alumina, magnesia, silica, zirconia, titania, ceria and a composite oxide or a mixed oxide of two or more of the same. In principle, any suitable support material can be used as the first support material.
[0050] Additionally or alternatively, the first support material may comprise, or consist essentially of, a hydrocarbon adsorber, such as a hydrocarbon adsorber, as described below.
[0051] It is preferred that the refractory oxide is selected from the group consisting of alumina, silica, zirconia, ceria and a composite oxide or a mixed oxide of two or more of the same. Preferred mixed oxides or composite oxides include silica-alumina and ceria-zirconia. More preferably, the refractory oxide is selected from the group consisting of alumina, silica, ceria, silica-alumina and ceria-zirconia. The refractory oxide can be alumina. The refractory oxide can be silica. Refractory oxide can be ceria. The refractory oxide can be silica-alumina. The refractory oxide can be cerium-zirconia.
[0052] When the refractory oxide is silica-alumina, then generally the refractory oxide consists essentially of 20 to 95% by weight of alumina and 5 to 80% by weight of silica (for example, 50 to 95% by weight alumina and 5 to 50% by weight of silica), preferably 35 to 80% by weight of alumina and 20 to 65% by weight of silica (e.g., 55 to 80% by weight of alumina and 20 to 45% by weight of silica), even more preferably 45 to 75% by weight of alumina and 25 to 55% by weight of silica.
[0053] When the refractory oxide is ceria-zirconia, then generally the refractory oxide consists essentially of 20 to 95% by weight of ceria and 5 to 80% by weight of zirconia (for example, 50 to 95% by weight of ceria and 5 to 50% by weight of zirconia), preferably 35 to 80% by weight of ceria and 20 to 65% by weight of zirconia (for example, 55 to 80% by weight of ceria and 20 to 45% by weight of zirconia) , even more preferably 45 to 75% by weight of ceria and 25 to 55% by weight of zirconia.
[0054] Refractory oxide can be doped with a dopant. The inclusion of a dopant can stabilize the refractory oxide or support material. Typically, the dopant can be selected from the group consisting of zirconium (Zr), titanium (Ti), silicon (Si), yttrium (Y), lanthanum (La), praseodymium (Pr), samarium (Sm), neodymium (Nd ), barium (Ba) and an oxide thereof. In general, the dopant is different from refractory oxide (that is, from the refractory oxide cation). So, for example, when the refractory oxide is titania, then the dopant is not titanium or an oxide thereof.
[0055] When the refractory oxide is doped with a dopant, then typically the refractory oxide comprises a total amount of dopant of 0.1 to 10% by weight. It is preferred that the total amount of dopant is from 0.25 to 5% by weight, more preferably 0.5 to 2.5% by weight (for example, about 1% by weight).
[0056] Typically, the catalyst layer comprises an amount of the first support material from 0.1 to 3.5 g / 16.38 cm3 (for example, 0.25 to 3.0 g / 16.38 cm3), preferably 0.3 to 2.5 g / 16.38 cm3, even more preferably 0.5 to 2.0 g / 16.38 cm3, and even more preferably 0.6 to 1.75 g / 16.38 cm3 ( for example, 0.75 to 1.5 g / 16.38 cm3).
[0057] In general, the first support material is in the form of particles. The first support material can have a D90 particle size of <50 pm, preferably <30 pm, and more preferably 20 pm <(as determined by conventional laser diffraction techniques). The particle size distribution of the support material is selected to aid adhesion to the substrate. The particles are generally obtained by grinding.
[0058] The first noble metal can be arranged or supported on the first support material. Thus, the first noble metal can be dispersed in the first support material and / or impregnated in the first support material.
[0059] Generally, the second noble metal can be selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium, platinum, silver and gold. The second noble metal is typically a different metal than the first noble metal.
[0060] It is preferred that the second noble metal be selected from the group consisting of rhodium, palladium, platinum and gold. More preferably, the second noble metal is selected from the group consisting of palladium, platinum and gold. The second noble metal can be palladium. The second noble metal can be platinum. The second noble metal may be gold. Even more preferably, the second noble metal is platinum.
[0061] When the first noble metal is palladium and the second noble metal is gold or vice versa, then palladium and gold can form a palladium-gold alloy.
[0062] The catalyst layer can have a uniform or non-uniform distribution of the second noble metal in a direction perpendicular to the substrate surface. It is preferred that the catalyst layer has a uniform distribution of the second noble metal in a direction perpendicular to the substrate surface.
[0063] When the catalyst layer has a non-uniform distribution of the second noble metal in a direction perpendicular to the substrate surface, then the amount of the second noble metal may increase or decrease in a direction perpendicular towards the substrate surface (ie , the amount of the second noble metal may increase or decrease in a perpendicular direction from the first surface to the second surface). It is preferred that (a) the quantity of the second noble metal increases in a direction perpendicular towards the substrate surface, when the quantity of the first noble metal decreases in a direction perpendicular towards the substrate surface, or (b) the quantity of the second noble metal decreases in a perpendicular direction towards the substrate surface, when the quantity of the first noble metal increases in a perpendicular direction towards the substrate surface.
[0064] The amount of the second noble metal can increase continuously, decrease continuously, increase discontinuously or decrease discontinuously, preferably continuously increase or decrease continuously, in a direction perpendicular towards the substrate surface.
[0065] The catalyst layer may have a linear or non-linear rate of increase or decrease in the amount of the second noble metal in a direction perpendicular to the substrate surface (i.e., a linear rate or a non-linear rate of increase or decrease in the amount of the second noble metal in a perpendicular direction from the first surface to the second surface).
[0066] Typically, at least 60%, preferably at least 70%, more preferably at least 75%, as at least 80%, even more preferably at least 90%, of the total amount of the second noble metal (e.g., the layer catalyst) are either distributed between (a) the second surface and a point or plane in the catalyst layer that is in the middle of the path between the first surface and the second surface (for example, 50% of the perpendicular distance between the first surface and second surface), or (b) the first surface and a point or plane in the catalyst layer that is in the middle of the path between the first surface and the second surface (for example, 50% of the perpendicular distance between the first surface and second surface. The plane is typically parallel to the first and / or second surface. The reference to "half way between" in this context generally refers to the distance to the middle half between the first surface and the second surface. surface.
[0067] Generally, at least 60%, preferably at least 70%, more preferably at least 75%, as at least 80%, even more preferably at least 90%, of the total amount of the second noble metal (e.g., the layer catalyst) are distributed between either (a) the second surface and a point or plane in the catalyst layer that is 25% of the perpendicular distance from the second surface to the first surface, or (b) the first surface and a point or plane in the catalyst layer that is 25% of the perpendicular distance from a first surface to the second surface. The plane is typically parallel to the first surface and / or the second surface.
[0068] At least 60%, preferably at least 70%, more preferably at least 75%, as at least 80%, even more preferably at least 90%, of the total amount of the second noble metal (e.g., the catalyst layer ) can be distributed between either (a) the second surface and a point or plane in the catalyst layer that is 10% of the perpendicular distance from the second surface to the first surface, or (b) the first surface and a point or a plane in the catalyst layer that is 10% of the perpendicular distance from a first surface to the second surface. The plane is typically parallel to the first surface and / or the second surface.
[0069] The non-uniform distribution of the second noble metal in a direction perpendicular to the substrate surface can, in general, be a graduated distribution of the second noble metal. Alternatively, the non-uniform distribution of the second noble metal in a direction perpendicular to the substrate surface can be a stepwise distribution of the second noble metal.
[0070] The catalyst layer can have a uniform horizontal distribution or a horizontal non-uniform distribution of the second noble metal.
[0071] Typically, the distribution of the second noble metal in a direction parallel to the substrate surface (that is, a longitudinal plane) and perpendicular to a central longitudinal axis of the substrate (that is, direction parallel to the entrance end face and / or the exit end face of the substrate) is uniform or non-uniform. It is preferred that the distribution of the second noble metal in a direction parallel to the surface of the substrate and perpendicular to a central longitudinal axis of the substrate is uniform.
[0072] Generally, the distribution of the second noble metal in a direction parallel to the substrate surface (ie, a longitudinal plane) and parallel to a central longitudinal axis of the substrate (ie, direction perpendicular to the entrance end face and / or the exit end face of the substrate) can be uniform or non-uniform. It is preferable that the distribution of the second noble metal in a direction parallel to the surface of the substrate and parallel to a central longitudinal axis of the substrate is uniform.
[0073] The catalyst layer typically comprises a total amount of the second noble metal from 0.5 to 15% by weight (e.g., 11.5 to 14% by weight or 12 to 15% by weight), preferably 1 to 10 % by weight, more preferably 2 to 9% by weight (for example, 3 to 8% by weight), such as 4 to 7% by weight (for example, 5 to 6% by weight).
[0074] The second noble metal is typically in particulate form. When the second noble metal is in particulate form, then typically the particles of the second noble metal have a D90 of <40 nm, more preferably <30 nm, and even more preferably <20 nm.
[0075] The second noble metal can be arranged or supported on the first support material. Thus, the second noble metal can be dispersed in the first support material and / or impregnated within the first support material.
[0076] Both the first noble metal and the second noble metal can be arranged or supported on the first support material. It is possible to fix a noble metal on a support material before preparing a reactive coating composition to coat a substrate. It is preferred that only the first noble metal is disposed or supported on the first support material.
[0077] Typically, the catalyst layer comprises a second noble metal in an amount of 5 to 300 g / 0.0283 m3, more preferably 10 to 250 g / 0.0283 m3, such as 25 to 200 g / 0.0283 m3 , even more preferably 35 to 175 g / 0.0283 m3, and even more preferably 50 to 150 g / 0.0283 m3 (e.g., 75 to 125 g / 0.0283 m3). For example, the catalyst layer may comprise the second noble metal in an amount of 110 to 300 g / 0.0283 m3, preferably 125 to 275 g / 0.0283 m3, such as 150 to 250 g / 0.0283 m3, plus preferably 175 to 200 g / 0.0283 m3.
[0078] Generally, the oxidation catalyst, preferably the catalyst layer, comprises a total amount of the first noble metal and a total amount of the second noble metal in a (mass) ratio of 20: 1 to 1:20. Preferably, the ratio is 10: 1 to 1:10 (e.g., 8: 1 to 1: 2.5), more preferably the ratio is 7.5: 1 to 1: 7.5, such as 5: 1 to 1 : 5, even more preferably the ratio is 4: 1 to 1: 4 (for example, 3: 1 to 1: 3), such as 2.5: 1 to 1: 2.5 (for example, 2: 1 to 1 : 2 or 1.5: 1 to 1: 1.5).
[0079] The oxidation catalyst typically comprises the first noble metal and the second noble metal in a total amount of 5 to 500 g / 0.0283 m3. Preferably, the total amount is 10 to 400 g / 0.0283 m3, more preferably 20 to 300 g / 0.0283 m3, even more preferably 25 to 250 g / 0.0283 m3, and even more preferably 35 to 200 g / 0.0283 m3.
[0080] Preferred combinations of the first noble metal and the second noble metal include Pt and Pd; Pd and Au; Pt and Rh; Pd and Rh. When the first noble metal is platinum and the second noble metal is palladium or vice versa, then preferably the ratio of the total mass of platinum (Pt) to the total mass of palladium (Pd) is 3: 1 to 1: 3, such as 2: 1 to 1: 2, and more preferably 1.5: 1 to 1: 1.5.
[0081] The catalyst layer may further comprise a third noble metal. Generally, the third noble metal can be selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium, platinum, silver and gold. The third noble metal is typically a different metal for both the first noble metal and the second noble metal.
[0082] It is preferred that the third noble metal is selected from the group consisting of rhodium, palladium, platinum and gold. Most preferably, the third noble metal is selected from the group consisting of rhodium and gold. The third noble metal can be rhodium. The third noble metal may be gold. Even more preferably, the third noble metal is rhodium.
[0083] Preferred combinations of the first noble metal, the second noble metal and the third noble metal include Pd, Pt and Au; Pd, Pt and Rh; Pd, Au and Rh. Most preferred is the combination of Pd, Pt and Au (for example, the first noble metal, the second noble metal and the third noble metal, respectively).
[0084] In general it is preferred that the oxidation catalyst comprises only two noble metals (that is, the first noble metal and the second noble metal).
[0085] The catalyst layer typically comprises a total amount of noble metal from 0.5 to 15% by weight (e.g., 11.5 to 14% by weight or 12 to 15% by weight), preferably 1 to 10% by weight, more preferably 2 to 9% by weight (for example, 3 to 8% by weight), as 4 to 7% by weight (for example, 5 to 6% by weight).
[0086] When the oxidation catalyst is used as a diesel oxidation catalyst, then generally the total amount of noble metal (for example, the first noble metal, the second noble metal and, if present, the third noble metal) is 25 to 200 g / 0.0283 m3, more preferably 40 to 160 g / 0.0283 m3. When the oxidation catalyst is used as a catalyzed soot filter, then the total amount of noble metal (for example, the first noble metal, the second noble metal and, if present, the third noble metal) is 5 to 100 g / 0.0283 m3, more preferably 10 to 40 g / 0.0283 m3.
[0087] The oxidation catalyst, or catalyst layer, may further comprise a hydrocarbon adsorber. The hydrocarbon adsorber can be present in a separate layer from the catalyst layer.
[0088] Typically, the hydrocarbon adsorber is selected from the group consisting of a zeolite, activated carbon, porous graphite and a combination of two or more of them. It is preferred that the hydrocarbon adsorber is a zeolite. More preferably, the zeolite is a mid-pore zeolite (for example, a zeolite with a maximum ring size of eight tetrahedral atoms) or a large pore zeolite (for example, a zeolite with a maximum ring size of ten tetrahedral atoms) ). Examples of appropriate zeolites or types of zeolites include faujasite, clinoptilolite, mordenite, silicalite, ferrierite, zeolite X, zeolite Y, ultra-stable zeolite Y, zeolite AEI, zeolite ZSM-5, zeolite ZSM-12, zeolite ZSM-20, zeolite ZSM-20 34, CHA zeolite, SSZ-3 zeolite, SAPO-5 zeolite, ofretite, a beta zeolite or a copper CHA zeolite. The zeolite is preferably ZSM-5, a beta zeolite or a zeolite Y.
[0089] Typically, zeolite has a molar ratio of silica to alumina of at least 25:11, preferably at least 25: 1, with usable ranges from 25: 1 to 1000: 1, 50: 1 to 500: 1 , as well as 25: 1 to 100: 1, 25: 1 to 300: 1, from 100: 1 to 250: 1. Zeolites having a high molar ratio of silica to alumina show improved hydrothermal stability.
[0090] When the oxidation catalyst comprises a hydrocarbon adsorbent, then typically the total amount of hydrocarbon adsorbent is 0.05 to 3.00 g / 16.38 cm3, particularly 0.10 to 2.00 g / 16.38 cm3 , more particularly 0.2 to 0.8 g / 16.38 cm3.
[0091] The oxidation catalyst of the invention may further comprise an oxygen storage material. Such materials are well known in the art. The oxygen storage material can be selected from ceria (CeO2) and ceria-zirconia (ZrO2-CeO2), such as a solid ceria-zirconia solution. It is preferred that the oxygen storage material is different from the refractory oxide of the first support material.
[0092] When the oxygen storage material is selected from ceria and ceria-zirconia, then preferably the oxygen storage material is either (a) ceria when the first support material comprises, or consists essentially of ceria-zirconia or (b) ceriazirconia, when the first support material comprises, or consists essentially of ceria.
[0093] The oxidation catalyst, the catalyst layer or the first support material may further comprise a reducible oxide. The reducible oxide can form a composite oxide or an oxide mixed with refractory oxide.
[0094] Typically, the reducible oxide can be selected from the group consisting of a manganese oxide (MnCh for example, and / or Mn2Ü3), an iron oxide (for example, FeiCh), a tin oxide (for example , SnCh), a copper oxide (for example, CuO), a cobalt oxide (for example, CoO and / orCθ2θ3), a titanium oxide (for example TIO2) and a cerium oxide (for example, CeO2). The reducible oxide is preferably different (that is, different from the composition) for the refractory oxide. Preferably, the reducible oxide is an iron oxide or a cerium oxide, more preferably the reducible oxide is an iron oxide.
[0095] When a reducible oxide is present, then typically the oxidation catalyst has a mass ratio of the reducible oxide to the refractory oxide from 10: 1 to 1:10, preferably 5: 1 to 1: 5 (for example, 1 : 1a 1: 5), even more preferably 1: 1a 1: 2.5.
[0096] The oxidation catalyst, or catalyst layer, may further comprise a base metal promoter. The metal based promoter can be selected from the group consisting of an alkali metal, an alkaline earth metal, a lanthanide metal and an oxide thereof. It is preferred that the metal-based promoter is an alkali metal, an alkaline earth metal or an oxide thereof. More preferably, the metal-based promoter is an alkaline earth metal (for example, Ca, Mg, Sr or Ba, preferably Ba) or an oxide thereof.
[0097] The oxidation catalyst of the invention can comprise a second layer. The second layer may comprise or consist essentially of a hydrocarbon adsorbent and / or a third noble metal (for example, a third noble metal, as defined above) and / or a refractory oxide (for example, a zeolite) and / or a reducible oxide and / or an oxygen storage material and / or a base metal promoter. Preferably, the second layer comprises, or consists essentially of, a hydrocarbon adsorbent and / or a third noble metal, and / or a refractory oxide. More preferably, the second layer comprises, or consists essentially of, a hydrocarbon adsorber and / or a refractory oxide.
[0098] When the second layer comprises a third noble metal, then preferably the second layer comprises platinum and / or palladium. It is further preferred that the second layer has a mass ratio of platinum (Pt) to palladium (Pd) from 10: 1 to 1:10, more preferably 5: 1 to 1: 5, even more preferably 2.5: 1 to 1: 2.5, such as 2: 1 to 1: 2 (e.g. 1: 1 to 1: 1.5). Other preferred ratios for the mass ratio of platinum (Pt) to palladium (Pd) in the second layer include 8.5: 1 to 1: 2.5, such as 7.5: 1 to 1: 2 (for example, 6: 1 to 1: 1.5), even more preferably 5: 1 to 1: 1.25 (e.g., 5: 1 to 1: 1).
[0099] The catalyst layer can be arranged or supported on the second layer. The second layer can be arranged directly on a substrate surface (that is, the second layer is in contact with a substrate surface). Thus, the second layer can be arranged between the catalyst layer and a substrate surface (i.e., the catalyst layer is placed on a second layer and optionally the second layer is placed directly on a substrate surface).
[00100] Alternatively, the second layer can be arranged or supported on the catalyst layer. The catalyst layer can be disposed directly on a substrate surface (i.e., the catalyst layer is in contact with a substrate surface). Thus, the catalyst layer can be arranged between the second layer and a surface of the substrate (i.e., the second layer is arranged on the catalyst layer and, optionally, the catalyst layer is placed directly on a surface of the substrate).
[00101] The oxidation catalyst of the invention typically comprises a single layer, the single layer of which is the catalyst layer. In general, the catalyst layer is placed directly on a substrate surface (i.e., the catalyst layer is in contact with a substrate surface).
[00102] In general, the oxidation catalyst of the invention comprises a single substrate (i.e., only one substrate).
[00103] Substrates to support oxidation catalysts for the treatment of exhaust gases from a combustion engine are well known in the art. The substrate is usually a ceramic material or a metallic material.
[00104] It is preferred that the substrate is made of or composed of cordierite (SiC> 2-A12O3-MgO), silicon carbide (SiC), Fe-Cr-Al alloy, Ni-Cr-Al alloy, or a stainless steel alloy.
[00105] Typically, the substrate is a monolith. It is preferred that the monolith is a flow-through monolith or a filtering monolith.
[00106] It is preferred that the oxidation catalyst of the invention is intended for use as a diesel oxidation catalyst (DOC) or a catalyzed soot filter (CSF). In practice, the catalyst formulations used in DOCs and CSFs are similar. Generally, however, a difference in principle between a DOC and a CSF is the substrate on which the catalyst formulation is coated and the amount of noble metal in the coating.
[00107] A flow-through monolith typically comprises a honeycomb monolith (for example, a metal or ceramic honeycomb monolith), having a plurality of channels extending through it, which are open channels in both ends. When the substrate is a flow-through monolith, then the oxidation catalyst of the invention is typically a diesel oxidation catalyst (DOC) or is intended for use as a diesel oxidation catalyst (DOC).
[00108] A filtering monolith generally comprises a plurality of inlet channels and a plurality of outlet channels, in which the inlet channels are open at one end upstream (i.e., the exhaust gas inlet side ) and are plugged or sealed at their downstream end (i.e., exhaust gas outlet side), the outlet channels are plugged or sealed at one end upstream and are open at their downstream end, and each input channel is separated from an output channel by a porous structure. When the substrate is a filtration monolith, then the oxidation catalyst of the invention is typically a catalytic soot filter (CSF) or is intended for use as a catalytic soot filter (CSF).
[00109] When the monolith is a filtering monolith, it is preferable that the filtering monolith is a wall flow filter. In the wall flow filter, each inlet channel is alternately separated from an outlet channel by a porous structure wall and vice versa. It is preferred that the input channel and the output channels have a honeycomb arrangement. When having a honeycomb arrangement, it is preferred that the channels vertically and laterally adjacent to an input channel are plugged at one end upstream and vice versa (for example, the channels vertically and laterally adjacent to an input channel). output are plugged at one end downstream). When viewed from each end, the alternately plugged and open ends of the channels take on the appearance of a chessboard.
[00110] In principle, the substrate can be of any shape or size. However, the shape and size of the substrate are generally selected to optimize the exposure of the catalytically active materials in the catalyst to the exhaust gas. The substrate may, for example, have a tubular, fiber or particulate shape. Examples of suitable support substrates include a monolithic or cordierite honeycomb substrate, a SiC monolithic honeycomb substrate, a layered fiber-type substrate or mesh fabric, a foam-type substrate , a cross flow type substrate, a wire mesh type substrate, a porous metal body type substrate and a ceramic particle type substrate.
[00111] The invention also relates to an exhaust system for a combustion engine comprising the oxidation catalyst, and at least one emission control device. In general, the emission control device is separate for the oxidation catalyst (for example, the emission control device has a substrate separate from the oxidation catalyst substrate) and, preferably, the oxidation catalyst is upstream of the device emission control.
[00112] The emission control device can be selected from a diesel particulate filter (DPF), a NOx adsorbent catalyst (NAC), a poor NOX catalyst (LNC), a selective catalytic reduction catalyst (SCR) , a diesel oxidation catalyst (DOC), a catalytic soot filter (CSF), a selective catalytic reduction filter catalyst (SCRF), and combinations of two or more of the same. Emission control devices represented by the terms of diesel particulate filters (DPFs), NOX adsorbent catalysts (NACs), poor NOX catalysts (LNCs), selective catalytic reduction catalysts (SCR), diesel oxidation catalysts (DOCs) Selective catalytic reduction filter (SCRF) filter catalysts (CSFs) are all well known in the art.
[00113] Examples of emission control devices for use with the oxidation catalyst of the invention or for inclusion in the exhaust system of the invention are provided below.
[00114] A diesel particulate filter is an emission control device having a filtering substrate. The diesel particulate filter preferably comprises a substrate, wherein the substrate is a filtering monolith or flow-through monolith, as defined above, preferably a filtering monolith. The substrate can be coated with a catalyst formulation.
[00115] The catalyst formulation of the diesel particulate filter may be suitable to oxidize (i) the particulate material (PM) and / or (ii) carbon monoxide (CO) and hydrocarbons (HCs). When the catalyst formulation is suitable for oxidizing PM, then the resulting emission control device is known as a catalyzed soot filter (CSF). Typically, the catalyst formulation of a CSF comprises a noble metal, such as a first noble metal and / or a second noble metal, as defined above.
[00116] The catalyst formulation of the diesel particulate filter can be a NOX adsorber composition. When the formulation is a NOX adsorber catalyst composition, an emission control device is an example of a NOX adsorber catalyst (NAC). Emission control devices in which the catalyst formulation is a NOX adsorbent composition have been described (see, for example, EP 0.766.993). NOX adsorbent compositions are well known in the art (see, for example, EP 0.766,993 and US 5,473,887). NOX adsorbent compositions are designed to adsorb NOX from the poor exhaust gas (lambda> 1) and to desorb NOX when the oxygen concentration in the exhaust gas is reduced. The desorbed NOX can then be reduced to N2 with an appropriate reducer (for example, motor fuel) and promoted by a catalyst component, such as rhodium, of the NOX adsorber composition itself or located downstream of the NOX adsorber composition.
[00117] Generally, a NOX adsorbent composition comprises an alkali metal component, an alkaline earth metal component or a rare earth metal component or a combination of two or more components thereof, wherein the metal component rare earth comprises lanthanum or yttrium. It is preferred that the alkali metal component comprises potassium or sodium, more preferably potassium. It is preferred that the alkaline earth metal component comprises barium or strontium, more preferably barium.
[00118] The NOX adsorbent composition may further comprise a support material and / or a catalytic metal component. The support material can be selected from alumina, ceria, titania, zirconia and mixtures thereof. The catalytic metal component can comprise a metal selected from platinum (Pt), palladium (Pd), rhodium (Rh) and combinations of two or more of them.
[00119] Poor NOX catalysts (LNCS) are well known in the art. Preferred poor NOX catalysts (LNC) comprise either (a) platinum (Pt) supported on alumina or (b) a copper-exchanged zeolite, particularly copper-exchanged ZSM-5.
[00120] SCR catalysts are also well known in the art. When the exhaust system of the invention comprises an SCR catalyst, then the exhaust system may further comprise an injector for injecting a nitrogen reducer, such as ammonia or urea, into the exhaust gas downstream of the carbon monoxide oxidation catalyst ( CO) and hydrocarbons (HCs) and upstream of the SCR catalyst. Alternatively, or in addition to the injector, the exhaust system may also include an engine control mechanism to enrich the exhaust gas with hydrocarbons. The SCR catalyst can then use the hydrocarbons as a reducer to reduce NOX. When the substrate of the SCR catalyst is a filtering monolith, then the catalyst is an SCRF catalyst. An SCRF catalyst is an emission control device having a filtering substrate.
[00121] Generally, SCR catalysts are unable to reduce substantial amounts of NOX in an exhaust gas shortly after starting a compression ignition engine, because the temperature of the exhaust gas (and therefore the temperature of the catalyst) it's too low. Poor NOX collector catalysts (eg NOX adsorbent catalysts) have, for example, been used upstream of SCR catalysts, so that NOX can be stored until the SCR catalyst becomes more active at higher gas temperatures exhaust. However, poor NOX collector catalysts are often unable to properly store NOX when there is a large mass of exhaust gas (for example, when the engine is operated on a high speed cycle).
[00122] In a first embodiment of the exhaust system, the exhaust system comprises the oxidation catalyst of the invention, preferably as a DOC, and a selective catalytic reduction catalyst (SCR). Such a provision can be called DOC / SCR. This modality also refers to the use of the oxidation catalyst for the treatment of an exhaust gas from a combustion engine, particularly a compression ignition engine, in combination with a selective catalytic reduction filter (SCRF) catalyst. Preferably, the oxidation catalyst is, or should be used as a diesel oxidation catalyst. The oxidation catalyst of the invention is typically followed by a (e.g., upstream of) selective catalytic reduction (SCR) catalyst. A nitrogen reducer injector can be placed between the oxidation catalyst and the selective catalytic reduction (SCR) catalyst. Thus, the oxidation catalyst can be followed by one (for example, upstream of) nitrogen reducer injector, and the nitrogen reducer injector can be followed by one (for example, upstream of) selective catalytic reduction catalyst (SCR).
[00123] A second embodiment of the exhaust system comprises the oxidation catalyst of the invention, preferably as a DOC, and a selective catalytic reduction filter (SCRF) catalyst. Such a provision can be called DOC / SCRF. This modality also refers to the use of the oxidation catalyst for the treatment of an exhaust gas from a combustion engine, in particular a compression ignition engine, in combination with a selective catalytic reduction filter catalyst (SCRF ). Preferably, the oxidation catalyst is, or should be used as a diesel oxidation catalyst. The oxidation catalyst of the invention is typically followed by a (e.g., upstream of) selective catalytic reduction filter (SCRF) catalyst. A nitrogen reducer injector can be arranged between the oxidation catalyst and the selective catalytic reduction filter (SCRF) catalyst. Thus, the oxidation catalyst can be followed by one (for example, upstream of) nitrogen reducer injector, and the nitrogen reducer injector can be followed by one (for example, upstream of) reduction filter catalyst selective catalytic (SCRF).
[00124] In a third embodiment of the exhaust system, the exhaust system comprises the oxidation catalyst of the invention, preferably as a DOC and or a diesel particulate filter (DPF) or a catalytic soot filter (CSF). Such a provision can be called DOC / DPF or a DOC / CSF. This modality also refers to the use of the oxidation catalyst for the treatment of an exhaust gas from a combustion engine, in particular a compression ignition engine, in combination with a diesel particulate filter or a catalyzed soot filter. Preferably, the oxidation catalyst is, or should be used as a diesel oxidation catalyst. The oxidation catalyst is typically followed by (for example, it is upstream) the diesel particulate filter or the catalyzed soot filter (CSF). Thus, for example, an oxidation catalyst outlet is connected to an inlet of the diesel particulate filter or the catalyzed soot filter.
[001251 In a fourth embodiment of the exhaust system, the exhaust device includes a diesel oxidation catalyst and the oxidation catalyst of the invention, preferably as a catalytic soot filter (CSF). This provision can also be called a DOC / CSF provision. The modality also refers to the use of the oxidation catalyst for the treatment of an exhaust gas from a compression ignition engine, in combination with a diesel oxidation catalyst (DOC), preferably in which the oxidation catalyst is, or should be used as a catalytic soot filter. Typically, the diesel oxidation catalyst (DOC) is followed by an (for example, upstream of) oxidation catalyst of the invention. Thus, an output of the diesel oxidation catalyst is connected to an input of the oxidation catalyst of the invention.
[00126] A fifth embodiment of the exhaust system relates to an exhaust system comprising the oxidation catalyst of the invention, preferably as a DOC, a diesel particulate filter or a catalyzed soot filter (CSF), and a catalyst. selective catalytic reduction (SCR). Such an arrangement can be called DOC / DPF / SCR or a DOC / CSF / SCR and is a preferred exhaust system for a light diesel vehicle. This modality also refers to the use of the oxidation catalyst for the treatment of an exhaust gas from a combustion engine, in particular a compression ignition engine, in combination with a diesel particulate filter or a catalyzed soot filter ( CSF), and a selective catalytic reduction catalyst (SCR), preferably, where the oxidation catalyst is, or should be used as a diesel oxidation catalyst. The oxidation catalyst is typically followed by (for example, upstream) the diesel particulate filter or the catalyzed soot filter (CSF). DPF or CSF is generally followed by a (eg, upstream of) selective catalytic reduction (SCR) catalyst. A nitrogen reducer injector can be arranged between DPF or CSF and the selective catalytic reduction (SCR) catalyst. Thus, DPF or LCR can be followed by one (for example, upstream of) nitrogen reducer injector, and the nitrogen reducer injector can be followed by one (for example, upstream of) selective catalytic reduction catalyst ( SCR).
[001271 A sixth mode of the exhaust system relates to an exhaust system comprising a diesel oxidation catalyst (DOC), the oxidation catalyst of the invention, preferably as a catalytic soot filter (CSF), and an exhaust catalyst selective catalytic reduction (SCR). This is also a DOC / CSF / SCR provision. Another aspect of this modality relates to the use of the oxidation catalyst for the treatment of an exhaust gas from a compression ignition engine, in combination with a diesel oxidation catalyst (DOC) and a catalytic reduction catalyst (SCR) selective, preferably, where the oxidation catalyst is, or should be used as, a catalyzed soot filter (CSF). The diesel oxidation catalyst (DOC) is usually followed by an (for example, upstream of) oxidation catalyst of the invention. The oxidation catalyst of the invention is typically followed by a (e.g., upstream of) selective catalytic reduction (SCR) catalyst. A nitrogen reducer injector can be placed between the oxidation catalyst and the selective catalytic reduction (SCR) catalyst. Thus, the oxidation catalyst can be followed by (for example, upstream of) nitrogen reducer injector, and the nitrogen reducer injector can be followed by one (for example, upstream of) selective catalytic reduction catalyst ( SCR).
[00128] In a seventh mode of the exhaust system, the exhaust system comprises the oxidation catalyst of the invention, preferably as a DOC, a catalytic selective reduction catalyst (SCR) and a catalytic soot filter (CSF) or a diesel particulate filter (DPF). The provision is either a DOC / SCR / CSF or a DOC / SCR / DPF. This modality also refers to the use of the oxidation catalyst for the treatment of an exhaust gas from a combustion engine, in particular a compression ignition engine, in combination with a selective catalytic reduction (SCR) of catalyst and a catalyzed soot filter (CSF) or a diesel diesel particulate filter (DPF), preferably where the oxidation catalyst is, or should be used as a diesel oxidation catalyst.
[00129] In the seventh mode of the exhaust system, the oxidation catalyst of the invention is typically followed by a (e.g., upstream of) selective catalytic reduction (SCR) catalyst. A nitrogen reducer injector can be placed between the oxidation catalyst and the selective catalytic reduction (SCR) catalyst. Thus, the oxidation catalyst can be followed by one (for example, upstream of) nitrogen reducer injector, and the nitrogen reducer injector can be followed by one (for example, upstream of) selective catalytic reduction catalyst (SCR). The selective catalytic reduction catalyst (SCR) is followed by (for example, it is upstream) the catalyzed soot filter (CSF) or the diesel particulate filter (DPF).
[00130] Another aspect of the invention relates to a vehicle or apparatus comprising an internal combustion engine and the oxidation catalyst of the invention or the exhaust system of the invention.
[00131] Typically, the engine can be used in a mobile application, such as a vehicle, or in a stationary application, such as a power generation unit.
[00132] The internal combustion engine can be a spark ignition engine (for example, a gasoline spark ignition engine) or a compression ignition engine. It is preferred that the internal combustion engine is a compression ignition engine. Most preferably, the compression ignition engine is a diesel engine. The diesel engine can be a homogeneous charge compression ignition engine (HCCI), a premixed charge compression ignition engine (PCCI) or a low temperature combustion engine (LTC). It is preferred that the diesel engine is a conventional (ie traditional) diesel engine.
[00133] When the internal combustion engine is a compression ignition engine, such as a diesel engine, then the vehicle may be a light diesel vehicle or heavy diesel vehicle.
[00134] The term "light diesel vehicle (LDV)" is defined in American or European legislation. A light-weight diesel vehicle typically has a weight of <2840 kg, more preferably a weight of <2610 kg.
[00135] In the United States, a light-weight diesel vehicle (LDV) refers to a diesel vehicle with a gross weight of <3855 kg. In Europe, the term light diesel vehicle (LDV) refers to (i) passenger vehicles, comprising no more than eight seats in addition to the driver's seat having a maximum mass not exceeding 5 tons, and (ii) vehicles for the transport of goods having a maximum mass not exceeding 12 tons.
[00136] In general, a heavy-duty diesel vehicle (HDV) is a diesel vehicle having a gross weight of over 3855 kg (8,500 American pounds), as defined in United States law.
[00137] A method of preparing an oxidation catalyst according to the invention is also provided. In general, the method involves using at least one noble metal component (for example, the first noble metal component) that does not attach quickly to the substrate or support material and is mobile within a coating. When a coating containing a noble metal component is applied to a substrate, then the coating is dried and calcined using conditions that allow the movement of the noble metal component within the coating, before being fixed in position. Such conditions are known in the art, in particular because the conditions of the prior art are usually selected to quickly fix the coating components (i.e., catalytic coating like reactive coating composition) to prevent their movement within the coating.
[001381 The transfer of solutes to or away from a wet surface during evaporation is an effect that is known in other technical areas. The transfer of the first noble metal (for example, a noble metal salt comprising the first noble metal) within a wet coating can be represented by the Richards equation:
where: t is the time (for example, the time before substantial or complete evaporation of the solvent (i.e., water)); θ is the solvent content (ie, water), typically of the coating; K is the hydraulic conductivity; z is the elevation; and ψ is the pressure head. The hydraulic conductivity can be approximated by the hydraulic conductivity of the first support material and / or any other support material that may be present.
[00139] The method of the invention therefore comprises: (a) providing an aqueous slurry comprising a precursor to the first support material, a first noble metal component and a second noble metal component; (b) applying the aqueous slurry to a substrate to form a coating; and (c) drying and calcining the coating, where the drying conditions allow at least the first noble metal component to flow close to or away from the substrate, in order to obtain a non-uniform distribution of the first noble metal in a direction perpendicular to a substrate surface. [00140] The method of the invention relates to a slurry. Usually, at least one precursor to the first support material, the first noble metal component and the second noble metal component is insoluble. However, it should be understood that the slurry can be a solution, as when the precursor to the first support material, the first noble metal component and the second noble metal component are all soluble (i.e., dissolved).
[00141] Typically, the precursor to the first support material is a compound that undergoes a conversion to the first support material after drying and / or calcining the coating. Such precursors of support materials are well known in the art. In some cases, the precursor to the first support material may be the first support material (i.e., it is not necessary to include a precursor that is converted to the support material during the method).
[00142] Generally, the first noble metal component is a salt of the first noble metal or is the first noble metal (that is, it is the first noble metal itself). Preferably, the first noble metal component is a salt of the first noble metal. The salt of the first noble metal can be a nitrate salt of the first noble metal, an acetate salt of the first noble metal or a carboxylate salt (e.g., citrate salt) of the first noble metal.
[00143] The second noble metal component is typically a salt of the second noble metal or is the second noble metal (ie, the second noble metal itself). It is preferred that the second noble metal component is a salt of the second noble metal. The salt of the second noble metal can be a nitrate salt of the second noble metal, an acetate salt of the second noble metal or a carboxylate salt (e.g., citrate salt) of the second noble metal.
[00144] When different noble metals are used (for example, the first noble metal is different from the second noble metal), then there may be a difference in the mobility of the first noble metal component compared to the second noble metal component, which results of the difference in metals that are present. It is possible to vary the mobility and also the preferred flow direction of the noble metal components by selecting an appropriate anion when the noble metal component is a noble metal salt. Noble metal components can also interact differently with the support material and can be selected based on this.
[00145] It is preferred that a counter-anion of the salt of the first noble metal is different from a counter-anion of the salt of the second noble metal. For example, the first noble metal component can be palladium nitrate and the second noble metal component can be a platinum carboxylate salt. The nitrate anion is different from the carboxylate anion.
[00146] The mobility of at least one of the noble metal components can be changed by supporting it on a support material (ie pre-fixing the noble metal component) before mixing with the other metal component noble.
[00147] A way that the first noble metal component can be supported on the precursor of the first support material by: (i) mixing a precursor of the first support material and a first noble metal component in solution, preferably to impregnate , or fill the pores of the precursor to the first support material; and (ii) drying and / or calcining the aqueous solution to give a first noble metal component (for example, first noble metal), supported on the precursor of the first support material (for example, the first support material). Step (i) can be followed by a step (i) (a), adding a reducing agent to reduce the first noble metal component, preferably to impregnate, or fill the pores of the precursor to the first support material. In step (i) and / or (i) (a), it is preferred that the only noble metal component present is the first noble metal component.
Thus, step (a) of the method of the invention can be a step of (a) providing an aqueous slurry comprising a second noble metal component and a first noble metal component supported on a precursor to the first support material.
[00149] With respect to step (b), methods for applying slurries or reactive coating compositions to a substrate are well known in the art (see for example WO 99/47260 by the present inventor).
[00150] In one embodiment, step (c) involves drying the coating using drying conditions that allow the first noble metal component and the second noble metal component to flow in directions opposite to each other in relation to the substrate. In another embodiment, step (c) involves drying the coating using drying conditions that allow only the first noble metal component to flow in or out of the substrate.
[00151] Step (c) determines the point at which the noble metal components are fixed, usually on the substrate or a support material. The drying conditions that are used will depend on the identity of the materials (for example, the noble metal components, the precursor of support material, etc.) that are present in the coating and the size of the oxidation catalyst (for example, the substrate size, which will vary depending on the application of the catalyst).
[00152] Typically, drying conditions involve drying the coating for at least 15 minutes, preferably at least 20 minutes. A non-uniform distribution of the first noble metal can be obtained using such conditions. Uniform distributions tend to be obtained when the drying time is about 5 minutes or less.
[00153] The coating can then be calcined at a temperature of 400 to 800 ° C, preferably 450-600 ° C, more preferably at a temperature of at least 500 ° C. DEFINITIONS
[00154] Any reference to the distribution of a noble metal (for example, first noble metal or second noble metal) in a direction (for example, a straight line) perpendicular to the surface of the substrate, generally refers to a direction perpendicular to it substrate surface on which the catalyst layer is arranged. For reference purposes, the surface of the substrate is generally in the horizontal (i.e., longitudinal) plane. The direction perpendicular to the substrate surface is typically a direction in a cross-section plane through the catalyst layer (i.e., a cross-section plane that exposes the thickness of the catalyst layer), perpendicular to the substrate surface. The cross-sectional plane is, in general, a vertical (ie, transversal) plane. The cross-sectional plane is perpendicular to the surface on which the catalyst layer is arranged. More typically, the cross-sectional plane is substantially parallel to an input end face of the substrate and / or the end end face of the substrate (i.e., the plane containing the input end face and / or the plane containing the exit end face). Any reference to "substantially parallel" in this context refers to an angle of less than 5 °, preferably less than 2.5 °, more preferably less than Io (for example, less than 0.5 °), between the cross-section plane and the inlet end face or outlet end face of the substrate.
[00155] Any reference to a "substrate surface" generally refers to the surface of a channel wall through the substrate.
[00156] The term "layer" (e.g., catalyst layer), as used herein, refers to a thickness of material spread over a surface, such as a surface of a substrate or a surface of another layer, which typically has distinct boundaries or edges (that is, it is possible to distinguish one layer from another layer using conventional analytical techniques (for example, transmission electron microscopy).
[00157] The term "uniform", as used herein, with reference to the distribution of a noble metal, generally refers to a composition (for example, a layer), where the amount of noble metal, at any point in the composition, it is within ± 20% of the average amount of noble metal in the complete composition (eg layer). It is preferred that the amount of noble metal, at any point in the composition, is within ± 10%, more preferably ± 5%, and even more preferably ± 1%, of the average amount of noble metal, in the complete composition (e.g. layer). The average amount of noble metal must correspond to the amount of noble metal that is measured during the preparation of that composition. The amount of noble metal at any point in a composition can be determined using conventional analytical techniques, such as by EDX analysis, using a transmission electron microscope.
[00158] The term "mixed oxide", as used herein, generally refers to a mixture of single phase oxides, as is conventionally known in the art.
[00159] The term "composite oxide", as used herein, generally refers to an oxide composition with more than one phase, as is conventionally known in the art.
[00160] Quantities given in units of g / 0.0283 m3 or g / 16.38 cm3 in general refer to the volume of the substrate that is used.
[00161] The expression "essentially consisting", as used herein, limits the scope of an aspect to include the specified materials or steps, and any other materials or steps that do not materially affect the basic characteristics of that characteristic, such as, for example, small impurities. The phrase "consisting essentially of" encompasses the phrase "consisting of".
[00162] Under the term "noble metal" (for example, first noble metal or second noble metal), it should be appreciated that it is often difficult to characterize the exact catalytic species in a catalyst and the noble metal may not be present in form elementary metal. Any reference to "consisting essentially of a noble metal ..." encompasses a "noble metal portion" in an elementary form of the noble metal, an alloy containing the noble metal or a compound comprising the noble metal (for example, an oxide of noble metal). Preferably, any such "noble metal portion" is an elementary form of the noble metal or an alloy containing the noble metal, more preferably an elemental form of the noble metal. EXAMPLES
[00163] The invention will now be illustrated by the following non-limiting examples. Example 1 Preparation of a single-layer non-uniform catalyst
[00164] Silica-alumina powder was suspended in water and ground to a dyo of less than 20 microns. A soluble platinum carboxylate salt and palladium nitrate was added to the slurry and the mixture was stirred to homogenize. The resulting reactive coating composition was then applied to a substrate (a cordierite flow-through monolith having 400 cells per 6.45 cm2), using conventional coating techniques. The resulting part was dried slowly, under a flow of heated air. The part was completely dry after 20 minutes of operation and was then calcined at 500 ° C. The fresh catalyst composition that coated the substrate was then aged by heating at 750 ° C for 15 hours under hydrothermal conditions (10% water).
[00165] Slow drying conditions were used to dry the reactive coating composition on the substrate. These conditions were selected to allow the movement of the palladium salt during drying (that is, as water in the reactive coating composition evaporated) until the palladium is fixed in position by means of complete evaporation of the liquid phase of the reactive coating composition. . The distribution of the platinum and palladium components of the catalyst layer is shown schematically in Figure 2 (platinum = noble metal 1; palladium = noble metal 2). Comparative Example 2 Preparation of a uniform single-layer catalyst
[00166] As a comparison, a catalyst was prepared using the materials that were used in Example 1 and was coated on the same type of substrate by the same method. The resulting part was dried quickly under a high speed flow of heated air. The part was completely dried after 5 minutes of operation and was then calcined at 500 ° C. The fresh catalyst composition that coated the substrate was then aged by heating at 750 ° C for 15 hours under hydrothermal conditions (10% water).
[00167] Conventional quick drying conditions were used to dry the reactive coating composition on the substrate to obtain a layer of catalyst having a uniform composition. The distribution of the platinum and palladium components of the catalyst layer is shown schematically in Figure 3 (platinum = noble metal = 1; palladium = noble metal 2). Example 3 Preparation and analysis of a multilayer catalyst with a non-uniform layer
[00168] A substrate monolith of 400 cells by 6.45 cm2 and a wall thickness of 6 thousandths of 2.54 cm was prepared having a two-layer structure. The first layer that was coated on the substrate (i.e., the bottom layer) contained platinum and palladium on an alumina support. The weight content of platinum was higher than that of palladium. The second layer (i.e., the top layer) had a composition that was prepared using the method described in Example 1 to give a layer having a non-uniform distribution of palladium.
[00169] A section of the catalyst was mounted on the resin, ground and polished, then coated with carbon under vacuum. EPMA-WDX analyzes showed that the first layer (ie, bottom layer) contained an even distribution of palladium and platinum particles (see Figure 1). The second layer (i.e., top layer) contained a non-uniform distribution of palladium particles. In particular, the second layer contained a high concentration of palladium closer to its exposed surface (where the exhaust emissions first contact the layer) compared to regions of the layer that are closer than the first layer. Example 4 Emission test results
[00170] Core samples were taken from each of the catalysts of Examples 1 and 2 using a 2.54 cm core drill. The catalyst compositions were tested in a simulated catalyst gas equipment (SCAT) activity test using the input gas mixture shown in Table 1, with a spatial speed of 55000 / hour to mimic engine emissions. Table 1

[00171] The results of the aged catalysts of Examples 1 and 2 are shown in Table 2. Table 2 lists the temperatures at which 50% of the conversion of CO (T50 CO) and 80% of conversion of HC (Tso HC) occurred. Table 2

[00172] The results in Table 2 show that when the simulated exhaust gas is exposed to the catalyst of Example 1, having a high concentration of palladium particles close to an exposed surface of the reactive coating composition, then the conversion temperatures 50% CO and 80% HC conversion are lower than those obtained for Comparative Example 2.
[00173] For the avoidance of doubt, the complete content of any and all documents cited herein is incorporated by reference into this application.

权利要求:
Claims (10)
[0001]
1. Fresh oxidation catalyst for treatment of an exhaust gas produced by a diesel engine, where the oxidation catalyst comprises a substrate and a first catalyst layer, where the first catalyst layer comprises: a first support material; a combination of a first noble metal, which is palladium; and a second noble metal, which is platinum, characterized by the fact that: the first catalyst layer is arranged on a substrate surface, and the first catalyst layer has a non-uniform distribution of the palladium metal in a direction perpendicular to the surface of the substrate, such that the amount of palladium continually decreases in a direction perpendicular to the surface of the substrate; and, the first catalyst layer has a uniform distribution of platinum in a direction perpendicular to the substrate surface, where the amount of platinum anywhere in the first catalyst layer is ± 10% of the average amount of platinum in the first catalyst layer. .
[0002]
2. Oxidation catalyst according to claim 1, characterized in that it comprises a second layer comprising a hydrocarbon adsorbent and / or a third noble metal and / or a refractory oxide, in which the second layer is arranged directly on a substrate surface and the first layer of catalyst is disposed on the second layer; or, the first layer of catalyst is disposed directly on a surface of the substrate and the second layer is disposed on the first layer of catalyst.
[0003]
Oxidation catalyst according to either of claims 1 or 2, characterized in that the first catalyst layer has a first upper surface, which is either an exposed surface of the first catalyst layer or a surface on which the second layer is arranged, and a second lower surface, which is in direct contact with the substrate surface or the surface of the second layer, in which at least 60% of the total amount of palladium is distributed between the first upper surface of the first catalyst layer and a plane in the first catalyst layer that is halfway between the first upper surface and the second lower surface.
[0004]
4. Oxidation catalyst according to any one of claims 1 to 3, characterized by the fact that the first support material comprises a refractory oxide selected from the group consisting of alumina, magnesia, silica, zirconia, titania, ceria and a composite oxide or a mixed oxide of two or more of the same.
[0005]
5. Oxidation catalyst according to claim 4, characterized by the fact that the refractory oxide is alumina, silica or silica-alumina.
[0006]
6. Oxidation catalyst according to any one of claims 1 to 5, characterized by the fact that palladium is in the form of particles.
[0007]
7. Oxidation catalyst according to claim 6, characterized by the fact that the palladium particles have a D90 <40 nm, as determined by laser diffraction techniques.
[0008]
8. Exhaust system for a diesel engine, characterized by the fact that it comprises an oxidation catalyst as defined in any of claims 1 to 7, and at least one emission control device selected from a diesel particulate filter (DPF), a NOX adsorbent catalyst (NAC), a poor NOX catalyst (LNC), a selective catalytic reduction catalyst (SCR), a diesel oxidation catalyst (DOC), a catalyzed soot filter (CSF), a filter catalyst selective catalytic reduction (SCRF), and combinations of two or more of them.
[0009]
9. Vehicle comprising an internal combustion diesel engine, characterized by the fact that it further comprises: an oxidation catalyst as defined in any of claims 1 to 7; or an exhaust system as defined in claim 8.
[0010]
10. Use of an oxidation catalyst, as defined in any of claims 1 to 7, characterized by the fact that it is for the treatment of an exhaust gas produced by a diesel engine.

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同族专利:

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公开号 | 公开日

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CN105073250A|2015-11-18|

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RU2688674C2|2019-05-22|

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BR112015020505A2|2017-07-18|

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JP2016513014A|2016-05-12|

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DE102014102023B4|2020-08-06|

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GB201402802D0|2014-04-02|

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DE102014102023A1|2014-08-28|

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GB2516133A|2015-01-14|

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US9138724B2|2015-09-22|

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US20140241964A1|2014-08-28|

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WO2014132034A1|2014-09-04|

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GB201303396D0|2013-04-10|

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GB2516133B|2017-05-24|

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CN105073250B|2018-11-13|

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RU2015140750A|2017-04-03|

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KR102275358B1|2021-07-09|

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EP2961526A1|2016-01-06|

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KR20150122219A|2015-10-30|

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EP2961526B1|2021-04-28|

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JP6483625B2|2019-03-13|

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法律状态:
2018-11-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-10-29| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-09-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-11-24| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 18/02/2014, OBSERVADAS AS CONDICOES LEGAIS. |

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