EXHAUST SYSTEM FOR A COMPRESSION IGNITION ENGINE, AND, VEHICLE

专利摘要:
CATALYTIC SOOT FILTER, EXHAUST SYSTEM FOR A COMPRESSION IGNITION ENGINE, VEHICLE, USE OF A CATALYTIC SOOT FILTER, AND, M ... ALL FOR TREATING CARBON MONOXIDE AND HYDROCARBONS AND NO 2 IN ONE GAS OF EXHAUSTING A COMPRESSION IGNITION ENGINE. A catalyzed soot filter comprising an oxidation catalyst for treating carbon monoxide (CO) and hydrocarbons (HCs) in exhaust g · s from a compression ignition engine disposed on a filter substrate, wherein the oxidation catalyst is described. comprises: a metal component of the platinum group (PGM) selected from the group consisting of a platinum component (Pt), a palladium component (Pd) and a combination thereof; an alkaline earth metal component; a support material comprising a modified alumina incorporating a heteroatom component.
公开号:BR112015011641B1
申请号:R112015011641-8
申请日:2013-11-21
公开日:2020-09-24
发明作者:David Bergeal；Gavin Michael Brown；Andrew Francis Chiffey；John Benjamin Goodwin；Daniel HATCHER；François Moreau；Agnes RAJ；Raj Rao Rajaram；Paul Richard Phillips；Cathal PRENDERGAST
申请人:Johnson Matthey Public Limited Company；
IPC主号:

专利说明:

[0001] [001] The invention relates to a catalyzed soot filter for a compression ignition engine, whose catalyzed soot filter comprises an oxidation catalyst disposed on a filter substrate and an exhaust system comprising the catalyzed soot filter, to a compression ignition engine comprising the exhaust system and to a vehicle comprising the exhaust system. The invention also relates to the use of the catalyzed soot filter and a method of treating an exhaust gas from a compression ignition engine. BACKGROUND OF THE INVENTION
[0002] [002] In general, there are four classes of pollutants that are subject to legislation by intergovernmental organizations worldwide: carbon monoxide (CO), unburned hydrocarbons (HCs), nitrogen oxides (NOx) and particulate matter (PM) . As the emission standards for permissible emission of pollutants in exhaust gases from vehicle engines become increasingly strict, there is a need to provide catalysts that are capable of meeting these standards and that are cost effective.
[0003] [003] For compression ignition engines, such as diesel engines, a catalytic soot filter (CSF) is typically used to treat the exhaust gas produced by such engines. CSFs generally catalyze the oxidation of (1) carbon monoxide (CO) to carbon dioxide (CO2), (2) HCs to carbon dioxide (CO2) and water (H2O) and (3) the oxidation of filtered PM from gas exhaust. The two most important PM oxidation reactions are oxidation to nitrogen dioxide (NO2 + C → NO + CO) and oxygen (O2 + 2C → 2CO or O2 + C → CO2). Sources of NO2 for the first reaction are the engine itself and nitrogen monoxide (also present in the exhaust gas) oxidized both to an upstream substrate monolith comprising a diesel oxidation catalyst (DOC) and to the filter catalyst itself. Exhaust gas temperatures for compression ignition engines, such as diesel engines, particularly for light duty diesel vehicles, are relatively low (for example, around 400 ° C) and so a challenge is to develop durable CSF catalyst formulations with low “operating” temperatures.
[0004] [004] The activity of oxidation catalysts, such as CSFs and DOCs, is often measured in terms of their “operating” temperature, which is the temperature at which the catalyst starts to perform a particular catalytic reaction or performs it at a certain level . Typically, "operating" temperatures are given in terms of a specific conversion level for a reagent, such as carbon monoxide conversion. Thus, a temperature T50 is often referred to as an "operating" temperature because it represents the lowest temperature at which a catalyst catalyzes the conversion of a reagent at 50% efficiency.
[0005] [005] Low emission zones (LEZs) are areas or roads in Europe, for example, Berlin, London, Stockholm, Eindhoven, etc., where the most polluting vehicles have restricted entry (see http: //www.lowemissionzonas.eu / what-are-lezs showall = 1 & limitstart =).
[0006] [006] There is growing evidence that poor air quality is bad for health and life expectancy. Nitrogen dioxide is considered to have health effects in both the short and long term. It affects the function of the lungs, and exposure increases the response to allergens in sensitized individuals. It has been suggested that the apparent health effects of nitrogen dioxide can be attributed to particles or their combination with particles. NO2 can also contribute to reactions that cause photochemical pollution. European Air Quality Standards (for EU Member States) set Limit Values for the protection of human health. The EU Air Quality Standard inter alia for NO2 was established on January 1, 2010 at an average of 200 µg / m3 (105 ppb) over a period of one hour, not to be exceeded> 18 times a calendar year; and an average 40 µg / m3 (21 ppb) per calendar year.
[0007] [007] There is therefore a need in the art for exhaust systems that prevent or reduce NO2 emissions into the atmosphere, particularly for vehicles that access LEZs. These can include factory-fitted exhaust systems and systems to be upgraded on existing vehicles.
[0008] [008] WO 00/34632 discloses a system for treating diesel engine exhaust gases comprising a first effective catalyst to oxidize hydrocarbons, a second effective catalyst to convert NO to NO2, a particulate trap, in which particulates can be burned in NO2. The first catalyst can be platinum dispersed in ceria or in a coating of catalytic metal oxide material that incorporates ceria. The Examples explain that: "It is evident that, once the HC (represented by C3H6) has been removed in the first oxidation step, the oxidation of NO to NO2 can occur more completely".
[0009] [009] Catalysts that are used to oxidize carbon monoxide (CO), hydrocarbons (HCs) and sometimes also nitrogen oxides (NOx) in an exhaust gas emitted by a compression ignition engine generally comprise at least one metal of the platinum group, such as platinum or palladium. Platinum is more active than palladium in catalyzing the oxidation of CO and HCs in the exhaust gas of a compression ignition engine, and the inclusion of palladium in such catalysts has generally been avoided because of its susceptibility to sulfur poisoning. However, the use of ultra-low sulfur fuels, the relative cost of palladium to platinum, and improvements in catalyst durability that can be obtained by including palladium make catalyst formulations comprising palladium, especially formulations comprising both palladium and platinum, become favored. .
[0010] [0010] Although, in general, the cost of palladium has historically been less than that of platinum, both palladium and platinum are expensive metals. Oxidation catalysts that have improved catalytic activity without increasing the total amount of platinum and palladium, or that have similar catalytic activity to existing oxidation catalysts with a lower amount of platinum and palladium, are desirable. SUMMARY OF THE INVENTION
[0011] [0011] The inventors surprisingly observed that an oxidation catalyst with advantageous activity including relatively low and stable NO oxidation activity can be obtained when a combination of (i) an alkaline earth metal component and (ii) a support material of alumina that has been modified to include a heteroatom component, is included in a catalyst formulation comprising at least one of platinum and palladium. Such catalysts can be used to advantage in exhaust systems for use in LEZs, where low NO2 emissions are required. It was observed that such catalysts have excellent CO oxidation activity at low temperature. Catalysts are particularly effective in converting relatively high levels of CO into exhaust gas produced by the compression ignition engine, particularly at temperatures below 250 ° C. Catalysts can also exhibit good oxidation activity for HCs, particularly unsaturated HCs, such as alkenes, at low temperatures. The relatively low temperature oxidation activity of the catalyst makes it particularly suitable for use in combination with other emissions control devices in an exhaust system. In particular, although NO oxidation is relatively low, the oxidation catalyst is capable of oxidizing nitrogen oxide (NO) to nitrogen dioxide (NO2), which can be advantageous when the oxidation catalyst is upstream of a catalytic reduction catalyst selective (SCR) or a catalyzed filter with a selective catalytic reduction catalyst.
[0012] [0012] Therefore, according to a first aspect, the invention provides a catalyzed soot filter comprising an oxidation catalyst to treat carbon monoxide (CO) and hydrocarbons (HCs) in exhaust gas from a compression ignition engine arranged on a filter substrate, where the oxidation catalyst comprises: a metal component from the platinum group (PGM) selected from the group consisting of a platinum component (Pt), a palladium component (Pd) and a combination thereof ; an alkaline earth metal component; a support material comprising a modified alumina incorporating a heteroatom component.
[0013] [0013] Without wishing to be bound by any particular theory, the inventors believe that the relatively low stable NO oxidation activity of oxidation catalysts for use in the present invention can be attributed to a combination of factors, including competitive selective oxidation of CO and HC species, that is, NO oxidation occurs only after CO and HC have been removed oxidatively; and NO2 oxidation of larger non-polar (for example, aliphatic) straight HC species such as dodecane (similar to the “classic” poor NOx catalyst (also known as HC-SCR), ie {HC} + NOx → N2 + CO2 + H2O In this way, it is believed that the oxidation catalyst for use in the present invention can not only reduce NO2 emissions from the soot filter catalyzed per se (by the relatively low NO oxidation activity), but also reduce NO2 emissions from upstream catalysts entering the catalyzed soot filter, i.e. the amount of NO2 leaving the catalyzed soot filter according to the invention may be less than the amount entering it.
[0014] [0014] The initial oxidative activity of a freshly prepared oxidation catalyst often deteriorates until the catalyst reaches an aged state. Repeated exposure of the oxidation catalyst to hot exhaust gas can cause sintering and / or binding of the platinum group metal component (PGM) s of the catalyst until it reaches an aged state. This deterioration in activity can be problematic, particularly when pairing the oxidation catalyst with one or more other emission control devices in an exhaust system. The oxidation catalyst of the invention can have stable activity in the direction of oxidation of nitrogen oxide (NO) to nitrogen dioxide (NO2) (that is, the “fresh” oxidative activity of the catalyst in the direction of NO is the same or similar to “aged” oxidative activity of the catalyst). This is particularly advantageous for exhaust systems where the oxidation catalyst is combined with a selective catalytic reduction catalyst (SCR) or a filter catalyzed with a selective catalytic reduction catalyst due to an exhaust gas with a stable NO ratio: NO2 can be passed to the SCR catalyst or SCR catalyzed filter.
[0015] [0015] A second aspect of the invention relates to an exhaust system for a compression ignition engine comprising a catalyzed soot filter according to the first aspect of the invention.
[0016] [0016] In a third aspect, the invention relates to a compression ignition engine comprising an exhaust system according to the second aspect of the invention.
[0017] [0017] In a fourth aspect, the invention relates to a vehicle comprising a compression ignition engine according to the third aspect of the invention.
[0018] [0018] In a fifth aspect, the invention provides the use of a catalytic soot filter according to the first aspect of the invention to oxidize carbon monoxide (CO) and hydrocarbons (HCs) and to reduce NO2 emissions in an exhaust gas of a compression ignition engine.
[0019] [0019] A sixth aspect of the invention relates to a method of treating carbon monoxide (CO) and hydrocarbons (HCs) and NO2 in an exhaust gas from a compression ignition engine, whose method comprises placing the exhaust gas in contact with a soot filter catalyzed according to the first aspect according to the invention DETAILED DESCRIPTION OF THE INVENTION
[0020] [0020] The invention relates to a catalyzed soot filter comprising an oxidation catalyst comprising an alkaline earth metal component. It has surprisingly been found that a catalyst with advantageous oxidizing activity, particularly a low T50 of CO, can be obtained for catalyst formulations comprising an alkaline earth metal component and a modified alumina incorporating a heteroatom component.
[0021] [0021] Typically, the alkaline earth metal component comprises magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) or a combination of two or more of them. It is preferred that the alkaline earth metal component comprises calcium (Ca), strontium (Sr), or barium (Ba), more preferably strontium (Sr) or barium (Ba), and above all preferably the alkaline earth metal component comprises barium (Ba).
[0022] [0022] In general, the alkaline earth metal component comprises a single alkaline earth metal selected from the group consisting of (Mg), calcium (Ca), strontium (Sr) and barium (Ba). Preferably, the alkaline earth metal component comprises a single alkaline earth metal selected from the group consisting of calcium (Ca), strontium (Sr) and barium (Ba), more preferably strontium (Sr) and barium (Ba), and above all preferably the alkaline earth metal component comprises a single alkaline earth metal which is barium (Ba).
[0023] [0023] Typically, the amount of the alkaline earth metal component is 2.49 to 133.91 mol / m3 (0.07 to 3.75 mol ft-3), particularly 3.57 to 107.13 mol / m3 ( 0.1 to 3.0 mol ft-3), more particularly 7.14 to 89.27 mol / m3 (0.2 to 2.5 mol ft-3) eg 8.92 to 35.71 mol / m3 (0.25 to 1.0 mol ft-3), such as 10.71 to 80.34 mol / m3 (0.3 to 2.25 mol ft-3), especially 12.49 to 66.06 mol / m3 (0.35 to 1.85 mol ft-3) preferably 14.28 to 53.56 mol / m3 (0.4 to 1.5 mol ft-3), even more preferably 17.85 to 44.63 mol / m m3 (0.5 to 1.25 mol ft-3). Without wishing to be bound by theory, it is believed that the number of alkaline earth metal atoms that are present contributes to the advantageous catalyst activity and that this activity is “leveled” once the number of alkaline earth metal atoms has reached a certain value. The ability of the catalyst to oxidize certain species of HC and NO can be reduced with an increase in the content of alkaline earth metal.
[0024] [0024] In general, the total amount of the alkaline earth metal component is 357.1 to 17.855 g / m3 (10 to 500 g ft-3) (for example, 2142.6 to 14.284 g / m3 (60 to 400 g ft-3) or 357.1 to 16.069.5 g / m3 (10 to 450 g ft-3), particularly 714.2 to 14.284 g / m3 (20 to 400 g ft-3), more particularly 1249.85 to 12,498.5 g / m3 (35 to 350 g ft-3), such as 1785.5 to 10,713 g / m3 (50 to 300 g ft-3), especially 2678.25 to 8927.5 g / m3 (75 to 250 g ft-3).
[0025] [0025] The oxidation catalyst for use in the present invention, in general, comprises an amount of the alkaline earth metal component of 0.1 to 20% by weight, preferably 0.5 to 17.5% by weight, more preferably 1 to 15% by weight, and even more preferably 1.5 to 12.5% by weight. The amount of the alkaline earth metal component can be from 1.0 to 8.0% by weight, such as 1.5 to 7.5% by weight, particularly 2.0 to 7.0% by weight (e.g. 2.5 to 6.5% by weight or 2.0 to 5.0% by weight). The amount of the alkaline earth metal component can be from 5.0 to 17.5% by weight, such as 7.5 to 15% by weight, particularly 8.0 to 14% by weight (e.g. 8.5 to 12.5% by weight or 9.0 to 13.5% by weight).
[0026] [0026] Typically, the ratio of the total mass of the alkaline earth metal component to the total mass of the metal component of the platinum group (PGM) is 0.25: 1 to 20: 1 (for example, 0.3: 1 to 20: 1). It is preferred that the ratio of the total mass of the alkaline earth metal component to the total mass of the metal component of the platinum group (PGM) is 0.5: 1 to 17: 1, more preferably 1: 1 to 15: 1, particularly 1.5: 1 to 10: 1, even more preferably 2: 1 to 7.5: 1, and even more preferably 2.5: 1 to 5: 1, when a platinum (Pt) component is present, then preferably the total mass of the alkaline earth component is greater than the total mass of the platinum component (Pt).
[0027] [0027] The support material typically comprises, or consists essentially of, a modified alumina incorporating a heteroatom component. The heteroatom component that is incorporated into alumina in general changes the chemical characteristics, physical structure and / or physical properties of the material compared to the alumina itself, and in general also compared to a mixture of alumina with the heteroatom component. The presence of the heteroatom component is considered to modify the interaction of alumina with the alkaline earth component. The modified alumina is typically alumina present in, or from, gamma (i.e., γ alumina).
[0028] [0028] Typically, the heteroatom component comprises an element selected from the group consisting of a lanthanide and any of groups 1 to 14 of the periodic table (the IUPAC nomenclature for numbering the groups of the periodic table is used here, in such a way that group 1 comprises alkali metals, group 4 comprises Ti, Zr, etc., and group 14 comprises C, Si, etc.). Preferably, the heteroatom component comprises an element selected from group 2 (for example, Mg, Ca, Sr or Ba), group 4 (for example, Ti or Zr), group 14 (for example, Si) from the periodic table and one lanthanide (for example, La or Ce), such as an element selected from group 4 (for example, Ti or Zr), group 14 (for example, Si) from the periodic table and a lanthanide (for example, La or Ce). The heteroatom component may be an element, ion or a compound, but it is not alumina and, preferably, it is not a constituent element or alumina ion (for example, oxygen, O2-, aluminum or Al3 +).
[0029] [0029] Modified alumina incorporating a heteroatom component in general comprises, or consists essentially of an alumina doped with a heteroatom component, an alkaline earth metal aluminate or a mixture thereof. It is preferable that the modified alumina incorporating a heteroatom component comprises, or consists essentially of, alumina doped with a heteroatom component or an alkaline earth metal aluminate.
[0030] [0030] When modified alumina incorporating a heteroatom component is alumina doped with a heteroatom component, then typically the heteroatom component comprises silicon, magnesium, barium, lanthanum, cerium, titanium, or zirconium or a combination of two or more of themselves. The heteroatom component 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 heteroatom component comprises, or consists essentially of silicon, magnesium, barium, or cerium, or an oxide thereof, particularly silicon, or cerium, or an oxide thereof. More preferably, the heteroatom component comprises, or consists essentially of silicon, magnesium, or barium, or an oxide thereof; particularly silicon, or magnesium, or an oxide thereof; especially silicon or an oxide thereof.
[0031] [0031] Examples of alumina doped with a heteroatom component include silica doped alumina, magnesium oxide doped alumina, barium or barium oxide doped alumina, lanthanum oxide doped alumina, or cerium doped alumina, particularly doped alumina with silica, alumina doped with lanthanum oxide, or alumina doped with ceria. It is preferred that the alumina doped with a heteroatom component is alumina doped with silica, alumina doped with barium or barium oxide, or alumina doped with magnesium oxide. More preferably, the alumina doped with a heteroatom component is alumina doped with silica or alumina doped with magnesium oxide. Even more preferably, the alumina doped with a heteroatom component is alumina doped with silica. Alumina doped with a heteroatom component can be prepared using methods known in the art or, for example, by a method described in US 5,045,519.
[0032] [0032] Typically, alumina doped with a heteroatom component comprises 0.5 to 45% by weight of the heteroatom component, preferably 1 to 40% by weight of the heteroatom component, more preferably 1.5 to 30% by weight of the heteroatom component, particularly 2.5 to 25% by weight of the heteroatom component.
[0033] [0033] When alumina doped with a heteroatom component comprises, or consists essentially of silica doped alumina, then the alumina is doped with silica in an amount of 0.5 to 45% by weight, 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.
[0034] [0034] When the alumina doped with a heteroatom component comprises, or consists essentially of alumina doped with magnesium oxide, then the alumina is doped with magnesium in an amount previously described or an amount of 5 to 30% by weight, preferably 10 to 25% by weight.
[0035] [0035] If the heteroatom component comprises, or consists essentially of an alkaline earth metal, then in general the oxidation catalyst comprises an alkaline earth metal component that is separated, or is not part of the modified alumina incorporating a heteroatom component. Thus, the oxidation catalyst includes an alkaline earth metal component in addition to any alkaline earth metal that may be present in the modified alumina.
[0036] [0036] In general, when the heteroatom component comprises, or consists essentially of an alkaline earth metal, then preferably the alkaline earth metal component is different from the heteroatom component. It is preferred that the heteroatom component and the alkaline earth metal component comprise different alkaline earth metals.
[0037] [0037] If the heteroatom component of the modified alumina comprises an alkaline earth metal, such as when it is a dopant in the alumina doped with a heteroatom component or when it is part of the alkaline earth metal aluminate, then the quantity of the “alkaline earth metal alkaline earth metal ”does not include the amount of any alkaline earth metal that is present as part of the modified alumina. Similarly, the amount of the heteroatom component does not include the amount of the alkaline earth metal component that is present. It is possible to control the quantities of each component during the manufacture of the oxidation catalyst.
[0038] [0038] The term "alkaline earth metal aluminate" in general 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. Such compounds can be prepared using conventional methods well known in the art or, for example, using a method described in EP 0945165, US 6,217,837 or US 6,517,795.
[0039] [0039] 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).
[0040] [0040] In general, when the support material comprises an alkaline earth metal aluminate, then the alkaline earth metal ("M") of the alkaline earth metal aluminate is different from the alkaline earth metal component. It is preferable that the alkaline earth metal aluminate and the alkaline earth metal component comprise different alkaline earth metals.
[0041] [0041] The oxidation catalyst for use in the invention in general comprises a total amount of support material from 6.13 to 306.75 kg / m3 (0.1 to 5 g in-3), preferably 12.27 to 245 , 4 kg / m3 (0.2 to 4 g in-3) (e.g., 30.67 to 214.72 kg / m3 (0.5 to 3.5 g in-3)). When the oxidation catalyst for use in the present invention comprises a second support material, in addition to the support material comprising the modified alumina, then the total amount refers to the amount of both the second support material and the support material comprising the alumina modified.
[0042] [0042] The total amount of support material in the catalytic soot filter oxidation catalyst is generally 12.27 to 245.4 kg / m3 (0.2 to 4 g in-3),
[0043] [0043] When the oxidation catalyst for use in the present invention comprises a second support material, then typically the amount of the support material comprising the modified alumina is 6.13 to 184.05 kg / m3 (0.1 to 3, 0 g in-3), preferably 12.27 to 153.37 kg / m3 (0.2 to 2.5 g in-3), even more preferably 18.4 to 122.7 kg / m3 (0.3 to 2.0 g in-3) and even more preferably 30.67 to 107.36 kg / m3 (0.5 to 1.75 g in-3).
[0044] [0044] In general, the ratio of the total mass of the alkaline earth metal component to the total mass of the support material comprising the modified alumina is 1: 200 to 1: 5, preferably 1: 150 to 1:10, even more preferably 1: 100 to 1:20,
[0045] [0045] Typically, the support material, particularly alumina doped with a heteroatom component, is in particulate form. The support material can have a particle size d90 ≤ 20 µm (determined by conventional laser diffraction techniques). The particle size distribution of the support material is selected to aid adhesion to the substrate. The particles are generally obtained by grinding.
[0046] [0046] In general, the support material has a specific surface area of 50 to 500 m2 g -1 (measured by BET according to DIN 66131 or after activation at 550 ° C for 3 hours). It is preferable that the support material has a specific surface area of 50 to 300 m2 g-1, more preferably 100 to 250 m2 g-1,
[0047] [0047] The oxidation catalyst for use in the present invention optionally further comprises a second support material. Typically, the alkaline earth metal component is disposed of or supported on the support material comprising the modified alumina and / or a second support material. When the oxidation catalyst for use in the present invention comprises a plurality of layers, then the second support material and the support material comprising the modified alumina are preferably in different layers.
[0048] [0048] In general, the alkaline earth metal component is disposed or supported on at least one support material which comprises, or consists essentially of, a modified alumina incorporating a heteroatom component. Typically, the catalyst for use in the invention comprises a single support material, the support material of which comprises or essentially consists of the modified alumina incorporating a heteroatom component.
[0049] [0049] If a second support material is present, especially when the second support material is on the same layer as the first support material, then it is preferable that the alkaline earth metal component is substantially disposed or supported on the support material comprising the modified alumina (the term "substantially" in this context refers to at least 90%, preferably at least 99%, more preferably at least 99%, of the mass of the alkaline earth component that is present, typically in the layer or otherwise) is disposed in the support material comprising the modified alumina). It is further preferable that the alkaline earth metal component is only disposed of or supported on the support material comprising the modified alumina. For some combinations of support materials in the same layer, it can be difficult to control the precise location of the alkaline earth metal component because of its solubility and the alkaline earth metal component can be disposed of or supported in all support materials.
[0050] [0050] The oxidation catalyst for use in the present invention also comprises a metal component from the platinum group (PGM) selected from the group consisting of a platinum component (Pt), a palladium component (Pd) and a combination thereof . The oxidation catalyst for use in the invention may comprise a single metal component of the platinum group (PGM), which is both a platinum (Pt) and a palladium (Pd) component.
[0051] [0051] In general, it is preferable that the oxidation catalyst comprises a platinum component (Pt) and a palladium component (Pd) (i.e., the metal component of the platinum group (PGM) is a platinum component (Pt) ) and a palladium component (Pd)). The ratio of the total mass of the platinum component (Pt) to the total mass of the palladium component (Pd) is typically 3: 1 to 1: 3, preferably 2: 1 to 1: 2, and more preferably 1.5: 1 to 1: 1.5, especially when, but not exclusively, the oxidation catalyst comprises a plurality of layers. However, in a particularly preferred embodiment, the total weight ratio of Pt: Pd is 4: 1 to 1: 1, preferably 2: 1 to 1: 1,
[0052] [0052] Typically, the total amount of the platinum group metal component (PGM) (for example, the total amount of the platinum component (Pt) and / or the palladium component (Pd)) is 178.5 to 17.855 g / m3 (5 to 500 g ft-3). Preferably, the total amount of the PGM component is 357.1 to 14.284 g / m3 (10 to 400 g ft-3), more preferably 714.2 to 10.713 g / m3 (20 to 300 g ft-3), even more preferably, 892.75 to 8927.5 g / m3 (25 to 250 g ft-3), and even more preferably 1249.8 to 7142 g / m3 (35 to 200 g ft3).
[0053] [0053] The total amount of the platinum group metal component (PGM) in the oxidation catalyst for use in the catalyzed soot filter according to the invention is 178.5 to 35.71 g / m3 (5 to 100 g ft- 3), more preferably 357.1 to 1428.4 g / m3 (10 to 40 g ft-3).
[0054] [0054] Typically, the oxidation catalyst comprises a total mass amount of the platinum group metal component (PGM) of 2.0 to 8.0 g. The total amount of PGM component that is used depends, among other things, on the size of the substrate.
[0055] [0055] In addition to the metal component of the platinum group (PGM), the oxidation catalyst for use in the invention may additionally comprise a noble metal component. The noble metal component comprises a noble metal selected from the group consisting of ruthenium (Ru), rhodium (Rh), iridium (Ir), gold (Au), silver (Ag) and a combination of two or more of them. It is preferable that the noble metal component comprises a noble metal selected from the group consisting of gold, silver and a combination thereof. More preferably, the noble metal component comprises, or consists of gold. When the catalyst comprises gold (Au), then a platinum group metal component (PGM), preferably a palladium (Pd) component is present as an alloy with gold (Au) (for example, a palladium-gold alloy). Catalysts comprising gold (Au) can be prepared using the method described in WO 2012/120292 by the present applicant.
[0056] [0056] The oxidation catalyst for use in the invention optionally further comprises a hydrocarbon adsorbent. The hydrocarbon adsorbent can be selected from a zeolite, active carbon, porous graphite and a combination of two or more of them. It is preferred that the hydrocarbon adsorbent is a zeolite. More preferably, the zeolite is a mid-pore zeolite (for example, a zeolite with a maximum ring size of eight tetrahedral atoms) or a large-pore zeolite (for example, a zeolite with a maximum ring size of ten tetrahedral atoms) ). Examples of suitable zeolites or types of zeolite include faujasite, clinoptilolite, mordenite, silicalite, ferrierite, zeolite X, zeolite Y, ultra-stable zeolite Y, zeolite AEI, zeolite ZSM-5, zeolite ZSM-12, zeolite ZSM-20, zeolite ZSM-20 34, CHA zeolite, SSZ-3 zeolite, SAPO5 zeolite, ofretite, a beta zeolite or a copper CHA zeolite. The zeolite is preferably ZSM-5, a beta zeolite or a Y zeolite.
[0057] [0057] Typically, zeolite has a silica to alumina molar ratio of at least 25: 1, preferably at least 25: 1, with usual ranges from 25: 1 to 1,000: 1, 50: 1 to 500: 1 as well as 25 : 1 to 100: 1, 25: 1 to 300: 1, from 100: 1 to 250: 1. Zeolites with a high molar ratio of silica to alumina have better hydrothermal stability.
[0058] [0058] When the catalyst comprises a hydrocarbon adsorbent, then typically the total amount of hydrocarbon adsorbent is 3.06 to 184.05 kg / m3 (0.05 to 3.00 g in-3) particularly 6.13 a 122.7 kg / m3 (0.10 to 2.00 g in-3), more particularly 12.27 to 49.08 kg / m3 (0.2 to 0.8 g in-3).
[0059] [0059] The catalyst for use in the invention optionally further comprises an oxygen storage material. Such materials are well known in the art. The oxygen storage material can be selected from ceria (CeO2) and ceria-zirconia (CeO2-ZrO2), as well as a solid ceria-zirconia solution.
[0060] [0060] Typically, at least one metal component of the platinum group (PGM) is supported on the support material comprising the modified alumina incorporating a heteroatom component. Thus, a platinum component (Pt) or a palladium component (Pd) or both a platinum component (Pt) and a palladium component (Pd) is supported on the support material.
[0061] [0061] In general, the alkaline earth metal component and at least one platinum group metal component (PGM) are supported on the support material comprising the modified alumina incorporating a heteroatom component. Thus, the oxidation catalyst for use in the invention may comprise a palladium (Pd) component and / or a platinum (Pt) component and an alkaline earth metal component supported on the same support material, namely, the support material comprising the modified alumina incorporating a heteroatom component. It is preferred that a palladium component (Pd), a platinum component (Pt) and an alkaline earth metal component are supported on the support material comprising the modified alumina incorporating a heteroatom component.
[0062] [0062] As previously mentioned, the oxidation catalyst may or may not additionally comprise a second support material. The second support material can be selected from the group consisting of alumina, silica, alumina-silica, zirconia, titania, ceria and a mixture of two or more of them. The second support material is preferably selected from the group consisting of alumina, silica, zirconia, titania and a mixture of two or more of them, particularly alumina, silica, titania and a mixture of two or more of the same. More preferably, the second support material comprises, or consists of, alumina.
[0063] [0063] When the oxidation catalyst for use in the present invention comprises a second support material, then preferably at least one platinum group metal (PGM) component is supported on the second support material. A platinum component (Pt), a palladium component (Pd) or both a platinum component (Pt) and a palladium component (Pd) can be supported on the second support material.
[0064] [0064] Additionally, or an alternative to be supported on the support material comprising the modified alumina, the alkaline earth metal component can be supported on the second support material. However, it is preferable that the alkaline earth metal component is only supported on the support material comprising the modified alumina (i.e., the alkaline earth metal component is not supported on the second support material).
[0065] [0065] If the oxidation catalyst for use in the present invention comprises a noble metal component and / or an oxygen storage material, then the noble metal component and / or the oxygen storage material can be supported on the support comprising the modified alumina and / or, if present, the second support material. When the oxidation catalyst for use in the present invention additionally comprises an oxygen storage material and a second support material, then the oxygen storage material and the second support material are different (for example, the oxygen storage material and the second support material are neither ceria nor ceria-zirconia).
[0066] [0066] In general, the platinum group metal component (s) (PGM), the alkaline earth metal component, the support material and any noble metal component, oxygen storage material, hydrocarbon adsorbent and / or second optional storage material are arranged or supported on the substrate.
[0067] [0067] The oxidation catalyst for use in the invention comprises a filter substrate. However, the oxidation catalyst can be comprised of a plurality of substrates in series (at least one being the filter substrate according to the first aspect of the invention (for example, 2, 3 or 4 substrates, at least one being the substrate filter according to the first aspect of the invention)), more preferably two substrates in series (i.e., only two substrates, at least one being the filter substrate according to the first aspect of the invention). When there are two substrates, then a first substrate can be in contact with or separated from a second substrate. When the first substrate is separated from the second substrate, then preferably the distance (for example, the perpendicular distance between faces) between an outlet end (for example, the face at an outlet end) of the first substrate and the input end (for example, example, the face at an inlet end) of the second substrate is 0.5 mm to 50 mm, preferably 1 mm to 40 mm, more preferably 1.5 mm to 30 mm (for example, 1.75 mm to 25 mm ), such as 2 mm to 20 mm (for example, 3 mm to 15 mm), and even more preferably 5 mm to 10 mm.
[0068] [0068] In general, it is preferable that the catalyzed soot filter according to the invention comprises a single filter substrate (i.e., only one filter substrate).
[0069] [0069] Filter substrates to support oxidation catalysts to treat the exhaust gas of a compression ignition engine are well known in the art. In general, the substrate is a ceramic material or a metallic material.
[0070] [0070] It is preferable 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 a stainless steel alloy.
[0071] [0071] Typically, the substrate is a monolith. A filter 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 downstream end (ie, exhaust gas outlet side), the outlet channels are capped or sealed at one upstream end and are opened at one downstream end, and each inlet channel is separated from an exit channel through a porous structure. When the substrate is a filter monolith, then the oxidation catalyst of the invention is typically a catalyzed soot filter (CSF) or is for use as a catalyzed soot filter (CSF).
[0072] [0072] When the monolith is a filter monolith, it is preferable that the filter monolith is a flow filter through the wall. In a through-wall flow filter, each input channel is alternately separated from an outlet channel by a wall of the porous structure and vice versa. It is preferable that the input channel and the output channels have a honeycomb arrangement. When a honeycomb arrangement exists, it is preferable 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 output channel are capped in downstream end). When viewed from either end, the alternately capped and open ends of the channels take on the appearance of a chessboard.
[0073] [0073] In principle, the filter substrate can be of any shape or size. However, the shape and size of the filter substrate are usually selected to optimize the exposure of the catalytically active materials in the catalyst to the exhaust gas. The filter substrate can, for example, have a tubular, fibrous or particulate shape. Examples of suitable support filter substrates include a monolithic honeycomb cordierite filter substrate, a monolithic honeycomb SiC filter substrate, a fiber-like filter substrate or woven cloth in layers, a foam-type filter substrate , a cross-flow filter substrate, a metal wire mesh filter substrate, a porous metal body filter substrate and a ceramic particle filter substrate.
[0074] [0074] In general, the oxidation catalyst for use in the invention comprises a single layer or a plurality of layers (e.g., 2, 3 or 4 layers) disposed on the substrate. Typically, each layer is formed by applying a coating of catalytic material that covers the substrate. However, preferably, the filter substrate is a filter monolith, in particular preferably a filter through-the-wall flow, and the oxidation catalyst for use in the invention comprises a single layer in its inlet channels and a single layer in output channels.
[0075] [0075] The oxidation catalyst for use in the invention may comprise, or consist of, a filter substrate and a single layer disposed on the filter substrate, wherein the single layer comprises a metal component of the platinum group (PGM) selected from the group which consists of a platinum component (Pt), a palladium component (Pd) and a combination thereof; an alkaline earth metal component; and the support material comprising the modified alumina incorporating a heteroatom component. The single layer may further comprise a noble metal component and / or an oxygen storage material and / or a hydrocarbon adsorbent and / or a second storage material. It is preferable that the single layer additionally comprises a hydrocarbon adsorbent and optionally an oxygen storage material.
[0076] [0076] When the oxidation catalyst for use in the present invention comprises, or consists of a filter substrate and a single layer disposed on the filter substrate, then preferably the single layer comprises a platinum component (Pt) and a palladium component (Pd) (ie the metal component of the platinum group (PGM) is a platinum component (Pt) and a palladium component (Pd)). When the single layer comprises a platinum component (Pt) and a palladium component (Pd), then the relative amount of the platinum component (Pt) to the palladium component (Pd) may vary.
[0077] [0077] Typically, the mass ratio of the platinum component (Pt) to the palladium component (Pd) is ≥ 35:65 (for example, ≥ 7:13). It is preferable that the mass ratio of the platinum component (Pt) to the palladium component (Pd) is ≥ 40:60 (for example, ≥ 2: 3), more preferably ≥ 42.5: 57.5 (for example , ≥ 17:23), particularly ≥ 45:55 (for example, ≥ 9:11), such as ≥ 47.5: 52.5 (for example, ≥ 19:21), and even more preferably ≥ 50:50 (for example, ≥ 1: 1). The mass ratio (i.e., mass ratio) of the platinum component (Pt) to the palladium component (Pd) is typically 80:20 to 35:65 (for example, 4: 1 to 7:13). It is preferable that the mass ratio of the platinum component (Pt) to the palladium component (Pd) is 75:25 to 40:60 (for example, 3: 1 to 2: 3), more preferably 70:30 to 42 , 5: 57.5 (e.g. 7: 3 to 17:23), even more preferably 67.5: 32.5 to 45:55 (e.g., 27:13 to 9:11), such as 65: 35 to 47.5: 52.5 (e.g., 13: 7 to 19:21), and even more preferably 60:40 to 50:50 (e.g., 3: 2 to 1: 1). Particularly preferred is a mass ratio of the component Pt to the component Pd from 4: 1 to 1: 1, preferably 2: 1 to 1: 1.
[0078] [0078] It is considered that oxidation catalysts for use in the present invention where the mass of the palladium component (Pd) is less than the mass of the platinum component (Pt) have advantageous activities. Thus, the catalyst of the invention preferably comprises a platinum component (Pt) and a palladium component (Pd) in a mass ratio of 65:35 to 52.5: 47.5 (for example, 13: 7 to 21:19 ), more preferably 60:40 to 55:45 (e.g., 3: 2 to 11: 9).
[0079] [0079] Typically, the mass ratio (i.e. mass ratio) of the alkaline earth metal component to the platinum group metal component (PGM) is 0.25: 1 to 20: 1, It is preferable that the ratio The mass of the alkaline earth metal component for the platinum group metal component (PGM) is 0.5: 1 to 17: 1, more preferably 1: 1 to 15: 1, particularly 1.5: 1 to 10: 1 , even more preferably 2: 1 to 7.5: 1, and even more preferably 2.5: 1 to 5: 1,
[0080] [0080] Alternatively, the oxidation catalyst for use in the present invention can comprise a plurality of layers, such as 2, 3 or 4 layers.
[0081] [0081] When there is a plurality of layers, then the oxidation catalyst can comprise a plurality of substrates (at least one being the filter substrate according to the first aspect of the invention), preferably two substrates (at least one being the substrate filter according to the first aspect of the invention). When there is a plurality of substrates (at least one being the filter substrate according to the first aspect of the invention (for example, two substrates)), then, in one embodiment, a first layer is arranged on a first substrate and a second layer is arranged on a second substrate. Thus, any reference after the first layer being disposed on the substrate can refer to the first layer being disposed on the first substrate. Similarly, any reference following the second layer being disposed on the second substrate can refer to the second layer being disposed on the second substrate.
[0082] [0082] When there is a plurality of substrates (at least one being the filter substrate according to the first aspect of the invention), then the first substrate can be the amount of the second substrate. Alternatively, the second substrate can be the amount of the first substrate.
[0083] [0083] In general, it is preferable that the catalyzed soot filter according to the invention comprises a single filter substrate, particularly when the oxidation catalyst comprises a plurality of layers.
[0084] [0084] When there is a plurality of layers, then in general a first layer is disposed on the filter substrate (for example, the first layer is preferably disposed directly on the substrate, such that the first layer is in contact with a surface of the substrate). The first layer can be arranged in a third layer or a fourth layer. It is preferable that the first layer is disposed directly on the filter substrate.
[0085] [0085] A second layer can be disposed on the filter substrate (for example, to form a zone as described below, which is separated, or partially overlaps the first layer) or the second layer can be disposed on the first layer.
[0086] [0086] When the second layer is placed on the first layer, it can completely or partially overlap (that is, cover) the first layer. If the catalyst comprises a third layer, then the third layer can be arranged in the second layer and / or in the first layer, preferably the third layer is arranged in the first layer. If the catalyst comprises a fourth layer, then the fourth layer can be arranged in the third layer and / or the second layer.
[0087] [0087] When the second layer is disposed on the filter substrate (for example, to form a zone), then the second layer can be disposed directly on the filter substrate (that is, the second layer is in contact with a substrate surface filter) or can be arranged in a third layer or a fourth layer.
[0088] [0088] The first layer can be a zone (for example, a first zone) and / or the second layer can be a zone (for example, a second zone). For the avoidance of doubt, resources described here relating to the “first layer” and “second layer”, especially the composition of the “first layer” and the “second layer”, also concern the “first zone” and “second zone”, respectively .
[0089] [0089] The first layer can be a first zone and the second layer can be a second zone, such as when the first zone and the second zone are side by side on the same filter substrate or the first zone is arranged on a first substrate and a second zone is arranged on a second substrate (i.e., the first substrate and the second substrate are different) and the first substrate and second substrate are side by side. Preferably, the first zone and the second zone are arranged on the same filter substrate.
[0090] [0090] The first zone can be the amount of the second zone. When the first zone is upstream of the second zone, inlet exhaust gas will contact the first zone before the second zone. Alternatively, the second zone can be the amount of the first zone. Similarly, when the second zone is the amount of the first zone, the inlet exhaust gas will come in contact with the second zone before the first zone.
[0091] [0091] When the first zone and the second zone are arranged on the same filter substrate, then the first zone can rest on the second zone or the first zone can be separated from the second zone. If the first zone supports the second zone, then preferably the first zone is in contact with the second zone. When the first zone is separated from the second zone, then there is typically a gap or space between the first zone and the second zone.
[0092] [0092] Typically, the first zone has a length of 10 to 80% of the length of the filter substrate (for example, 10 to 45%), preferably 15 to 75% of the length of the filter substrate (for example, 15 to 40 %), more preferably 20 to 60% (for example, 25 to 45%) of the length of the filter substrate, even more preferably 25 to 50%.
[0093] [0093] The second zone typically has a length of 10 to 80% of the length of the filter substrate (for example, 10 to 45%), preferably 15 to 75% of the length of the filter substrate (for example, 15 to 40% ), more preferably 20 to 60% (for example, 25 to 45%) of the length of the filter substrate, even more preferably 25 to 50%.
[0094] [0094] An oxidation catalyst for use in the present invention comprises two layers (e.g., only two layers), wherein a first layer is arranged on the substrate and a second layer is arranged on the first layer.
[0095] [0095] Typically, the second layer completely or partially overlaps the first layer.
[0096] [0096] The first layer and the second layer can have different lengths, or the first layer and the second layer can be approximately the same length. In general, the length of the first layer and the length of the second layer are each substantially uniform.
[0097] [0097] The first layer typically extends substantially the entire length of the channels in the substrate, particularly when the filter substrate is a monolith.
[0098] [0098] In an oxidation catalyst for use in the present invention comprising a plurality of layers, the second layer can be arranged in a zone of substantially uniform length at one end downstream of the filter substrate. It is preferable that the zone at the downstream end is closer to the outlet end of the filter substrate than the inlet end. Methods of producing layered coatings of different lengths are known in the art (see, for example, WO 99/47260 of the present applicant).
[0099] [0099] When the oxidation catalyst for use in the present invention comprises a plurality of layers, then the platinum group metal component (PGM), the alkaline earth metal component and the support material comprising the modified alumina can be distributed among layers in a variety of ways.
[0100] [00100] In general, the first layer (or first zone) comprises a metal component from the platinum group (PGM) selected from the group consisting of a platinum component (Pt), a palladium component (Pd) and a combination of same, and the second layer (or second zone) comprises a metal component of the platinum group (PGM) selected from the group consisting of a platinum component (Pt), a palladium component (Pd) and a combination thereof. It is preferable that the first layer / zone is different (for example, in composition) from the second layer / zone. For example, the first and second layers / zones may comprise different metal components of the platinum group (PGM) and / or the first and second layers / zones may comprise a different total amount of the metal component of the platinum group (PGM).
[0101] [00101] In a first embodiment, the first layer (or first zone) comprises a PGM component selected from the group consisting of a Pd component and a combination (ie, both) of a Pd component and a Pt component , and the second layer (or second zone) comprises a PGM component consisting of a Pt component. This means that the first layer / zone comprises a Pd component and optionally a Pt component as the only PGM component and the second layer / zone comprises a Pt component as the only PGM component. Preferably, the first layer / zone comprises a PGM component consisting of a combination of (i.e., both) a Pd component and a Pt component. Thus, it is preferable that the first layer / zone comprises both a Pt and a component a Pd component as the only PGM component, and the second layer / zone comprises a Pt component as the only PGM component.
[0102] [00102] Typically, in the first embodiment, the first layer (or first zone) additionally comprises the alkaline earth metal component and the support material comprising a modified alumina incorporating a heteroatom component, and / or the second layer (or second zone) ) further comprises the alkaline earth metal component and the support material comprising a modified alumina incorporating a heteroatom component. It is preferable that the first layer / zone further comprises the alkaline earth metal component and the support material comprising a modified alumina incorporating a heteroatom component.
[0103] [00103] When the first layer / zone comprises a Pd component as the only PGM component, then the first layer / zone can comprise a second support material. Preferably, the second support material is ceria, ceria-zirconia, alumina or silica-alumina. The second support material can be clear. The second support material can be ceria-zirconia. The second support material can be alumina. The second support material can be silica-alumina. More preferably, the first layer / zone comprises a PGM component selected from the group consisting of a Pd component, and a second support material, wherein the second support material is ceria.
[0104] [00104] In a second embodiment, the first layer (or first zone) comprises a PGM component selected from the group consisting of a Pt component and a combination of (ie, both) a Pd component and a Pt component , and the second layer (or second zone) comprises a PGM component consisting of a Pd component. This means that the first layer / zone comprises a Pt component and optionally a Pd component as the only PGM component and the second layer / zone comprises a Pd component as the only PGM component. Preferably, the first layer / zone comprises a PGM component consisting of a combination of (i.e., both) a Pd component and a Pt component. Thus, it is preferable that the first layer / zone comprises both a Pt and a component a Pd component as the only PGM component, and the second layer / zone comprises a Pd component as the only PGM component. Typically, the amount of the Pt component in the first layer / zone is greater than the amount of the Pd component in the first layer / zone (the amount being measured in g ft-3 or as a molar amount).
[0105] [00105] In the second embodiment, the first layer (or first zone) can additionally comprise the alkaline earth metal component and the support material comprising a modified alumina incorporating a heteroatom component, and / or the second layer (or second zone) it may further comprise the alkaline earth metal component and the support material comprising a modified alumina incorporating a heteroatom component. It is preferable that the first layer / zone further comprises the alkaline earth metal component and the support material comprises a modified alumina incorporating a heteroatom component.
[0106] [00106] In the second embodiment, the second layer / zone typically comprises a second support material. Preferably the second support material is ceria, ceria-zirconia, alumina or silica-alumina. The second support material can be clear. The second support material can be ceria-zirconia. The second support material can be alumina. The second support material can be silica-alumina.
[0107] [00107] In a third embodiment, the first layer (or first zone) comprises a PGM component selected from the group consisting of a Pt component and a Pd component, and the second layer (or second zone) comprises a component of PGM consisting of a combination of (i.e., both) a Pd component and a Pt component. This means that the first layer / zone comprises a Pt component or a Pd component as the only PGM component, and the second layer / zone comprises a Pt component and a Pd component as the only PGM component. Preferably, the first layer / zone comprises a PGM component consisting of a Pt component. Thus, it is preferred that the first layer / zone comprises a Pt component as the only PGM component, and the second layer / zone comprising a component Pt and a Pd component as the only PGM component.
[0108] [00108] In the third embodiment, when the first layer / zone comprises a Pt component as the only PGM component, then typically the mass ratio of the Pt component in the second layer / zone to the Pd component in the second layer / zone is ≤2: 1, preferably <2: 1. When the first layer / zone comprises a Pd component as the only PGM component, then typically the amount of the Pd component in the second layer / zone is less than the amount of the Pt component in the second layer / zone (the amount being measured in g / m3 (g ft-3) or is a molar amount).
[0109] [00109] Typically, in the third embodiment, the first layer (or first zone) additionally comprises the alkaline earth metal component and the support material comprising a modified alumina incorporating a heteroatom component, and / or the second layer (or second zone) ) further comprises the alkaline earth metal component and the support material comprising a modified alumina incorporating a heteroatom component. When the first layer / zone comprises a Pt component as the only PGM component, then it is preferable that the first layer / zone additionally comprises the alkaline earth metal component and the support material comprising a modified alumina incorporating a heteroatom component. When the first layer / zone comprises a Pd component as the only PGM component, then it is preferable that the second layer / zone additionally comprises the alkaline earth metal component and the support material comprising a modified alumina incorporating a heteroatom component.
[0110] [00110] In the third embodiment, when the first layer / zone comprises a Pd component as the only PGM component, then the first layer / zone can comprise a second support material. Preferably, the second support material is ceria, ceria-zirconia, alumina or silica-alumina. The second support material can be clear. The second support material can be ceria-zirconia. The second support material can be alumina. The second support material can be silicaalumin.
[0111] [00111] In a fourth embodiment, the first layer (or first zone) comprises a PGM component consisting of a combination (ie, both) of a Pt component and a Pd component, and the second layer (or second zone) ) comprises a PGM component consisting of a combination of (i.e., both) a Pd component and a Pt component. This means that the first layer / zone comprises a Pt component and a Pd component as the only PGM component , and the second layer / zone comprises a Pt component or a Pd component as the only PGM component. In the fourth embodiment, the first layer / zone and second layer / zone typically comprise a different mass ratio of the Pt component to the Pd component. Thus, the mass ratio of the Pt component to the Pd component in the first layer / zone is different from the mass ratio of the Pt component to the Pd component in the second / zone layer.
[0112] [00112] In the fourth modality, when the amount of the Pd component in the first layer / zone is less than the amount of the Pt component in the first layer / zone (the amount being measured in g / m3 (gft-3) or is a molar amount), then preferably the amount of the Pd component in the second layer / zone is greater than the amount of the Pt component in the second layer / zone. Alternatively, when the amount of the Pd component in the first layer / zone is greater than the amount of the Pt component in the first layer / zone (the amount being measured in g / m3 (gft-3) or is a molar amount), then preferably the amount of the Pd component in the second layer / zone is less than the amount of the Pt component in the second layer / zone.
[0113] [00113] In general, the mass ratio of the platinum component (Pt) to the palladium component (Pd), particularly in the first layer / zone of the first or second modalities, the second layer / zone of the third modality, or the first layer / zone and / or second layer / zone of the fourth modality, preferably the second layer / zone of the fourth modality, is ≥ 35:65 (for example, ≥ 7:13). It is preferable that the mass ratio of the platinum component (Pt) to the palladium component (Pd) is ≥ 40:60 (for example, ≥ 2: 3), more preferably ≥ 42.5: 57.5 (for example , ≥ 17:23), particularly ≥ 45:55 (for example, ≥ 9:11), such as ≥ 47.5: 52.5 (for example, ≥ 19:21), and even more preferably ≥ 50:50 (for example, ≥ 1: 1).
[0114] [00114] It is preferable that the mass ratio of the platinum component (Pt) to the palladium component (Pd), particularly in the first layer / zone of the first or second modalities, the second layer / zone of the third modality, or the first layer / zone and / or second layer / zone of the fourth modality, preferably the second layer / zone of the fourth modality, is 80:20 to 35:65 (for example, 4: 1 to 7:13), particularly 75:25 to 40:60 (e.g., 3: 1 to 2: 3), more preferably 70:30 to 42.5: 57.5 (e.g., 7: 3 to 17:23), even more preferably 67.5: 32 , 5 to 45:55 (e.g., 27:13 to 9:11), such as 65:35 to 47.5: 52.5 (e.g., 13: 7 to 19:21), and even more preferably 60 : 40 to 50:50 (e.g., 3: 2 to 1: 1). For the second layer of the third embodiment, it is particularly preferable that the mass ratio of the platinum component (Pt) to the palladium component (Pd) is 2: 1 to 7:13, particularly 13: 7 to 2: 3, more preferably 60:40 to 50:50 (e.g., 3: 2 to 1: 1).
[0115] [00115] It is considered that oxidation catalysts for use in the present invention where the mass of the palladium component (Pd) is less than the mass of the platinum component (Pt) have advantageous activity, especially when both a platinum component (Pt) ), a palladium component (Pd) and an alkaline earth metal component are present in the same layer / zone. Thus, in the first layer / zone of the first modality, the first layer / zone of the second modality, the second layer / zone of the third modality, or the first layer / zone and / or second layer / zone of the fourth modality, preferably the second layer / zone of the fourth embodiment, the oxidation catalyst of the invention preferably comprises a platinum component (Pt) and a palladium component (Pd) in a mass ratio of 65:35 to 52.5: 47.5 (for example, 13 : 7 to 21:19), more preferably 60:40 to 55:45 (e.g., 3: 2 to 11: 9).
[0116] [00116] In a fifth embodiment, the first layer (or first zone) comprises a PGM component selected from the group consisting of a Pt component and a Pd component, and the second layer (or second zone) comprises a component PGM selected from the group consisting of a Pd component and a Pt component, in which the first and second layer / zone each comprise the same PGM component. This means that the first layer / zone and the second layer / zone each comprise a Pt component or a Pd component as the only PGM component. Typically, the total amount of PGM component in the first layer / zone is different from the total amount of PGM component in the second layer / zone.
[0117] [00117] When both the first layer / zone and the second layer / zone each comprise a Pd component as the only PGM component, then preferably the first layer / zone comprises a second support material and / or the second layer / The zone comprises a second support material. It is preferable that the second support material is ceria, ceria-zirconia, alumina or silica-alumina. The second support material can be clear. The second support material can be ceria-zirconia. The second support material can be alumina. The second support material can be silica-alumina.
[0118] [00118] In the first to fifth embodiment, the first layer / zone can comprise an alkaline earth metal component and / or the second layer / zone can comprise an alkaline earth metal component. When the first layer / zone comprises the alkaline earth metal component, the second layer / zone cannot comprise an alkaline earth metal component. Alternatively, when the second layer / zone comprises the alkaline earth metal component, the first layer / zone cannot comprise an alkaline earth metal component.
[0119] [00119] In the first to fifth embodiment, the first layer / zone can comprise the support material comprising the modified alumina, and / or the second layer / zone can comprise the support material comprising the modified alumina. Typically, it is preferable that a layer or zone comprising a platinum (Pt) component also comprises the support material comprising the modified alumina.
[0120] [00120] In the first to fifth embodiment, the first layer / zone can comprise a second support material and / or the second layer / zone can comprise a second support material. The first layer / zone and the second layer / zone can comprise different support materials. It is preferred that the second support material and the support material comprising the modified alumina are in different layers / zones.
[0121] [00121] In general, the alkaline earth metal component and the support material comprising the modified alumina are present in at least one of the same layers / zones.
[0122] [00122] When the first layer / zone comprises the alkaline earth metal component, then typically the ratio of the mass of the alkaline earth metal component to the mass of the metal component of the platinum group (PGM) in the first layer is 0.25: 1 to 20: 1, preferably 0.5: 1 to 17: 1, more preferably 1: 1 to 15: 1, particularly 1.5: 1 to 10: 1, even more preferably 2: 1 to 7.5: 1 , and even more preferably 2.5: 1 to 5: 1,
[0123] [00123] When the second layer / zone comprises the alkaline earth metal component, then typically the ratio of the mass of the alkaline earth metal component to the mass of the platinum group metal component (PGM) in the second layer is 0.25: 1 to 20: 1, preferably 0.5: 1 to 17: 1, more preferably 1: 1 to 15: 1, particularly 1.5: 1 to 10: 1, even more preferably 2: 1 to 7.5: 1 , and even more preferably 2.5: 1 to 5: 1,
[0124] [00124] In the first to fifth modality, the first layer / zone can optionally further comprise a noble metal component and / or an oxygen storage material and / or a hydrocarbon adsorbent. Preferably, the first layer / zone further comprises a hydrocarbon adsorbent.
[0125] [00125] In the first to fifth embodiments, the second layer / zone can optionally additionally comprise a noble metal component and / or an oxygen storage material and / or a hydrocarbon adsorbent. Preferably, the second layer / zone further comprises a hydrocarbon adsorbent.
[0126] [00126] In an arrangement of the first embodiment, the first layer / zone typically comprises a Pd component, a Pt component, an alkaline earth metal component and the support material comprising the modified alumina; and the second layer / zone comprises a Pt component and either the second support material or a support material comprising the modified alumina, and optionally an alkaline earth metal component. When the second layer / zone comprises a second support material, then preferably the second support material is alumina.
[0127] [00127] In an arrangement of the fourth embodiment, the first layer / zone comprises a Pt component, a Pd component, an alkaline earth metal component and the support material comprising the modified alumina; and the second layer / zone comprises a Pt component, a Pd component and both a second support material and a support material comprising the modified alumina, and optionally an alkaline earth metal component. It is preferable that the mass ratio of the Pt component in the second layer / zone to the Pd component in the second layer is ≤10: 1 (eg 10: 1 to 1: 2), more preferably ≤15: 2 (eg example, 7.5: 1 to 1: 1.5), and even more preferably ≤5: 1 (for example, 5: 1 to 1.5: 1). When the second layer / zone comprises a second support material, then preferably the second support material is alumina.
[0128] [00128] When the first layer is a first zone and the second layer is a second zone, then (a) in the first and third mode, it is preferable that the first layer / zone is upstream of the second layer / zone, (b) in the second embodiment, it is preferable that the second layer / zone is upstream of the first layer / zone, and (c) in the fifth embodiment, it is preferable that the layer / zone comprising the second support material is upstream of the layer / zone comprising the support material comprising the modified alumina.
[0129] [00129] In modalities where there is a second support material, especially when the second support material is both ceria and ceria-zirconia, then it may be advantageous to arrange the layer or zone comprising the second support material to come into contact with the gas of escape after the other layer or zone. Thus, when there is a second support material, especially when the second support material is ceria or ceria-zirconia, it is preferable that (a) in the first and third modality it is preferable that the first layer / zone is downstream of the second layer / zone, (b) in the second mode, it is preferable that the second layer / zone is downstream of the first layer / zone, and (c) in the fifth mode, it is preferable that the layer / zone comprising the second support material is downstream of the layer / zone comprising the support material comprising the modified alumina.
[0130] [00130] In general, the oxidation catalyst of the invention may or may not comprise rhodium. It is preferable that the oxidation catalyst does not comprise ruthenium, rhodium and iridium.
[0131] [00131] Another general feature of the oxidation catalyst for use in the invention is that, when any cerium or ceria is present, then typically only the heteroatom component of the support material comprises cerium or ceria. It is further preferable that the oxidation catalyst of the invention does not comprise ceria, particularly as a support material or as an oxygen storage material.
[0132] [00132] An additional general feature of the oxidation catalyst of the invention is that, when an alkali metal, particularly sodium or potassium, and especially potassium, is present, then preferably only the hydrocarbon adsorbent comprises alkali metal, especially when the hydrocarbon adsorbent it is a zeolite. It is further preferable that the oxidation catalyst for use in the invention does not comprise an alkali metal, particularly sodium or potassium.
[0133] [00133] Another general feature of the invention is that the oxidation catalyst for use in the invention does not comprise an NOx absorbent composition. Thus, it is preferred that the oxidation catalyst of the invention is not an NOx absorbent catalyst (also known as a NOx trap) or not for use as an absorbent NOx catalyst.
[0134] [00134] The first aspect of the invention relates to a catalyzed soot filter comprising an oxidation catalyst in the manner defined herein. The second aspect of the invention relates to an exhaust system for a compression ignition engine, such as a diesel engine, whose system comprises catalyzed soot filter as defined herein. The fifth aspect of the invention relates to the use of the catalyzed soot filter. The advantageous activity of the oxidation catalyst for use in the invention, particularly its low CO “operating” temperature make it particularly suitable for use in combination with certain other emission control devices.
[0135] [00135] The second aspect of the invention relates to an exhaust system comprising a catalyzed soot filter according to the invention. Typically, the exhaust system according to the invention may additionally comprise at least one emission control device, or the catalyzed soot filter is for use in combination with it, preferably disposed in a separate substrate monolith located both upstream downstream of the CSF according to the invention. The emission control device can be selected from a diesel particulate filter (DPF) (ie, a non-catalyzed filter, which can be a bare filter or a filter with a catalytic material coating with a non-catalytic catalytic material coating, alumina or as described below), a NOx absorbent catalyst (NAC), a poor NOx catalyst (LNC), a selective catalytic reduction catalyst (SCR), a diesel oxidation catalyst (DOC), a catalyzed soot filter (CSF), a catalyzed filter with a selective catalytic reduction catalyst, a residual ammonia catalyst (ASC) and combinations of two or more of them. Emission control devices represented by the terms diesel particulate filters (DPFs), NOx absorbent catalysts (NACs), poor NOx catalysts (LNCs), selective catalytic reduction catalysts (SCR), diesel oxidation catalysts (DOCs), catalyzed soot filters (CSFs) and filters catalyzed with a selective catalytic reduction catalyst are all well known in the art.
[0136] [00136] A highly preferred exhaust system according to the present invention comprises a diesel oxidation catalyst (DOC) disposed in a separate through-flow substrate monolith, which is disposed upstream of the catalyzed soot filter. The diesel oxidation catalyst formulation can be an oxidation catalyst described here, that is, a metal component of the platinum group (PGM) selected from the group consisting of a platinum component (Pt), a palladium component (Pd ) and a combination thereof; an alkaline earth metal component; a support material comprising a modified alumina incorporating a heteroatom component. However, it is preferred to use a DOC composition that is active for NO oxidation, thereby producing NO2 for passive combustion of particulate matter trapped in the downstream CSF device, according to the effect of the well-known CRT® technology, that is, NO2 + C → CO + NO. Therefore, in order to promote NO oxidation, low alkaline earth loads are preferred, or, in one embodiment, the upstream DOC does not contain substantially any alkaline earth metal. Such a "no alkaline earth metal" DOC may otherwise have a composition described for the oxidation catalyst here.
[0137] [00137] A flow-through monolith typically comprises a honeycomb-like monolith (for example, a metallic or ceramic honeycomb-like monolith) with a plurality of channels extending through it, whose channels are open at both ends. When the substrate is a through-flow monolith, then the oxidation catalyst of the invention is typically a diesel oxidation catalyst (DOC) or is for use as a diesel oxidation catalyst (DOC).
[0138] [00138] Examples of emission control devices for use with the catalytic soot filter according to the invention or for inclusion in the exhaust system of the invention are provided below.
[0139] [00139] The catalyst formulation of the diesel particulate filter may be an NOx absorbent composition. When the catalyst formulation is an NOx absorbent composition, the emission control device is an example of an NOx absorbent catalyst (NAC) . Emission control devices where the catalyst formulation is an NOx absorbent composition have been described (see, for example, EP 0766993). NOx absorbent compositions are well known in the art (see, for example, EP 0766993 and US 5,473,887). Absorbent NOx compositions are designed to adsorb NOx from poor exhaust gas (lambda> 1) and desorb NOx when the oxygen concentration in the exhaust gas is decreased. Desorbed NOx can then be reduced to N2 with a suitable reducing agent (eg motor fuel) and promoted by a catalyst component, such as rhodium, from the NOx absorbent composition itself or located downstream of the NOx absorbent composition.
[0140] [00140] Modern NOx absorber catalysts coated on through-flow honeycomb monolith substrates are typically arranged in layers. However, multiple layers applied to a filter substrate can create back pressure problems. It is highly preferable, therefore, that the NOx absorption catalyst for use in the present invention is a "single layer" NOx absorption catalyst. Particularly preferred "single layer" NOx absorber catalysts comprise a first rhodium component supported on a mixed cerium-zirconia oxide or an optionally stabilized alumina (for example, stabilized with silica or lanthan or another rare earth element) in combination with second components that support platinum and / or palladium. The second components comprise platinum and / or palladium supported on a high surface area support based on alumina and a “bulky” particulate ceria (CeO2) component, that is, not a soluble ceria supported on a particulate support, but ceria "Bulky" capable of supporting Pt and / or Pd as such. The particulate ceria comprises an absorbent NOx component and supports an alkaline earth metal and / or an alkali metal, preferably barium, in addition to platinum and / or palladium. The high surface area support based on alumina can be magnesium aluminate, for example, MgAl2O4, for example.
[0141] [00141] The preferred "single layer" NAC composition comprises a mixture of the components of the rhodium and platinum and / or palladium support. These components can be prepared separately, that is, preformed before combining them into a mixture, or rhodium, platinum and palladium salts and the supports and other components can be combined and the rhodium, platinum and hydrolyzed palladium components preferably for deposition in the desired support.
[0142] [00142] In general, an NOx absorbent composition comprises an alkali metal component, an alkaline earth metal component or a rare earth metal component or a combination of two or more components thereof, wherein the rare earth metal component comprises lanthanum or yttrium. It is preferable that the alkali metal component comprises potassium or sodium, more preferably potassium. It is preferable that the alkaline earth metal component comprises barium or strontium, more preferably barium.
[0143] The NOx absorbent composition may additionally comprise a support material and / or a catalytic metal component. The support material can be selected from alumina, ceria, titania, zirconia and mixtures thereof. The catalytic metal component may comprise a metal selected from platinum (Pt), palladium (Pd), rhodium (Rh) and combinations of two or more of the same.
[0144] [00144] Poor NOx catalysts (LNCs) are well known in the art. Preferred NOx poor (LNC) catalysts comprise either (a) platinum (Pt) supported on alumina or (b) a copper-exchanged zeolite, particularly copper-exchanged ZSM-5.
[0145] [00145] SCR catalysts are also well known in the art. Preferably, a substrate monolith comprising the SCR catalyst or filter comprising the SCR catalyst is disposed downstream of the CSF according to the invention (or, in the preferred embodiment, the combination of DOC + CSF). When the exhaust system of the invention comprises an SCR catalyst, then the exhaust system can additionally comprise an injector for injecting a nitrogen reducing agent, such as ammonia or an ammonia precursor such as urea or ammonium formate, preferably urea, in gas exhaust downstream of the catalyst to oxidize carbon monoxide (CO) and hydrocarbons (HCs) and SCR upstream of the catalyst. Such injector is fluidly connected to a source of such a precursor of the nitrogen reducing agent, for example, a tank thereof, and the dosage controlled by the precursor valve in the exhaust stream is regulated by a properly programmed control motor device and closed loop feedback. or open circuit provided by sensors that monitor the composition of the relevant exhaust gas. Ammonia can also be generated by heating ammonium carbamate (a solid) and the generated ammonia can be injected into the exhaust gas.
[0146] [00146] Alternatively, or in addition to the injector, ammonia can be generated in situ, for example, during rich regeneration of a filter-mounted NAC or by placing a filter-mounted DOC in contact with rich exhaust gas derived from the engine (see the alternatives for reactions (4) and (5) below).
[0147] [00147] SCR catalysts for use in the present invention selectively promote reactions 4NH3 + 4NO + O2 → 4N2 + 6H2O (i.e., 1: 1 NH3: NO); 4NH3 + 2NO + 2NO2 → 4N2 + 6H2O (that is, 1: 1 NH3: NOx; and 8NH3 + 6NO2 → 7N2 + 12H2O (that is, 4: 3 NH3: NOx) in preference to unwanted non-selective side reactions, such as 2NH3 + 2NO2 → N2O + 3H2O + N2
[0148] [00148] The SCR catalyst can comprise a metal selected from the group consisting of at least one from Cu, Hf, La, Au, In, V, lanthanides and transition metals from group VIII, such as Fe, whose metal is supported in a refractory oxide or molecular sieve. Particularly preferred metals are Ce, Fe and Cu and combinations of any two or more of them.
[0149] [00149] Refractory oxide can be selected from the group consisting of Al2O3, TiO2, CeO2, SiO2, ZrO2 and mixed oxides containing two or more of them. The non-zeolite catalyst may also include tungsten oxide, for example, V2O5 / WO3 / TiO2, WOx / CeZrO2, WOx / ZrO2 or Fe / WOx / ZrO2
[0150] [00150] It is particularly preferred when an SCR catalyst or coating of catalytic material 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, for example. "Small pore molecular sieve" here means molecular sieves containing a maximum ring size of 8, such as CHA; "Medium pore molecular sieve" here means 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 - see, for example, WO 2008/132452,
[0151] [00151] Preferred molecular sieves with application as SCR catalysts in the present invention are synthetic aluminosilicate zeolite molecular sieves selected from the group consisting of AEI, ZSM-5, ZSM-20, ERI including ZSM-34, mordenite, ferrierite, 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 ,
[0152] [00152] In its most basic form, a residual ammonia catalyst (ASC) can be an oxidation catalyst to oxidize ammonia that passes in addition to an upstream SCR or unreacted catalyzed SCR filter. The desired (simplified) reaction can be represented by 4NO + 4NH3 + O2 → 4 N2 + 6H2O. Ammonia is a strong-smelling and potentially irritating compound for animal mucous surfaces, for example, eyes and airways, and therefore its emission into the atmosphere should be limited as much as possible. Possible ammonia catalyst residues include relatively low charged metals of the platinum group, preferably including Pt, for example, 1-15 g / ft3, on a suitable relatively high surface area oxide support, for example, alumina coated on a monolith. suitable substrate.
[0153] [00153] In a particularly preferred arrangement, however, the platinum group metal and the support material (for example, comprising a modified alumina incorporating a heteroatom component) is disposed on a substrate (i.e. substrate monolith) in a first layer below a second top layer overlying the first layer. The second layer is an SCR catalyst, selected from any of those mentioned here, particularly molecular sieves containing transition metals, such as Cu or Fe. A particularly preferred ASC in the layered arrangement comprises CuCHA in the second layer, or upper layer.
[0154] [00154] In a first embodiment of the exhaust system, the exhaust system comprises the soot filter catalyzed according to the invention with a substrate monolith arranged upstream comprising a DOC. Such an arrangement can be called a DOC / 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.
[0155] [00155] The first mode of the exhaust system may additionally comprise a poor NOx catalyst (LNC). Thus, the modality additionally refers to the use of the oxidation catalyst to treat an exhaust gas from a compression ignition engine in combination with a NOx absorbent catalyst (NAC) and the catalyzed soot filter (CSF) according to the invention. Typically, a DOC is followed (for example, upstream) by the NOx absorbent catalyst (NAC), and the NOx absorbent catalyst (NAC) is followed (for example, upstream) by the catalyzed soot filter (CSF) according to the invention. In general, DOC, the NOx absorbent catalyst (NAC) and the catalyzed soot filter (CSF) are connected in series. Thus, for example, an output of the DOC is connected to an input of the NOx absorbent catalyst (NAC), and an output of the NOx absorbent catalyst is connected to an input of the catalyzed soot filter (CSF) according to the invention. Such an arrangement can be called a DOC / NAC / CSF.
[0156] [00156] In a second embodiment of the exhaust system, the exhaust system comprises a diesel oxidation catalyst and the catalytic soot filter (CSF) of the invention. This arrangement can also be called a DOC / CSF arrangement. The embodiment additionally relates to the use of the catalyzed soot filter according to the invention to treat an exhaust gas from a compression ignition engine in combination with a diesel oxidation catalyst (DOC). Typically, the diesel oxidation catalyst (DOC) is followed (for example, upstream) by the catalyzed soot filter according to the invention. Thus, an output of the diesel oxidation catalyst is connected to an inlet of the catalyzed soot filter of the invention.
[0157] [00157] A third embodiment of the exhaust system refers to an exhaust system comprising a DOC, a catalytic soot filter (CSF) according to the invention and a selective catalytic reduction catalyst (SCR). Such an arrangement can be called a DOC / CSF / SCR and can be for use in a heavy duty diesel vehicle or a light duty diesel vehicle, preferably an exhaust system for a light duty diesel vehicle. This modality also refers to the use of the catalyzed soot filter of the invention to treat an exhaust gas from a compression ignition engine in combination with a diesel oxidation catalyst (DOC) and a selective catalytic reduction catalyst (SCR) . The diesel oxidation catalyst (DOC) 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 nitrogenous reducing agent injector can be followed (for example, upstream) by the nitrogen catalyst. selective catalytic reduction (SCR).
[0158] [00158] A fourth embodiment of the exhaust system refers to an exhaust system comprising a NOx absorbent catalyst (NAC), the catalytic soot filter of the invention and a selective catalytic reduction catalyst (SCR). This is also a NAC / CSF / SCR arrangement. An additional aspect of this modality concerns the use of the catalyzed soot filter to treat an exhaust gas from a compression ignition engine in combination with a NOx absorbent catalyst (NAC) and a selective catalytic reduction catalyst (SCR). The NOx absorbent catalyst (NAC) is typically followed (for example, upstream) by the catalyzed soot filter of the invention. The inventive catalytic 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 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). Alternatively, or in addition to the nitrogen reducing agent injector, ammonia can be generated in situ, for example, during rich regeneration of a NAC willing to filter upstream.
[0159] [00159] In a fifth embodiment of the exhaust system, the exhaust system comprises the oxidation catalyst of the invention, preferably as a DOC, a selective catalytic reduction catalyst (SCR) and both a catalytic soot filter (CSF) and a diesel particulate filter (DPF). The arrangement is both a DOC / SCR / CSF and a DOC / SCR / DPF. This modality also refers to the use of the oxidation catalyst to treat an exhaust gas from a compression ignition engine in combination with a selective catalytic reduction catalyst (SCR) and both a catalytic soot filter (CSF) and a filter diesel particulate (DPF), preferably wherein the oxidation catalyst is a diesel oxidation catalyst or is for use as such.
[0160] [00160] In the fifth embodiment of the exhaust system, the catalytic soot filter 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 catalyzed soot filter of the invention 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 reduction catalyst selective catalytic (SCR). The selective catalytic reduction (SCR) catalyst is followed (for example, upstream) by the catalytic soot filter (CSF) of the invention.
[0161] [00161] A sixth embodiment of the exhaust system comprises the catalytic soot filter of the invention and a filter comprising a selective catalytic reduction catalyst. Such an arrangement can be called a CSF / SCR filter. This modality also refers to the use of the catalyzed soot filter to treat an exhaust gas from a compression ignition engine in combination with a selective catalytic reduction catalyst of the filter. The catalytic soot filter of the invention is typically followed (for example, upstream) by the filter selective catalytic reduction catalyst. A nitrogen reducing agent injector can be arranged between the catalytic soot filter of the invention and the selective catalytic reduction catalyst of the filter. Thus, the catalyzed soot filter of the invention 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 reduction catalyst selective catalytic filter.
[0162] [00162] In a seventh embodiment of the exhaust system, the exhaust system comprises a NOx absorbent catalyst (NAC) and the catalytic soot filter (CSF) of the invention. This arrangement can also be called a NAC / CSF arrangement. The modality additionally refers to the use of the catalyzed soot filter to treat an exhaust gas from a compression ignition engine in combination with a NOx absorbent catalyst (NAC). Typically, the catalyzed soot filter (CSF) is downstream from the NOx absorbent catalyst (NAC). Thus, an outlet of the NOx absorbent catalyst (NAC) is connected to an inlet of the invention's catalyzed soot filter.
[0163] [00163] The seventh mode of the exhaust system can additionally comprise a selective catalytic reduction (SCR) catalyst. Thus, the modality additionally refers to the use of the catalyzed soot filter to treat an exhaust gas from a compression ignition engine in combination with a NOx absorbent catalyst (NAC) and a selective catalytic reduction catalyst (SCR). Typically, the NOx absorbent catalyst (NAC) is followed (for example, upstream) by the catalyzed soot filter of the invention, and the catalyzed soot filter of the invention is followed (for example, upstream) by the reduction catalyst selective catalytic (SCR). Such an arrangement can be called a NAC / CSF / SCR. A nitrogen reducing agent injector can be arranged between the catalyzed soot filter and the selective catalytic reduction (SCR) catalyst. Thus, the catalyzed soot filter 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 selective catalytic reduction catalyst (SCR). Alternatively, or in addition to the nitrogen reducing agent injector, ammonia can be generated in situ, for example, during rich regeneration of a NAC willing to filter upstream.
[0164] [00164] In the seventh mode of the exhaust system with an SCR catalyst, the NOx absorbent catalyst (NAC), the catalyzed soot filter and the selective catalytic reduction catalyst (SCR) are generally connected in series with an agent injector optional nitrogen reducer being connected between the oxidation catalyst and the selective catalytic reduction (SCR) catalyst. Thus, for example, an outlet of the NOx absorbent catalyst (NAC) is connected to an inlet of the catalyzed soot filter, and the outlet of the catalyzed soot filter is connected to an inlet of the selective catalytic reduction catalyst (SCR).
[0165] [00165] In any of the first to seventh embodiments including the exhaust systems described herein containing an SCR catalyst (including catalyzed SCR filters), an ASC catalyst can be arranged downstream of the SCR catalyst or catalyzed SCR filter (for example, as a monolith) separate substrate), or, more preferably, a zone at a downstream end or trailing end of the substrate monolith comprising the SCR catalyst can be used as a support for the ASC.
[0166] [00166] A third aspect of the invention relates to a compression ignition engine comprising an exhaust system according to the second aspect of the invention. The compression ignition engine can be a homogeneous charge compression ignition engine (HCCI) or a pre-mixed charge compression ignition engine (PCCI) (see DieselNet Technology Guide “Motor Design for Low Emissions”, revision 2010 , 12a), or more compression ignition engines of the fuel injected type through conventional orifices.
[0167] [00167] A fourth aspect of the invention relates to a vehicle comprising a compression ignition engine and the exhaust system for the compression ignition engine. In general, the compression ignition engine is a diesel engine.
[0168] [00168] The vehicle may be a heavy duty diesel vehicle (LDV), as defined in United States or Europe legislation. A light-duty diesel vehicle typically has a weight of <2,840 kg, more preferably a weight of <2,610 kg.
[0169] [00169] In the United States, a light duty diesel vehicle (LDV) refers to a diesel vehicle with a gross weight of ≤ 8,500 pounds (lbs US). 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 freight car with a maximum mass not exceeding 12 tonnes.
[0170] [00170] Alternatively, the vehicle may be a heavy duty diesel vehicle (HDV), such as a diesel vehicle with a gross weight of> 8,500 pounds (lbs US), as defined by United States law.
[0171] [00171] A fifth aspect refers to the use of a catalyzed soot filter according to the first aspect of the invention to oxidize carbon monoxide (CO) and hydrocarbons (HCs) and to reduce NO2 emissions in an exhaust gas from one compression ignition engine; and the sixth aspect of the invention relates to a method of treating an exhaust gas from a compression ignition engine, the method of which comprises putting the exhaust gas in contact with the catalyzed soot filter according to the first aspect of the invention. .
[0172] [00172] Typically, the use and the corresponding method involves placing the exhaust gas directly from the compression ignition engine in contact with the catalyzed soot filter. Thus, it is preferable that additional hydrocarbon (HC) in general is not injected into the exhaust gas before putting the exhaust gas in contact with the oxidation catalyst. The amount of hydrocarbon in the exhaust gas is preferably less than 1,000 ppm by volume, converted to methane, more preferably less than 950 ppm by volume, even more preferably less than 750 ppm, typically before putting the exhaust gas in contact with the oxidation catalyst. DEFINITIONS
[0173] [00173] For the avoidance of doubt, the expression “modified alumina incorporating a heteroatom component” does not cover “pure” alumina (ie alumina with a purity of ≥ 99.9%), a mixture of alumina and the heteroatom component, such as a mixture of silica and alumina, or a zeolite. In the context of “modified alumina incorporating a heteroatom component”, any amount in% by weight refers to the amount of heteroatom component, whether an element, ion or a compound, which is present in the alumina host lattice, with the remainder consisting essentially of alumina.
[0174] [00174] The term "alumina doped with a heteroatom component" in general refers to a material comprising an alumina host lattice that is doped by substitution or interstitially doped with a heteroatom component. In some cases, small amounts of the heteroatom component may be present (that is, as a dopant) on an alumina surface. However, most of the dopant in general will be present in the body of the alumina host lattice. Alumina doped with a heteroatom component in general is, or can be prepared by conventional methods that are well known in the art or using a method described in US 5,045,519.
[0175] [00175] The term "alkaline earth metal component" as used herein generally refers to an element or ion from Group 2 of the Periodic Table, a compound comprising an element or ion from Group 2 of the Periodic Table, or an alloy metal comprising an element of Group 2 of the Periodic Table, unless otherwise specified. The term "alkaline earth metal component" typically does not include or include "modified alumina incorporating a heteroatom component". The "alkaline earth metal component" is not an "alumina doped with a heteroatom component" or an "alkaline earth metal aluminate" as described herein.
[0176] [00176] In general, the "alkaline earth metal component" is (i) a compound comprising an alkaline earth metal, and / or (ii) a metal alloy comprising an alkaline earth metal. In the compound comprising an alkaline earth metal, the alkaline earth metal is typically present as a cation. The compound can, for example, be an alkaline earth metal oxide, an alkaline earth metal nitrate, an alkaline earth metal carbonate, or an alkaline earth metal hydroxide. In the metal alloy, alkaline earth metal is typically present in elemental form (that is, as a metal). The alkaline earth metal component is preferably a compound comprising an alkaline earth metal, more preferably a compound comprising a single alkaline earth metal.
[0177] [00177] The term "platinum group metal (PGM)" as used herein generally refers to platinum or palladium, unless otherwise specified. For the avoidance of doubt, this expression does not generally include rhodium.
[0178] [00178] The term "platinum group metal component (PGM)" as used herein refers to any fraction comprising a platinum group metal (PGM), such as elementary PGM (for example, a PGM metal), a PGM ion (for example, a cation, such as Pt2 +), a compound comprising a PGM (for example, a PGM salt or a PGM oxide) or an alloy comprising a PGM (for example, a platinum alloy -palladium). The term "platinum component (Pt)" as used herein refers to any fraction comprising platinum, such as elementary platinum (for example, metallic platinum), a platinum ion (for example, a cation, such as Pt2 + ), a platinum compound (for example, a platinum salt or a platinum oxide) or an alloy comprising platinum (for example, a platinum-palladium alloy). The term "palladium component (Pd)" as used herein refers to any fraction comprising palladium, such as elementary palladium (for example, metallic palladium), a palladium ion (for example, a cation, such as Pd2 + ), a palladium compound (for example, a palladium salt or a palladium oxide) or an alloy comprising palladium (for example, a platinum-palladium alloy).
[0179] [00179] The "platinum component (Pt)" is typically metallic platinum or an alloy comprising platinum, particularly a platinum-palladium alloy. Preferably, the "platinum component (Pt)" is metallic platinum.
[0180] [00180] The "palladium (Pd) component" is typically metallic palladium, palladium oxide or an alloy comprising palladium, particularly a platinum-palladium alloy. Preferably, the "palladium (Pd) component" is metallic palladium.
[0181] [00181] The term "noble metal component" as used herein refers to any fraction comprising a noble metal, such as an elemental form of noble metal, a noble metal ion, a noble metal compound or an alloy comprising noble metal (for example, a noble metal-platinum alloy or a noble metal-palladium alloy). It is preferable that the "noble metal component" is a noble metal itself (that is, in elementary form) or an alloy comprising the noble metal. Most preferably, the "noble metal component" is the noble metal itself (i.e., in elementary form).
[0182] [00182] Any reference to an amount of the “platinum group metal component (PGM)”, “platinum component (Pt)”, “palladium component (Pd)”, “alkaline earth metal component” or the “component "noble metal" as used here generally refers to the amount, respectively, of PGM, platinum, palladium, alkaline earth metal or noble metal that is present. So, for example, if the “platinum group metal component (PGM)”, “platinum component (Pt)”, “palladium component (Pd)”, “alkaline earth metal component” or “metal component noble ”is a compound comprising, respectively, a PGM, platinum, palladium, an alkaline earth metal or a noble metal, so the declared amount refers only to the total amount of said metal that is present and does not include other components of the compound.
[0183] [00183] The quantities given in units of g / m3 (g ft-3) or kg / m3 (g in-3) generally refer to the volume of the substrate that is used.
[0184] [00184] Any reference to a quantity of a material in terms of% by weight, such as the quantity of alkaline earth metal component, typically refers to a percentage of the overall weight of the layer / zone (e.g. coating of catalytic material) comprising that material.
[0185] [00185] The term "substantially cover" as used herein refers to at least 90% coverage, preferably at least 95% coverage, more preferably at least 99% coverage, of the surface area of the first layer by the second layer .
[0186] [00186] The term "substantially uniform length" as used herein refers to the layer length that does not deviate more than 10%, preferably does not deviate more than 5%, more preferably does not deviate more than 1% from the average value of the length layer.
[0187] [00187] The expression “essentially consisting” as used herein limits the scope of a resource to include specified materials or steps, and any other material or step that does not materially affect the basic characteristics of that resource, such as, for example, secondary impurities. The term "consisting essentially of" encompasses the term "consisting of".
[0188] [00188] The term "zone" as used herein refers to a region or layer of coating of catalytic material with a length that is less than the total length of the substrate. In general, the "zone" has a substantially uniform length. The term usually refers to the arrangement side by side of two or more regions or layers of coating of catalytic material on the same substrate.
[0189] [00189] In order that the invention may be more fully understood, the following examples are provided by way of illustration only and with reference to the accompanying drawings, in which: BRIEF DESCRIPTION OF THE DRAWINGS
[0190] [00190] Figure 1 is a histogram showing measurements of carbon monoxide "operating" temperatures (° C) at 50% conversion (CO T50) for catalyst formulations comprising varying amounts of platinum and palladium. The X axis shows the weight% of platinum in relation to the total metal content of the platinum group in the formulation. At each point on the X axis, the first bar (from the left) represents a sample containing standard alumina and no barium, the second bar represents a sample containing alumina and barium, the third bar represents a sample containing a modified alumina and without barium , and the fourth bar represents a sample containing a modified alumina and barium; and Figure 2 is a histogram showing measurements of carbon monoxide “operating” temperatures (° C) at 50% conversion (CO T50) for catalyst formulations according to examples 6, 7 and 8 when tested on an engine Euro 5 turbocharged diesel mounted on bench running on fuel <10 ppm sulfur. EXAMPLES Example 1 Preparatory Methods
[0191] [00191] Samples containing an alkaline earth metal component and alumina doped with a heteroatom component as a support material were prepared as follows.
[0192] [00192] Alumina powder doped with silica was pasted in water and ground to a d90 <20 micron. Barium acetate was added to the slurry followed by appropriate amounts of soluble platinum and palladium salts. The slurry was then stirred to homogenize. The resulting coating of catalytic material was applied to a flow of cordierite through the monolith with 400 cells per square inch using established coating techniques. The part was dried and calcined at 500 ° C.
[0193] [00193] For comparative purposes, samples containing alumina doped with a heteroatom component as a support material, but without an alkaline earth metal component were also prepared. The aforementioned method was used to prepare the samples, except that the step of adding barium acetate was omitted.
[0194] [00194] As a further comparison, samples containing conventional alumina as a support material with and without an alkaline earth metal component were prepared as follows.
[0195] [00195] Alumina powder was pasted in water and ground to a d90 <20 micron. Barium acetate was added to the slurry followed by appropriate amounts of soluble platinum and palladium salts. The slurry was then stirred to homogenize. The resulting coating of catalytic material was applied to a flow of cordierite through the monolith with 400 cells per square inch using established coating techniques. The part was dried and calcined at 500 ° C.
[0196] [00196] Similar alumina samples without alkaline earth metal component were prepared by omitting the barium addition step acetate
[0197] [00197] The formulations contained a total load of 1785.5 g / m3 (50 gft-3) of metal from the platinum group. Barium-containing samples were prepared using a load of 5356.5 g / m3 (150 gft-3) Alumina doped with 5% silica was used as the modified alumina. CO T50 measurement
[0198] [00198] Catalytic activity was determined using a synthetic gas bench activity test (SCAT). Parts to be tested were first drilled using a drill and aged in an oven at 750 ° C for 5 hours using hydrothermal conditions (10% water). The 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.
[0199] [00199] The results of the measurements are shown in figure 1. Figure 1 shows the improved activity of catalysts of the invention, which comprise both modified and barium alumina at a loading of 5356.5 g / m3 (150 gft-3). The catalysts of the invention have a lower operating temperature T50 of CO than comparative catalysts that do not contain barium. This is particularly apparent when the mass ratio of Pt: Pd is in the range of 1: 2 to 2: 1. Catalysts containing conventional alumina as a support material and barium do not show an improved operating temperature T50 of CO purchased with catalysts containing conventional alumina and without barium. Example 2
[0200] [00200] Samples containing alumina doped with 5% silica, Pt: Pd in a mass ratio of 1: 1 at a total PGM load of 1785.5 g / m3 (50 gft-3) and varying amounts of barium were prepared using the method described here. The operating temperatures T50 of CO were also measured using the same procedure presented here. Results
[0201] [00201] The results of CO “operation” measurements are shown in table 2 below.
[0202] [00202] Alumina powder doped with silica was pasted in water and ground to d90 <20 micron. Strontium acetate was added to the slurry followed by appropriate amounts of soluble platinum and palladium salts. The mass ratio of Pt: Pd was 1: 1 at a total PGM load of 1785.5 g / m3 (50 gft-3). The slurry was then stirred to homogenize. The resulting coating of catalytic material was applied to a flow of cordierite through the monolith with 400 cells per square inch using established coating techniques. The part was dried and calcined at 500 ° C. The operating temperatures T50 of CO were also measured using the same procedure presented here. Results
[0203] [00203] The results of CO “operation” measurements are shown in table 3 below.
[0204] [00204] Strontium-containing catalysts have a lower operating temperature T50 of CO than a comparative catalyst without strontium (see sample 2-1 in table 2). Samples 3-1 and 3-2 show that a reduction in operating temperature T50 of CO is achieved using two different heteroatom-doped aluminas. Support A1 is a doped alumina with 5% silica and support A2 is a doped alumina with 10% silica. Example 4 Preparative Method
[0205] [00205] Alumina powder doped with magnesium was pasted in water and crushed to d90 <20 micron. Barium acetate was added to the slurry followed by appropriate amounts of soluble platinum and palladium salts. The mass ratio of Pt: Pd was 2: 1 in a total PGM load of 1785.5 g / m3 (50 gft-3). The slurry was then stirred to homogenize. The resulting coating of catalytic material was applied to a flow of cordierite through the monolith with 400 cells per square inch using established coating techniques. The part was dried and calcined at 500 ° C.
[0206] [00206] For comparative purposes, catalysts containing magnesium doped alumina as a support material without an alkaline earth metal were prepared in the same way, except that the barium acetate addition step was omitted.
[0207] [00207] The operating temperatures T50 of CO were also measured using the procedures presented here. Results
[0208] [00208] The results of CO “operation” measurements are shown in table 4 below.
[0209] [00209] Samples containing a support material comprising magnesium aluminate show a lower operating temperature T50 of CO when barium is included in the formulation than those samples prepared without barium. The operating temperature is reduced by 19 ° C. Example 5 Preparative Method
[0210] [00210] A catalyst (5-1) was prepared via incipient wet impregnation of barium acetate solution in a support of silica-doped alumina. The material was dried at 105 ° C. A second solution of platinum and palladium salts was then added by incipient wet impregnation. The resulting material was dried at 105 ° C then calcined at 500 ° C. The final composition was 0.65 wt% Pt, 0.35 wt% Pd and 10 wt% Ba.
[0211] [00211] A comparative catalyst (5-2) was prepared using the same method, but without barium acetate impregnation on the silica-doped alumina support. The final composition was 0.65 wt% Pt and 0.35 wt% Pd.
[0212] [00212] The% oxidation activity of NO as a function of the temperature of each catalyst was tested when the catalyst was freshly prepared (for example, "fresh" catalyst) and after hydrothermal aging of each catalyst at 750 ° C for 48 hours ( for example, “aged” catalyst). The test gas mixture is given in table 5. In each case, the balance is nitrogen.
[0213] [00213] The difference between the activity of the "fresh" and "aged" versions of each catalyst is shown in table 6 below.
[0214] [00214] The results in table 6 show that catalyst 5-1 has a smaller difference in the% oxidation of NO performance between "fresh" and "aged" than catalyst 5-2. This difference is important for the exhaust system where there is a downstream emission control device, particularly an SCR or SCRF catalyst, as the activity of such downstream emission control devices may be affected by the NOx content of the gas exhaust, especially the NO: NO2 ratio. Example 6
[0215] [00215] Alumina powder was pasted in water and ground to a particle size d90 <6 µm. Appropriate amounts of soluble platinum and palladium salts were added to the slurry, followed by beta zeolite in such a way that the slurry comprised 80% alumina and 20% zeolite by mass. The slurry was stirred to homogenize. The resulting catalytic coating was applied to a volume of 3.0 liters of silicon carbide substrate with 300 cells per square inch (cpsi), 12 thousandths of an inch of wall thickness and 42% porosity using established coating techniques. The part was dried and calcined at 500 ° C.
[0216] [00216] The finished catalyzed soot filter had a total PGM load of 714 g / m3 (20 g ft-3). Example 7
[0217] [00217] Alumina powder was pasted in water and ground to a particle size d90 <6 µm. Barium acetate was added to the slurry followed by appropriate amounts of soluble platinum and palladium salts and beta zeolite in such a way that the slurry comprised 80% alumina and 20% zeolite by mass. The slurry was stirred to homogenize. The resulting coating of catalytic material was applied to a volume of 3.0 liters of 300 cpsi silicon carbide substrate, 12 thousandths of an inch of wall thickness and 42% porosity using established coating techniques. The part was dried and calcined at 500 ° C.
[0218] [00218] The finished catalyzed soot filter had a total PGM load of 714 g / m3 (20 g ft-3). Example 8
[0219] [00219] Alumina powder doped with silica was pasted in water and ground to a particle size d90 <6 µm. Barium acetate was added to the slurry followed by appropriate amounts of soluble platinum and palladium salts and beta zeolite in such a way that the slurry comprised 80% silica-doped alumina and 20% zeolite by mass. The slurry was stirred to homogenize. The resulting catalytic material coating was applied to a volume of 3.0 liters silicon carbide substrate with 300 cpsi, 12 thousandths of an inch of wall thickness and 42% porosity using established coating techniques. The part was dried and calcined at 500 ° C.
[0220] [00220] The finished catalyzed soot filter had a total PGM load of 714 g / m3 (20 g ft-3). Example 9 - Test
[0221] [00221] The samples prepared according to Examples 6, 7 and 8 were each hydrothermally aged in an oven at 800 ° C for 16 hours. They were then exposed to exhaust gas emissions from a Euro 5 turbocharged diesel engine running on fuel with <10 ppm sulfur. Pollutant emissions were measured both before and after catalyzed soot filters. The operating activity of the catalysts was determined by increasing the temperature of the exhaust gas by applying load to the engine by means of a dynamometer.
[0222] [00222] Figure 2 shows the T50 CO operating activity of Example 6, Example 7 and Example 8. In Figure 2, we see that the samples in Example 6 and Example 8 have very similar operating temperatures. However, the sample of Example 7 has a higher CO operating temperature.
[0223] [00223] Table 7 shows the percentage of NO2 in NOx emitted by the soot filter catalyzed at 300 ° C during the operation test. Example 6 has a relatively high percentage of NO2 to 15% NOx. Example 7 and Example 8 both show only 1% NO2 in NOx. Table 7 - NO2 in NOx at 300 ° C (Diesel engine emissions mounted on Euro 5 turbocharged bench running on fuel <10 ppm sulfur)
[0224] [00224] Example 8 according to the invention shows low NO2 in NOx, still maintaining good CO oxidation activity.
[0225] [00225] In order to avoid any doubt, the entire content of any or all of the documents mentioned here is incorporated by reference in this application.

权利要求:
Claims (15)
[0001]
Exhaust system for a compression ignition engine comprising a catalyzed soot filter, characterized by the fact that the catalyzed soot filter comprises an oxidation catalyst to treat carbon monoxide (CO) and hydrocarbons (HCs) in exhaust gas from a compression ignition engine disposed on a filter substrate, which is a wall flow filter, the oxidation catalyst comprising: a first zone comprising a metal component of the platinum group (PGM) selected from the group consisting of a platinum component (Pt), a palladium component (Pd) and a combination thereof; an alkaline earth metal component and a support material comprising a silica doped alumina, in which the alumina is doped with silica in an amount of 1.5 to 30% by weight, in which the alkaline earth metal component is supported in the support material, and where the metal component of the platinum group (PGM) is supported on the support material; a second zone comprising a metal component of the platinum group (PGM) selected from the group consisting of a platinum component (Pt), a palladium component (Pd) and a combination thereof; and where the first zone and the second zone are in a side-by-side arrangement on the substrate and the second zone is upstream of the first zone, and where the first zone is different from the second zone in composition.
[0002]
Exhaust system according to claim 1, characterized by the fact that the alumina is doped with silica in an amount of 1.5 to 10% by weight.
[0003]
Exhaust system according to either of claims 1 or 2, characterized in that the alkaline earth metal component comprises magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) or a combination of two or more of them.
[0004]
Exhaust system according to claim 3, characterized by the fact that the alkaline earth metal component comprises strontium (Sr) or barium (Ba).
[0005]
Exhaust system according to any one of claims 1 to 4, characterized in that the oxidation catalyst does not comprise rhodium.
[0006]
Exhaust system according to any one of claims 1 to 5, characterized in that the oxidation catalyst does not comprise ceria.
[0007]
Exhaust system according to any one of claims 1 to 6, characterized in that the first zone comprises a metal component of the platinum group (PGM) consisting of a combination of a platinum component (Pt) and a palladium component ( Pd), and the second zone comprises a platinum group metal component (PGM) consisting of a combination of a palladium component (Pd) and a platinum component (Pt), and in which the platinum mass ratio in the component platinum (Pt) to palladium in the palladium (Pt) component in the first zone is different from the platinum (Pt) mass ratio in the platinum (Pt) to palladium in the palladium (Pd) component in the second zone.
[0008]
Exhaust system according to any one of claims 1 to 6, characterized in that the first zone comprises a metal component from the platinum group (PGM) selected from the group consisting of a palladium (Pd) component and a combination of a a palladium component (Pd) and a platinum component (Pt), and wherein the second zone comprises a platinum group metal (PGM) component consisting of a platinum component (Pt).
[0009]
Exhaust system according to any one of claims 1 to 6, characterized in that the first zone comprises a metal component of the platinum group (PGM) selected from the group consisting of a platinum component (Pt) and a combination of a palladium component (Pd) and platinum component (Pt), and the second zone comprises a platinum group metal component (PGM) consisting of a palladium component (Pd).
[0010]
Exhaust system according to any one of claims 1 to 6, characterized in that the first zone comprises a platinum group component (PGM) selected from the group consisting of a platinum component (Pt) and a palladium component (Pd) , and the second zone comprises a metal component of the platinum group (PGM) consisting of a combination of a palladium (Pd) and a platinum (Pt) component.
[0011]
Exhaust system according to any one of claims 1 to 10, characterized by the fact that it further comprises at least one emission control device, wherein the at least one emission control device is arranged in a substrate monolith disposed to amount of the catalyst soot filter.
[0012]
Exhaust system according to any one of claims 1 to 10, characterized in that it comprises at least one emission control device arranged in a substrate monolith located either upstream or downstream of the catalyzed soot filter, in which the at least one emission control device is selected from a particulate diesel filter, a NOx adsorbent catalyst. a poor NOx catalyst, a selective catalytic reduction catalyst, a diesel oxidation catalyst, a catalytic soot filter, a filter catalyzed with a selective catalytic reduction catalyst, a residual ammonia catalyst and combinations of two or more of the same.
[0013]
Exhaust system according to any one of claims 1 to 10, characterized in that it comprises a diesel oxidation catalyst (DOC), a catalytic soot filter (CSF) and a selective catalytic reduction catalyst (SCR), in which the diesel oxidation catalyst (DOC) is upstream of the catalyzed soot filter (CSF), and the catalyzed soot filter (CSF) is upstream of the selective catalytic reduction catalyst (SCR).
[0014]
Exhaust system according to claim 11, characterized by the fact that it comprises a NOx adsorber catalyst (NAC), a catalytic soot filter (CSF) and a selective catalytic reduction catalyst (SCR), in which NOx adsorber catalyst ( NAC) is upstream of the filter comprising a selective catalytic reduction (SCR) catalyst.
[0015]
Vehicle, characterized by the fact that it comprises a compression ignition engine and an exhaust system as defined in any one of claims 1 to 14.

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

CA1025636A|1972-12-15|1978-02-07|Uop Inc.|Exhaust gas conversion catalyst and use thereof|

---

DE3244972C1|1982-12-04|1984-02-09|Condea Chemie GmbH, 2212 Brunsbüttel|Process and device for the continuous production of aluminum alcoholates|

---

US4727052A†|1986-06-27|1988-02-23|Engelhard Corporation|Catalyst compositions and methods of making the same|

---

DE3839580C1|1988-11-24|1990-07-05|Condea Chemie Gmbh, 2212 Brunsbuettel, De|

---

US5248251A|1990-11-26|1993-09-28|Catalytica, Inc.|Graded palladium-containing partial combustion catalyst and a process for using it|

---

ES2104943T5|1991-10-03|2005-04-16|Toyota Jidosha Kabushiki Kaisha|PURIFICATION DEVICE OF EXHAUST GASES OF AN INTERNAL COMBUSTION ENGINE.|

---

US5593654A|1992-03-12|1997-01-14|Condea Vista Company|Preparation of stabilized alumina having enhanced resistance to loss of surface area at high temperatures|

---

CA2131795C|1992-03-12|2004-02-03|Lewis Bernard Decker Jr.|Preparation of stabilized alumina having enhanced resistance to loss of surface area at high temperatures|

---

US5837634A|1992-11-12|1998-11-17|Condea Vista Company|Process for producing stabilized alumina having enhanced resistance to loss of surface area at high temperatures|

---

FR2715580B1|1994-01-31|1996-04-05|Inst Francais Du Petrole|Catalyst for treating exhaust gases from internal combustion engines.|

---

DE4436890A1|1994-10-15|1996-04-18|Degussa|Process for the simultaneous reduction of the hydrocarbons, carbon monoxide and nitrogen oxides contained in the exhaust gas of an internal combustion engine|

---

DE19503522A1|1995-02-03|1996-08-08|Rwe Dea Ag|Production of mixed layered metal hydroxides and their metal oxides|

---

JP3387290B2|1995-10-02|2003-03-17|トヨタ自動車株式会社|Exhaust gas purification filter|

---

JPH10180099A|1996-12-20|1998-07-07|Ngk Insulators Ltd|Catalyst for purifying waste gas and waste gas purifying system|

---

GB9805815D0|1998-03-19|1998-05-13|Johnson Matthey Plc|Manufacturing process|

---

DE19813655C2|1998-03-27|2000-04-27|Degussa|Storage material for sulfur oxides, process for its production and use|

---

US6217837B1|1998-11-02|2001-04-17|Ford Global Technologies, Inc.|Use of sol-gel processed alumina-based metal oxides for absorbing nitrogen oxides in oxidizing exhaust gas|

---

AT224507T|1998-12-05|2002-10-15|Johnson Matthey Plc|IMPROVEMENTS IN EXHAUST PARTICLE CONTROL|

---

US6224846B1|1999-08-21|2001-05-01|Condea Vista Company|Method for making modified boehmite alumina|

---

JP3724708B2|1999-11-26|2005-12-07|日産自動車株式会社|Exhaust gas purification catalyst|

---

US6699448B2|2001-01-26|2004-03-02|Engelhard Corporation|SOx tolerant NOx trap catalysts and methods of making and using the same|

---

US6585945B2|2001-01-26|2003-07-01|Engelhard Corporation|SOx tolerant NOx trap catalysts and methods of making and using the same|

---

US7276212B2|2001-10-01|2007-10-02|Engelhard Corporation|Exhaust articles for internal combustion engines|

---

JP2003201832A|2001-10-25|2003-07-18|Nissan Motor Co Ltd|Exhaust emission control catalyst system|

---

EP1316354A1|2001-11-30|2003-06-04|OMG AG &amp; Co. KG|Catalyst for the reduction of nitrogen oxides in exhaust gas of lean burn engines|

---

US20040001781A1|2002-06-27|2004-01-01|Engelhard Corporation|Multi-zone catalytic converter|

---

JP2005538300A|2002-09-13|2005-12-15|ジョンソン、マッセイ、パブリック、リミテッド、カンパニー|Compression ignition engine and exhaust mechanism therefor|

---

US20050056006A1|2003-08-15|2005-03-17|Yinyan Huang|Process for reducing diesel enigne emissions|

---

US7235507B2|2004-08-14|2007-06-26|Sud-Chemie Inc.|Catalyst for purifying diesel engine exhaust emissions|

---

US7722829B2†|2004-09-14|2010-05-25|Basf Catalysts Llc|Pressure-balanced, catalyzed soot filter|

---

JP2006272288A|2005-03-30|2006-10-12|Toyota Central Res & Dev Lab Inc|Catalyst for purifying diesel exhaust gas|

---

EP1924528A4|2005-08-25|2013-07-31|Sasol North America Inc|Process for producing high porosity boehmite aluminas|

---

US20070058867A1|2005-09-15|2007-03-15|Shieh Johnny M|Portable device which does translation and retrieval of information related to a text object|

---

US8119075B2†|2005-11-10|2012-02-21|Basf Corporation|Diesel particulate filters having ultra-thin catalyzed oxidation coatings|

---

GB0600130D0|2006-01-06|2006-02-15|Johnson Matthey Plc|Exhaust system comprising zoned oxidation catalyst|

---

US8242045B2|2006-01-12|2012-08-14|Siemens Energy, Inc.|Ceramic wash-coat for catalyst support|

---

US7771669B2|2006-03-20|2010-08-10|Ford Global Technologies, Llc|Soot oxidation catalyst and method of making|

---

RU2395341C1|2006-03-28|2010-07-27|Тойота Дзидося Кабусики Кайся|Catalyst for cleaning exhaust gases, method of regenerating said catalyst, as well as device and method of cleaning exhaust gases using said catalyst|

---

JP5639337B2|2006-03-30|2014-12-10|ユミコア日本触媒株式会社|Internal combustion engine exhaust gas purification method|

---

US7576031B2†|2006-06-09|2009-08-18|Basf Catalysts Llc|Pt-Pd diesel oxidation catalyst with CO/HC light-off and HC storage function|

---

US7534738B2|2006-11-27|2009-05-19|Nanostellar, Inc.|Engine exhaust catalysts containing palladium-gold|

---

EP3300791B1|2007-04-26|2019-03-27|Johnson Matthey Public Limited Company|Transition metal/zeolite scr catalysts|

---

EP2070581A1|2007-12-10|2009-06-17|HTE Aktiengesellschaft The High Throughput Experimentation Company|Oxidation catalyst containing Pt and Pd|

---

US8114354B2|2007-12-18|2012-02-14|Basf Corporation|Catalyzed soot filter manufacture and systems|

---

WO2009116468A1|2008-03-19|2009-09-24|株式会社アイシーティー|Catalyst for cleaning internal combustion engine exhaust gas and method for cleaning exhaust gas using said catalyst|

---

KR100969378B1†|2008-03-31|2010-07-09|현대자동차주식회사|Apparatus for purifying exhaust gas|

---

JP2010046870A|2008-08-20|2010-03-04|Seiko Epson Corp|Drive device and recording apparatus|

---

US8329607B2|2009-01-16|2012-12-11|Basf Corporation|Layered diesel oxidation catalyst composites|

---

US8252258B2|2009-01-16|2012-08-28|Basf Corporation|Diesel oxidation catalyst with layer structure for improved hydrocarbon conversion|

---

US8211392B2|2009-01-16|2012-07-03|Basf Corporation|Diesel oxidation catalyst composite with layer structure for carbon monoxide and hydrocarbon conversion|

---

US8637426B2†|2009-04-08|2014-01-28|Basf Corporation|Zoned catalysts for diesel applications|

---

US8246923B2|2009-05-18|2012-08-21|Umicore Ag & Co. Kg|High Pd content diesel oxidation catalysts with improved hydrothermal durability|

---

CN102448606B|2009-05-27|2014-03-26|株式会社科特拉|Catalyst for purification of exhaust gas|

---

CN102470362A|2009-07-09|2012-05-23|丰田自动车株式会社|Exhaust gas purifying catalyst and method for producing same|

---

US8409515B2|2009-07-14|2013-04-02|GM Global Technology Operations LLC|Exhaust gas treatment system|

---

PL2322773T3|2009-10-28|2017-01-31|Umicore Ag & Co. Kg|Method for cleaning combustion engine exhaust gases|

---

US8557203B2|2009-11-03|2013-10-15|Umicore Ag & Co. Kg|Architectural diesel oxidation catalyst for enhanced NO2 generator|

---

WO2011057649A1|2009-11-12|2011-05-19|Umicore Ag & Co. Kg|Improved diesel oxidation catalytic converter|

---

WO2011061321A1†|2009-11-20|2011-05-26|Basf Se|Zoned catalyzed soot filter|

---

GB0922194D0|2009-12-21|2010-02-03|Johnson Matthey Plc|Improvements in emission control|

---

US8263033B2†|2010-02-23|2012-09-11|Ford Global Technologies, Llc|Palladium-contaning oxidation catalyst|

---

EP2539040B1|2010-02-23|2018-07-18|Basf Se|Improved catalyzed soot filter|

---

GB201003781D0†|2010-03-08|2010-04-21|Johnson Matthey Plc|Improvements in the control of vehicle emissions|

---

US8734743B2|2010-06-10|2014-05-27|Basf Se|NOx storage catalyst with improved hydrocarbon conversion activity|

---

JP5937579B2|2010-06-10|2016-06-22|ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ|NOx storage catalyst with improved hydrocarbon conversion activity|

---

US9242242B2|2010-09-02|2016-01-26|Basf Se|Catalyst for gasoline lean burn engines with improved NO oxidation activity|

---

JP2012055842A|2010-09-09|2012-03-22|Toyota Motor Corp|Exhaust gas purifying catalyst|

---

GB2484911B|2010-10-22|2013-04-03|Johnson Matthey Plc|NOx absorber catalyst comprising caesium silicate and at least one platinum group metal|

---

US8557204B2|2010-11-22|2013-10-15|Umicore Ag & Co. Kg|Three-way catalyst having an upstream single-layer catalyst|

---

US8845974B2|2010-11-24|2014-09-30|Basf Corporation|Advanced catalyzed soot filters and method of making and using the same|

---

US8668877B2|2010-11-24|2014-03-11|Basf Corporation|Diesel oxidation catalyst articles and methods of making and using|

---

KR20130129241A†|2010-12-14|2013-11-27|우미코레 아게 운트 코 카게|Architectural diesel oxidation catalyst for enhanced no2 generator|

---

GB201021887D0|2010-12-21|2011-02-02|Johnson Matthey Plc|Oxidation catalyst for a lean burn internal combustion engine|

---

GB201110850D0|2011-03-04|2011-08-10|Johnson Matthey Plc|Catalyst and mehtod of preparation|

---

EP3187263A1|2011-03-24|2017-07-05|Umicore Shokubai Japan Co., Ltd.|Oxidation catalyst for exhaust gas purification, method for producing the same, and exhaust gas purification method using the same|

---

US9044734B2|2011-09-23|2015-06-02|Basf Se|Diesel oxidation catalyst with layered structure containing ceria composition as palladium support material for enhanced HC and CO gas conversion|

---

CN104321506B|2012-05-14|2016-11-16|恩亿凯嘉股份有限公司|Waste gas purification apparatus|

---

US8568674B1|2012-08-10|2013-10-29|Basf Corporation|Diesel oxidation catalyst composites|

---

KR102118663B1|2012-11-12|2020-06-03|바스프 에스이|Oxidation catalyst and method for its preparation|

---

US10464052B2|2012-11-12|2019-11-05|Basf Se|Oxidation catalyst and method for its preparation|

---

GB201220912D0|2012-11-21|2013-01-02|Johnson Matthey Plc|Oxidation catalyst for treating the exhaust gas of a compression ignition engine|WO2013149881A1|2012-04-05|2013-10-10|Umicore Ag & Co. Kg|Method for removing carbon monoxide and hydrocarbons from the exhaust gas of lean-burn internal combustion engines|

---

US10464052B2|2012-11-12|2019-11-05|Basf Se|Oxidation catalyst and method for its preparation|

---

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---

GB201220912D0|2012-11-21|2013-01-02|Johnson Matthey Plc|Oxidation catalyst for treating the exhaust gas of a compression ignition engine|

---

GB201221025D0|2012-11-22|2013-01-09|Johnson Matthey Plc|Zoned catalysed substrate monolith|

---

KR20150090176A|2012-11-29|2015-08-05|바스프 에스이|Diesel oxidation catalyst comprising palladium, gold and ceria|

---

JP5938515B2|2013-02-25|2016-06-22|ユミコア日本触媒株式会社|Exhaust gas purification catalyst and exhaust gas purification method using the same|

---

US9333490B2|2013-03-14|2016-05-10|Basf Corporation|Zoned catalyst for diesel applications|

---

GB2514177A|2013-05-17|2014-11-19|Johnson Matthey Plc|Oxidation catalyst for a compression ignition engine|

---

DE102013108054A1|2013-07-26|2015-01-29|Jenoptik Katasorb Gmbh|Device for applying mixtures of substances to a material web and method for cleaning exhaust gases of the device|

---

JP2016534871A|2013-08-28|2016-11-10|ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃ Ｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ|CO slip catalyst and method of use|

---

DE102014113304B4|2013-09-16|2017-06-29|Johnson Matthey Public Limited Company|Exhaust system with a modified lean NOx trap|

---

GB2518418A|2013-09-20|2015-03-25|Johnson Matthey Plc|Electrically heated catalyst for a compression ignition engine|

---

US9662636B2|2014-04-17|2017-05-30|Basf Corporation|Zoned catalyst composites|

---

EP3164211A1|2014-07-02|2017-05-10|Johnson Matthey Public Limited Company|Perovskite with an ovlerlayer scr component as an ammonia oxidation catalyst and a system for exhaust emission control on diesel engines|

---

JP2016123958A|2015-01-07|2016-07-11|株式会社キャタラー|Catalyst for exhaust gas purification and system for exhaust gas purification|

---

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---

RU2730511C2|2015-02-13|2020-08-24|Джонсон Мэтти Паблик Лимитед Компани|Exhaust system for an engine with compression ignition having a gripping region for evaporating platinum|

---

US9616386B2|2015-03-23|2017-04-11|Kabushiki Kaisha Toyota Chuo Kenkyusho|Catalyst for purification of exhaust gas, NOx storage-reduction catalyst, and method for purifying exhaust gas|

---

JP6219871B2|2015-03-27|2017-10-25|トヨタ自動車株式会社|Exhaust gas purification catalyst|

---

CN107690353A|2015-06-16|2018-02-13|巴斯夫欧洲公司|Soot filter is catalyzed for the SCR with integrated lean-burn NOx trap catalyst in passive selective catalytic reduction|

---

US10201807B2|2015-06-18|2019-02-12|Johnson Matthey Public Limited Company|Ammonia slip catalyst designed to be first in an SCR system|

---

US9937489B2|2015-06-18|2018-04-10|Johnson Matthey Public Limited Company|Exhaust system without a DOC having an ASC acting as a DOC in a system with an SCR catalyst before the ASC|

---

GB2543849B|2015-11-02|2021-08-11|Johnson Matthey Plc|Oxidation catalyst|

---

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---

GB201521123D0|2015-11-30|2016-01-13|Johnson Matthey Plc|Diesel oxidation catalyst having a capture region for exhaust gas impurities|

---

US11260372B2|2015-12-16|2022-03-01|Basf Corporation|Catalyst system for lean gasoline direct injection engines|

---

DE102015225579A1|2015-12-17|2017-06-22|Umicore Ag & Co. Kg|Method for preventing the contamination of an SCR catalyst with platinum|

---

EP3426394A4|2016-03-09|2019-12-18|BASF Corporation|Core/shell hydrocarbon trap catalyst and method of manufacture|

---

RU2018141223A|2016-04-26|2020-05-26|Басф Корпорейшн|ZONED CONFIGURATION FOR COMBINATIONS OF OXIDATION CATALYST|

---

EP3448548B1|2016-04-29|2021-06-30|Johnson Matthey Public Limited Company|Exhaust system|

---

CA3027822A1|2016-06-17|2017-12-21|Basf Corporation|Palladium diesel oxidation catalyst|

---

GB2552262B|2016-07-12|2021-02-10|Johnson Matthey Plc|Oxidation catalyst for a stoichiometric natural gas engine|

---

GB201613849D0|2016-08-12|2016-09-28|Johnson Matthey Plc|Exhaust system for a compression ignition engine having a capture region for volatilised platinum|

---

GB201614677D0|2016-08-30|2016-10-12|Johnson Matthey Plc|Oxidation catalyst for a diesel engine exhaust|

---

GB201616812D0|2016-10-04|2016-11-16|Johnson Matthey Public Limited Company|NOx adsorber catalyst|

---

GB2554859A|2016-10-04|2018-04-18|Johnson Matthey Plc|NOx adsorber catalyst|

---

US10159960B2|2016-10-25|2018-12-25|GM Global Technology Operations LLC|Catalysts with atomically dispersed platinum group metal complexes|

---

US10035133B2|2016-10-25|2018-07-31|GM Global Technology Operations LLC|Catalysts with atomically dispersed platinum group metal complexes and a barrier disposed between the complexes|

---

JP2018143955A|2017-03-06|2018-09-20|イビデン株式会社|Honeycomb filter|

---

BR112019020282A2|2017-03-30|2020-04-28|Johnson Matthey Plc|catalyst article, and, method to reduce emissions from an exhaust stream.|

---

US20200197911A1|2017-05-15|2020-06-25|Starfire Energy|Metal-decorated barium calcium aluminum oxide and related materials for nh3 catalysis|

---

JP2018196858A|2017-05-24|2018-12-13|東京濾器株式会社|Exhaust gas purification catalyst for achieving low temperature purification of unsaturated hydrocarbon and saturated hydrocarbon|

---

JP6865664B2|2017-09-25|2021-04-28|株式会社キャタラー|Oxidation catalyst device for exhaust gas purification|

---

US10753247B2|2018-02-22|2020-08-25|GM Global Technology Operations LLC|Bi-metallic oxidation catalyst materials and appurtenant devices and systems|

---

CN108379983A|2018-03-20|2018-08-10|燕山大学|A kind of biomass incinerator exhaust gas treating method|

---

US11161098B2|2018-05-18|2021-11-02|Umicore Ag & Co. Kg|Three-way catalyst|

---

US10850264B2|2018-05-18|2020-12-01|Umicore Ag & Co. Kg|Hydrocarbon trap catalyst|

---

JP6781742B2|2018-09-12|2020-11-04|イビデン株式会社|Honeycomb structure|

---

US11253840B2|2018-12-13|2022-02-22|Johnson Matthey Public Limited Company|Transition metal doped alumina for improved TWC performance|

---

GB201914958D0|2019-06-26|2019-11-27|Johnson Matthey Plc|Composite, zoned oxidation catalyst for a compression ignition internal combustion engine|

---

EP3888774A1|2020-03-31|2021-10-06|Johnson Matthey Public Limited Company|Composite, zone-coated oxidation and exotherm generation catalyst|

---

WO2021074652A1|2019-10-16|2021-04-22|Johnson Matthey Public Limited Company|Composite, zone-coated, dual-use ammoniaand nitric oxide oxidation catalyst|

---

WO2021023741A1|2019-08-08|2021-02-11|Johnson Matthey Public Limited Company|System comprising vehicular compression ignition engine and an emissions control device comprising an electrically heatable element|

---

GB202004769D0|2019-10-16|2020-05-13|Johnson Matthey Plc|Composite, zoned oxidation catalyst for a compression ignition internal combustion engine|

---

RU2756178C2|2019-12-06|2021-09-28|Федеральное государственное автономное образовательное учреждение высшего образования "Уральский федеральный университет имени первого Президента России Б.Н. Ельцина"|Method for preparing automobile three-way catalyst|

法律状态:
2018-11-21| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-08-06| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-08-18| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-09-24| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/11/2013, 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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US201261728834P| true| 2012-11-21|2012-11-21|

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US61/728,834|2012-11-21|

---

GB201220912A|GB201220912D0|2012-11-21|2012-11-21|Oxidation catalyst for treating the exhaust gas of a compression ignition engine|

---

GB1220912.8|2012-11-21|

---

GB201308934A|GB201308934D0|2012-11-21|2013-05-17|Oxidation catalyst for treating the exhaust gas of a compression ignition engine|

---

GB1308934.7|2013-05-17|

---

PCT/GB2013/053068|WO2014080202A1|2012-11-21|2013-11-21|Catalysed soot filter for treating the exhaust gas of a compression ignition engine|

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