oxidation catalyst and exhaust system

专利摘要:
OXIDATION CATALYST, EXHAUST SYSTEM, AND, VEHICLE OR APPARATUS. oxidation catalyst to treat an exhaust gas from a diesel engine, the oxidation catalyst of which comprises: a first reactive coating region comprising a first platinum group metal (PGM), a first support material and a storage component NOx; a second reactive coating region comprising platinum (Pt), manganese (Mn) and a second support material; and a substrate with an input end and an output end.
公开号:BR112016016926B1
申请号:R112016016926-3
申请日:2015-01-23
公开日:2020-12-29
发明作者:Andrew Francis Chiffey；John Goodwin；James Leeland；Francois Moreau；Stuart David Reid；Daniel Swallow
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 a diesel engine and an exhaust system for a diesel engine comprising the oxidation catalyst. The invention also relates to methods and uses of the oxidation catalyst to treat an exhaust gas from a diesel engine. BACKGROUND OF THE INVENTION
[002] Diesel engines produce an exhaust emission that generally contains at least four classes of pollutant that are legislated by intergovernmental organizations worldwide: carbon monoxide (CO), unburned hydrocarbons (HCs), nitrogen oxides (NOx) and particulate matter (PM). Emission standards for diesel engines, whether stationary or mobile (for example, vehicle diesel engines), are becoming increasingly stringent. There is a need to provide improved catalysts and exhaust systems that are able to meet these standards, which are cost effective.
[003] Exhaust systems for diesel engines can include various emission control devices. Each emission control device has a specialized function and is responsible for treating one or more classes of pollutants in the exhaust gas. The performance of an upstream emission control device may affect the performance of a downstream emission control device. This is because the exhaust gas from the output of the upstream emission control device is passed to the input of the downstream emission control device. The interaction of each emission control device in the exhaust system is important for the overall efficiency of the system.
[004] Oxidation catalysts, such as diesel oxidation catalysts (DOCs), typically oxidize carbon monoxide (CO) and hydrocarbons (HCs) in an exhaust gas produced by a diesel engine. Diesel oxidation catalysts can also oxidize part of the nitric oxide (NO) that is present in the exhaust gas to nitrogen dioxide (NO2). Although nitrogen dioxide (NO2) is itself a pollutant, the conversion of NO to NO2 can be beneficial. The NO2 that is produced can be used to regenerate particulate matter (PM) that has been captured, for example, a downstream diesel particulate filter (DPF) or a downstream catalyzed soot filter (CSF). Generally, the NO2 generated by the oxidation catalyst increases the NO2: NO ratio in the exhaust gas from the oxidation catalyst outlet compared to the exhaust gas at the inlet. This increased ratio can be advantageous for exhaust systems comprising a downstream selective catalytic reduction (SCR) catalyst or a selective catalytic reduction filter (SCRF ™) catalyst. The NO2: NO ratio in the exhaust gas produced directly by a diesel engine can be too low for optimal SCR or SCRF catalyst performance.
[005] Although it is generally advantageous to include an oxidation catalyst that has good NO2 generation activity in an exhaust system, the use of an oxidation catalyst in this way can be problematic when seeking to achieve optimal performance from a gas control device downstream emissions (for example, an SCR or SCRF ™ catalyst). The average amount of NO2 that is generated by an oxidation catalyst at a given exhaust gas temperature can vary considerably in its useful life. This can lead to difficulties in calibrating the dosage of the nitrogen reducing agent to perform active SCR. SUMMARY OF THE INVENTION
[006] The inventors observed that excellent activity for the oxidation of nitric oxide (NO) in an exhaust gas of a diesel engine can be obtained when manganese (Mn) is combined with platinum (Pt) in an oxidation catalyst. Platinum is expensive and is often included in oxidation catalysts in relatively large amounts for, among other things, its oxidation activity for NO. The inclusion of manganese (Mn) in combination with platinum (Pt) may result in an improvement in NO oxidation activity or allow the use of a reduced amount of Pt to achieve a given level of NO oxidation. The oxidation catalyst, particularly the region containing Mn and Pt, may have good activity to oxidize carbon monoxide (CO) and hydrocarbons (HCs) in an exhaust gas produced by a diesel engine.
[007] The invention provides an oxidation catalyst to treat an exhaust gas from a diesel engine, the oxidation catalyst of which comprises: a first reactive coating region comprising a first platinum group metal (PGM) and a first Support; a second reactive coating region comprising platinum (Pt), manganese (Mn) and a second support material; and a substrate with an input end and an output end.
[008] The first reactive coating region is suitable for storage of NOx (ie NOx adsorption). It may also be suitable for oxidizing carbon monoxide (CO) and hydrocarbons (HCs). The second reactive coating region is suitable for oxidizing nitric oxide (NO), but may also be suitable for oxidizing carbon monoxide (CO) and / or hydrocarbons (HCs), particularly when the second reactive coating region is substantially palladium free. .
[009] The oxidizing activity of the combination of Pt and Mn for nitric oxide (NO) and also CO and / or HCs can be particularly advantageous when certain alumina-based materials are used as a support material.
[0010] The combination of a reactive coating region comprising Pt and Mn together with a coating region of catalytic material formulated for NOx storage (i.e., NOx adsorption) can be advantageous. The Pt and Mn-containing region of the reactive coating can convert NOx to NO2 to facilitate the storage of NOx and / or can assist in the conversion of any NO to NO2 that passes through the NOx storage region.
[0011] The invention additionally provides an exhaust system for a diesel engine. The exhaust system comprises an oxidation catalyst of the invention and an emission control device.
[0012] The amount of NO2 in an exhaust gas can affect the performance of a downstream emission control device for the selective catalytic reduction of nitrogen oxides (NOx). Selective catalytic reduction (SCR) catalysts and selective catalytic reduction filter (SCRF ™) catalysts to treat NOx (for example, NO2 + NO) often require that the NO2 to NO ratio in the inlet gas be within a specific range for optimal catalytic performance. The ideal NO2 to NOx ratio typically depends on the type of composition used in the SCR or SCRF ™ catalyst, but the NO2 to NO ratio in an exhaust gas directly from a diesel engine is usually too low for optimal catalyst performance.
[0013] The oxidation catalyst of the invention can be used to convert NO to NO2 and thereby increase the amount of NO2 in the exhaust gas leaving the catalyst compared to the amount of NO2 in the exhaust gas at the entrance of the catalyst ( that is, the NO2: NOx and NO2: NO ratios in the exhaust gas exiting the oxidation catalyst are greater than the corresponding exhaust gas ratios at the oxidation catalyst inlet). The oxidation catalyst can alter the NOx composition of the exhaust gas for optimal SCR performance.
[0014] A problem with using an oxidation catalyst to "intensify" the NO2 content of an exhaust gas is that the NO oxidation activity of the oxidation catalyst normally varies with its useful life. Generally, as the catalyst "ages" (that is, the catalyst has been used for an extended period), the NO oxidation activity of the catalyst decreases. While the amount of NO2 in the exhaust gas leaving an “aged” oxidation catalyst may be sufficient for the optimal performance of a downstream emission control device (for example, an SCR catalyst), this variation in the amount of NO2 that is generated is problematic to calibrate the nitrogen reducing agent dosage to perform active SCR.
[0015] It has been observed that the oxidation catalyst of the invention can have relatively stable NO oxidation activity in its useful life. Thus, the difference in NO oxidation activity of the oxidation catalyst in a fresh state (that is, when it is "new" and has not been subjected to prolonged and repeated use) and an aged state is typically small.
[0016] A further aspect of the invention relates to a vehicle or an apparatus (for example, a stationary or mobile apparatus). The vehicle or apparatus comprises a diesel engine and both the oxidation catalyst and the exhaust system of the invention.
[0017] The invention also refers to several uses and methods.
[0018] A first aspect of the method of the invention provides a method for treating an exhaust gas from a diesel engine. The method comprises both putting the exhaust gas in contact with an oxidation catalyst of the invention or passing the exhaust gas through an exhaust system of the invention. The term “treating an exhaust gas” in this context refers to oxidizing carbon monoxide (CO), hydrocarbons (HCs) and nitric oxide (NO) in an exhaust gas from a diesel engine.
[0019] A second aspect of the method provides a method of modulating the NOx content in an exhaust gas from a diesel engine for an emission control device. The method comprises: (a) controlling the NOx content of an exhaust gas by placing the exhaust gas in contact with an oxidation catalyst of the invention to produce a treated exhaust gas; and (b) passing the treated exhaust gas to an emission control device.
[0020] A first aspect of use of the invention concerns the use of an oxidation catalyst to treat an exhaust gas from a diesel engine, optionally in combination with an emission control device. Generally, the oxidation catalyst is used to treat (for example, oxidize) carbon monoxide (CO) and hydrocarbons (HCs) in an exhaust gas from a diesel engine.
[0021] In a second aspect of use, the invention relates to the use of an oxidation catalyst to modulate the NOx content in an exhaust gas from a diesel engine to an emission control device (for example, a device emission control systems).
[0022] A third aspect of use refers to the use of an oxidation catalyst in the regeneration of an emission control device with a filtration substrate (for example, a downstream emission control device having a filtration substrate).
[0023] A fourth aspect of use refers to the use of manganese (Mn), preferably in combination with platinum (Pt), in an oxidation catalyst for a diesel engine to intensify the oxidation of nitric oxide (NO) in a gas exhaust of the diesel engine.
[0024] A fifth aspect of use refers to the use of manganese (Mn), preferably in combination with platinum (Pt), in an oxidation catalyst for a diesel engine to stabilize the NO oxidation activity of the oxidation catalyst in its useful life.
[0025] In the first to fifth aspects of use, the oxidation catalyst is an oxidation catalyst according to the invention. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Figures 1 to 10 are schematic representations of oxidation catalysts of the invention. The exhaust gas can enter through both the left and right sides of the oxidation catalyst.
[0027] Figure 1 shows an oxidation catalyst comprising a first reactive coating region (1) and a second reactive coating region / zone (2) arranged on a substrate (3).
[0028] Figure 2 shows an oxidation catalyst comprising a first reactive coating region (1) and a second reactive coating region / zone (2). The first reactive coating region (1) is arranged directly on the substrate (3). The second reactive coating region / zone (2) is arranged in the first reactive coating region (1).
[0029] Figure 3 shows an oxidation catalyst comprising a first reactive coating region (1) and a second reactive coating region / zone (2). There is an overlap between the first reactive coating region (1) and the second reactive coating region / zone (2). A portion of the first reactive coating region (1) is arranged in the second reactive coating region / zone (2). Both the first reactive coating region (1) and the second reactive coating region / zone (2) are arranged on the substrate (3).
[0030] Figure 4 shows an oxidation catalyst comprising a first reactive coating region (1) and a second reactive coating region / zone (2). There is an overlap between the first reactive coating region (1) and the second reactive coating region / zone (2). A part of the second reactive coating region / zone (2) is arranged in the first reactive coating region (1). Both the first reactive coating region (1) and the second reactive coating region / zone (2) are arranged on the substrate (3).
[0031] Figure 5 shows an oxidation catalyst comprising a first reactive coating layer (1) and a second reactive coating layer (2) arranged on a substrate (3). The second reactive coating layer (2) is arranged on the first reactive coating layer (1).
[0032] Figure 6 shows an oxidation catalyst comprising a first reactive coating zone (1) and a second reactive coating zone / region (2). Both the first reactive coating region / zone (1) and the second reactive coating region / zone (2) are arranged in a third reactive coating region / layer (4). The third reactive coating region / layer (4) is arranged on a substrate (3).
[0033] Figure 7 shows an oxidation catalyst comprising a first reactive coating zone (1), a second reactive coating zone (2) and a third reactive coating zone (4). Both the first reactive coating zone (1) and the second reactive coating zone (2) are arranged on a substrate (3). The third reactive coating zone (4) is arranged in the second reactive coating zone (2).
[0034] Figure 8 shows an oxidation catalyst comprising a first reactive coating zone (1), a second reactive coating zone (2) and a third reactive coating zone (4). Both the first reactive coating zone (1) and the third reactive coating zone (4) are arranged on a substrate (3). The second reactive coating zone (2) is arranged in the third reactive coating zone (2).
[0035] Figure 9 shows an oxidation catalyst comprising a first reactive coating zone (1), a second reactive coating zone (2) and a third reactive coating zone (4). Both the first reactive coating zone (1) and the second reactive coating zone (2) are arranged on a substrate (3). The third reactive coating zone (4) is arranged in the first reactive coating zone (1).
[0036] Figure 10 shows an oxidation catalyst comprising a first reactive coating zone (1), a second reactive coating zone (2), a third reactive coating zone (4) and a fourth reactive coating zone (5) . Both the first reactive coating zone (1) and the third reactive coating zone (4) are arranged on a substrate (3). The second reactive coating zone (4) is arranged in the third reactive coating zone (2). The fourth reactive coating zone (5) is arranged in the first reactive coating zone (1). DETAILED DESCRIPTION OF THE INVENTION
[0037] The oxidation catalyst of the invention comprises, or may consist of a first reactive coating region for NOx storage, a second reactive coating region for oxidizing nitric oxide (NO) and a substrate.
[0038] The first reactive coating region comprises a first platinum group metal (PGM), a first support material and a NOx storage component.
[0039] The first PGM can be selected from the group consisting of platinum, palladium, rhodium and a combination of any two or more of them. Preferably, the first PGM is selected from platinum, palladium, a combination of platinum and palladium, a combination of platinum and rhodium, a combination of palladium and rhodium, and a combination of platinum, palladium and rhodium.
[0040] It may be preferable that the first PGM is selected from the group consisting of platinum, palladium and a combination of platinum and palladium. The first PGM can be platinum. The first PGM can consist essentially of platinum (for example, the first PGM is platinum only). The first PGM can be palladium. The first PGM can consist essentially of palladium (for example, the first PGM is palladium only). The first PGM can be a combination of platinum and palladium. The first PGM can consist essentially of platinum and palladium (for example, the first PGM is platinum and palladium only). It is preferred that the first PGM is selected from the group consisting of platinum and a combination of platinum and palladium.
[0041] The first reactive coating region may comprise the first PGM as the only metal in the platinum group (s). Thus, the only PGM (s) present in the first reactive coating region is / are defined by the first PGM.
[0042] When the first PGM is a combination of platinum and palladium, then the first PGM can be in the form of an alloy, preferably a bimetallic alloy. Thus, the first PGM may comprise, or consist essentially of, an alloy of platinum and palladium.
[0043] The first reactive coating region typically has a total loading of the first PGM of 5 to 300 g ft-3. It is preferred that the first reactive coating region has a total loading of the first PGM of 10 to 250 g ft-3 (for example, 75 to 175 g ft-3), more preferably 15 to 200 g ft-3 (for example, 50 to 150 g ft-3), even more preferably 20 to 150 g ft-3.
[0044] When the first PGM is a combination of platinum and palladium, then typically the first reactive coating region comprises a platinum to palladium weight ratio of 20: 1 to 1:20 (for example, 15: 1 to 1: 15), preferably 10: 1 to 1:10 (for example, 7.5: 1 to 1: 7.5), more preferably 5: 1 to 1: 5 (for example, 3: 1 to 1: 3), and further more preferably 2.5: 1 to 1: 1.
[0045] It is preferred that, when the first PGM is a combination of platinum and palladium, then the first reactive coating region comprises a total weight of platinum that is greater than or equal to the total weight of palladium (for example, the ratio of Pt: Pd by weight is> 1: 1). More preferably, the first reactive coating region comprises a total weight of platinum that is greater than the total weight of palladium (for example, the ratio of Pt: Pd by weight is> 1: 1).
[0046] Advantageous CO and / or HC extinction activity can be obtained when the total weight of platinum is greater than or equal to the total weight of palladium in the first reactive coating region.
[0047] It is generally preferred that the first reactive coating region comprises a weight ratio of platinum to palladium from 20: 1 to 1: 1 (e.g., 15.1: 1 to 1.1: 1), more preferably 10 : 1 to 1.25: 1 (e.g., 7.5: 1 to 1.5: 1), and even more preferably 5: 1 to 2: 1.
[0048] It is intended that the primary function of the first reactive coating region is NOx storage. However, it is realized that, in some modalities of the oxidation catalyst, the first reactive coating region can also oxidize carbon monoxide (CO) and hydrocarbons (HCs).
[0049] Typically, the first PGM is arranged or supported on the first support material. The first PGM can be arranged directly or be supported directly on the first support material (for example, there is no intervening support material between the first PGM and the first support material). For example, platinum and / or palladium can be dispersed in the first support material.
[0050] When the first PGM is a combination of platinum and palladium, then the platinum can be arranged or supported on the first support material and / or the palladium can be arranged or supported on the first support material. It may be preferable for both platinum and palladium to be arranged or supported on the first support material (i.e., the same support material is used for both platinum and palladium).
[0051] When the first PGM is a combination of platinum and palladium, a combination of palladium and rhodium or a combination of platinum, palladium and rhodium, then the first reactive coating region can additionally comprise a palladium support material. The first reactive coating region can therefore comprise, or consist essentially of, a first PGM, a first support material, a palladium support material and a NOx storage component. The platinum and / or rhodium can be arranged or supported on the first support material and the palladium can be arranged or supported on the palladium support material. The first support material and the palladium support material are preferably different (for example, different composition).
[0052] When the first PGM is a combination of platinum and palladium, a combination of platinum and rhodium or a combination of platinum, palladium and rhodium, then the first reactive coating region may additionally comprise a platinum support material. The first reactive coating region can therefore comprise, or consist essentially of, a first PGM, a first support material, a platinum support material and a NOx storage component. The platinum can be arranged or supported on the platinum support and palladium and / or rhodium can be arranged or supported on the first support material. The first support material and the platinum support material are preferably different (for example, different composition).
[0053] Typically, the first support material comprises, or consists essentially of, a refractory metal oxide. Refractory metal oxides suitable for use as a catalytic component of an oxidation catalyst for a diesel engine are well known in the art.
[0054] Refractory metal oxide is typically selected from the group consisting of alumina, silica, titania, zirconia, ceria and a mixed oxide or composite thereof, such as a mixed oxide or composite of two or more of them. For example, refractory metal oxide can be selected from the group consisting of alumina, silica, titania, zirconia, ceria, silica-alumina, titania-alumina, zirconia-alumina, ceria-alumina, titania-silica, zirconia-silica, zirconia-titania, ceria-zirconia and alumina-magnesium oxide.
[0055] The first support material, or the refractory metal oxide thereof, can optionally be doped (for example, with a dopant). 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) and an oxide of them.
[0056] The inclusion of a dopant can thermally stabilize the refractory metal oxide or support material. It should be understood that any reference to “doped” in this context refers to a material where the total lattice or host of the refractory metal oxide is doped by substitution or interstitially doped with a dopant. In some cases, small amounts of the dopant may be present on a refractory metal oxide surface. However, the majority of the dopant in general will be present in the refractory metal oxide body. The chemical and / or physical properties of a refractory metal oxide are often affected by the presence of a dopant.
[0057] When the first support material, or the refractory metal oxide thereof, is doped, the total amount of dopant is 0.25 to 5% by weight, preferably 0.5 to 3% by weight (for example, about 1% by weight).
[0058] The first support material, or the refractory metal oxide thereof, may comprise, or consist essentially of, alumina doped with a dopant. It is particularly preferred that the first support material or refractory metal oxide thereof comprises, or consists essentially of, alumina doped with a dopant when the first reactive coating region comprises an alkaline earth metal.
[0059] Alumina can be doped with a dopant comprising silicon (Si), magnesium (Mg), barium (Ba), lanthanum (La), cerium (Ce), titanium (Ti), or zirconium (Zr) or a combination two or more of them. The dopant may comprise, or consist essentially of, a silicon oxide, a magnesium oxide, a barium oxide, a lanthanum oxide, a cerium oxide, a titanium oxide or a zirconium oxide. Preferably, the dopant comprises, or consists essentially of silicon, magnesium, barium, cerium, or an oxide thereof, particularly silicon, or cerium, or an oxide thereof. More preferably, the dopant comprises, or consists essentially of silicon, magnesium, barium, or an oxide thereof; particularly silicon, magnesium, or an oxide thereof; especially magnesium or an oxide thereof.
[0060] Examples of doped alumina doped with silica include alumina doped with magnesium oxide, alumina doped with barium or barium oxide, alumina doped with lanthanum oxide, or alumina doped with ceria, particularly alumina doped with silica , alumina doped with lanthanum oxide, or alumina doped with ceria. It is preferred that alumina doped with a dopant is alumina doped with silica, alumina doped with barium or barium oxide, or alumina doped with magnesium oxide. More preferably, the doped alumina is silica doped alumina or magnesium oxide doped alumina. Even more preferably, the alumina doped with a dopant is alumina doped with magnesium oxide. Alumina doped with a dopant can be prepared using methods known in the art.
[0061] When alumina is silica-doped alumina, then alumina is doped with silica in a total amount of 0.5 to 45% by weight (i.e.,% by weight of alumina), preferably 1 to 40% by weight , more preferably 1.5 to 30% by weight (for example, 1.5 to 10% by weight), particularly 2.5 to 25% by weight, more particularly 3.5 to 20% by weight (for example, 5 to 20% by weight), even more preferably 4.5 to 15% by weight.
[0062] When alumina is doped with magnesium oxide, then alumina is doped with magnesium oxide in an amount as defined above, or an amount of 1 to 40% by weight (i.e.,% by weight of alumina) , such as 1 to 30% by weight, preferably 5 to 28% by weight, such as 5 to 25% by weight. More preferably, the alumina is doped with magnesium oxide in an amount of 10 to 25% by weight.
[0063] It is preferred that the first support material, or the refractory metal oxide thereof, is not doped with a dopant comprising, or consisting essentially of manganese. Thus, the first support material, or its refractory metal oxide, is not promoted with a promoter, such as a promoter selected from the group consisting of tin, manganese, indium, group VIII metal (for example, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt, particularly Ir) and combinations thereof.
[0064] Alternatively, or in addition, the first support material, or refractory metal oxide thereof, may comprise, or consist essentially of, an alkaline earth metal aluminate. The term "alkaline earth metal aluminate" generally refers to a compound of the formula MAl2O4 where "M" represents alkaline earth metal, such as Mg, Ca, Sr or Ba. Such compounds generally comprise a spinel structure. These compounds can be prepared using conventional methods known in the art or using a method described in EP 0945165, US 6,217,837 or US 6,517,795.
[0065] Typically, alkaline earth metal aluminate is magnesium aluminate (MgAl2O4), calcium aluminate (CaAl2O4), strontium aluminate (SrAl2O4), barium aluminate (BaAl2O4), or a mixture of two or more of the same. Preferably, the alkaline earth metal aluminate is magnesium aluminate (MgAl2O4).
[0066] In general, when the first support material, or the refractory metal oxide thereof, comprises or consists essentially of a mixed oxide or alumina composite (for example, silica-alumina, magnesium alumina-oxide or a mixture of alumina and ceria), then preferably the mixed oxide or alumina composite comprises at least 50 to 99% by weight of alumina, more preferably 70 to 95% by weight of alumina, even more preferably 75 to 90% by weight of alumina.
[0067] When the first support material, or refractory metal oxide thereof, comprises or consists essentially of ceriazirconia, then ceriazirconia may consist essentially of 20 to 95% by weight of ceria and 5 to 80% in zirconia weight (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.
[0068] In general, the palladium support material comprises, or consists essentially of, a refractory metal oxide. The palladium support material, or the refractory metal oxide thereof, can be a support material as defined herein before with reference to the first support material. When the first reactive coating region comprises a palladium support material, it is preferred that the palladium support material, or the refractory metal oxide thereof, comprises, or consists essentially of ceria and / or a mixed oxide or composite ceria, such as ceria-zirconia.
[0069] Typically, the platinum support material comprises, or consists essentially of, a refractory metal oxide. The platinum support material, or the refractory metal oxide thereof, can be a support material as defined herein before with reference to the first support material. When the first reactive coating region comprises a platinum support material, it is preferred that the platinum support material or the refractory metal oxide thereof comprises, or consists essentially of alumina, in which the alumina is optionally doped with a dopant , as previously described. When the platinum support material comprises alumina doped with a dopant, it is preferred that the dopant comprises, or consists essentially of silicon, magnesium, cerium, lanthanum or an oxide thereof, more preferably magnesium or an oxide thereof.
[0070] The first support material (or the refractory metal oxide thereof), the platinum support material (or the refractory metal oxide thereof) and the palladium support material (or the refractory metal oxide same) are not doped with a dopant comprising, or consisting essentially of manganese. Thus, the platinum support material (or the refractory metal oxide thereof) and / or the palladium support material (or the refractory metal oxide thereof) is not promoted with a promoter, such as a promoter selected from the group consisting of tin, manganese, indium, group VIII metal (for example, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt, particularly Ir) and combinations thereof.
[0071] The first reactive coating region can comprise an amount of support material (e.g., the total amount of the first support material and, when present, platinum support material and palladium support material) of 1.0 to 8.0 g in-3 (for example, 4.0 to 7.5 g in-3), preferably 1.5 to 7.5 g in-3 (for example, 4.5 to 7.0 g in -3), even more preferably 2.0 to 7.0 g in-3 (5.0 to 7.0 g in-3 or 4.5 to 6.5 g in-3), and even more preferably 2, 5 to 6.5 g in-3 (for example, 4.0 to 6.5 g in-3).
[0072] The first reactive coating region may additionally comprise a hydrocarbon adsorbent material. The hydrocarbon adsorbent material can be a zeolite.
[0073] It is preferred that the zeolite is a mid-pore zeolite (for example, a zeolite with a maximum ring size of ten tetrahedral atoms) or a large pore zeolite (for example, a zeolite with a maximum ring size of twelve tetrahedral atoms). It may be preferable that the zeolite is not a small pore zeolite (for example, a zeolite with a maximum ring size of eight tetrahedral atoms).
[0074] Examples of suitable zeolites or types of zeolite include faujasite, clinoptilolite, mordenite, silicalite, ferrierite, zeolite X, zeolite Y, ultra-stable zeolite, zeolite AEI, zeolite ZSM-5, zeolite ZSM-12, zeolite ZSM-12, zeolite ZSM-12, zeolite zeolite ZSM-34, zeolite CHA, zeolite SSZ-3, zeolite SAPO-5, ofretite, a beta zeolite or a copper CHA zeolite. The zeolite is preferably ZSM-5, a beta zeolite or a Y zeolite.
[0075] When the first reactive coating region comprises a hydrocarbon adsorbent, the total amount of hydrocarbon adsorbent is 0.05 to 3.00 g in-3, particularly 0.10 to 2.00 g in-3, more particularly 0.2 to 1.0 g in-3. For example, the total amount of hydrocarbon adsorbent can be 0.8 to 1.75 g in-3, such as 1.0 to 1.5 g in-3.
[0076] However, it may be preferable that the first reactive coating region does not comprise a hydrocarbon adsorbent material.
[0077] Typically, the NOx storage component comprises an alkali metal, alkaline earth metal and / or a rare earth metal, wherein the rare earth metal is selected from the group consisting of lanthanum, yttrium and a combination thereof. The NOx storage component generally comprises, or consists essentially of (i) an alkali metal oxide, carbonate or hydroxide; (ii) an alkaline earth metal oxide, carbonate or hydroxide; and / or (iii) a rare earth metal oxide, carbonate or hydroxide, in which the rare earth metal is selected from the group consisting of lanthanum, yttrium and a combination thereof.
[0078] When the NOx storage component comprises an alkali metal (or an oxide, carbonate or hydroxide thereof), then preferably the alkali metal is selected from the group consisting of potassium (K), sodium (Na), lithium (Li), cesium (Cs) and a combination of two or more of them. It is preferred that the alkali metal is potassium (K), sodium (Na) or lithium (Li), more preferably the alkali metal is potassium (K) or sodium (Na), and most preferably the alkali metal is potassium (K ).
[0079] When the NOx storage component comprises an alkaline earth metal (or an oxide, carbonate or hydroxide thereof), then preferably the alkaline earth metal is selected from the group consisting of magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and a combination of two or more of them. It is preferred that the alkaline earth metal is calcium (Ca), strontium (Sr), or barium (Ba), more preferably strontium (Sr) or barium (Ba), and most preferably the alkaline earth metal is barium (Ba).
[0080] It is preferred that the NOx storage component comprises potassium or barium (for example, a potassium oxide, carbonate or hydroxide or a barium oxide, carbonate or hydroxide). More preferably, the NOx storage component comprises barium (for example, an oxide, carbonate or barium hydroxide).
[0081] The NOx storage component can be arranged or supported (for example, directly arranged or directly supported) on the first support material. It is preferred that the NOx storage component is disposed of or supported on the first support material when the first support material or the refractory metal oxide thereof comprises or consists essentially of alumina, alumina doped with a dopant, magnesium aluminate, ceria or a mixed oxide or composite of ceria, which is preferably ceria-zirconia. Alumina doped with a dopant is preferably alumina doped with magnesium or an oxide thereof.
[0082] When the first reactive coating region comprises a platinum support material, the NOx storage component can be arranged or supported (for example, directly arranged or directly supported) on the platinum support material (the storage component of NOx can be disposed or supported on the platinum support material in addition to or alternatively to the NOx storage component being disposed of or supported on the first support material). Preferably, the platinum support material or the refractory metal oxide thereof comprises, or consists essentially of alumina, alumina doped with a dopant or magnesium aluminate. Alumina doped with a dopant is preferably alumina doped with lanthanum (or an oxide thereof) or alumina doped with magnesium (or an oxide thereof). It is preferred that the platinum support material or the refractory metal oxide thereof comprise, or consist essentially of, alumina doped with magnesium oxide.
[0083] When the NOx storage component is disposed or supported on the platinum support material, then preferably the first support material or the refractory metal oxide thereof comprises, or consists essentially of ceria or a mixed oxide or composite of ceria (for example, ceria-zirconia). More preferably, the palladium support material or the refractory metal oxide thereof comprises, or consists essentially of ceria.
[0084] The first reactive coating region can comprise a palladium support material. When the first reactive coating region comprises a palladium support material, the NOx storage component can be arranged or supported (for example, directly arranged or directly supported) on the palladium support material (the NOx storage component can be be arranged or supported on the platinum support material in addition to or alternatively to the NOx storage component being arranged or supported on the first support material). Preferably, the palladium support material or refractory metal oxide thereof comprises, or consists essentially of alumina, alumina doped with a dopant, magnesium aluminate, ceria or a mixed oxide or ceria composite, which is preferably ceria-zirconia . Alumina doped with a dopant is preferably alumina doped with lanthanum (or an oxide thereof) or alumina doped with magnesium (or an oxide thereof). It is preferred that the palladium support material or refractory metal oxide thereof comprises, or consists essentially of ceria or a mixed oxide or ceria composite (e.g., ceria-zirconia). More preferably, the palladium support material or the refractory metal oxide thereof comprises, or consists essentially of ceria.
[0085] When the NOx storage component is disposed or supported on the palladium support material, then preferably the first support material or the refractory metal oxide thereof comprises, or consists essentially of alumina, alumina doped with a dopant or magnesium aluminate. Alumina doped with a dopant is preferably alumina doped with lanthanum (or an oxide thereof) or alumina doped with magnesium (or an oxide thereof). It is preferred that the first support material or the refractory metal oxide thereof comprise, or consist essentially of, alumina doped with magnesium oxide.
[0086] Additionally, or alternatively, the first reactive coating region may additionally comprise a support material for the NOx storage component. The NOx storage component is disposed or supported (for example, directly disposed or directly supported) in the support material for the NOx storage component. The first PGM is not disposed or supported in the support material for the NOx storage component.
[0087] Typically, the support material for the NOx storage component comprises, or consists essentially of ceria or a mixed oxide or ceria composite, such as a mixed oxide or ceria composite as previously defined. The mixed oxide or composite of ceria is preferably ceria-zirconia. It is preferred that the support material for the NOx storage component comprises, or consists essentially of, ceria.
[0088] When the first PGM comprises rhodium (for example, it is a combination of Pt and Rh, a combination of Pd or Rh, or a combination of Pt, Pd and Rh), the rhodium can be arranged or supported in the first material of support and / or the platinum support material (if present) and / or the palladium support material (if present) and / or the support material for the NOx storage component (if present).
[0089] In general, the oxidation catalyst or the first reactive coating region comprises a total amount of NOx storage component of the alkaline earth metal from 250 to 900 g ft-3 (for example, 250 to 500 g ft-3) , particularly 300 to 850 g ft-3 (e.g., 300 a-3 -3 -3 450 g ft), more particularly 400 to 800 g ft, such as 450 to 600 g ft.
[0090] When the first PGM comprises, or consists essentially of platinum (Pt), then preferably the first reactive coating region comprises a total weight of the alkaline earth metal which is greater than the total weight of the platinum (Pt).
[0091] However, it may be preferable that the first reactive coating region does not comprise rhodium and / or an alkali metal. Thus, the first reactive coating region may not comprise rhodium and / or an alkali metal, particularly an alkali metal disposed or supported on a support material.
[0092] For the avoidance of doubt, a general feature of the first reactive coating region (ie, in any or all of the aforementioned modalities) is that the first reactive coating region is substantially free of manganese or an oxide thereof. The first reactive coating region preferably does not comprise manganese or an oxide thereof.
[0093] The oxidation catalyst of the invention comprises a second reactive coating region to oxidize nitric oxide (NO) to nitrogen dioxide (NO2). The second reactive coating region comprises or can consist essentially of platinum (Pt), manganese or an oxide thereof, and a second support material.
[0094] The second reactive coating region may further comprise palladium, such as palladium disposed or supported on the second support material. When the second reactive coating region comprises palladium, then the ratio of platinum to palladium in total weight is generally> 2: 1 (for example, Pt: Pd 1: 0 to 2: 1), more preferably> 4: 1 (for example, Pt: Pd 1: 0 to 4: 1). Advantageous extinguishing activity of CO and / or HC can be obtained when the total weight of platinum is greater than the total weight of palladium in the first reactive coating region.
[0095] It is generally preferred that the second reactive coating region is substantially free of palladium, particularly substantially free of palladium (Pd) disposed of or supported on the second support material. More preferably, the second reactive coating region does not comprise palladium, particularly palladium disposed or supported on the second support material. The presence of palladium, particularly in a large amount, in the second reactive coating region can be detrimental to NO oxidation activity. The oxidation activity of palladium NO is generally weak under typical conditions of use for a diesel oxidation catalyst. Also, any palladium that is present can react with part of the platinum that is present to form an alloy. This can also be detrimental to the NO oxidation activity of the second reactive coating region because platinum-palladium alloys are not as active for NO oxidation as platinum is itself.
[0096] Generally, the second reactive coating region comprises platinum (Pt) as the only metal in the platinum group. The second reactive coating region preferably does not comprise one or more other metals of the platinum group, such as ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os) and / or iridium (Ir). More preferably, the second reactive coating region does not comprise one or more other metals of the platinum group, such as ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os) and / or iridium (Ir), supported on the second support material.
[0097] Platinum (Pt) is typically arranged or supported on the second support material. The stage can be arranged directly or be supported directly by the second support material (for example, there is no intervening support material between the stage and the second support material). For example, platinum can be dispersed in the second support material.
[0098] The second reactive coating region typically has a total platinum load of 5 to 300 g ft-3. It is preferred that the second reactive coating region has a total platinum loading of 10 to 250 g ft-3 (for example, 75 to 175 g ft-3), more preferably 15 to 200 g ft-3 (for example, 50 to 150 g ft-3), even more preferably 20 to 150 g ft-3.
[0099] It is intended that the primary function of the second reactive coating region is to oxidize nitric oxide (NO) to nitrogen dioxide (NO2). However, it is clear that, in some modalities of the oxidation catalyst, the second reactive coating region can also oxidize part of carbon monoxide (CO) and / or part of hydrocarbons (HCs) during use.
[00100] The second reactive coating region comprises manganese (Mn). Manganese can be present in an elemental form or as an oxide. The second reactive coating region typically comprises manganese or an oxide thereof.
[00101] Manganese (Mn) is typically disposed of or supported on the second support material. Manganese (Mn) can be disposed directly or supported directly on the second support material (for example, there is no intervening support material between Mn and the second support material).
[00102] The second reactive coating region typically has a total manganese load (Mn) of 5 to 500 g ft-3. It is preferred that the second reactive coating region has a total load of manganese (Mn) from 10 to 250 g ft-3 (eg 75 to 175 g ft-3), more preferably 15 to 200 g ft-3 (eg example 50 to 150 g ft-3), even more preferably 20 to 150 g ft-3.
[00103] Typically, the second reactive coating region comprises an Mn: Pt weight ratio of <5: 1, more preferably <5: 1.
[00104] In general, the second reactive coating region comprises a Mn: Pt weight ratio of> 0.2: 1 (e.g.> 0.5: 1), more preferably> 0.2: 1 (for example,> 0.5: 1).
[00105] The second reactive coating region may comprise a ratio of total weight of manganese (Mn) to platinum from 5: 1 to 0.2: 1, such as 5: 1 to 0.5: 1 (for example, 5 : 1 to 2: 3 or 5: 1 to 1: 2), preferably 4.5: 1 to 1: 1 (for example, 4: 1 to 1.1: 1), more preferably 4: 1 to 1.5 :1. The Mn: Pt to weight ratio may be important in obtaining the NO activity described here.
[00106] Typically, the second support material comprises, or consists essentially of, a refractory metal oxide. Refractory metal oxide is typically selected from the group consisting of alumina, silica, titania, zirconia, ceria and a mixed oxide or composite thereof, such as a mixed oxide or composite of two or more of them. For example, refractory metal oxide can be selected from the group consisting of alumina, silica, titania, zirconia, ceria, silica-alumina, titania-alumina, zirconia-alumina, ceria-alumina, titania-silica, zirconia-silica, zirconia-titania, ceria-zirconia and alumina-magnesium oxide.
[00107] The second support material, or the refractory metal oxide thereof, can optionally be doped (for example, with a dopant). 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) and an oxide of them.
[00108] When the second support material, or the refractory metal oxide thereof, is doped, the total amount of dopant is 0.25 to 5% by weight, preferably 0.5 to 3% by weight (for example, about 1% by weight).
[00109] The second support material, or the refractory metal oxide thereof, may comprise, or consist essentially of, alumina doped with a dopant. It is particularly preferred that the second support material, or the refractory metal oxide thereof, comprise, or consist essentially of, alumina doped with a dopant. It has been observed that the combination of manganese (Mn), platinum (Pt) and a doped alumina support material, particularly a support material of doped aluminum with silica, provides excellent NO oxidation activity and can stabilize NO oxidation activity oxidation catalyst in its useful life.
[00110] Alumina can be doped with a dopant comprising silicon (Si), magnesium (Mg), barium (Ba), lanthanum (La), cerium (Ce), titanium (Ti), or zirconium (Zr) or a combination two or more of them. The dopant may comprise, or consist essentially of, a silicon oxide, a magnesium oxide, a barium oxide, a lanthanum oxide, a cerium oxide, a titanium oxide or a zirconium oxide. Preferably, the dopant comprises, or consists essentially of silicon, magnesium, barium, cerium, or an oxide thereof; particularly silicon, cerium, or an oxide thereof. More preferably, the dopant comprises, or consists essentially of silicon, magnesium, barium, or an oxide thereof; particularly silicon, magnesium, or an oxide thereof; especially silicon or an oxide of the same.
[00111] Examples of doped alumina doped with silica include alumina doped with magnesium oxide, alumina doped with barium or barium oxide, alumina doped with lanthanum oxide, or alumina doped with cerium, particularly alumina doped with silica , alumina doped with lanthanum oxide, or alumina doped with ceria. It is preferred that alumina doped with a dopant is alumina doped with silica, alumina doped with barium or barium oxide, or alumina doped with magnesium oxide. More preferably, the doped alumina is silica doped alumina or magnesium oxide doped alumina. Even more preferably, the doped alumina is silica doped alumina.
[00112] When the alumina is silica-doped alumina, then the alumina is doped with silica in a total amount of 0.5 to 45% by weight (i.e.,% by weight of the alumina), preferably 1 to 40% by weight , more preferably 1.5 to 30% by weight (for example, 1.5 to 10% by weight), particularly 2.5 to 25% by weight, more particularly 3.5 to 20% by weight (for example, 5 to 20% by weight), even more preferably 4.5 to 15% by weight.
[00113] When alumina is doped with magnesium oxide, then alumina is doped with magnesium in an amount as defined above, or an amount of 1 to 30% by weight (i.e.,% by weight of alumina), preferably 5 to 25% by weight.
[00114] It is preferred that the second support material, or the refractory metal oxide thereof, is not doped with a dopant comprising, or consisting essentially of manganese. Thus, the second support material, or the refractory metal oxide thereof, is not promoted with a promoter, such as a promoter selected from the group consisting of tin, manganese, indium, group VIII metal (for example, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt, particularly Ir) and combinations thereof.
[00115] Alternatively, or in addition, the second support material, or refractory metal oxide thereof, may comprise, or consist essentially of, an alkaline earth metal aluminate, such as an alkaline earth metal aluminate with a spinel structure.
[00116] Typically, alkaline earth metal aluminate is magnesium aluminate (MgAl2O4), calcium aluminate (CaAl2O4), strontium aluminate (SrAl2O4), or barium aluminate (BaAl2O4), or a mixture of two or more of the same. Preferably, the alkaline earth metal aluminate is magnesium aluminate (MgAl2O4).
[00117] In general, when the second support material, or the refractory metal oxide thereof, comprises or consists essentially of a mixed oxide or alumina composite (for example, silica-alumina, magnesium alumina-oxide or a mixture of alumina and ceria), then preferably the mixed oxide or alumina composite comprises at least 50 to 99% by weight of alumina, more preferably 70 to 95% by weight of alumina, even more preferably 75 to 90% by weight of alumina.
[00118] When the second support material, or refractory metal oxide thereof, comprises or consists essentially of ceriazirconia, then ceriazirconia may consist essentially of 20 to 95% by weight of ceria and 5 to 80% in zirconia weight (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.
[00119] Typically, the second reactive coating region comprises an amount of the second support material from 0.1 to 4.5 g in-3 (e.g., 0.25 to 4.0 g in-3), preferably 0 , 5 to 3.0 g in-3, more preferably 0.6 to 2.5 g in-3 (e.g. 0.75 to 1.5 g in-3).
[00120] In some applications, it may generally be preferable for the second reactive coating region to be substantially free of a hydrocarbon adsorbent material, particularly a zeolite. Thus, the second reactive coating region may not comprise a hydrocarbon adsorbent material.
[00121] It may be additionally preferable that the second reactive coating region is substantially free of a zeolite catalyst. Thus, the second reactive coating region may not comprise the zeolite catalyst.
[00122] The second reactive coating region typically does not comprise indium and / or iridium. More preferably, the second reactive coating region does not comprise indium, iridium and / or magnesium.
[00123] It may be preferable that the second reactive coating region does not comprise cerium oxide or a mixed oxide or composite thereof, such as (i) a mixed oxide or composite of cerium oxide and alumina and / or (ii) a mixed oxide or composite of cerium oxide and zirconia.
[00124] Additionally, or alternatively, the second reactive coating region can be substantially free of rhodium, an alkali metal and / or an alkaline earth metal, particularly an alkali metal and / or an alkaline earth metal disposed or supported on the second support material. Thus, the second reactive coating may not comprise rhodium, an alkali metal and / or an alkaline earth metal, particularly an alkali metal and / or an alkaline earth metal disposed or supported on the second support material.
[00125] Typically, the first reactive coating region comprises> 25% of the total metal concentration of the platinum group (i.e., the oxidation catalyst). It is preferred that the first reactive coating region comprises> 30%, more preferably> 40% of the total metal concentration of the platinum group.
[00126] In general, the total concentration of the first PGM is greater than the total concentration of platinum in the second reactive coating region.
[00127] The first reactive coating region and / or the second reactive coating region can be arranged or supported on the substrate.
[00128] The first reactive coating region can be placed directly on the substrate (that is, the first reactive coating region is in contact with a substrate surface; see Figures 1 to 5). The second reactive coating region can be: (a) arranged or supported in the first reactive coating region (for example, see Figures 2, 4 and 5); and / or (b) disposed directly on the substrate [that is, the second reactive coating region is in contact with a substrate surface] (for example, see Figures 1, 3, 4); and / or (c) in contact with the first reactive coating region [i.e., the second reactive coating region is adjacent to or rests on the first reactive coating region].
[00129] When the second reactive coating region is disposed directly on the substrate, then a part or portion of the second reactive coating region may come in contact with the first reactive coating region or the first reactive coating region and the second region of reactive coating can be separated (for example, by an interstice).
[00130] When the second reactive coating region is arranged or supported in the first reactive coating region, all or part of the second reactive coating region is preferably disposed directly in the first reactive coating region (i.e., the second reactive coating region is in contact with a surface of the first reactive coating region). The second reactive coating region can be a second reactive coating layer and the first reactive coating region can be a first reactive coating layer.
[00131] The second reactive coating region can be placed directly on the substrate (that is, the second reactive coating region is in contact with a substrate surface; see Figures 1, 3 and 4). The first reactive coating region can be: (i) arranged or supported in the second reactive coating region (for example, see Figures 3 and 4); and / or (ii) disposed directly on the substrate [that is, the first reactive coating region is in contact with a substrate surface] (for example, see Figures 3 and 4); and / or (iii) in contact with the second reactive coating region [that is, the first reactive coating region is adjacent to or rests on the second reactive coating region].
[00132] The first reactive coating region can be arranged directly in the second reactive coating region (that is, the first reactive coating region is in contact with a surface of the second reactive coating region).
[00133] It is preferred that only a portion or part of the first reactive coating region is arranged or supported in the second reactive coating region. Thus, the first reactive coating region does not overlap or completely cover the second reactive coating region.
[00134] In general, it is possible that both the first reactive coating region and the second reactive coating region are not directly disposed on the substrate (that is, in the first reactive coating region in the second reactive coating region is in contact with a substrate surface).
[00135] The first reactive coating region can be a first reactive coating layer or a first reactive coating zone. When the first reactive coating region is a first reactive coating zone, then typically the first reactive coating zone is 10 to 90% of the substrate length (e.g. 10 to 45%), preferably 15 to 75% the substrate length (for example, 15 to 40%), more preferably 20 to 70% (for example, 30 to 65%, such as 25 to 45%) of the substrate length, even more preferably 25 to 65% (for example, 35 to 50%). It is preferred that the length of the first reactive coating zone is greater than the length of the second reactive coating zone.
[00136] The second reactive coating region can be a second reactive coating layer or a second reactive coating zone. When the second reactive coating region is a second reactive coating zone, then typically the second reactive coating zone has a length of 10 to 90% of the substrate length (e.g., 10 to 45%), preferably 15 to 75% the substrate length (for example, 15 to 40%), more preferably 20 to 70% (for example, 30 to 65%, such as 25 to 45%) of the substrate length, even more preferably 25 to 65% (for example, 35 to 50%).
[00137] The first reactive coating zone can join in the second reactive coating zone. Preferably, the first reactive coating zone comes in contact with the second reactive coating zone. When the first reactive coating zone joins the second reactive coating zone or the first reactive coating zone is in contact with the second reactive coating zone, then the first reactive coating zone and the second reactive coating zone can be arranged or supported on the substrate as a layer (for example, a single layer). Thus, a layer (for example, a single one) can be formed on the substrate when the first and second reactive coating zones join or come into contact with each other. Such an arrangement can avoid problems with back pressure.
[00138] The first reactive coating zone can be separated from the second reactive coating zone. There may be an interstice (for example, a space) between the first reactive coating zone and the second reactive coating zone.
[00139] The first reactive coating zone can overlap the second reactive coating zone. Thus, a portion or end part of the first reactive coating zone can be arranged or supported in the second reactive coating zone. The first reactive coating zone can completely or partially overlap the second reactive coating zone. When the first reactive coating zone overlaps the second reactive coating zone, it is preferred that the first reactive coating zone only partially overlaps the second reactive coating zone (i.e., the upper outermost surface of the second reactive coating zone is not completely covered by the first reactive coating zone).
[00140] Alternatively, the second reactive coating zone can overlap the first reactive coating zone. Thus, a portion or end part of the second reactive coating zone can be arranged or supported in the first reactive coating zone. The second reactive coating zone generally overlaps only the first reactive coating zone.
[00141] It is preferred that the first reactive coating zone and the second reactive coating zone do not overlap substantially.
[00142] In the oxidation catalyst of the invention, the second reactive coating region can be arranged to come into contact with the exhaust gas at the outlet end of the substrate, typically after the contact of the exhaust gas with the first reactive coating region . This can, for example, be achieved by arranging the second reactive coating region / layer / zone at an outlet end of the substrate. The first reactive coating region can be arranged or oriented to make contact with exhaust gas before the second reactive coating region. Thus, the first reactive coating region can be arranged to make contact with the exhaust gas as it enters the oxidation catalyst and the second reactive coating region can be arranged to make contact with the exhaust gas as it goes. leaves the oxidation catalyst.
[00143] The oxidation catalyst may have advantageous oxidizing activity (for example, for CO, HCs and NO), and particularly for NO, when it has an arrangement that facilitates the contact of the exhaust gas with the reactive coating region containing the Pt and Mn just before the exhaust gas leaves the catalyst and after it has come in contact with the reactive coating region to oxidize CO and HCs. In an arrangement like this of the oxidation catalyst, as the exhaust gas enters the catalyst, it first comes into contact with the first reactive coating region. After the exhaust gas has passed through or passed the first reactive coating region, it comes in contact with the second reactive coating region to oxidize NO before finally passing through the oxidation catalyst outlet. It was further observed that, when the oxidation catalyst is arranged in such a way, the reactive coating region containing Mn is surprisingly tolerant to diesel fuel sulfur poisoning and can retain its NO oxidation activity.
[00144] The second reactive coating region is arranged or oriented to make contact with the exhaust after it has come into contact with the first reactive coating region when: (a) the second reactive coating region is a second coating zone reactive layer arranged on an outlet end of the substrate and optionally the first reactive coating region is a first zone of reactive coating arranged on an inlet end of the substrate; or (b) the first reactive coating region is a first reactive coating layer and the second reactive coating region is a second reactive coating zone, wherein the second reactive coating zone is arranged in the first reactive coating layer in a exit end of the substrate; or (c) the first reactive coating region is a first reactive coating layer and the second reactive coating region is a second reactive coating layer, and the second reactive coating layer is disposed on the first reactive coating layer.
[00145] Typically, the first reactive coating region is arranged or oriented to make contact with the exhaust gas before the second reactive coating region. Thus, the first reactive coating region can be arranged to make contact with the exhaust gas as it enters the oxidation catalyst and the second reactive coating region can be arranged to make contact with the exhaust gas as it goes. leaves the oxidation catalyst. The zoned arrangement of the first and second region of coatings of catalytic material shown in Figures 1 and 6 to 10 is particularly advantageous in this respect (the exhaust gas enters the left side).
[00146] The second reactive coating region is arranged to come in contact with the exhaust gas at the outlet end of the substrate and after contacting the exhaust gas with the first reactive coating region in any one of the first to the third oxidation catalyst described hereinafter.
[00147] It is preferred that the second reactive coating region is a second reactive coating zone. More preferably, the second reactive coating zone is arranged or supported at or near an outlet end of the substrate.
[00148] In a first oxidation catalyst arrangement, the first reactive coating region is arranged or supported upstream of the second reactive coating zone. Preferably, the first reactive coating region is a first reactive coating zone. More preferably, the first reactive coating zone is arranged or supported at or near an inlet end of the substrate. The second reactive coating zone containing Mn can show good sulfur tolerance when the oxidation catalyst has a “zoned” arrangement like this.
[00149] In a second oxidation catalyst arrangement, the first reactive coating region is a first reactive coating layer. It is preferred that the first layer of reactive coating extends the entire length (i.e., substantially the entire length) of the substrate, particularly the entire length of the channels of a substrate monolith.
[00150] The second reactive coating zone is typically arranged or supported on the first reactive coating layer. Preferably, the second reactive coating zone is disposed directly on the first reactive coating layer (i.e., the second reactive coating zone is in contact with a surface of the first reactive coating layer).
[00151] When the second reactive coating zone is arranged or supported on the first reactive coating layer, it is preferred that the entire length of the second reactive coating zone is arranged or supported on the first reactive coating layer. The length of the second reactive coating zone is less than the length of the first reactive coating layer.
[00152] In a third oxidation catalyst arrangement, the first reactive coating region is a first reactive coating layer. It is preferred that the first layer of reactive coating extends the entire length (i.e., substantially the entire length) of the substrate, particularly the entire length of the channels of a substrate monolith.
[00153] The second reactive coating region is a second reactive coating layer. It is preferred that the second layer of reactive coating extends the entire length (i.e., substantially the entire length) of the substrate, particularly the entire length of the channels of a substrate monolith.
[00154] The second layer of reactive coating is arranged or supported on the first layer of reactive coating. Preferably, the second reactive coating layer is arranged directly on the first reactive coating layer (i.e., the second reactive coating layer is in contact with a surface of the first reactive coating layer).
[00155] Alternatively, in the oxidation catalyst of the invention, the second reactive coating region can be arranged to come into contact with the exhaust gas at the inlet end of the substrate, typically before contact of the exhaust gas with the first exhaust region. reactive coating. This can, for example, be achieved by arranging the second reactive coating region / layer / zone at an inlet end of the substrate. The first reactive coating region can be arranged or oriented to make contact with exhaust gas after the second reactive coating region. Thus, the second reactive coating region can be arranged to make contact with the exhaust gas as it enters the oxidation catalyst and the first reactive coating region can be arranged to make contact with the exhaust gas as it goes. leaves the oxidation catalyst.
[00156] The oxidation catalyst may have an arrangement that facilitates the contact of the exhaust gas with the reactive coating region containing the Pt and Mn before the exhaust gas comes in contact with the reactive coating region for NOx storage. In an arrangement like this, as the exhaust gas enters the catalyst, it first comes into contact with the second reactive coating region, which can oxidize NO to NO2. After the exhaust gas has passed through or passed the second reactive coating region, it comes in contact with the first reactive coating region for storage of NOx before finally passing through the oxidation catalyst outlet. For the NOx storage component in the first reactive coating region to adsorb or store NOx, the NO component of NOx has to be converted to NO2. The second reactive coating region facilitates this conversion.
[00157] The second reactive coating region is arranged or oriented to make contact with the exhaust before coming into contact with the first reactive coating region when: (a) the second reactive coating region is a second reactive coating zone arranged at an inlet end of the substrate and optionally the first reactive coating region is a first reactive coating zone disposed at an outlet end of the substrate; or (b) the first reactive coating region is a first reactive coating layer and the second reactive coating region is a second reactive coating zone, wherein the second reactive coating zone is arranged in the first reactive coating layer in a inlet end of the substrate; or (c) the first reactive coating region is a first reactive coating layer and the second reactive coating region is a second reactive coating layer, and wherein the first reactive coating layer is disposed on the second reactive coating layer.
[00158] Typically, the first reactive coating region is arranged or oriented to make contact with the exhaust gas after the second reactive coating region. Thus, the first reactive coating region can be arranged to make contact with the exhaust gas as it exits the oxidation catalyst and the second reactive coating region can be arranged to make contact with the exhaust gas as it exits. enters the oxidation catalyst. The zoned arrangement of the first and second region of coatings of catalytic material shown in Figures 1 and 6 to 10 is particularly advantageous in this respect (the exhaust gas enters the right side).
[00159] The second reactive coating region is arranged to come into contact with the exhaust gas at the inlet end of the substrate and after contacting the exhaust gas with the first reactive coating region in any of the fourth to sixth oxidation catalyst described hereinafter.
[00160] It is preferred that the second reactive coating region is a second reactive coating zone. More preferably, the second reactive coating zone is arranged or supported at or near an inlet end of the substrate.
[00161] In a fourth oxidation catalyst arrangement, the first reactive coating region is arranged or supported downstream of the second reactive coating zone. Preferably, the first reactive coating region is a first reactive coating zone. More preferably, the first reactive coating zone is arranged or supported at or near an outlet end of the substrate.
[00162] In a fifth oxidation catalyst arrangement, the second reactive coating region is a second reactive coating layer. It is preferred that the second layer of reactive coating extends the entire length (i.e., substantially the entire length) of the substrate, particularly the entire length of the channels of a substrate monolith.
[00163] The first reactive coating region is a first reactive coating zone, which is typically arranged or supported on the second reactive coating layer. Preferably, the first reactive coating zone is disposed directly on the second reactive coating layer (i.e., the first reactive coating zone is in contact with a surface of the second reactive coating layer).
[00164] When the first reactive coating zone is arranged or supported on the second reactive coating layer, it is preferred that the entire length of the first reactive coating zone is arranged or supported on the second reactive coating layer. The length of the first reactive coating zone is less than the length of the second reactive coating layer.
[00165] In a sixth oxidation catalyst arrangement, the first reactive coating region is a first reactive coating layer. It is preferred that the first layer of reactive coating extends the entire length (i.e., substantially the entire length) of the substrate, particularly the entire length of the channels of a substrate monolith.
[00166] The second reactive coating region is a second reactive coating layer. It is preferred that the second layer of reactive coating extends the entire length (i.e., substantially the entire length) of the substrate, particularly the entire length of the channels of a substrate monolith.
[00167] The first reactive coating layer is arranged or supported on the second reactive coating layer. Preferably, the first reactive coating layer is disposed directly on the second reactive coating layer (i.e., the first reactive coating layer is in contact with a surface of the second reactive coating layer). The second layer of reactive coating containing Mn can show good sulfur tolerance when the oxidation catalyst has a "layered" arrangement like this.
[00168] In general (including the first to sixth oxidation catalyst arrangements cited), the oxidation catalyst may additionally comprise a third reactive coating region. Thus, at least one of the first reactive coating region and the second reactive coating region can be arranged or supported in a third reactive coating region. The third reactive coating region may or may not comprise a platinum group metal.
[00169] The third reactive coating region can be placed directly on the substrate (that is, the third reactive coating region is in contact with a substrate surface; see Figures 6, 8 and 10). The second reactive coating region can be: (a) arranged or supported in the third reactive coating region (for example, see Figures 6, 8 and 10); and / or (b) disposed directly on the substrate [that is, the second reactive coating region is in contact with a substrate surface]; and / or (c) in contact with the third reactive coating region [i.e., the second reactive coating region is adjacent to or rests on the third reactive coating region].
[00170] Additionally, or alternatively, the third reactive coating region can be arranged or supported in the first reactive coating region and / or the second reactive coating region (for example, see Figures 7 and 9).
[00171] When the third reactive coating region is placed directly on the substrate, then the first reactive coating region can be arranged or supported in the third reactive coating region (for example, see Figure 6). The second reactive coating region can also be arranged or supported in the third reactive coating region. The third reactive coating region can be a third reactive coating layer, the first reactive coating region can be a first reactive coating zone and the second reactive coating region can be a second reactive coating zone. The second reactive coating region / zone may be in contact with the first reactive coating region / zone [ie, the second reactive coating region / zone is adjacent to or rests on the first reactive coating region / zone]. Alternatively, the first reactive coating region / zone and the second reactive coating region / zone can be separated (for example, by an interstice).
[00172] When the third reactive coating region is laid directly on the substrate, then the first reactive coating region can be laid directly on the substrate (for example, see Figures 8 and 10). The second reactive coating region can be arranged or supported in the third reactive coating region and / or the first reactive coating region. Preferably, the second reactive coating region is arranged or supported in the third reactive coating region. The third reactive coating region can be a third reactive coating zone and the first reactive coating region can be a first reactive coating zone. The third reactive coating region / zone may be in contact with the first reactive coating region / zone [ie, the third reactive coating region / zone is adjacent to or rests on the first reactive coating region / zone]. Alternatively, the first reactive coating region / zone and the third reactive coating region / zone can be separated (for example, by an interstice).
[00173] The second reactive coating region can be a second reactive coating layer or a second reactive coating zone, preferably a second reactive coating zone. When the second reactive coating region is a second reactive coating region, the oxidation catalyst may additionally comprise a fourth reactive coating region (for example, see Figure 10). The fourth reactive coating region can be arranged or supported in the first reactive coating zone. The fourth reactive coating region can be in contact with the second reactive coating zone [that is, the fourth reactive coating region is adjacent to or rests on the second reactive coating zone]. Alternatively, the fourth reactive coating region and the second reactive coating zone can be separated (for example, by an interstice).
[00174] The fourth reactive coating region can be a fourth reactive coating zone.
[00175] The third reactive coating region can be arranged or supported in the second reactive coating region (for example, see Figure 9). The second reactive coating region can be a second reactive coating zone and the first reactive coating region can be a first reactive coating zone. The second reactive coating region / zone may be in contact with the first reactive coating region / zone [ie, the second reactive coating region / zone is adjacent to or rests on the first reactive coating region / zone]. Alternatively, the first reactive coating region / zone and the second reactive coating region / zone can be separated (for example, by an interstice).
[00176] The third reactive coating region can be a third reactive coating layer or a third reactive coating zone.
[00177] When the third reactive coating region is a third reactive coating zone, then the third reactive coating zone typically has a length of 10 to 90% of the substrate length (e.g. 10 to 45%), preferably 15 75% of the substrate length (for example, 15 to 40%), more preferably 20 to 70% (for example, 30 to 65%, such as 25 to 45%) of the substrate length, even more preferably 25 to 65 % (e.g. 35 to 50%).
[00178] When the third reactive coating region is a third reactive coating zone, then the third reactive coating zone can be arranged or supported in the second reactive coating zone (for example, see Figure 7). The first reactive coating region can be a first reactive coating zone. The third reactive coating zone may be in contact with the first reactive coating zone [ie, the third reactive coating zone is adjacent to or rests on the first reactive coating zone]. Alternatively, the first reactive coating zone and the third reactive coating zone can be separated (for example, by an interstice).
[00179] When the third reactive coating region is a third reactive coating zone, then the third reactive coating zone can be arranged or supported in the first reactive coating zone (for example, see Figure 9). The second reactive coating region can be a second reactive coating zone. The third reactive coating zone may be in contact with the second reactive coating zone [ie, the third reactive coating zone is adjacent to or rests on the second reactive coating zone]. Alternatively, the second reactive coating zone and the third reactive coating zone can be separated (for example, by an interstice) and / or not be in contact (for example, the second reactive coating zone is not in physical contact with the third reactive coating zone).
[00180] When the third reactive coating region is a third reactive coating layer, then the third reactive coating layer can be arranged or supported both in the first reactive coating region / zone and in the second reactive coating zone / region.
[00181] Substrates to support oxidation catalysts to treat an exhaust gas from a diesel engine are well known in the art. Methods of making coatings of catalytic material and applying coatings of catalytic material to a substrate are also known in the art (see, for example, our WO 99/47260, WO 2007/077462 and WO 2011/080525).
[00182] The substrate typically has a plurality of channels (for example, for the exhaust gas to flow through them). The substrate is usually a ceramic material or a metallic material.
[00183] It is preferred that the substrate is made of or composed of cordierite (SiO2-Al2O3-MgO), silicon carbide (SiC), Fe-Cr-Al alloy, Ni-Cr-Al alloy, or an alloyed stainless steel.
[00184] Typically, the substrate is a monolith (also referred to here as a substrate monolith). Such monoliths are well known in the art. The substrate monolith can be a direct flow monolith or a filtration monolith.
[00185] A direct flow monolith typically comprises a honeycomb monolith (for example, a metal or ceramic honeycomb monolith) with a plurality of channels extending through it, whose channels are open at both ends. When the substrate is a direct flow monolith, then the oxidation catalyst of the invention is typically a poor NOx trap (LNT) [also referred to as a NOx catalyst storage (NSC)] or is for use as a NOx trap poor (LNT).
[00186] A filtration monolith generally comprises a plurality of inlet channels and a plurality of outlet channels, in which the inlet channels are opened at one end upstream (i.e., inlet side of the exhaust gas) and are capped or sealed at one end downstream (i.e., exhaust gas outlet side), the outlet channels are capped or sealed at one end upstream and are opened at one end downstream, with each inlet channel it is separated from an outlet channel by a porous structure.
[00187] When the monolith is a filtration monolith, it is preferred that the filtration monolith is a flow wall filter. In a flow wall filter, each inlet channel is alternately separated from an outlet channel by a wall of the porous structure and vice versa. It is preferred that the input channels and the output channels are arranged in a honeycomb arrangement. When a honeycomb arrangement exists, it is preferred that the channels vertically and laterally adjacent to an input channel are capped at one end upstream and vice versa (that is, the channels vertically and laterally adjacent to an outlet channel are capped in downstream end). When viewed from either end, the ends of the channels alternately capped and open take on the appearance of a chessboard.
[00188] It is preferred that the substrate is a direct flow monolith.
[00189] In principle, the substrate can be of any shape or size. However, the shape and size of the substrate are usually selected to optimize the exposure of the catalytically active materials in the catalyst to the exhaust gas. The substrate can, for example, have a tubular, fibrous or particulate shape. Examples of suitable support substrates include a monolithic honeycomb cordierite type substrate, a monolithic honeycomb type SiC substrate, a layered fiber or cloth type substrate, a foam type substrate, a cross flow substrate, a metal wire mesh substrate, a porous metal body substrate and a ceramic particle substrate.
[00190] In general, the oxidation catalyst of the invention is for use as a poor NOx scavenger (LNT).
[00191] It should be understood that any reference to an oxidation catalyst of the invention for use as a poor NOx scavenger (LNT) may include passive NOx adsorbent activity (DOC-PNA) or cold start catalyst activity (DOC -CSC).
[00192] The invention also provides an exhaust system comprising the oxidation catalyst and an emission control device. The emission control device is preferably downstream of the oxidation catalyst.
[00193] Examples of an emission control device include a diesel particulate filter (DPF), a poor NOx pickup (LNT), 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 ™), a residual ammonia catalyst (ASC) and combinations of two or more of the same. Such emission control devices are all well known in the art. It is preferred that the emission control device is a selective catalytic reduction (SCR) catalyst or a selective catalytic reduction filter (SCRF ™) catalyst
[00194] Some of the aforementioned emission control devices have filtration substrates. An emission control device with a filtration substrate can be selected from the group consisting of a diesel particulate filter (DPF), a catalytic soot filter (CSF), and a selective catalytic reduction filter catalyst (SCRF ™) .
[00195] It is preferred that the exhaust system comprises an emission control device selected from the group consisting of a poor NOx collector (LNT), a residual ammonia catalyst (ASC), diesel particulate filter (DPF), a selective catalytic reduction catalyst (SCR), a catalytic soot filter (CSF), a selective catalytic reduction filter catalyst (SCRF ™), and combinations of two or more of the same. More preferably, the emission control device is selected from the group consisting of a diesel particulate filter (DPF), a selective catalytic reduction catalyst (SCR), a catalytic soot filter (CSF), a reduction filter catalyst selective catalytic (SCRF ™), and combinations of two or more of them. Even more preferably, the emission control device is a selective catalytic reduction (SCR) catalyst or a selective catalytic reduction filter (SCRF ™) catalyst.
[00196] When the exhaust system of the invention comprises an SCR catalyst or an SCRF ™ catalyst, then the exhaust system may additionally comprise an injector for injecting a nitrogen reducing agent, such as ammonia, or an ammonia precursor, such as as urea or ammonium formate, preferably urea, in the exhaust gas downstream of the oxidation catalyst and upstream of the SCR catalyst or SCRF ™ catalyst. An injector like this can be fluidly connected to a source (for example, a tank) of a nitrogen reducing agent precursor. Dosage controlled by precursor valve in the exhaust gas can be regulated by a properly programmed engine management device and closed-loop or open-loop feedback provided by sensors that monitor the composition of the exhaust gas. Ammonia can also be generated by heating ammonium carbamate (a solid) and the generated ammonia can be injected into the exhaust gas.
[00197] Alternatively, or in addition to the injector, ammonia can be generated IN SITU (for example, during rich regeneration of the LNT arranged upstream of the SCR catalyst or SCRF ™ catalyst). Thus, the exhaust system may additionally comprise an engine management device for enriching the exhaust gas with hydrocarbons.
[00198] The SCR catalyst or SCRF ™ catalyst can comprise a metal selected from the group consisting of at least one of Cu, Hf, La, Au, In, V, lanthanides and Group VIII transition metals (for example , Fe), in which the metal is supported in a refractory oxide or molecular sieve. The metal is preferably selected from Ce, Fe, Cu and combinations of any two or more of them, more preferably the metal is Fe or Cu.
[00199] The refractory oxide for the SCR catalyst or the SCRF ™ catalyst can be selected from the group consisting of Al2O3, TiO2, CeO2, SiO2, ZrO2 and mixed oxides containing two or more of these. The non-zeolite catalyst may also include tungsten oxide (for example, V2O5 / WO3 / TiO2, WOx / CeZrO2, WOx / ZrO2 or Fe / WOx / ZrO2).
[00200] It is particularly preferred when an SCR catalyst, an SCRF ™ catalyst or a reactive coating thereof comprises at least one molecular sieve, such as an aluminosilicate zeolite or a SAPO. At least one molecular sieve can be a small, medium or large pore molecular sieve. By "small pore molecular sieve" is meant here molecular sieves containing a maximum ring size of 8, such as CHA; By "medium pore molecular sieve" is meant here a molecular sieve containing a maximum ring size of 10, such as ZSM-5; and "large pore molecular sieve" here means a molecular sieve with a maximum ring size of 12, such as beta. Small-pore molecular sieves are potentially advantageous for use in SCR catalysts.
[00201] In the exhaust system of the invention, preferred molecular sieves for an SCR catalyst or an SCRF ™ catalyst are synthetic aluminosilicate zeolite molecular sieves selected from the group consisting of AEI, ZSM-5, ZSM-20, ERI including ZSM-34, mordenite, ferrierita, BEA including Beta, Y, CHA, LEV including Nu-3, MCM-22 and EU-1, preferably AEI or CHA, and with a silica to alumina ratio of about 10 to about 50, such as about 15 to about 40.
[00202] In a first embodiment of the exhaust system, the exhaust system comprises the oxidation catalyst of the invention and a catalyzed soot filter (CSF). The oxidation catalyst is typically followed (for example, upstream) by the catalyzed soot filter (CSF). Thus, for example, an oxidation catalyst outlet is connected to an inlet of the catalyzed soot filter.
[00203] In a second embodiment of the exhaust system, the exhaust system comprises the oxidation catalyst of the invention, a catalytic soot filter (CSF) and a selective catalytic reduction catalyst (SCR). The oxidation catalyst is typically followed (for example, upstream) by the catalyzed soot filter (CSF). The catalyzed soot filter is typically followed (for example, upstream) by the selective catalytic reduction catalyst (SCR). A nitrogen reducing agent injector can be arranged between the catalytic soot filter (CSF) and the selective catalytic reduction catalyst (SCR). Thus, the catalyzed soot filter (CSF) can be followed (for example, upstream) by a nitrogen reducing agent injector, and the nitrogen reducing agent injector can be followed (for example, upstream) by the nitrogen catalyst. selective catalytic reduction (SCR).
[00204] In a third embodiment of the exhaust system, the exhaust system comprises the oxidation catalyst of the invention, a selective catalytic reduction catalyst (SCR) and both a catalytic soot filter (CSF) and a diesel particulate filter ( DPF).
[00205] In the third mode of the exhaust system, the oxidation catalyst of the invention is typically followed (for example, upstream) by the selective catalytic reduction catalyst (SCR). A nitrogen reducing agent injector can be arranged between the oxidation catalyst and the selective catalytic reduction (SCR) catalyst. Thus, the oxidation catalyst can be followed (for example, upstream) by a nitrogen reducing agent injector, and the nitrogen reducing agent can be followed (for example, upstream) by the selective catalytic reduction catalyst ( SCR). The selective catalytic reduction catalyst (SCR) is followed (for example, upstream) by the catalyzed soot filter (CSF) or the diesel particulate filter (DPF).
[00206] A fourth embodiment of the exhaust system comprises the oxidation catalyst of the invention and a selective catalytic reduction filter catalyst (SCRF ™). The oxidation catalyst of the invention is typically followed (for example, upstream) by the selective catalytic reduction filter catalyst (SCRF ™). A nitrogen reducing agent injector can be arranged between the oxidation catalyst and the selective catalytic reduction filter (SCRF ™) catalyst. Thus, the oxidation catalyst can be followed (eg upstream) by a nitrogen reducing agent injector, and the nitrogen reducing agent injector can be followed (eg upstream) by the catalytic reduction filter catalyst selective (SCRF ™).
[00207] When the exhaust system comprises a selective catalytic reduction catalyst (SCR) or a selective catalytic reduction filter catalyst (SCRF ™), such as in the second to fourth modes of the exhaust systems described above, an ASC can be arranged downstream of the SCR catalyst or SCRF ™ catalyst (i.e., as a separate substrate monolith), or more preferably a zone at a downstream or outlet end of the substrate monolith comprising the SCR catalyst can be used as a support for ASC.
[00208] Another aspect of the invention concerns a vehicle or an apparatus. The vehicle or apparatus comprises a diesel engine. The diesel engine can be a homogeneous charge compression ignition engine, a premixed charge compression ignition engine (PCCI) or a low temperature combustion engine (LTC). It is preferred that the diesel engine is a conventional (i.e., traditional) diesel engine.
[00209] The vehicle may be a light duty diesel vehicle (LDV), as defined in U.S. or European legislation. A light-duty diesel vehicle typically has a weight of <2,840 kg, more preferably a weight of <2,610 kg.
[00210] In the United States, a light duty diesel vehicle (LDV) refers to a diesel vehicle with a gross weight of <8,500 pounds (US lbs). In Europe, the term light duty diesel vehicle (LDV) refers to (i) passenger vehicles comprising no more than eight seats in addition to the driver's seat and with a maximum mass not exceeding 5 tonnes, and (ii) vehicles for the transport of goods with a maximum mass not exceeding 12 tonnes.
[00211] Alternatively, the vehicle may be a heavy duty diesel vehicle (HDV), such as a diesel vehicle with a gross weight of> 8,500 pounds (US lbs), as defined in U.S. law.
[00212] The invention also provides a method of modulating the NOx content in an exhaust gas from a diesel engine for an emission control device. The step of (b) passing the treated exhaust gas to an emission control device typically involves passing the treated exhaust gas directly to the emission control device. Thus, an output of the oxidation catalyst is directly connected (for example, without an intermediate) to an input of the emission control device.
[00213] Typically, the emission control device is a selective catalytic reduction catalyst (SCR), a selective catalytic reduction filter catalyst (SCRF ™), a diesel particulate filter (DPF), or a catalyzed soot filter (CSF). It is preferred that the emission control device is a selective catalytic reduction (SCR) catalyst or a selective catalytic reduction filter (SCRF ™) catalyst.
[00214] Any reference to “modulating the NOx content” in the form used here, particularly in relation to the method or aspects of use of the invention, refers to changing (ie adjusting) or maintaining, preferably changing, the reason (in ppm or% by volume, typically at the temperature and pressure of the exhaust gas) of NO: NO2 to stay in a predefined ratio at a specific temperature or temperature range of the exhaust gas. The preset ratio is typically less than 17: 3, preferably to be 5: 1 to 1: 5, more preferably 2.5: 1 to 1: 2.5, and even more preferably 2: 1 to 1: 2 (for example, 1.5: 1 to 1: 1.5 or about 1: 1).
[00215] The invention also relates to the use of the oxidation catalyst in the regeneration of an emission control device with a filtration substrate (for example, a downstream emission control device having a filtration substrate).
[00216] The emission control device with a filtration substrate can be selected from the group consisting of a diesel particulate filter (DPF), a catalytic soot filter (CSF), a selective catalytic reduction filter catalyst (SCRF ™) and a combination of two or more of the same.
[00217] When the oxidation catalyst of the invention is used in the regeneration of an emission control device with a filtration substrate, it can be used in the active or passive regeneration of the emission control device, preferably in active regeneration.
[00218] The oxidation catalyst can be used to regenerate the emission control device with a filtration substrate at a temperature of at least 220 ° C, preferably at least 240 ° C, more preferably at least 260 ° C, even more preferably at least 280 ° C, by oxidation of nitric oxide (NO) to nitrogen dioxide (NO2). DEFINITIONS
[00219] The term "reactive coating" is well known in the art and refers to an adherent coating that is applied to a substrate normally during production of a catalyst.
[00220] The term "reactive coating region" in the form used here refers to an area of reactive coating on a substrate. A "reactive coating region" can, for example, be arranged or supported on a substrate such as a "layer" or a "zone". The area or arrangement of a reactive coating on a substrate is generally controlled during the process of applying the reactive coating to the substrate. The "reactive coating region" typically has different boundaries or borders (that is, it is possible to distinguish a reactive coating region from another reactive coating region using conventional analytical techniques).
[00221] Typically, the "reactive coating region" has a substantially uniform length. The reference to a “substantially uniform length” in this context refers to a length that does not deviate (for example, the difference between maximum and minimum length) by more than 10%, preferably does not deviate by more than 5%, more preferably not deviates by more than 1% from its average value.
[00222] It is preferable that each "reactive coating region" has a substantially uniform composition (that is, there is no substantial difference in the reactive coating composition when comparing a part of the reactive coating region with another part of that reactive coating region ). Substantially uniform composition in this context refers to a material (for example, reactive coating region) where the difference in composition when comparing a part of the reactive coating region with another part of the reactive coating region is 5% or less, usually 2.5% or less, and more commonly 1% or less.
[00223] The term "reactive coating zone" in the form used herein refers to a region of reactive coating with a length that is less than the total length of the substrate, such as <75% of the total length of the substrate. A "reactive coating zone" typically has a length (i.e., a substantially uniform length) of at least 5% (e.g.,> 5%) of the total substrate length.
[00224] The total length of a substrate is the distance between its input end and its output end (for example, the opposite ends of the substrate).
[00225] Any reference to a “reactive coating zone arranged on an inlet end of the substrate” used here refers to a reactive coating zone arranged or supported on a substrate where the reactive coating zone is closest to an end of substrate inlet than the reactive coating zone is an outlet end of the substrate. Thus, the midpoint of the reactive coating zone (i.e., half its length) is closer to the inlet end of the substrate than the midpoint is to the outlet end of the substrate. Similarly, any reference to a “reactive coating zone arranged on an exit end of the substrate” used here refers to a reactive coating zone arranged or supported on a substrate where the reactive coating zone is closest to an exit end of the substrate than the reactive coating zone is an inlet end of the substrate. Thus, the midpoint of the reactive coating zone (i.e., half its length) is closer to the outlet end of the substrate than the midpoint is to the inlet end of the substrate.
[00226] When the substrate is a flow wall filter, then generally any reference to a "reactive coating zone arranged at an inlet end of the substrate" refers to a reactive coating zone arranged or supported on the substrate which is: (a) closer to an inlet end (for example, open end) of a substrate inlet channel than the reactive coating zone is to a closed end (for example, blocked or capped end) of the inlet channel, and / or (b) closer to a closed end (e.g., blocked or capped end) of a substrate outlet channel than the reactive coating zone is to an outlet end (e.g., open end) of the channel about to leave.
[00227] Thus, the midpoint of the reactive coating zone (ie, half its length) is (a) closer to an inlet end of a substrate inlet channel than the midpoint is to the closed end of the inlet channel, and / or (b) closer to a closed end of an outlet channel of the substrate than the midpoint is to an outlet end of the outlet channel.
[00228] Similarly, any reference to a “reactive coating zone arranged at an outlet end of the substrate” when the substrate is a flow wall filter refers to a reactive coating zone arranged or supported on the substrate which is: ( a) closer to an outlet end (e.g., an open end) of an outlet channel of the substrate than the reactive coating zone is to a closed end (e.g., blocked or capped) of the outlet channel, and / or (b) closer to a closed end (e.g., blocked or capped end) of an input channel of the substrate than to an input end (e.g., an open end) of the input channel.
[00229] Thus, the midpoint of the reactive coating zone (ie, half its length) is (a) closer to an outlet end of a substrate outlet channel than the midpoint is to the closed end of the output channel, and / or (b) closer to a closed end of an input channel of the substrate than the midpoint is an input end of the input channel.
[00230] A reactive coating zone can satisfy both of (a) and (b) when the reactive coating is present on the wall of the flow wall filter (i.e., the reactive coating zone is on the wall).
[00231] The acronym "PGM" in the form used here refers to "metal of the platinum group". The term "platinum group metal" generally refers to a metal selected from the group consisting of Ru, Rh, Pd, Os, Ir and Pt, preferably a metal selected from the group consisting of Ru, Rh, Pd, Ir and Pt. In general, the term "PGM" preferably refers to a metal selected from the group consisting of Rh, Pt and Pd.
[00232] The term "mixed oxide" in the form used here generally refers to a mixture of oxides in a single phase, as is conventionally known in the art. The term "composite oxide" in the form used herein generally refers to an oxide composition with more than one phase, as is conventionally known in the art.
[00233] Any reference to reactive coating zones that do not "substantially overlap" in the form used herein refers to an overlap (that is, between the ends of neighboring zones on a substrate) of less than 10% of the length of the substrate, preferably less than 7.5% of the substrate length, more preferably less than 5% of the substrate length, particularly less than 2.5% of the substrate length, even more preferably less than 1% of the substrate length, and above everything preferably does not overlap.
[00234] The expression “essentially consists” in the form used here limits the scope of a resource to include specified materials, and any other materials or steps that do not materially affect the basic characteristics of that resource, such as, for example, secondary impurities. The term “consists essentially of” encompasses the term “consisting of”.
[00235] The term "substantially free of" in the form used here with reference to a material, typically in the context of the content of a reactive coating region, a reactive coating layer or a reactive coating zone, means the material to a lesser extent amount, such as <5% by weight, preferably <2% by weight, more preferably <1% by weight. The term "substantially free from" encompasses the term "does not understand".
[00236] Any reference to a dopant amount, particularly a total amount, expressed as% by weight in the form used herein refers to the weight of the support material or the refractory metal oxide thereof. EXAMPLES
[00237] The invention will now be illustrated by the following non-limiting examples. Example 1
[00238] Alumina powder doped with silica was pasted in water and ground to a d90 <20 microns. Barium acetate was added to the slurry followed by appropriate amounts of soluble platinum and palladium salts. Beta zeolite was added in such a way that the slurry comprised 78% silica doped alumina and 22% zeolite by mass. The slurry was then stirred to homogenize. The resulting reactive coating was applied to the inlet channels of a 400-cell cordierite direct-flow monolith using established coating techniques, and then dried.
[00239] A second slurry was prepared by taking silica-doped alumina powder and grinding to a d90 <20 microns. Soluble platinum salt was added to the slurry followed by a manganese nitrate solution. The slurry was stirred to homogenize. This second slurry was applied to the direct flow monolith outlet channels using conventional coating techniques. The part was dried and then calcined at 500 ° C. The finished catalyst had a total PGM load of 75 g ft-3 and a manganese load in the outlet coating of 100 g ft-3. The weight ratio of platinum to manganese was 3: 5. Example 2
[00240] Alumina powder doped with silica was pasted in water and ground to a d90 <20 microns. Barium acetate was added to the slurry followed by appropriate amounts of soluble platinum and palladium salts. Beta zeolite was added in such a way that the slurry comprised 78% silica doped alumina and 22% zeolite by mass. The slurry was then stirred to homogenize. The resulting reactive coating was applied to the inlet channels of a 400-cell cordierite direct-flow monolith using established coating techniques, and then dried.
[00241] A second slurry was prepared by taking silica-doped alumina powder and grinding to a d90 <20 microns. An appropriate amount of soluble platinum salt was added to the slurry and was stirred to homogenize. This second slurry was applied to the direct flow monolith outlet channels using conventional coating techniques. The part was dried and then calcined at 500 ° C. The finished catalyst had a total PGM load of 75 g ft-3. Experimental Results NO OXIDATION MEASUREMENT
[00242] Core core samples were taken from the catalysts of Examples 1 and 2. All cores were hydrothermally "aged" in an oven at 750 ° C for 15 hours. Additional cores were removed and kept in the “fresh” condition (that is, they were kept without any heat treatment in the oven).
[00243] The catalytic activity was determined using a synthetic gas bench activity test (SCAT). The fresh and aged cores were tested in a simulated catalyst activity test gas (SCAT) apparatus using the input gas mixtures in Table 1. In each case, the balance is nitrogen. Table 1
RESULTS
[00244] The results of the SCATs are shown in Tables 2 and 3 below.Table 2

[00245] The results in Table 2 show that the catalyst of Example 1 (comprises manganese in the Pt zone) in the condition aged at 200 ° C has a higher NO oxidation performance than the catalyst of Example 2. Table 1

[00246] The results in Table 3 show that the catalyst of Example 1 in the condition aged at 220 ° C shows better NO oxidation activity than the catalyst of Example 2.
[00247] Tables 2 and 3 also show that the difference in NO oxidation activity between the fresh and aged conditions of the catalyst is smaller for example 1 than for example 2. Thus, the catalyst in Example 1 shows oxidation performance of More stable NO than Example 2. A stable NO oxidation performance between fresh and aged conditions is advantageous for SCR dosage calibrations downstream. Example 3
[00248] A first slurry was prepared as follows: silica-alumina powder was pasted in water and ground to a d90 <20 microns. Soluble platinum salt was added followed by manganese nitrate. The mixture was stirred to homogenize.
[00249] The slurry was applied to the outlet end of a direct flow monolith of cordierite with 400 cells per square inch using established coating techniques. It was then dried and calcined at 500 ° C. The Pt load in the part was 15 g ft-3. The manganese load in the part was 50 g ft-3.
[00250] A second slurry was prepared by taking silica-alumina powder and grinding to a d90 <20 microns. Barium acetate was added to the slurry followed by appropriate amounts of soluble platinum and palladium salts. Beta zeolite was added in such a way that the slurry comprised 77% silica-alumina and 23% zeolite by mass. The slurry was then stirred to homogenize. The resulting reactive coating was applied to the direct flow monolith inlet channels using established coating techniques. The part was dried and calcined at 500 ° C. The finished catalyst had a total Pt load of 45 g ft-3 and a Pd load of 15 g ft-3. Example 4
[00251] A first slurry was prepared and applied to a direct flow monolith of cordierite with 400 cells per square using the same methods as in Example 3. The Pt loading in the part was 15 g ft- 3. The manganese loading in the part was 50 g ft-3.
[00252] A second slurry was prepared by taking silica-alumina powder and grinding to a d90 <20 microns. Soluble platinum salt was added followed by manganese nitrate. Beta zeolite was added in such a way that the slurry comprised 77% silica-alumina and 23% zeolite by mass. The slurry was then stirred to homogenize. The resulting reactive coating was applied to the direct flow monolith inlet channels using established coating techniques. The part was dried and calcined at 500 ° C. The finished catalyst had a total Pt load of 54 g ft-3 and a manganese load of 100 g ft-3. Experimental Results MEASUREMENT OF OXIDATION ACTIVITY
[00253] Core core samples were taken from each of the catalysts in Examples 3 and 4. The cores were hydrothermally "aged" in an oven at 750 ° C for 15 hours using 10% water. Catalytic activity was determined using a synthetic gas bench test. The cores were tested in a simulated catalyst activity test gas (SCAT) apparatus using the input gas mixture in Table 1. In each case, the balance is nitrogen. The oxidation activity for CO and HC is determined by the extinction temperature whereby 50% conversion is achieved (T50). The oxidation activity for NO is determined as the percentage of conversion at 300 ° C. RESULTS The results of the SCATs are shown in Table 4 below.

[00254] Results in Table 4 show that Examples 3 and 4 have very similar T50 extinction temperatures for CO and HC. This means that Examples 3 and 4 have very similar CO and HC oxidation activity. Example 4 comprises both platinum and manganese in the inlet coating as well as in the outlet coating. Example 3 comprises both platinum and manganese in the outlet coating only. Example 4 has a higher NO oxidation performance at 300 ° C than Example 3. Example 5
[00255] Silica-alumina powder was pasted in water and ground to a d90 <20 microns. Appropriate amounts of soluble platinum and palladium salts were added. The mixture was stirred to homogenize. The reactive coating was applied to a direct flow monolith of cordierite with 400 cells per square inch using established coating techniques. It was then dried and calcined at 500 ° C. The general PGM load for the part was 60 g ft-3. The Pt: Pd ratio was 4: 1 by mass. Example 6
[00256] Silica-alumina powder was pasted in water and ground to a d90 <20 microns. Appropriate amounts of soluble platinum and palladium salts were added followed by manganese nitrate. The mixture was stirred to homogenize. The reactive coating was applied to a direct flow monolith of cordierite with 400 cells per square inch using established coating techniques. It was then dried and calcined at 500 ° C. The general PGM load for the part was 60 g ft-3. The Pt: Pd ratio was 4: 1 by mass. The manganese load was 100 g ft-3. Example 7
[00257] Silica-alumina powder was pasted in water and ground to a d90 <20 microns. Appropriate amounts of soluble platinum and palladium salts were added. The mixture was stirred to homogenize. The reactive coating was applied to a direct flow monolith of cordierite with 400 cells per square inch using established coating techniques. It was then dried and calcined at 500 ° C. The general PGM load for the part was 60 g ft-3. The Pt: Pd ratio was 10: 1 by mass. Example 8
[00258] Silica-alumina powder was pasted in water and ground to a d90 <20 microns. Appropriate amounts of soluble platinum and palladium salts were added followed by manganese nitrate. The mixture was stirred to homogenize. The reactive coating was applied to a direct flow monolith of cordierite with 400 cells per square inch using established coating techniques. It was then dried and calcined at 500 ° C. The general PGM load for the part was 60 g ft-3. The Pt: Pd ratio was 10: 1 by mass. The manganese load was 100 g ft-3. Experimental Results MEASUREMENT OF OXIDATION ACTIVITY
[00259] Core core samples were taken from each of the catalysts of Examples 5, 6, 7 and 8. The cores were hydrothermally "aged" in an oven at 800 ° C for 16 hours using 10% water. The catalytic activity was determined using a synthetic gas bench test. The cores were tested in a simulated catalyst activity test gas (SCAT) apparatus using the input gas mixture in Table 1. In each case, the balance is nitrogen. The oxidation activity for CO and HC is determined by the extinction temperature whereby 50% conversion is achieved (T50). RESULTS
[00260] The results of the SCATs are shown in Table 5 below. Table 5

[00261] Results in Table 5 show the extinction temperatures of T50 of CO and HC for examples 5, 6, 7 and 8. Examples 5 and 6 have the same precious metal loading and a weight ratio of Pt: Pd of 4: 1. Example 6 which comprises manganese has a lower T50 extinguishing temperature of CO than Example 5 which does not comprise manganese. Extinguishing temperature T50 of HC for examples 5 and 6 are identical. Examples 7 and 8 have the same precious metal loading and 10: 1 Pt: Pd weight ratio. Example 8 which comprises manganese has lower T50 extinguishing temperatures for CO and HC than Example 7 which does not comprise manganese.
[00262] A greater improvement in the extinction temperature is observed with the catalyst containing manganese at a 10: 1 Pt: Pd weight ratio than 4: 1.
[00263] To avoid any doubt, the total content of all or any document cited here is incorporated by reference in this application.

权利要求:
Claims (15)
[0001]
1. Oxidation catalyst to treat an exhaust gas from a diesel engine, characterized by the fact that it comprises: a first reactive coating region comprising a first platinum group metal (PGM), a first support material and a component NOx storage material, in which the first support material comprises a refractory metal oxide selected from the group consisting of alumina, silica, titania, zirconia, ceria and a mixed or composite oxide thereof, the NOx storage component comprises: (i) an alkali metal oxide, carbonate or hydroxide; (ii) an alkaline earth metal oxide, carbonate or hydroxide; and / or (iii) a rare earth metal oxide, carbonate or hydroxide selected from the group consisting of lanthanum, yttrium and a combination thereof; and wherein the NOx storage component is arranged or supported on the first support material; a second reactive coating region comprising platinum (Pt), manganese (Mn) and a second support material comprising a refractory metal oxide, which is silica-doped alumina in a total amount of 0.5 to 15% by weight that the platinum (Pt) is arranged or supported on the second support material and the manganese (Mn) is arranged or supported on the second support material; and a substrate with an inlet end and an outlet end, where the substrate is a direct flow substrate.
[0002]
2. Oxidation catalyst according to claim 1, characterized in that the alumina is doped with silica in a total amount of 1.5 to 10% by weight.
[0003]
Oxidation catalyst according to either of claims 1 or 2, characterized in that the second reactive coating region has a ratio of total weight of manganese (Mn) to platinum from 5: 1 to 0.2: 1 .
[0004]
Oxidation catalyst according to any one of claims 1 to 3, characterized in that the second reactive coating region comprises palladium.
[0005]
Oxidation catalyst according to any one of claims 1 to 4, characterized in that the second reactive coating region has a ratio of platinum to palladium in total weight from 1: 0 to 2: 1.
[0006]
Oxidation catalyst according to any one of claims 1 to 5, characterized in that the NOx storage component comprises an alkaline earth metal oxide, carbonate or hydroxide, wherein the alkaline earth metal is selected from the group that consists of magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and a combination of two or more of them.
[0007]
Oxidation catalyst according to any one of claims 1 to 6, characterized in that the first PGM is arranged or supported on the first support material, wherein the first support material comprises a refractory metal oxide optionally doped with a dopant.
[0008]
8. Oxidation catalyst according to claim 7, characterized by the fact that the refractory metal oxide is alumina doped with magnesium oxide.
[0009]
9. Oxidation catalyst according to any one of claims 1 to 8, characterized in that the first PGM is selected from platinum, palladium, a combination of platinum and palladium, a combination of platinum and rhodium, a combination of palladium and rhodium, and a combination of platinum, palladium and rhodium.
[0010]
Oxidation catalyst according to claim 9, characterized in that the first PGM is a combination of platinum and palladium, and the platinum is arranged or supported on the first support material and / or the palladium is arranged or supported on the first support material.
[0011]
An oxidation catalyst according to any one of claims 1 to 9, characterized in that the first PGM is a combination of platinum and palladium, a combination of palladium and rhodium or a combination of platinum, palladium and rhodium, and in that the first reactive coating region further comprises a palladium support material, wherein the palladium support material comprises a refractory metal oxide comprising ceria or a mixed oxide or ceria composite.
[0012]
Oxidation catalyst according to claim 11, characterized in that the platinum and / or rhodium is arranged or supported on the first support material and the palladium is arranged or supported on the palladium support material.
[0013]
Oxidation catalyst according to either of claims 11 or 12, characterized in that the NOx storage component is disposed of or supported on the palladium support material.
[0014]
14. Exhaust system, characterized by the fact that it comprises an oxidation catalyst as defined in any one of claims 1 to 13 and an emission control device.
[0015]
15. Exhaust system according to claim 14, characterized by the fact that the emission control device is selected from the group consisting of emission control device selected from the group consisting of a diesel particulate filter (DPF), a poor NOx pickup (LNT), 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 ™), a residual ammonia catalyst (ASC) and combinations of two or more of the same.

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法律状态:
2019-12-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-07-21| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-11-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-12-29| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 23/01/2015, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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GBGB1401115.9A|GB201401115D0|2014-01-23|2014-01-23|Diesel oxidation catalyst and exhaust system|

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GB1401115.9|2014-01-23|

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GBGB1405871.3A|GB201405871D0|2014-01-23|2014-04-01|Diesel oxidation catalyst and exhaust system|

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GB1405871.3|2014-04-01|

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PCT/GB2015/050145|WO2015110817A1|2014-01-23|2015-01-23|Diesel oxidation catalyst and exhaust system|

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