exhaust system for treating an exhaust gas from a compression-ignition engine

专利摘要:
OXIDATION CATALYST, EXHAUST SYSTEM, VEHICLE, AND, METHOD TO MODULE NOX CONTENT IN AN EXHAUST GAS. An oxidation catalyst for treating an exhaust gas from a compression ignition engine, which oxidation catalyst comprises: a substrate; a first reactive coating region comprising palladium (Pd) and a first support material comprising cerium oxide; and a second reactive coating region comprising platinum (Pt) and a second support material.
公开号:BR112015028557B1
申请号:R112015028557-0
申请日:2014-05-16
公开日:2021-05-04
发明作者:Andrew Francis Chiffey；Francois Moreau；Neil Robert Collins；John Benjamin Goodwin；Paul Richard Phillips
申请人:Johnson Matthey Public Limited Company；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[001] The invention relates to an oxidation catalyst for a compression ignition engine, particularly a diesel engine, and its uses. The invention also relates to methods involving the oxidation catalyst. The invention further relates to an exhaust system comprising the oxidation catalyst, and to a vehicle comprising the oxidation catalyst or the exhaust system. FUNDAMENTALS OF THE INVENTION
[002] Compression ignition engines, such as diesel engines, produce an exhaust emission that generally contains at least four classes of pollutants that are otherwise legislated by intergovernmental organizations across the world: carbon monoxide (CO), hydrocarbons unburned (HCs), nitrogen oxides (NOx) and particulate matter (PM). As emission standards for the permissible emission of pollutants from compression ignition engines, particularly vehicular engines, become progressively tighter, there is a need to provide improved exhaust and catalysis systems that are capable of meeting these standards and that have good cost benefit.
[003] Oxidation catalysts comprising platinum group metals were used to treat carbon monoxide (CO) and hydrocarbons (HCs), including the volatile organic fraction (VOF) of particulate matter (PM), in the exhaust emissions produced by diesel engines. compression ignition. Such catalysts treat carbon monoxide (CO) by oxidizing it to carbon dioxide (CO2), and treat hydrocarbons (HCs) by oxidizing them to water (H2O) and carbon dioxide (CO2).
[004] Some platinum group metals, particularly when supported on a refractory oxide, can also promote the oxidation of nitric oxide (NO) to nitrogen dioxide (NO2).
[005] It has been discovered that platinum (Pt) and palladium (Pd) are capable of oxidizing carbon monoxide (CO) and hydrocarbons (HCs) in an exhaust gas from a compression ignition engine. Palladium is generally cheaper than platinum, but is less active for CO and HCs (eg Pd has a higher start-up temperature for CO and HCs than Pt). Palladium is also more susceptible to sulfur poisoning in fuel compared to platinum. However, platinum-based oxidation catalysts have been discovered to generate nitrous oxide (N2O) through the reduction of NOx (Catalysis Today 26 (1995) 185-206).
[006] Current legislation to regulate engine emissions does not limit nitrous oxide (N2O) as it is separately regulated as a greenhouse gas (GHG). Regardless of this, it is desirable that emissions contain a minimum of nitrous oxide (N2O). The US Environmental Protection Agency has stated that the impact of 1 pound of nitrous oxide (N2O) on warming the atmosphere is more than 300 times that of 1 pound of carbon dioxide (CO2). Nitrous oxide (N2O) is also an ozone depleting substance (ODS). It has been estimated that nitrous oxide (N2O) molecules stay in the atmosphere for about 120 years before being removed or destroyed.
[007] Typically, an exhaust gas from a compression ignition engine will be treated using an exhaust system where an oxidation catalyst has been combined with at least one other emission control device. In general, the emission control device will not remove any nitrous oxide (N2O) generated by the oxidation catalyst, even when the emission control device receives treated exhaust gas from an oxidation catalyst outlet (ie. emission control device is downstream of the oxidation catalyst). SUMMARY OF THE INVENTION
[008] An objective of the invention is to provide an oxidation catalyst to treat an exhaust gas produced by a compression ignition engine, such as a diesel engine, which catalyst has advantageous oxidative activity for carbon monoxide (CO) and/or hydrocarbons (HCs). In particular, the oxidation catalyst of the invention has excellent CO oxidizing activity at low temperatures (i.e. a low starting temperature for CO (e.g. a low T50)).
[009] The oxidation catalyst of the invention additionally or alternatively may provide the following advantages: (i) it does not, in use, generate or produce a substantial amount of nitrous oxide (N2O); (ii) it can act as a passive NOx adsorber (PNA); and/or (iii) it can modulate the NOx content of an exhaust gas to a downstream emission control device.
[0010] The invention provides an oxidation catalyst for treating an exhaust gas from a compression ignition engine, which oxidation catalyst comprises: a substrate; a first reactive coating region comprising palladium (Pd) and a first support material comprising cerium oxide; and a second reactive coating region comprising platinum (Pt) and a second support material.
[0011] The invention also provides an exhaust system for a compression ignition engine, an exhaust system which comprises an oxidation catalyst and an emission control device, wherein the oxidation catalyst comprises: a substrate; a first reactive coating region comprising palladium (Pd) and a first support material comprising cerium oxide; and a second reactive coating region comprising platinum (Pt) and a second support material.
[0012] Also provided by the invention is a vehicle comprising a compression ignition engine and either an oxidation catalyst of the invention or an exhaust system of the invention.
[0013] The invention also provides various uses of the oxidation catalyst and methods involving the oxidation catalyst.
[0014] A first aspect of the method of the invention relates to a method for treating an exhaust gas from a compression ignition engine, which method comprises contacting the exhaust gas with an oxidation catalyst comprising: a substrate; a first reactive coating region comprising palladium (Pd) and a first support material comprising cerium oxide; and a second reactive coating region comprising platinum (Pt) and a second support material. In general, the method for treating an exhaust gas from a compression ignition engine is a method for treating (eg oxidation) carbon monoxide (CO) and hydrocarbons (HCs) in an exhaust gas from a compression-ignition engine, preferably without producing a substantial amount of nitrous oxide (N2O).
[0015] A second aspect of the method of the invention relates to a method for modulating the NOx content in an exhaust gas from a compression ignition engine to an emission control device, the method comprising: (a) controlling the NOx content of an exhaust gas by contacting the exhaust gas with an oxidation catalyst to produce a treated exhaust gas; and (b) passing the treated exhaust gas to an emission control device; wherein the oxidation catalyst comprises: a substrate; a first reactive coating region comprising palladium (Pd) and a first support material comprising cerium oxide; and a second reactive coating region comprising platinum (Pt) and a second support material. Typically, the method is also a method for treating an exhaust gas from a compression-ignition engine and modulating the NOx content in the exhaust gas to an emission control device. The method may further refer to a method for treating (eg, oxidizing) carbon monoxide (CO) and hydrocarbons (HCs) in an exhaust gas from a compression ignition engine and modulating the NOx content in the gas exhaust to an emission control device, preferably without producing a substantial amount of nitrous oxide (N2O).
[0016] A first aspect of use of the invention relates to the use of an oxidation catalyst to treat an exhaust gas from a compression ignition engine, optionally in combination with an emission control device, in which the catalyst of oxidation comprises: a substrate; a first reactive coating region comprising palladium (Pd) and a first support material comprising cerium oxide; and a second reactive coating region comprising platinum (Pt) and a second support material. In general, the oxidation catalyst is used to treat (eg oxidize) carbon monoxide (CO) and hydrocarbons (HCs) in an exhaust gas from a compression ignition engine, preferably without producing a substantial amount of nitrous oxide (N2O), optionally in combination with an emission control device. Thus, the oxidation catalyst can be used to treat (eg oxidize) carbon monoxide (CO) and hydrocarbons (HCs) in an exhaust gas from a compression ignition engine and produce a treated exhaust gas comprising substantially in nitrous oxide (N2O). Typically, the treated exhaust gas is then passed to an emission control device.
[0017] A second use aspect of the invention relates to the use of an oxidation catalyst as a passive NOx absorber (PNA) in an exhaust gas from a compression ignition engine optionally in combination with a control device emissions, wherein the oxidation catalyst comprises: a substrate; a first reactive coating region comprising palladium (Pd) and a first support material comprising cerium oxide; and a second reactive coating region comprising platinum (Pt) and a second support material. In general, the oxidation catalyst is used as a passive NOx absorber (PNA) and to treat (eg oxidize) carbon monoxide (CO) and hydrocarbons (HCs) in an exhaust gas from an ignition engine. by compression, preferably without producing a substantial amount of nitrous oxide (N2O), optionally in combination with an emission control device.
[0018] In a third aspect of use, the invention relates to the use of an oxidation catalyst to modulate the NOx content in an exhaust gas from a compression ignition engine to an emission control device, in that the oxidation catalyst comprises a substrate, the first reactive coating region and a second reactive coating region, wherein the first reactive coating region comprises palladium (Pd) and a first support material comprising cerium oxide, and wherein the second reactive coating region comprises platinum (Pt) and a second support material.
[0019] A fourth aspect of use relates to the use of an oxidation catalyst in the regeneration of an emission control device having a filtering substrate, wherein the oxidation catalyst comprises a substrate monolith, the first reactive coating region and a second reactive coating region, wherein the first reactive coating region comprises palladium (Pd) and a first support material comprising cerium oxide, and wherein the second reactive coating region comprises platinum (Pt) and a second support material. Support.
[0020] In a fifth aspect of use, the invention relates to the use of a first reactive coating region in an oxidation catalyst (e.g., in an oxidation catalyst comprising the first reactive coating region) to reduce or prevent the N2O production in an exhaust gas from a compression ignition engine, wherein the oxidation catalyst comprises a substrate, the first reactive coating region, and a second reactive coating region, wherein the first reactive coating region comprises palladium (Pd) and a first support material comprising cerium oxide, and wherein the second reactive coating region comprises platinum (Pt) and a second support material. Typically, the oxidation catalyst is used to reduce or prevent the production of N2O from NOx (eg, by the second reactive coating region comprising platinum) in an exhaust gas from a compression ignition engine. BRIEF DESCRIPTION OF THE DRAWINGS
[0021] Figure 1 shows a graph of the amount of N2O (ppm) in an exhaust gas that was passed over a catalyst (Example 1 = dotted line; Example 2 = solid line) and which was produced by an engine run per one cycle of MVEG.
[0022] Figure 2 is a graph showing the effect of palladium loading on the amount of NOx stored in g L-1 (geometric y axis) at various temperatures in °C (geometric x axis). Palladium was supported in an amount of 1% by weight (■), 2% by weight (▲) or 4% by weight (•) on ceria, which was loaded in an amount of 0.1647 g cm3 (2.7 g in-3) on a substrate.
[0023] Figure 3 is a graph showing the effect of varying both palladium and cerium loading on the amount of NOx stored in g L-1 (geometric y axis) at various temperatures in °C (geometric x axis).
[0024] Palladium and cerium were loaded in an amount of 1% by weight of Pd and 0.1647 g cm3 (2.7 g in-3) of ceria (▲); 2% by weight of Pd and 0.08 g cm3 (1.35 g in-3) of ceria (•); 3% by weight of Pd and 0.05 g cm3 (0.9 g in-3) of ceria (♦); and 4% by weight of Pd and 0.041 g cm3 (0.675 g in-3) of ceria (■). DETAILED DESCRIPTION OF THE INVENTION
[0025] The oxidation catalyst of the invention has been found to have excellent CO oxidation activity, especially for compression ignition engines that produce an exhaust gas containing a relatively high concentration of CO. The catalyst of the invention contains both platinum (Pt) and palladium (Pd) as the combination of these platinum group metals provides advantageous oxidative activity. For example, platinum can oxidize nitric oxide (NO) to nitrogen dioxide (NO2) under certain conditions, which can be advantageous for downstream emission control devices. It has also been found that inclusion of platinum in a separate reactive coating region for a reactive coating region comprising both palladium and cerium oxide can reduce or prevent the generation of nitrous oxide (N2O).
[0026] The oxidation catalyst of the invention comprises a first reactive coating region. The first reactive coating region comprises, or consists essentially of, palladium (Pd) and a first support material comprising cerium oxide. Palladium (Pd) is typically disposed or supported on the first support material. For example, palladium (Pd) can be dispersed in the first support material and/or impregnated in the first support material.
[0027] Palladium is generally disposed directly to or supported directly by the first support material (for example, there is no intervening support material between the palladium and the first support material). It is preferred that palladium is in direct contact with cerium oxide (ie ceria).
[0028] Typically, the first support material comprises, or consists essentially of, ceria (CeO2) or ceria - zirconia (CeO2 - ZrO2), wherein the ceria or ceria - zirconia is optionally doped. Ceria-zirconia can be a solid solution of ceria-zirconia.
[0029] The inclusion of a dopant can thermally stabilize the first support material. It should be understood that any reference to "doped" in this context refers to a material where the host network or volume of the ceria or ceria-zirconia is doped by substitution or interstitially doped with a dopant. In some cases, small amounts of the dopant may be present on a surface of ceria or ceria - zirconia. However, more of the dopant in general will be present in the body of ceria or ceria - zirconia.
[0030] When the first support material comprises ceria - zirconia, then typically the ceria - zirconia comprises at least 45% by weight of ceria, preferably at least 50% by weight of ceria, more preferably at least 55% by weight of ceria , such as at least 70% by weight ceria. The ceria-zirconia may further comprise a total of 1 to 15% by weight, preferably 2 to 12.5% by weight (eg 5 to 10% by weight), of an oxide or oxides of a second rare earth metal (eg the second rare earth metal is not cerium). The second rare earth metal is typically selected from the group consisting of lanthanum (La), praseodymium (Pr) and combinations thereof.
[0031] In general, ceria - zirconia consists essentially of 20 to 95% by weight of ceria and 5 to 80% by weight of zirconia (for example, 50 to 95% by weight of ceria and 5 to 50% by weight of zirconia), preferably 35 to 80% by weight ceria and 20 to 65% by weight zirconia (for example 55 to 80% by weight ceria and 20 to 45% by weight zirconia), even more preferably 45 to 75 % by weight of ceria and 25 to 55% by weight of zirconia.
[0032] When ceria or ceria - zirconia is doped, then the total amount of dopant is 0.1 to 5% by weight (ie % by weight of the ceria or ceria - zirconia). It is preferred that the total amount of dopant is 0.25 to 2.5% by weight, more preferably 0.5 to 1.5% by weight (for example about 1% by weight). Ceria can be doped with one or more dopants selected from the group consisting of zirconium (Zr), titanium (Ti), silicon (Si), yttrium (Y), lanthanum (La), praseodymium (Pr), samarium (Sm ), neodymium (Nd) and an oxide thereof. Ceria - zirconia can be doped with one or more dopants selected from the group consisting of titanium (Ti), silicon (Si), yttrium (Y), lanthanum (La), praseodymium (Pr), samarium (Sm), neodymium (Nd) and an oxide thereof.
[0033] It is preferred that ceria or ceria - zirconia has a high surface area. Typically, ceria or ceria-zirconia has a surface area of 30 to 300 m2/g, preferably 60 to 200 m2/g. Surface area is measured using conventional nitrogen physiosorption techniques.
[0034] It is preferred that the first support material comprises, or consists essentially of, ceria (CeO2) or ceria - zirconia (CeO2-ZrO2), which is not doped. The inclusion of a dopant in the first support material can decrease the catalytic activity of the first reactive coating region.
[0035] It is preferred that the first support material consists essentially of ceria. More preferably, the first support material essentially consists of ceria in a microporous form or a mesoporous form.
[0036] Typically, the first reactive coating region comprises an amount of the first support material of (0.006 to 0.27 g cm3 (0.1 to 4.5 g in-3)) (e.g., 0.015 to 0, 25 g cm3 (0.25 to 4.2 g in-3)), preferably 0.018 to 0.23 g cm3 (0.3 to 3.8 g in-3), even more preferably 0.03 to 0.18 g cm3 (0.5 to 3.0 g in-3) and even more preferably 0.03 to 0.15 g cm3 (0.6 to 2.5 g in-3) (for example, 0.045 to 0.1403 g in-3 (0.75 to 2.3 g in-3)).
[0037] In general, the first reactive coating region comprises an amount of palladium (Pd) from 0.2 to 15% by weight (for example, 11.5 to 14% by weight or 12 to 15% by weight), preferably 0.5 to 10% by weight, more preferably 1 to 9% by weight (for example 1.5 to 8% by weight), such as 2 to 7% by weight (for example 4 to 6% by weight ). The % by weight in this context is with reference to the amount of the first support material.
Typically, the first washable region comprises palladium (Pd) in an amount of 178.5 to 10.710 g m3 (5 to 300 g ft-3) more preferably 357 to 8925 g m3 (10 to 250 g ft-3) such as 714 to 7140 g m3 (20 to 200 g ft-3), even more preferably 892.5 to 6247.5 g m3 (25 to 175 g ft-3), and even more preferably 1249.5 to 5355 g m3 (35 to 150 g ft-3) (for example, 1785 to 4462.5 g m3 (50 to 125 g ft-3)).
[0039] For example, the first reactive coating region may comprise palladium (Pd) in an amount of 1785 to 10.710 g m3 (50 to 300 g ft-3) preferably 3570 to 9817.5 g m3 (100 to 275 g ft. -3) such as 5355 to 8925 g m3 (150 to 250 g ft-3) more preferably 6247.5 to 7140 g m3 (175 to 200 g ft-3). In some cases, a relatively high loading of palladium is beneficial (eg for CO oxidizing activity).
Typically, the first reactive coating region comprises a weight ratio of palladium (Pd) to cerium (Ce) of from 1:1000 to 1:10, preferably 1:500 to 1:15, more preferably 1:250 to 1:25.
[0041] It has been found that oxidation catalysts comprising palladium disposed or supported on cerium oxide can possess passive NOx adsorber (PNA) activity. The terms "passive NOx absorber" or "passive NOx adsorber" (PNA) as used herein (and as understood in the art) are used interchangeably and refer to the ability of a catalyst to (a) absorb (ie adsorb) NOx from an exhaust gas (eg from a compression-ignition engine) in a first temperature range and (b) releasing NOx in a second temperature range, where the second temperature range is greater than than the first temperature range (for example, the midpoint of the second temperature range is greater than the midpoint of the first temperature range). It is preferable that the second temperature range does not overlap with the first temperature range.
[0042] Unlike lean NOx trap catalysts (sometimes referred to as a NOx trap catalyst (NAC), a NOx trap catalyst (DNT), a NOx storage catalyst, a lean NOx trap (LNT) ) or a NOx storage/reduction (NSR) catalyst), it is not necessary to change the ratio of air to reductant (eg hydrocarbon, carbon monoxide or hydrogen) in an exhaust gas (eg lean to rich ), such as changing the operating mode of a motor, to release stored NOx from PNA. PNAs can be used to store NOx when exhaust gas temperatures are relatively cold, such as right after starting a compression-ignition engine. The storage of NOx, and in general also releases NOx, occurs at temperatures that are lower than the temperature at which significant oxidation of nitric oxide (NO) to nitrogen dioxide (NO2) by platinum occurs.
[0043] Typically, PNA activity can be expected to increase as the number of active sites on the catalyst is increased (eg, increasing the amount of palladium or the amount of palladium relative to ceria) to other effects that inhibit NOx contact with active sites from the catalyst begin to compete or dominate. However, it was unexpectedly found that excellent PNA activity can be obtained when the amount of palladium supported on cerium oxide is relatively low. In fact, surprisingly the threshold of additional benefit (in relation to PNA activity) is obtained when the palladium loading on the support material (eg ceria) is greater than 2% by weight. This finding is advantageous as both palladium and cerium oxide are inexpensive materials. PNA activity can be obtained when the oxidation catalyst has a relatively high loading of the first support material (eg ceria or ceria - zirconia), particularly in relation to palladium loading.
[0044] The first reactive coating region preferably comprises an amount of the first support material from 0.03 to 0.21 g cm3 (0.5 to 3.5 g in-3), more preferably 0.06 to 116, 02 g cm3 (1 to 3.25 g in-3), even more preferably 0.067 to 0.18 g cm3 (1.1 to 3.0 g in-3) (for example, 0.076 to 0.16 g cm3 ( 1.25 to 2.75 g in-3) or 0.091 to 0.16 g cm3 (1.5 to 2.75 g in-3), and even more preferably 0.076 to 0.15 g cm3 (1.25 to 2.5 g in-3).
[0045] The first reactive coating region may comprise an amount of palladium (Pd) of 0.25 to 4% by weight (eg 0.4 to 3.5% by weight), preferably 0.5 to 3. 0% by weight (for example 0.75 to 2.5% by weight or 1 to 1.75% by weight), and even more preferably 0.75 to 1.5% by weight.
[0046] It is advantageous if the first reactive coating region comprises an amount of palladium less than 2% by weight. It is preferred that the first reactive coating region comprises an amount of palladium from 0.25 to 1.9% by weight, more preferably 0.4 to 1.8% by weight, such as 0.5 to 1.75% by weight. weight, and even more preferably 0.75 to 1.5% by weight.
[0047] It is preferable that the first reactive coating region comprises a weight ratio of palladium (Pd) to cerium (Ce) of 1:1000 to 1:10, preferably 1:500 to 1:15, more preferably 1:200 at 1:20.
[0048] The first reactive coating region may comprise palladium (Pd) in an amount of 178.5 to 4248 g m3 (5 to 120 g ft-3), preferably 357 to 3570 g m3 (10 to 100 g ft-3 ), such as 892.5 to 3034.5 g m3 (25 to 85 g ft-3), even more preferably 1249.5 to 2856 g m3 (35 to 80 g ft-3) and even more preferably 1785 to 2677, 5 g m3 (50 to 75 g ft-3).
[0049] The first reactive coating region may comprise 95% or less of the total weight of palladium in the oxidation catalyst, preferably 80% or less, more preferably 60% or less.
[0050] A low palladium loading may be advantageous for passive NOx absorber activity or in applications where the oxidation catalyst is a catalytic soot filter (CSF).
[0051] More generally, it is possible to modify the activity of the oxidation catalyst by including other metals, such as catalytically active metals, in the first reactive coating region, the second reactive coating region, or in one or more additional reactive coating regions ( for example, a third reactive coating region or a fourth reactive coating region etc.).
[0052] For example, the first reactive coating region may further comprise a first catalytically active metal selected from the group consisting of platinum (Pt), gold (Au), ruthenium (Ru), rhodium (Rh), iridium ( Ir), silver (Ag) and a combination of two or more of them.
[0053] If a first catalytically active metal is present in the first reactive coating region, then preferably the first catalytically active metal is platinum (Pt) or gold (Au), more preferably the first catalytically active metal is platinum (Pt). When the metal is gold (Au), then palladium (Pd) and gold (Au) can be an alloy of palladium - gold. Catalysts comprising gold (Au) can be prepared using the method described in WO 2012/120292 by the present Applicant.
[0054] When the first reactive coating region comprises a first catalytically active metal, then typically the first reactive coating region comprises a total amount of first catalytically active metal from 71.4 to 5355 g m3 (2 to 150 g ft-3 ), more preferably 178.5 to 4462.5 g m3 (5 to 125 g ft-3), such as 357 to 3927 g m3 (10 to 110 g ft-3), even more preferably 892.5 to 3570 g m3 (25 to 100 g ft-3), and even more preferably 1071 to 2677.5 g m3 (30 to 75 g ft-3) (eg 1428 to 4462.5 g m3 (40 to 125 g ft-3) ).
[0055] When the first reactive coating region comprises a first catalytically active metal, it is preferred that the first reactive coating region comprises a total molar amount of first catalytically active metal that is less than the molar amount of palladium (Pd). Thus, the first reactive coating region comprises a ratio of the total molar amount of palladium (Pd) to the total molar amount of first catalytically active metal of >1:1 (eg, Pd: from 20:1 to 1.1: 1; 10:1 to 1.25:1; 7.5:1 to 2:1; 5:1 to 2.5:1; where Mi represents the first catalytically active metal).
[0056] The first reactive coating region may additionally comprise a hydrocarbon adsorbent. The hydrocarbon adsorbent can be selected from a zeolite, active carbon, porous graphite and a combination of two or more thereof. It is preferred that the hydrocarbon adsorbent is a zeolite.
[0057] When the first reactive coating region comprises a hydrocarbon adsorbent, then typically the total amount of hydrocarbon adsorbent is 0.003 to 0.183 g cm3 (0.05 to 3.00 g in-3), particularly 0.0061 to 0.122 g cm3 (0.10 to 2.00 g in-3) more particularly 0.012 to 0.048 g cm3 (0.2 to 0.8 g in-3).
[0058] When the hydrocarbon adsorbent is a zeolite, then preferably the zeolite is a medium pore zeolite (eg a zeolite having a maximum ring size of eight tetrahedral atoms) or a large pore zeolite (eg a zeolite having a maximum ring size of ten tetrahedral atoms).
[0059] 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 , ZSM-34 zeolite, CHA zeolite, SSZ-3 zeolite, SAPO-5 zeolite, offretite, a beta zeolite or a copper CHA zeolite. The zeolite is preferably ZSM-5, a beta zeolite or a Y zeolite.
[0060] In general, it is preferred that the first reactive coating region does not comprise a zeolite, more preferably the first reactive coating region does not comprise a hydrocarbon adsorbent. Thus, the first reactive coating region may be substantially free of hydrocarbon adsorbent or zeolite. If the oxidation catalyst comprises a hydrocarbon adsorbent, such as a zeolite, then preferably the second reactive coating region and/or a third reactive coating region comprises the hydrocarbon adsorbent or zeolite.
[0061] Typically, the first reactive coating region consists essentially of palladium (Pd), the first catalytically active metal, the first support material and optionally a hydrocarbon adsorbent. More preferably, the first reactive coating region consists essentially of palladium (Pd), the first catalytically active metal and the first support material.
[0062] In general, the first reactive coating region does not comprise a first catalytically active metal as described here (i.e. palladium is the only active metal for catalysis in the first reactive coating region). The first support material may, however, include one or more other materials, but in general such materials are included to stabilize the first support material (for example, they form part of the volumetric composition of the support material) and they are not itself catalytically active. Preferably, the first reactive coating region is substantially free of or does not comprise platinum. More preferably, the first reactive coating region consists essentially of palladium (Pd) and the first support material.
[0063] The function of a passive NOx adsorber (PNA) is different for a lean NOx trap catalyst. Therefore, it is unnecessary to include materials in the oxidation catalyst that function as a NOx adsorber. Such NOx adsorbing materials store NOx when the exhaust gas is poor and release NOx when the exhaust gas is rich.
[0064] In general, it is preferred that the first reactive coating region is substantially free of or does not comprise a NOx adsorber material to a poor NOx trap catalyst. NOx adsorbing materials for a lean NOx trap catalyst typically comprise an alkali metal (eg Li, Na, K), an alkaline earth metal (eg Mg, Ca, Sr, Ba) and/or a metal of rare Lands.
[0065] The first reactive coating region typically is substantially free of or does not comprise an alkali metal (eg Li, Na, K), an alkaline earth metal (eg Mg, Ca, Sr, Ba) and/or a rare earth metal, particularly a rare earth metal selected from the group consisting of lanthanum (La), yttrium (Y) and a combination thereof. The general exclusion referring to a rare earth metal does not apply to ceria or ceria - zirconia which is part of the first support material.
[0066] In general, the first reactive coating region is substantially free of or does not comprise rhodium (Rh).
[0067] In general it is preferred that the first reactive coating region does not comprise rhodium (Rh), a hydrocarbon adsorbent, an alkali metal (eg Li, Na, K), an alkaline earth metal (eg Mg, Ca, Sr, Ba) and a rare earth metal, particularly a rare earth metal selected from the group consisting of lanthanum (La), yttrium (Y) and a combination thereof.
[0068] The second reactive coating region of the invention comprises platinum (Pt) and a second support material. The second reactive coating region and the first reactive coating region generally have different compositions. It has been found that N2O generation by a Pt-containing reactive coating region (eg, the second reactive coating region) can be reduced or avoided when it is combined with the first reactive coating region.
[0069] The second reactive coating region typically comprises platinum disposed or supported on the second support material. Platinum can be arranged on the second support material and/or impregnated on the second support material.
Typically, the second reactive coating region comprises an amount of platinum (Pt) from 0.2 to 15% by weight, preferably 0.5 to 10% by weight, more preferably 1 to 9% by weight (for example , 1.5 to 8% by weight), such as 2 to 7% by weight (for example 4 to 6% by weight). The % by weight in this context is with reference to the amount of the second support material.
[0071] The second reactive coating region typically comprises platinum (Pt) in an amount of 178.5 to 10,710 g m3 (5 to 300 g ft-3), more preferably 357 to 8925 g m3 (10 to 250 g ft- 3), such as 714 to 7140 g m3 (20 to 200 g ft-3) even more preferably 892.5 to 6247.5 g m3 (25 to 175 g ft-3) and even more preferably 1249.5 to 5355 g m3 (35 to 150 g ft-3) (eg 1785 to 4462.5 g m3 (50 to 125 g ft-3).
[0072] The second reactive coating region may comprise 50% or more of the total weight of platinum in the oxidation catalyst, preferably 70% or more, more preferably 90% or more.
[0073] In the second reactive coating region, platinum may be the only catalytically active metal.
[0074] Thus, for example, the second reactive coating region does not include a catalytically active second metal as defined below.
[0075] However, the activity of the oxidation catalyst can be modified by including other metals, such as a catalytically active second metal, in the second reactive coating region. Thus, the second reactive coating region may further comprise a second catalytically active metal selected from the group consisting of palladium (Pd), gold (Au), ruthenium (Ru), rhodium (Rh), iridium (Ir), silver (Ag) and a combination of two or more of them. It is preferred that the second catalytically active metal is palladium (Pd).
[0076] The second catalytically active metal may be disposed or supported on the second support material. Thus, the catalytically active second metal can be dispersed in the second support material and/or impregnated in the second support material.
[0077] When the second reactive coating region comprises a second catalytically active metal, then typically the second reactive coating region comprises a total amount of second catalytically active metal from 71.4 to 5355 g m3 (2 to 150 g ft-3 ), more preferably 178.5 to 4462.5 g m3 (5 to 125 g ft-3), such as 357 to 3927 g m3 (10 to 110 g ft-3), even more preferably 714 to 3570 g m3 (20 to 100 g ft-3), and even more preferably 1071 to 2677.5 g m3 (30 to 75 g ft-3) (for example 1428 to 4462.5 g m3 (40 to 125 g ft-3).
[0078] When the second reactive coating region comprises a second catalytically active metal, then it is preferred that the second reactive coating region comprises a total molar amount of second catalytically active metal(s) that is less than the molar amount of platinum (Pt). Thus, second reactive coating region comprises a ratio of molar amount of platinum (Pt) to total molar amount of second catalytically active metal of >1:1 (eg Pt:m2 from 20:1 to 1.1:1 ; 10 :1 to 1.25:1; 7.5:1 to 2: 1; 5:1 to 2.5:1; where m2 represents the catalytically active metal).
[0079] In general, it is preferred that the second reactive coating region comprises, or consists essentially of, platinum (Pt), palladium (Pd) and a second support material. Typically, the second reactive coating region has a mass ratio of platinum (Pt) to palladium (Pd) of 10:1 to 1:3, more preferably 8.5:1 to 1:2.5, such as 7, 5:1 to 1:2 (eg 7:1 to 1:1.5), even more preferably 6:1 to 1:1.25 (eg 5:1 to 1:1).
[0080] In the second reactive coating region, the mass of platinum (Pt) typically is greater than the mass of palladium (Pd). Advantageous oxidative activity can be obtained when there is more platinum than palladium in the second reactive coating region. Thus, the second reactive coating region preferably has a mass ratio of platinum (Pt) to palladium (Pd) of 10:1 to 1.25:1, more preferably 8:1 to 1.5:1, such as 7 :1 to 1.75:1, and even more preferably 6:1 to 2:1.
[0081] Typically, the second support material comprises, or consists essentially of, a refractory metal oxide. Refractory metal oxides suitable for use as a catalyst component of an oxidation catalyst for a compression ignition engine are well known in the art.
[0082] The refractory metal oxide is preferably selected from the group consisting of alumina, silica, titania, zirconia, ceria and composite or mixed oxides of two or more thereof. More preferably, the refractory metal oxide is selected from alumina, silica and composite or mixed oxides thereof. Even more preferably, the refractory metal oxide is selected from alumina, silica-alumina and a mixture of alumina and ceria.
[0083] When the refractory metal oxide is a mixed oxide or alumina compound, such as silica-alumina or a mixture of alumina and ceria, then preferably the mixed oxide or alumina compound comprises at least 50 to 99% by weight of alumina, more preferably 70 to 95% by weight alumina, even more preferably 75 to 90% by weight alumina.
[0084] For the avoidance of doubt, alumina or a mixed oxide or compound comprising alumina is not a modified alumina that incorporates a heteroatom component, particularly a modified alumina that incorporates a heteroatom component that comprises, or consists essentially of, a doped alumina with a heteroatom component or an alkaline earth metal aluminate. In this context, the heteroatom component comprises silicon, magnesium, barium, lanthanum, cerium, titanium, or zirconium or a combination of two or more thereof.
[0085] It is preferred that the refractory metal oxide is alumina. Alumina can be α-Ahθ3, β-Ahθ3, or Y-AI2O3. Preferably the alumina comprises, or consists essentially of, Y-Al2O3.
[0086] More preferably, the second reactive coating region comprises, or consists essentially of, platinum, palladium and a second support material, wherein the second support material comprises, or consists essentially of, alumina.
[0087] Typically, the second reactive coating region comprises an amount of the second support material from 0.0061 to 0.213 g cm3 (0.1 to 3.5 g in-3), preferably 0.012 to 0.152 g cm3 (0, 2 to 2.5 g in-3) even more preferably 0.018 to 0.122 g cm3 (0.3 to 2.0 g in-3) and even more preferably 0.030 to 0.106 g cm3 (0.5 to 1.75 g in-3) -3) (for example, 0.045 to 0.091 g cm3 (0.75 to 1.5 g in-3)).
[0088] The second reactive coating region may additionally comprise a hydrocarbon adsorbent. The hydrocarbon adsorbent can be selected from a zeolite, active carbon, porous graphite and a combination of two or more thereof. It is preferred that the hydrocarbon adsorbent is a zeolite, more preferably a zeolite as defined above.
[0089] The second reactive coating region typically comprises an amount of hydrocarbon adsorbent from 0.003 to 0.183 g cm3 (0.05 to 3.00 g in-3), particularly 0.0061 to 0.122 g cm3 (0.10 to 2.00 g in-3), more particularly 0.012 to 0.048 g cm3 (0.2 to 0.8 g in-3).
[0090] The second reactive coating region may additionally comprise an oxygen storage material. Such materials are well known in the art. The second reactive coating region may comprise an oxygen storage material in a total amount of 0.1 to 10% (eg 0.25 to 2.5%, or 0.5 to 1%) of the total amount of second support material.
[0091] The oxygen storage material can be selected from ceria (CeO2) and ceria - zirconia (CeO2-ZrO2), such as a solid solution of ceria - zirconia. When the oxygen storage material is selected from ceria and ceria - zirconia, then preferably the oxygen storage material is either (a) ceria when the first support material comprises, or consists essentially of, ceria - zirconia, or (b) ceria - zirconia when the first support material comprises, or consists essentially of, ceria.
[0092] In general, it is preferable that the second reactive coating region consists essentially of platinum, palladium, the second support material and optionally a zeolite.
[0093] It is preferred that the second reactive coating region, or the oxidation catalyst itself, is substantially free of or does not comprise a material NOx trap to a poor NOx trap catalyst. NOx adsorbing materials for a lean NOx trap catalyst typically comprise an alkali metal (eg Li, Na, K), an alkaline earth metal (eg Mg, Ca, Sr, Ba) and/or a metal of rare Lands. Cerium and cerium oxide are not considered as a material NOx adsorber in this context.
[0094] The second reactive coating region typically is substantially free of or does not comprise an alkali metal (eg Li, Na, K), an alkaline earth metal (eg Mg, Ca, Sr, Ba) and/or a rare earth metal, particularly a rare earth metal selected from the group consisting of lanthanum (La), yttrium (Y) and a combination thereof.
[0095] In general, the second reactive coating region or the oxidation catalyst of the invention is substantially free of or does not comprise rhodium (Rh).
[0096] In general it is preferred that the second reactive coating region does not comprise rhodium (Rh), a hydrocarbon adsorbent, an alkali metal (eg Li, Na, K), an alkaline earth metal (eg Mg, Ca, Sr, Ba) and a rare earth metal, particularly a rare earth metal selected from the group consisting of lanthanum (La), yttrium (Y) and a combination thereof.
[0097] In general, the first support material and/or the second support material is in particulate form. Each support material can have a d90 particle size of < 20 µm (as determined by conventional laser diffraction techniques). The particle size distribution of the support material is selected to aid adhesion to the substrate. Particles are generally obtained by grinding.
[0098] Typically, the oxidation catalyst comprises a total amount (by mass) of platinum and palladium of 1.0 to 10.0 g. The total amount of platinum and palladium that is used depends, among other things, on the size of the substrate and the intended application of the oxidation catalyst.
[0099] In general, the total amount of platinum in the first reactive coating region and the second reactive coating region to the total amount of palladium in the first reactive coating region and the second reactive coating region have a ratio (by mass) from 20:1 to 1:20. Thus, the mass ratio of platinum to palladium contained in both the first reactive coating region and the second reactive coating region can be 20:1 to 1:20. Preferably, the ratio is 10:1 to 1:10 (eg 8:1 to 1:8), more preferably the ratio is 7.5:1 to 1:7.5, such as 5:1 to 1: 5, even more preferably the ratio is 4:1 to 1:4 (eg 3:1 to 1:3), such as 2.5:1 to 1:2.5 (eg 2:1 to 1 :two).
[00100] Typically, the oxidation catalyst comprises a total amount of platinum (Pt) and a total amount of palladium (Pd) in a ratio (by mass) of > 1:3.5. It is preferred that the ratio (by mass) is > 1:2.5, more preferably > 1:2, particularly > 1:1.5, such as > 1:1.
[00101] The oxidation catalysts of the invention where the total amount (by mass) of palladium (Pd) is less than the total amount (by mass) of platinum (Pt), typically where each total amount refers to the combined amount of palladium or platinum in the first and second reactive coating regions or in the oxidation catalyst as a whole may have advantageous activity.
[00102] The ratio (by mass) of platinum (Pt) to palladium (Pd) is typically 20:1 to 1.1:1 (eg 15:1 to 1.2:1), preferably the ratio is 10 :1 to 1.3:1 (for example 9:1 to 1.4:1), more preferably 8:1 to 1.5:1, even more preferably 7.5:1 to 1.75:1, such as 6:1 to 2:1, and even more preferably 5.5:1 to 2.5:1 (for example, 5:1 to 3:1). The oxidation catalyst of the invention generally comprises a total amount of first support material and second support material from 0.012 to 0.488 (0.2 to 8 g in-3), preferably 0.024 to 0.427 g cm3 (0.4 to 7 g in-3) (for example 0.0305 to 0.366 g cm3 (0.5 to 6 g in-3), more preferably 0.045 to 0.305 g cm3 (0.75 to 5 g in-3) (for example, 0.048 to 0.244 g cm3 (0.8 to 4 g in-3)), even more preferably 0.061 to 0.183 g cm3 (1.0 to 3 g in-3).
[00103] The first reactive coating region and the second reactive coating region are arranged or supported on the same substrate. Methods for making reactive coating regions of different arrangements are known in the art (see, for example, WO 99/47260 by the present Applicant). However, it should be understood that certain arrangements of the first reactive coating region and the second reactive coating region on the substrate may be particularly advantageous for oxidizing CO, for reducing or preventing the generation of nitrous oxide (N2O) or for absorbing CO activity. passive NOx.
[00104] In general, the first reactive coating region can be disposed directly on the substrate (i.e. the first reactive coating region is in contact with a surface of the substrate). The second reactive coating region can be (a) disposed or supported in the first reactive coating region, (b) disposed directly on the substrate (i.e. the second reactive coating region is in contact with a surface of the substrate), and/or (c) in contact with the first reactive coating region. Alternatively, the second reactive coating region can be disposed directly to an additional reactive coating region (eg, a third reactive coating region).
[00105] When the second reactive coating region is disposed or supported in the first reactive coating region, the second reactive coating region can be disposed directly to the first reactive coating region (i.e. the second reactive coating region is in contact with a surface of the first reactive coating region) or the second reactive coating region can be disposed directly to an additional reactive coating region (e.g. a third reactive coating region) where the additional reactive coating region is disposed (eg, directly or otherwise) or supported in the first reactive coating region. When the second reactive coating region is disposed directly onto the substrate, then the second reactive coating region may be in contact with the first reactive coating region or the first reactive coating region and the second reactive coating region may be separated ( for example, by an intervening third reactive coating region or by a gap).
[00106] Typically, the second reactive coating region is disposed directly onto the substrate (i.e. the second reactive coating region is in contact with a surface of the substrate). The first reactive coating region can be (i) disposed or supported on the second reactive coating region, (ii) disposed directly to the substrate (i.e. the first reactive coating region is in contact with a surface of the substrate), and /or (iii) in contact with the second reactive coating region. Alternatively, the first reactive coating region can be disposed directly to an additional reactive coating region (eg a third reactive coating region).
[00107] When the first reactive coating region is disposed or supported in the second reactive coating region, the first reactive coating region can be disposed directly to the second reactive coating region (i.e. the first reactive coating region is in contact with a surface of the second reactive coating region) or the first reactive coating region can be disposed directly to an additional reactive coating region (e.g. a third reactive coating region) where the additional reactive coating region is disposed (eg, directly or otherwise) or supported in the second reactive coating region. When the first reactive coating region is disposed directly onto the substrate, then the first reactive coating region may be in contact with the second reactive coating region or the second reactive coating region and the first reactive coating region may be separated ( for example, by an intervening third reactive coating region or by a gap).
[00108] In general, it is possible that both the first reactive coating region and the second reactive coating are not directly disposed on the substrate (i.e. neither the first reactive coating region nor the second reactive coating region is in contact with a surface of the substrate). Thus, at least one of the first reactive coating region and the second reactive coating region is disposed or supported in an additional reactive coating region (e.g., a third reactive coating region). Both the first reactive coating region and the second reactive coating region can be disposed or supported in the same additional reactive coating region (e.g., a third reactive coating region).
[00109] Some oxidation catalysts of the invention are described below where the first reactive coating region and the second reactive coating region have "zoned" arrangements. For the avoidance of doubt, these arrangements are general functionalities of the oxidation catalyst of the invention and can be combined with the arrangements of the first and second reactive coating regions described above.
[00110] In a first oxidation catalyst arrangement, the first reactive coating region is a first reactive coating zone disposed or supported at or near an input end of the substrate. The second reactive coating region may be disposed or supported upstream or downstream of the first reactive coating zone, preferably downstream. Preferably, the second reactive coating region is a second reactive coating zone. More preferably, the second reactive coating zone is disposed or supported downstream of the first reactive coating zone.
[00111] In a second oxidation catalyst arrangement, the first reactive coating region is a first reactive coating zone disposed or supported on an exit end of the substrate. The second reactive coating region may be disposed or supported upstream or downstream of the first reactive coating zone, preferably upstream. Preferably, the second reactive coating region is a second reactive coating zone. More preferably, the second reactive coating zone is disposed or supported upstream of the first reactive coating zone.
[00112] In a third oxidation catalyst arrangement, the second reactive coating region is a second reactive coating zone disposed or supported at an input end of the substrate. The first reactive coating region may be disposed or supported upstream or downstream of the second reactive coating zone, preferably downstream. Preferably, the first reactive coating region is a first reactive coating zone. More preferably, the first reactive coating zone is disposed or supported downstream of the second reactive coating zone.
[00113] In a fourth oxidation catalyst arrangement, the second reactive coating region is a second reactive coating zone disposed or supported at an exit end of the substrate. The first reactive coating region may be disposed or supported upstream or downstream of the second reactive coating zone, preferably upstream. Preferably, the first reactive coating region is a first reactive coating zone. More preferably, the first reactive coating zone is disposed or supported upstream of the second reactive coating zone.
[00114] The first reactive coating zone may be adjacent to the second reactive coating zone. More preferably, the first reactive coating zone is in contact with the second reactive coating zone. When the first reactive coating zone is adjacent to the second reactive coating zone or the first reactive coating zone is in contact with the second reactive coating zone, the first reactive coating zone and the second reactive coating zone can be arranged or supported on the substrate as a layer, such as a single layer (for example, a single layer). Thus, a layer can be formed on the substrate when the first and second reactive coating zones are adjacent or in contact with each other.
[00115] The first reactive coating zone can be separated from the second reactive coating zone. Thus, there may be an additional reactive coating zone or intervening region (e.g., a third reactive coating zone or region) between the first reactive coating zone and the second reactive coating zone, and/or there may be a gap (by example, a space) between the first reactive coating zone and the second reactive coating zone.
[00116] The first reactive coating zone may overlap the second reactive coating zone. Thus, an end portion of the first reactive coating zone may be disposed or supported in the second reactive coating zone. The first reactive coating zone may completely or partially overlap the second reactive coating zone. When the first reactive coating zone completely overlaps the second reactive coating zone, then typically a surface of the second reactive coating zone (typically a surface in the longitudinal plane of the catalyst, i.e. the plane that is perpendicular to the plane of the inlet ends and substrate exit) is completely covered by the first reactive coating zone.
[00117] Alternatively, the second reactive coating zone may overlap the first reactive coating zone. Thus, an end portion of the second reactive coating zone may be disposed or supported in the first reactive coating zone. The second reactive coating zone may completely or partially overlap the first reactive coating zone. When the second reactive coating zone completely overlaps the first reactive coating zone, then typically a surface of the first reactive coating zone (typically a surface in the longitudinal plane of the catalyst, i.e. the plane that is perpendicular to the plane of the inlet ends and substrate outlet) is completely covered by the second reactive coating zone.
[00118] Typically, the first reactive coating zone has a length of 10 to 90% of the length of the substrate (eg 10 to 45%), preferably 15 to 75% of the length of the substrate (eg 15 to 40% ), more preferably 20 to 65% (e.g. 25 to 45%) of the length of the substrate, even more preferably 25 to 50%.
[00119] The second reactive coating zone typically has a length of 10 to 90% of the length of the substrate (eg 10 to 45%), preferably 15 to 75% of the length of the substrate (eg 15 to 40%) more preferably 20 to 65% (eg 25 to 45%) of the length of the substrate, even more preferably 25 to 50%.
[00120] Oxidation catalysts of the invention are described below where the first reactive coating region and the second reactive coating region have "layered" arrangements. For the avoidance of doubt, these arrangements are general functionalities of the oxidation catalyst of the invention and can be combined with any of the arrangements of the first and second reactive coating regions described above.
[00121] The first reactive coating region can be a first reactive coating layer and the second reactive coating region can be a second reactive coating layer. The first reactive coating layer and the second reactive coating layer can be of different lengths, or the first reactive coating layer and the second reactive coating layer can be about the same length. In general, the length of the first reactive coating layer and the length of the second reactive coating layer are each substantially uniform.
[00122] Typically, at least one of the first reactive coating layer and the second reactive coating layer extends over substantially the entire length of the substrate, particularly the entire length of the channels of a substrate monolith. More preferably, the first reactive coating layer and the second reactive coating layer each extend over substantially the entire length of the substrate.
[00123] In a fifth oxidation catalyst arrangement, the first reactive coating layer is disposed or supported on the second reactive coating layer. The first reactive coating layer can be disposed directly to the second reactive coating layer (i.e. the first reactive coating layer is in contact with a surface of the second reactive coating layer) or the first reactive coating layer can be disposed directly to an additional reactive coating region or layer (eg a third reactive coating region or layer), additional reactive coating region or layer which is disposed or supported on the second reactive coating layer. Preferably, the entire length of the first reactive coating layer is disposed or supported on the second reactive coating layer. Thus, the length of the first reactive coating layer is less than or equal to the length of the second reactive coating layer. More preferably, one end of the first reactive coating layer does not extend beyond an end of the second reactive coating layer (i.e. the ends or boundaries of the first reactive coating layer are within the ends or boundaries of the second reactive coating layer) .
[00124] In the fifth oxidation catalyst arrangement, the first reactive coating layer may be arranged or supported in an additional reactive coating region (e.g. a third or fourth reactive coating region), particularly an additional coating layer reactive or zone. The additional reactive coating region can be laid directly onto the substrate.
[00125] It is preferred in the fifth oxidation catalyst arrangement that the second reactive coating layer is disposed directly onto the substrate (i.e. the second reactive coating layer is in contact with a surface of the substrate).
[00126] In the fifth oxidation catalyst arrangement, an additional reactive coating region (for example, a third, fourth or fifth reactive coating region), particularly an additional reactive coating layer or zone, can be arranged directly to the second reactive coating layer (ie the region of additional reactive coating is in contact with a surface of the second reactive coating layer).
[00127] In a sixth oxidation catalyst arrangement, the second reactive coating layer is disposed or supported on the first reactive coating layer. The second reactive coating layer can be disposed directly to the first reactive coating layer (i.e. the second reactive coating layer is in contact with a surface of the first reactive coating layer) or the second reactive coating layer can be disposed directly for an additional reactive coating region or layer (e.g. a third reactive coating region or layer), additional reactive coating region or layer which is disposed or supported on the first reactive coating layer. Preferably, the entire length of the second reactive coating layer is disposed or supported on the first reactive coating layer. Thus, the length of the second reactive coating layer is less than or equal to the length of the first reactive coating layer. More preferably, one end of the second reactive coating layer does not extend beyond an end of the first reactive coating layer (i.e. the ends or boundaries of the second reactive coating layer are within the ends or boundaries of the first reactive coating layer) .
[00128] In the sixth oxidation catalyst arrangement, the second reactive coating layer may be disposed or supported in an additional reactive coating region (for example, a third or fourth reactive coating region), particularly an additional reactive coating layer or zone. The additional reactive coating region can be laid directly onto the substrate.
[00129] It is preferred in the sixth oxidation catalyst arrangement that the first reactive coating layer is disposed directly onto the substrate (ie the first reactive coating layer is in contact with a surface of the substrate).
[00130] In the sixth oxidation catalyst arrangement, an additional reactive coating region (for example, a third, fourth or fifth reactive coating region), particularly an additional reactive coating layer or zone, can be arranged directly to the first reactive coating layer (ie the region of additional reactive coating is in contact with a surface of the first reactive coating layer).
[00131] The oxidation catalyst of the invention may comprise a plurality of reactive coating regions, in addition to the first reactive coating region and the second reactive coating region.
[00132] In general, it is preferred that the oxidation catalyst comprises only three or four reactive coating regions (including the first reactive coating region and the second reactive coating region). Thus, the oxidation catalyst may further comprise a third reactive coating region (e.g., a third reactive coating layer or zone) and a fourth reactive coating region (e.g., a fourth reactive coating layer or zone. More preferably, , the oxidation catalyst comprises only three reactive coating regions (including the first reactive coating region and the second reactive coating region). Thus, the oxidation catalyst further comprises a third reactive coating region. Even more preferably, the catalyst The oxidation of oxidation comprises only two reactive coating regions, reactive coating regions which are the first reactive coating region and the second reactive coating region.
[00133] Certain oxidation catalyst arrangements are particularly advantageous for reducing the amount of nitrous oxide (N2O) that is generated. Oxidation catalyst arrangements where most or all of the exhaust gas contacts the first reactive coating region before the second reactive coating region has been found to generate less N2O.
[00134] It is preferred that the first reactive coating region is arranged to contact inlet exhaust gas before the second reactive coating region, such as in any one of the first to fifth oxidation catalyst arrangements, and wherein in the first to fourth oxidation catalyst arrays the second reactive coating region is disposed or supported downstream of the first reactive coating region. More preferably, the oxidation catalyst has the first oxidation catalyst arrangement or the fifth oxidation catalyst arrangement, wherein in the first oxidation catalyst arrangement the second reactive coating region is disposed or supported downstream of the first coating region reactive.
[00135] Advantageous oxidation activity and/or the amount of nitrous oxide (N2O) produced by the oxidation catalyst can be reduced or avoided when the oxidation catalyst comprises a substrate, and: (a) a first reactive coating zone comprising palladium (Pd) and a first support material comprising cerium oxide; and a second reactive coating zone comprising platinum (Pt) and a second support material; wherein the second reactive coating zone is disposed or supported on the substrate downstream of the first reactive coating zone; or (b) a first reactive coating layer comprising palladium (Pd) and a first support material comprising cerium oxide; and a second reactive coating layer comprising platinum (Pt) and a second support material; wherein the first reactive coating layer is disposed or supported on the second reactive coating layer.
[00136] In general, the oxidation catalyst additionally comprises an additional reactive coating region (e.g., a third reactive coating region), wherein the additional reactive coating region is arranged to contact inlet exhaust gas before the first reactive coating region and the second reactive coating region, and wherein the additional reactive coating region comprises a hydrocarbon adsorbent. Thus, the additional reactive coating region may be downstream of both the first reactive coating region and the second reactive coating region and/or the additional reactive coating region may be disposed or supported in both the first reactive coating region and the second reactive coating region (for example, the additional reactive coating region may be the uppermost layer). The hydrocarbon adsorbent may be present in the additional reactive coating region in an amount as defined above for the first reactive coating region or the second reactive coating region. Preferably, the hydrocarbon adsorbent is a zeolite, such as a zeolite as defined above.
[00137] Substrates to support oxidation catalysts to treat the exhaust gas of a compression ignition engine are well known in the art. The substrate typically has a plurality of channels (eg for exhaust gas to flow through). In general, the substrate is a ceramic material or a metallic material.
[00138] It is preferred that the substrate is made or composed of cordierite (SiO2-Al2O3-MgO), silicon carbide (SiC), Fe-Cr-AI alloy, Ni-Cr-Al alloy, or a steel alloy stainless.
[00139] Typically, the substrate is a monolith (also referred to herein as a substrate monolith). Such monoliths are well known in the art. The substrate monolith can be a flow-through monolith or a filtering monolith.
[00140] A flow-through monolith typically comprises a honeycomb monolith (eg a metal or ceramic honeycomb monolith) having a plurality of channels extending therethrough, channels which are open at both ends . When the substrate is a flow-through monolith then the oxidation catalyst of the invention is typically a diesel oxidation catalyst (DOC) and/or a passive NOx absorber (PNA) or is for use as a diesel oxidation catalyst. diesel (DOC) and/or as a passive NOx absorber (PNA).
[00141] A filtering monolith generally comprises a plurality of inlet channels and a plurality of outlet channels, wherein the inlet channels are open at an upstream end (i.e. exhaust gas inlet side) and are plugged or sealed at a downstream end (ie exhaust gas outlet side), the outlet channels are plugged or sealed at an upstream end and are open at a downstream end, and where each inlet channel is separate of an exit channel by a porous structure. When the substrate is a filtering 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).
[00142] When the monolith is a filtering monolith, it is preferred that the filtering monolith is a wall flow filter. In a wall flow filter, each inlet channel is alternately separated from an outlet channel by a wall of the porous structure and vice versa. It is preferred that the input channels and output channels be arranged in a honeycomb arrangement.
[00143] When a honeycomb arrangement exists, it is preferred that channels vertically and laterally adjacent to an inlet channel are plugged into an upstream end and vice versa (i.e., channels vertically and laterally adjacent to a channel outlets are plugged into a downstream end). When viewed from both ends, the alternately plugged and open ends of the channels take on the appearance of a chessboard.
[00144] In principle, the substrate can be of any shape or size. However, substrate shape and size is commonly selected to optimize the exposure of catalytically active materials in the catalyst to the exhaust gas. The substrate, for example, can have a particulate, fibrous or tubular form. Examples of suitable support substrates include a monolithic honeycomb cordierite type substrate, a monolithic honeycomb SiC type substrate, a knitted fabric or layered fiber type substrate, a foam type substrate, a substrate of cross-flow type, a metal wire mesh type substrate, a porous body type of metal substrate and a ceramic particle type substrate.
[00145] In general, the oxidation catalyst of the invention is for use as (i) a passive NOx absorber (PNA) and/or (ii) a diesel oxidation catalyst (DOC) or a catalyzed soot filter ( CSF). In practice, catalyst formulations employed in DOCs and CSFs are similar. In general, however, a major difference between DOC and CSF is the substrate on which the catalyst formulation is coated and the total amount of platinum, palladium and any other catalytically active metals that are coated onto the substrate.
[00146] The invention also provides an exhaust system comprising the oxidation catalyst and an emission control device. In general, the emission control device is separate from the oxidation catalyst (for example, the emission control device has a substrate separate from the oxidation catalyst substrate), and preferably the oxidation catalyst is upstream of the control device of emissions.
[00147] The exhaust system of the invention may further comprise a fuel sulfur removal device. A fuel sulfur removal device can be upstream or downstream of the oxidation catalyst. Preferably the fuel sulfur removal device is upstream of the oxidation catalyst. Fuel sulfur removal devices are known in the art. The oxidation catalyst of the invention may be susceptible to sulfur deactivation. Deactivation of the fuel sulfur oxidation catalyst can be reduced or avoided when a fuel sulfur removal device is upstream of the oxidation catalyst. Platinum-containing oxidation catalysts generally oxidize fuel sulfur to SO2 or can increase sulphate particulate emissions, particularly at higher exhaust temperatures.
[00148] The emission control device can be selected from a diesel particulate filter (DPF), a NOx adsorbing catalyst (NAC), a lean NOx catalyst (LNC), a selective catalytic reduction catalyst ( SCR), a diesel oxidation catalyst (DOC), a catalyzed soot filter (CSF), a selective catalytic reduction filter catalyst (SCRF™), and combinations of two or more thereof. Emission control devices represented by the terms diesel particulate filters (DPFs), NOx adsorbing catalysts (NACs), lean NOx catalysts (LNCs), selective catalytic reduction (SCR) catalysts, diesel oxidation catalyst (DOCs) , catalyzed soot filters (CSFs) and selective catalytic reduction filter catalysts (SCRF™) are all well known in the art.
[00149] Examples of emission control devices for use with the oxidation catalyst of the invention or for inclusion in the exhaust system of the invention are provided below.
[00150] A diesel particulate filter is an emissions control device having a filter substrate. The diesel particulate filter preferably comprises a substrate, wherein the substrate is a filter monolith or a flow-through monolith as defined above, preferably a filter monolith. The substrate can be coated with a catalyst formulation.
[00151] The diesel particulate filter catalyst formulation may be suitable for oxidizing (i) particulate matter (PM) and/or (ii) carbon monoxide (CO) and hydrocarbons (HCs). When the catalyst formulation is suitable for oxidizing PM, then the resulting emission control device is known as a catalyzed soot filter (CSF). A catalyzed soot filter (CSF) is also an emission control device having a filter substrate. Typically, the CSF catalyst formulation comprises a noble metal as defined above and/or platinum and/or palladium.
[00152] The catalyst formulation of the diesel particulate filter can be a NOx adsorber composition. When the catalyst formulation is a NOx adsorber composition, the emission control device is an example of a NOx adsorber catalyst. NOx (NAC) (eg a NOx adsorber composition in a filter). Emission control devices where the catalyst formulation is a NOx adsorber composition have been described (see, for example, EP 0766993). NOx adsorber compositions are well known in the art (see, for example, EP 0766993 and US 5,473,887). NOx adsorber compositions are designed to adsorb NOx from lean exhaust gas (lambda >1) and to desorb NOx when the oxygen concentration in the exhaust gas is decreased. Desorbed NOx can then be reduced to N2 with a suitable reducer (eg motor fuel) and promoted by a catalyst component, such as rhodium, from the NOx adsorber composition itself or located downstream of the NOx adsorber composition .
[00153] In general, NOx adsorber catalysts comprising coated on monolith substrates flowing through honeycomb typically are arranged in layered arrangements. However, multiple layers applied to a filter substrate can create back pressure problems. It is highly preferable, therefore, if the NOx absorber catalyst for use in the present invention is a "single layer" NOx absorber catalyst. Particularly preferred "single layer" NOx absorber catalysts comprise a first rhodium component supported on a mixed oxide of ceria - zirconia or an optionally stabilized alumina (e.g. stabilized with silica or lantana or other 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 large surface area support based on alumina and a particulate "bulk" ceria (CeO2) component, i.e. not a soluble ceria supported on a particulate support, but “bulk” ceria capable of supporting Pt and/or Pd in this way. The particulate ceria comprises a NOx absorber component and bears an alkaline earth metal and/or an alkali metal, preferably barium, in addition to platinum and/or palladium. The alumina-based large surface area support can be magnesium aluminate, eg MgAl2O4, for example.
The preferred "single layer" NAC composition comprises a mixture of rhodium and platinum and/or palladium support components. These components can be prepared separately, i.e. 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 palladium components hydrolyzed preferably to deposit on the desired support.
[00155] In general, a NOx adsorber composition comprises an alkali metal component, an alkaline earth metal component or a rare earth metal component or a combination of two or more components thereof, wherein the metal component of rare earths comprises lanthanum or yttrium. It is preferred that the alkali metal component comprises potassium or sodium, more preferably potassium. It is preferred that the alkaline earth metal component comprises barium or strontium, more preferably barium.
[00156] The NOx adsorber composition may further comprise a support material and/or a catalytic metal component. The support material can be selected from alumina, ceria, titania, zirconia and mixtures thereof. The catalytic metal component can comprise a metal selected from platinum (Pt), palladium (Pd), rhodium (Rh) and combinations of two or more thereof.
[00157] Poor NOx catalysts (LNCs) are well known in the art. Preferred lean NOx catalysts (LNC) comprise both (a) platinum (Pt) supported on alumina and (b) a copper exchanged zeolite, particularly copper exchanged ZSM-5.
[00158] SCR catalysts are also well known in the art. When the exhaust system of the invention comprises an SCR catalyst, then the exhaust system may further comprise an injector for injecting a nitrogen reductant, such as ammonia, or an ammonia precursor, such as urea or ammonium formate, preferably urea, in the exhaust gas downstream of the catalyst to oxidize carbon monoxide (CO) and hydrocarbons (HCs) and upstream of the SCR catalyst. Such an injector is fluidly connected with a source of such a nitrogen reducer precursor, eg a tank thereof, and valve-controlled dosing of the precursor to the exhaust stream is regulated by appropriately programmed management means and response of closed loop or open loop provided by sensors that monitor the relevant exhaust gas composition. Ammonia can also be generated by heating ammonium carbamate (a solid) and the ammonia generated can be injected into the exhaust gas.
[00159] Alternatively or in addition to the injector, ammonia can be generated on site, for example during rich regeneration of NAC disposed upstream of the filter or contacting DOC disposed upstream of the filter with rich exhaust gas derived from the engine. Thus, the exhaust system can further comprise an engine management means for enriching the exhaust gas with hydrocarbons. The SCR catalyst can then use the hydrocarbons as a reductant to reduce NOx.
[00160] SCR catalysts for use in the present invention selectively promote the reactions 4NH3 + 4NO + O2 ^ 4N2 + 6H2O (ie 1:1 NH3:NO); 4NH3 + 2NO + 2NO2 ^ 4N2 + 6H2O (ie 1:1 NH3:NOx; and 8NH3 + 6NO2^ 7N2 + 12H2O (ie 4:3 NH3:NOx) in preference to undesirable, non-selective side reactions such as 2NH3 + 2NO2^ N2O + 3H2O + N2.
[00161] The SCR catalyst may comprise a metal selected from the group consisting of at least one of Cu, Hf, La, Au, In, V, lanthanides and Group VIII transition metals such as Fe, which metal it is supported on a refractory oxide or molecular sieve. Particularly preferred metals are Ce, Fe and Cu and combinations of any two or more thereof.
[00162] The refractory oxide can be selected from the group consisting of Al2O3, TiO2, CeO2, SiO2, ZrO2 and mixed oxides containing two or more of them. Catalyst other than zeolite may also include tungsten oxide, for example, V2O5/WO3/TiO2, WOx/CeZrO2, WOx/ZrO2 or Fe/WOx/ZrO2.
It is particularly preferred when an SCR catalyst or reactive coating thereof comprises at least one molecular sieve, such as an aluminosilicate zeolite or SAPO. The at least one molecular sieve can be a small, medium or large pore molecular sieve, for example.
[00164] By "small pore molecular sieve" here we mean molecular sieves containing a maximum ring size of 8, such as CHA; by "medium pore molecular sieve" here we mean the molecular sieve containing a maximum ring size of 10, such as ZSM-5; and by "large pore molecular sieve" here we mean the molecular sieve having 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.
[00165] 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 having a silica to alumina ratio of about 10 to about 50, such as about 15 to about 40.
[00166] In its most basic mode, an ammonia leakage catalyst (ASC) can be an oxidation catalyst to oxidize ammonia that goes beyond an unreacted upstream SCR or SCRF catalyst. The desired (simplified) reaction can be represented by 4NO + 4NH3 + O2 ^ 4 N2 + 6H2O. Ammonia is a strong-smelling compound that is potentially irritating to animal mucosal surfaces, eg, eyes and airways, and so its emission to the atmosphere should be limited as much as possible. Possible ammonia leakage catalysts include metals with relatively low charge of the platinum group, preferably including Pt eg 35.7 to 535.5 g/m3 (1 to 15 g/ft3), on a surface area oxide support suitable relatively high, eg alumina coated on a suitable substrate monolith.
[00167] In a particularly preferred arrangement, however, the platinum group metal and support material (eg comprising a modified alumina that incorporates a heteroatom component) is disposed on a substrate (i.e. a substrate monolith ) on a first layer below a second top layer that overlays the first layer. The second layer is an SCR catalyst, selected from any of those mentioned hereinabove, 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 top layer .
[00168] When the SCR catalyst substrate is a filtering monolith, then the catalyst is an SCRF™ catalyst. An SCRF™ catalyst is an emissions control device having a filter substrate.
[00169] In general, SCR catalysts are unable to reduce substantial amounts of NOx in an exhaust gas soon after starting a compression-ignition engine since the exhaust gas temperature (and thus the catalyst temperature) is very low. Poor NOx trapping catalysts, for example, have been employed upstream of SCR catalysts, so that NOx can be stored until the SCR catalyst becomes active at higher exhaust gas temperatures. However, poor NOx trap catalysts are often unable to adequately store NOx when there is a large mass flow of exhaust gas (eg when the engine is operated on a high speed cycle).
[00170] The NOx content of an exhaust gas directly from a compression-ignition engine depends on a number of factors, such as the engine's operating mode, engine temperature and the speed at which the engine is run. However, it is common for an engine to produce an exhaust gas where the NOx content is 85 to 95% (by volume) of nitric oxide (NO) and 5 to 15% (by volume) of nitrogen dioxide (NO2 ). The NO:NO2 ratio is typically 19:1 to 17:3. However, in general it is favorable that the NO2 content be much higher for selective catalytic reduction (SCR) catalysts to reduce NOx or to regenerate an emission control device having a filter substrate burning particulate matter. The PNA activity of the oxidation catalyst can be used to modulate the NOx content of an exhaust gas from a compression ignition engine.
[00171] The PNA activity of the oxidation catalyst of the present invention allows the NOx, particularly NO, to be stored at low exhaust temperatures. At higher exhaust gas temperatures, the oxidation catalyst is capable of oxidizing NO to NO2. It is therefore advantageous to combine the oxidation catalyst of the invention with certain types of emission control devices as part of an exhaust system.
[00172] In a first mode exhaust system, the exhaust system comprises the oxidation catalyst of the invention, preferably as PNA and/or DOC, and a selective catalytic reduction (SCR) catalyst. This embodiment also relates to the use of the oxidation catalyst to treat an exhaust gas from a compression ignition engine in combination with the selective catalytic reduction filter (SCRF™) catalyst, preferably wherein the oxidation catalyst is , or is for use as a diesel oxidation catalyst. The oxidation catalyst of the invention is typically followed by (e.g. is upstream of) selective catalytic reduction (SCR) catalyst. A nitrogen reductant injector can be arranged between the oxidation catalyst and the selective catalytic reduction (SCR) catalyst. Thus, the oxidation catalyst can be followed by (eg is upstream of) a nitrogen reducing injector, and the nitrogen reducing injector can be followed by (eg, is upstream of) the selective catalytic reduction catalyst (SCR).
[00173] A second mode exhaust system comprises the oxidation catalyst of the invention, preferably as PNA and/or DOC, and a selective catalytic reduction filter (SCRF™) catalyst. This embodiment also relates to the use of the oxidation catalyst to treat an exhaust gas from a compression ignition engine in combination with a selective catalytic reduction filter (SCRF™) catalyst, preferably wherein the oxidation catalyst is , or is for use as a diesel oxidation catalyst. The oxidation catalyst of the invention is typically followed by (e.g. is upstream of) the selective catalytic reduction filter (SCRF™) catalyst. A nitrogen reductant injector can be arranged between the oxidation catalyst and the selective catalytic reduction filter (SCRF™) catalyst. Thus, the oxidation catalyst can be followed by (eg is upstream of) a nitrogen reducing injector, and the nitrogen reducing injector can be followed by (eg, is upstream of) the reducing filter catalyst selective catalytic (SCRF™).
[00174] In a third mode exhaust system, the exhaust system comprises the oxidation catalyst of the invention, preferably as PNA and/or DOC, and both a diesel particulate filter (DPF) and a catalyzed soot filter (CSF ). This embodiment also relates to the use of the oxidation catalyst to treat an exhaust gas from a compression ignition engine in combination with a diesel particulate filter or a catalyzed soot filter, preferably wherein the oxidation catalyst is , or is for use as a diesel oxidation catalyst. The oxidation catalyst is typically followed by (eg is upstream of) the diesel particulate filter or the catalyzed soot filter (CSF). Thus, for example, an oxidation catalyst output is connected with an input of the diesel particulate filter or the catalyzed soot filter.
[00175] In a fourth embodiment exhaust system, the exhaust system comprises a diesel oxidation catalyst and the oxidation catalyst of the invention, preferably as a catalyzed soot filter (CSF). The embodiment further refers to the use of the oxidation catalyst to treat an exhaust gas from a compression ignition engine in combination with a diesel oxidation catalyst (DOC), preferably wherein the oxidation catalyst is, or is for use as a catalyzed, soot filter. Typically, the diesel oxidation catalyst (DOC) is followed by (for example, it is upstream of) the oxidation catalyst of the invention. Thus, an output of the diesel oxidation catalyst is connected with an input of the oxidation catalyst of the invention.
[00176] A fifth modality exhaust system refers to an exhaust system comprising the oxidation catalyst of the invention, preferably as PNA and/or DOC, a diesel particulate filter or a catalyzed soot filter (CSF), and the selective catalytic reduction (SCR) catalyst. The DOC/DPF/SCR or DOC/CSF/SCR arrangement is a preferred exhaust system for a light duty diesel vehicle. This embodiment also refers to the use of the oxidation catalyst to treat an exhaust gas from a compression ignition engine in combination with both a diesel particulate filter and a catalyzed soot filter (CSF), and the diesel catalyst. selective catalytic reduction (SCR), preferably wherein the oxidation catalyst is, or is for use as, a diesel oxidation catalyst. The oxidation catalyst is typically followed by (eg is upstream of) the diesel particulate filter or the catalyzed soot filter (CSF). DPF or CSF is typically followed by (eg is upstream of) the selective catalytic reduction (SCR) catalyst. A nitrogen reductant injector can be arranged between DPF or CSF and the selective catalytic reduction (SCR) catalyst. Thus, DPF or CSF can be followed by (eg is upstream of) a nitrogen reducing injector, and the nitrogen reducing injector can be followed by (eg is upstream of) the selective catalytic reduction catalyst ( SCR).
[00177] A sixth modality exhaust system refers to an exhaust system comprising a diesel oxidation catalyst (DOC), the oxidation catalyst of the invention, preferably as a catalyzed soot filter (CSF), and the reduction catalyst selective catalytic (SCR). This is also a DOC/CSF/SCR arrangement. A further aspect of this embodiment concerns the use of the oxidation catalyst to treat an exhaust gas from a compression ignition engine in combination with a diesel oxidation catalyst (DOC) and selective catalytic reduction (SCR) catalyst , preferably wherein the oxidation catalyst is, or is for use as, a catalyzed soot filter (CSF). The diesel oxidation catalyst (DOC) is typically followed by (for example, it is upstream of) the oxidation catalyst of the invention. The oxidation catalyst of the invention is typically followed by (for example, it is upstream of) the selective catalytic reduction (SCR) catalyst. A nitrogen reductant injector can be arranged between the oxidation catalyst and the selective catalytic reduction (SCR) catalyst. Thus, the oxidation catalyst can be followed by (eg is upstream of) a nitrogen reducing injector, and the nitrogen reducing injector can be followed by (eg, is upstream of) the selective catalytic reduction catalyst (SCR).
[00178] In a seventh modality exhaust system, the exhaust system comprises the oxidation catalyst of the invention, preferably as PNA and/or DOC, the selective catalytic reduction catalyst (SCR) and both a catalyzed soot filter (CSF) as well as a diesel particulate filter (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 (SCR) catalyst and either a catalyzed soot filter (CSF) or a diesel particulate filter (DPF), preferably wherein the oxidation catalyst is, or is for use as, a diesel oxidation catalyst.
[00179] In the seventh modality exhaust system, the oxidation catalyst of the invention is typically followed by (eg is upstream of) the selective catalytic reduction (SCR) catalyst. A nitrogen reductant injector can be arranged between the oxidation catalyst and the selective catalytic reduction (SCR) catalyst. Thus, the oxidation catalyst can be followed by (eg is upstream of) a nitrogen reducing injector, and the nitrogen reducing injector can be followed by (eg, is upstream of) the selective catalytic reduction catalyst (SCR). Selective catalytic reduction (SCR) catalysts are followed by (eg are upstream of) the catalyzed soot filter (CSF) or diesel particulate filter (DPF).
[00180] In any of the first, second, or fifth through seventh exhaust system embodiments described herein above containing an SCR catalyst (including SCRF™ catalyst), an ASC catalyst may be disposed downstream of the exhaust catalyst. SCR or the SCRF™ catalyst (i.e. as a separate substrate monolith), or more preferably a zone at a downstream or rear end of the substrate monolith comprising the SCR catalyst can be used as a support for ASC.
[00181] In general, it is preferred that the exhaust system of the invention does not comprise a lean NOx trap (LNT) (sometimes referred to as a lean NOx trap catalyst, a NOx adsorber catalyst (NAC), a catalyst of NOx trap (DNT), a NOx storage catalyst, or a NOx storage/reduction (NSR) catalyst).
[00182] The invention further provides a vehicle comprising a compression ignition engine and both an exhaust system of the invention and an oxidation catalyst of the invention.
[00183] In general, the compression ignition engine is a diesel engine. The diesel engine can be a homogeneous charge compression ignition (HCCI) engine, a premixed charge compression ignition (PCCI) engine, or a low temperature combustion engine (LTC). It is preferred that the diesel engine is a conventional (this is traditional) diesel engine.
[00184] The vehicle may be a light duty diesel vehicle (LDV) as defined in US or European legislation. A light duty diesel vehicle typically has a weight of <2840 kg, more preferably a weight of <2610 kg.
[00185] In the US, a light duty diesel vehicle (LDV) refers to a diesel vehicle having a gross weight of < 8,500 pounds (US lbs). In Europe, the term light-duty diesel vehicle (LDV) refers to (i) passenger vehicles comprising no more than eight seats in addition to the driver's seat and having a maximum mass not exceeding 5 tonnes, and (ii ) vehicles for the transport of goods having a maximum mass not exceeding 12 tonnes.
[00186] Alternatively, the vehicle may be a heavy duty diesel vehicle (HDV), such as a diesel vehicle having a gross weight of >8,500 pounds (US lbs), as defined in US law.
[00187] The invention also relates to various methods and uses involving the oxidation catalyst. A general objective of all methods or uses of the invention is to treat an exhaust gas from a compression ignition engine without producing a substantial amount of nitrous oxide (N2O), if the exhaust gas is treated (i) through the treatment (eg oxidation) of carbon monoxide (CO) and hydrocarbons (HCs) in the exhaust gas, (ii) by modulating the NOx content in the exhaust gas, and/or (iii) using the oxidation catalyst as a passive NOx absorber (PNA).
[00188] The term "substantial amount of nitrous oxide (N2O)" in this context, at least for light cargo vehicles, refers to >0.030 g/mile of N2O as measured using Federal Test Procedure 75 (FTP-75) , preferably > 0.025 g/mile, more preferably > 0.020 g/mile, such as > 0.015 g/mile, and even more preferably 0.010 g/mile (e.g. > 0.005 g/mile. Any reference to "without producing an amount substantial amount of nitrous oxide" in the context of a treated exhaust gas or "a treated exhaust gas that does not contain a substantial amount of nitrous oxide" may refer to the exhaust gas that is passed into the atmosphere (ie as the gas exhaust that has passed through an exhaust system, as measured at the output of a vehicle tailpipe) or to exhaust gas directly obtained from the output of the oxidation catalyst (this is when there are emission control devices downstream that can generate N2O).
[00189] In general, the methods aspect of the invention may include a step of producing a treated exhaust gas that does not contain a substantial amount of nitrous oxide (N2O). This step typically follows the step of contacting the exhaust gas with the oxidation catalyst. This step typically also precedes any step of passing the treated exhaust gas to an emission control device. Similarly, the oxidation catalyst of the invention can be used to produce a treated exhaust gas that does not contain a substantial amount of nitrous oxide (N2O).
[00190] In the methods and uses of the invention, typically the composition of the exhaust gas contacted with the oxidation catalyst is not changed (for example, by changing or cycling the compression ignition engine mode of operation to substantially change the ratio from air to fuel (ie lean to rich or vice versa)) to facilitate storage of NOx from the exhaust gas or to release NOx from the oxidation catalyst.
[00191] The methods or uses of the invention may also include a step of removing sulfur stored in the oxidation catalyst. Typically, sulfur can be removed under poor conditions at a noticeable rate for practical use in automotive aftertreatment systems when the oxidation catalyst has a temperature greater than 550°C. The oxidation catalyst can reach this temperature by transferring heat from the exhaust gas. However, it may be necessary to heat the oxidation catalyst to a temperature greater than 700°C, for example up to 780°C or more, to remove stored sulfur.
[00192] In general, the oxidation catalyst can be used in combination with an emission control device. Typically, the oxidation catalyst is used in combination with: (i) the selective catalytic reduction (SCR) catalyst, preferably an SCR catalyst downstream of the oxidation catalyst, particularly when the oxidation catalyst is or is used as a catalyst diesel oxidation (DOC); (ii) a selective catalytic reduction filter (SCRF™) catalyst, preferably an SCRF™ catalyst downstream of the oxidation catalyst, particularly when the oxidation catalyst is or is used as a diesel oxidation catalyst (DOC); (iii) a diesel particulate filter (DPF) or a catalyzed soot filter (CSF), preferably DPF or CSF downstream of the oxidation catalyst, particularly when the oxidation catalyst is or is used as a diesel oxidation catalyst (DOC); (iv) a diesel oxidation catalyst (DOC), preferably the DOC upstream of the oxidation catalyst of the invention, particularly when the oxidation catalyst is or is used as a catalyzed soot filter (CSF); (v) a diesel particulate filter (DPF) or a catalyzed soot filter (CSF) and the selective catalytic reduction (SCR) catalyst, preferably DPF or CSF downstream of the oxidation catalyst and an SCR catalyst downstream of DPF or CSF, particularly when the oxidation catalyst is or is used as a diesel oxidation catalyst (DOC); (vi) a diesel oxidation catalyst (DOC) and a selective catalytic reduction (SCR) catalyst, preferably DOC upstream of the oxidation catalyst of the invention and an SCR catalyst downstream of the oxidation catalyst of the invention, particularly when the oxidation catalyst is or is used as a catalyzed soot filter (CSF); or (vii) the selective catalytic reduction (SCR) catalyst and either a diesel particulate filter (DPF) or a catalyzed soot filter (CSF), preferably an SCR catalyst downstream of the oxidation catalyst and the DPF or CSF downstream of the SCR catalyst, particularly when the oxidation catalyst is or is used as a diesel oxidation catalyst (DOC).
[00193] When the oxidation catalyst is used as a passive NOx absorber (PNA), the oxidation catalyst absorbs or stores NOx from the exhaust gas in a first temperature range and releases NOx in a second temperature range, where the second temperature range is greater than the first temperature range (for example, the midpoint of the second temperature range is greater than the midpoint of the first temperature range). It is preferable that the second temperature range does not overlap with the first temperature range. There may be a gap between the upper limit of the first temperature range and the lower limit of the second temperature range.
[00194] Typically, the oxidation catalyst releases NOx at a temperature greater than 200°C. This is the lower limit of the second temperature range. Preferably, the oxidation catalyst releases NOx at a temperature of 220°C or above, such as 230°C or above, 240°C or above, 250°C or above, or 260°C or above.
[00195] The oxidation catalyst absorbs or stores NOx at a temperature of 200°C or less. This is the upper limit of the first temperature range. Preferably, the oxidation catalyst absorbs or stores NOx at a temperature of 195°C or less, such as 190°C or less, 185°C or less, 180°C or less, or 175°C or less.
[00196] The oxidation catalyst can preferably absorb or store nitric oxide (NO). Thus, any reference to absorbing, storing or releasing NOx in this context can refer to absorbing, storing or releasing nitric oxide (NO). Absorption or preferential storage of NO will decrease the NO:NO2 ratio in the exhaust gas.
[00197] In addition to or as an alternative to using the oxidation catalyst as a passive NOx absorber (PNA), the oxidation catalyst can be used to modulate the NOx content in an exhaust gas from an ignition engine by compression, such as for a downstream emission control device.
[00198] Any reference to "modulating the NOx content" as used herein, particularly in relation to the method or aspect of uses of the invention, refers to altering (i.e. adjusting) or maintaining the ratio (in ppm or % by volume, typically at an exhaust gas temperature and pressure) of NO:NO2 to be within a predefined range at a specific exhaust gas temperature or specific temperature range.
[00199] In general, "modulating the NOx content" refers to altering or maintaining, preferably altering, the ratio (in ppm or % by volume) of NO:NO2 in an exhaust gas, typically directly from the engine. compression ignition, to be less than 17:3 (ie the amount of NO to NO2 is less than what is normally found in an exhaust gas from a compression ignition engine), preferably the ratio of NO: NO2 is from 5:1 to 1:5, more preferably 2.5:1 to 1:2.5, and even more preferably 2:1 to 1:2 (for example, 1.5:1 to 1:1, 5 or about 1:1). The NO:NO2 ratio when the temperature is in the first temperature range (ie the temperature at which NOx is stored or absorbed) may be less than the ratio in the second temperature range (ie the temperature at which NOx is released ).
[00200] In the second aspect of the method of the invention, the step of "(a) controlling the NOx content of an exhaust gas by contacting the exhaust gas with an oxidation catalyst..." may additionally include the steps of (i ) absorbing or storing NOx from the exhaust gas in a first temperature range, and (ii) releasing NOx in a second temperature range, thereby producing a treated exhaust gas. Preferably, the second temperature range is greater than the first temperature range (for example, the midpoint of the second temperature range is greater than the midpoint of the first temperature range). More preferably the second temperature range does not overlap with the first temperature range. There may be a gap between the upper limit of the first temperature range and the lower limit of the second temperature range.
[00201] Typically, the second temperature range is a temperature greater than 200°C, preferably a temperature of 220°C or above, such as 230°C or above, 240°C or above, 250°C or above , or 260°C or above.
[00202] The first temperature range is typically a temperature of 200°C or less, preferably a temperature of 195°C or less, such as 190°C or less, 185°C or less, 180°C or less, or 175°C or less.
[00203] In general, the step of (b) passing the treated exhaust gas to an emission control device typically involves directly passing the treated exhaust gas to the emission control device. Thus, an oxidation catalyst output is directly connected (eg without intermediate) with an emission control device input.
[00204] The emission control device is typically the selective catalytic reduction catalyst (SCR), a selective catalytic reduction filter (SCRF™) catalyst, a diesel particulate filter (DPF), or a catalyzed soot filter (CSF).
[00205] In the second aspect of the method of the invention, references to "NOx content", "absorb or store NO" or "release NOx" may refer to nitric oxide (NO), such as when the oxidation catalyst preferentially stores AT THE.
[00206] In the fourth use aspect of the invention, the oxidation catalyst is used in the regeneration of an emission control device having a filter substrate. Typically, the emission control device having a filter substrate is downstream of the oxidation catalyst.
[00207] The emission control device having a filtering substrate can be selected from the group consisting of a diesel particulate filter (DPF), a catalyzed soot filter (CSF), a selective catalytic reduction filter catalyst (SCRF™) and a combination of two or more of them.
[00208] The oxidation catalyst can be used to regenerate the emission control device having a filter substrate by oxidizing nitric oxide (NO) to nitrogen dioxide (NO2) at a temperature of at least 220°C, preferably by minus 240°C, more preferably at least 260°C, even more preferably at least 280°C. DEFINITIONS
[00209] The term "reactive coating" is well known in the art and refers to an adherent coating that is applied to a substrate commonly during the production of a catalyst. The reactive coating or coating generally comprises one or more components of a catalyst formulation, components which are typically selected from a platinum group metal, a support material, an oxygen storage component and a hydrocarbon adsorbent .
[00210] The term "reactive coating region" as used herein refers to an area of reactive coating on a substrate. The "reactive coating region", for example, can be arranged or supported on a substrate as a "layer" or a "zone". The area or arrangement of reactive coating on a substrate is generally controlled during the process of applying reactive coating to the substrate. The "reactive coating region" typically has distinct boundaries or distinct edges (that is, it is possible to distinguish a reactive coating region from another reactive coating region using conventional analytical techniques).
[00211] It is preferable that each "reactive coating region" has a substantially uniform composition (i.e. there is no substantial difference in the composition of the reactive coating when comparing a part of the reactive coating region with another part of that reactive coating region) . Substantially uniform composition in this context refers to a material (eg reactive coating region) where the difference in composition when comparing one part of the reactive coating region to another part of the reactive coating region is 5% or less, commonly 2.5% or less, and even more commonly 1% or less.
[00212] The term "reactive coating zone" as used herein refers to a reactive coating region of substantially uniform length. The length of a reactive coating zone can be the same as the total length of the substrate. In general, the length of a reactive coating zone is less than the total length of the substrate. The total length of a substrate is the distance between its input end and its output end (for example, opposite ends of the substrate). The "reactive coating zone" typically has a length (i.e. a substantially uniform length) of at least 5% of the total length of the substrate.
[00213] Any reference to "substantially uniform" in the context of a length or to "substantially uniform length" as used herein refers to a length that does not deviate by more than 10%, preferably does not deviate by more than 5%, more preferably it does not deviate by more than 1% from its mean value.
[00214] Any reference to "reactive coating zone disposed at an input end of the substrate" used herein refers to a reactive coating zone disposed or supported on a substrate that is closer to an input end of the substrate than it is. from an output end of the substrate. Thus, the midpoint of the reactive coating zone (i.e., at half its length) is closer to the input end of the substrate than the midpoint is to the output end of the substrate. Similarly, any reference to "reactive coating zone disposed at an exiting end of the substrate" used herein refers to a reactive coating zone disposed or supported on a substrate that is closer to an exiting end of the substrate than is an inlet end of the substrate. Thus, the midpoint of the reactive coating zone (i.e. at half its length) is closer to the exit end of the substrate than the midpoint is to the entry end of the substrate.
[00215] When the substrate is a wall flow filter, then in general any reference to "reactive coating zone disposed at an inlet end of the substrate" refers to a reactive coating zone disposed or supported on the substrate that is ( a) closer to an inlet end of a substrate inlet channel than it is to a closed end of the inlet channel, and/or (b) closer to a closed end of a substrate inlet channel than it is from an output end of the output channel. Thus, the midpoint of the reactive coating zone (i.e. at half its length) is (a) closer to an inlet end of a substrate inlet channel than the midpoint is to the closed end of the inlet channel. , and/or (b) closer to a closed end of an exit channel of the substrate than the midpoint is to an exit end of the exit channel. Similarly, any reference to "reactive coating zone disposed at an exiting end of the substrate" when the substrate is a wall flow filter refers to a reactive coating zone disposed or supported on the substrate that is (a) closest to an output end of a substrate input channel than a closed end of the output channel, and/or (b) closer to a closed end of a substrate input channel than an input end of the input channel. Thus, the midpoint of the reactive coating zone (i.e. at half its length) is (a) closer to an exit end of a substrate exit channel than the midpoint is to the closed end of the exit channel. , and/or (b) closer to a closed end of an inlet channel of the substrate than the midpoint is to an inlet end of the inlet channel.
[00216] Any reference to "absorbing NOx" from an exhaust gas as used herein refers to removing NOx from the exhaust gas by storing it in the oxidation catalyst. Storage can be an adsorption process, but the oxidation catalyst is not limited to storing NOx in this specific way.
[00217] The term "mixed oxide" as used herein generally refers to a mixture of oxides in a single phase, as is conventionally known in the art.
[00218] The term "compound oxide" as used herein generally refers to a composition of oxides having more than one phase, as is conventionally known in the art.
[00219] Any reference to a temperature or temperature range, such as the "first temperature range" or the "second temperature range" as used herein generally refers to the exhaust gas temperature, preferably the exhaust gas temperature. exhaust in an inlet of the oxidation catalyst.
[00220] Any reference here to a quantity in units of g m3 (g ft-3) (grams per cubic foot) or g in-3 (g cm-3) (grams per cubic inch) refers to the average weight of a component by substrate volume and typically includes the volume of substrate voids.
[00221] The expression "consisting essentially" as used herein limits the scope of a functionality to include the specified materials or steps, and any other materials or steps that do not materially affect the basic characteristics of that functionality, such as, for example, impurities of mirror. For the avoidance of doubt, the expression "consisting essentially of" incorporates the expression "consisting of".
[00222] In the context of platinum (Pt) or palladium (Pd), it should be noted that it is generally difficult to characterize the exact catalytic species in a catalyst and platinum or palladium may not be present in the elemental metallic form. Any reference to "consisting essentially of platinum..."incorporates a "platinum component" where the platinum portion may be an elemental form of platinum, an alloy containing platinum or a compound comprising platinum (e.g., a platinum oxide ), preferably an elemental form of platinum or a platinum-containing alloy, more preferably an elemental form of platinum. Similarly, any reference to "consisting essentially of palladium..." incorporates a "palladium component of" where the palladium moiety may be an elemental form of palladium, an alloy containing palladium or a compound comprising palladium (e.g., an oxide of palladium), preferably an elemental form of palladium or a palladium-containing alloy, more preferably an elemental form of palladium.
[00223] The term "substantially free" as used herein in the context of a particular chemical entity refers to a composition or material that contains less than 0.5% by weight of the chemical entity, typically less than 0.1% by weight. weight of the chemical entity, such as less than 0.01% by weight of the chemical entity. In general, the chemical entity is not detectable using conventional analytical techniques. EXAMPLES
[00224] The invention will now be illustrated by the following non-limiting examples. Example 1
[00225] Palladium nitrate was added to a slurry of ceria in water. The slurry containing palladium nitrate was stirred to homogenize then coated onto a 300 cells per square inch metal substrate using conventional coating techniques to form a first layer. The coated part was dried and calcined at 500°C.
[00226] A second slurry was prepared by taking alumina powder and milling to a particle size where the d90 was less than 20 microns. Soluble salts of platinum and palladium were added and the resulting slurry was stirred to homogenize. This second slurry was coated onto the part using conventional coating techniques to form a second layer. The part was dried and calcined at 500°C.
[00227] The resulting catalyst had a total platinum and palladium loading (i.e. the total PGM loading in both layers) of 6,000 g/m3 (160 g/ft3) and the total mass ratio (i.e. both layers ) of Pt:Pd was 5:11. Example 2
[00228] An alumina slurry was prepared using an alumina powder which was ground to a particle size where the d90 was less than 20 microns. Soluble salts of platinum and palladium were added and the resulting slurry was stirred to homogenize. This slurry was then coated onto a 300 cells per square inch metal substrate using conventional coating techniques to form a first layer. The part was dried and calcined at 500°C.
[00229] Palladium nitrate was added to a slurry of ceria in water. This second slurry containing palladium nitrate was stirred to homogenize and then was coated in part using conventional coating techniques to form a second layer. The coated part was dried and calcined at 500°C.
[00230] The resulting catalyst had a total platinum and palladium loading (ie the total PGM loading in both layers) of 6,000 m/g3 (160g/ft3) and the total mass ratio (ie both layers) of Pt:Pd was 5:11. Experimental Results
[00231] The catalysts of Examples 1 and 2 were hydrothermally aged at 800°C for 16 hours. Each catalyst was installed in a bench-mounted engine and tested for (a) its CO start using a temperature ramp and (b) its N2O emissions by a simulated MVEG-B driving cycle. Emission measurements were continuously recorded both upstream and downstream of each catalyst.
[00232] The CO start results are reported as a T80, which is the temperature at which 80% of the CO emission from the engine has been converted to CO2. The results are shown in Table 1 below. Table 1

[00233] The amount of N2O in the exhaust emission from each catalyst after the engine has run through the MVEG cycle is shown in Figure 1. The N2O emission when the catalyst from Example 2 was used (see full line in Figure 1) was less than that of Example 1 (see dotted line in Figure 1). Examples 3 to 5
[00234] Palladium nitrate was added to a slurry of ceria in water. The slurry containing the palladium nitrate was stirred to homogenize and then coated onto a ceramic substrate using conventional coating techniques. The coated part was dried and calcined at 500°C. The ceria loading was 0.1647 g cm3 (2.7 g in-3) (Examples 3 to 5). Palladium loading as a percentage of ceria loading was varied as follows: 1% by weight (Example 3); 2% by weight (Example 4); 4% by weight (Example 5). Each of the coated parts was hydrothermally aged at 750°C for 15 hours. Experimental Results
[00235] A 1 x 3" core sample from each of the catalysts of Examples 3, 4 and 5 was taken and tested in a synthetic gas equipment. The gas mixture that was used to perform the tests is shown in Table 2 below. Table 2

[00236] Each of the core samples was brought to 80°C and then exposed to the gas mixture in Table 2 for 10 minutes for the purpose of storing NOx. The gas mixture was then changed to nitrogen and each core sample was heated to 600°C in order to thermally release any stored NOx.
[00237] The above procedure was repeated except that each core sample was brought to 120°C, 160°C and 200°C before being exposed to the gas mixture in Table 2. The amount of NOx stored for each period of 10 minutes was measured and the results are shown in Figure 2.
[00238] Figure 2 shows that increasing the loading of Pd from 1% by weight (■) to 2% by weight (▲) increases the amount of NOx that is stored. A further increase in Pd loading from 2 wt% (▲) to 4 wt% (•) provides a relatively small increase in NOx storage. Examples 6 to 8
[00239] Palladium nitrate was added to a slurry of ceria in water. The slurry containing palladium nitrate was stirred to homogenize and then coated onto a ceramic substrate using conventional coating techniques. The coated part was dried and calcined at 500°C. Palladium loading was 1667.19 g m3 (46.7 g ft-3) (Examples 6 to 8). Ceria loading was varied as follows: 0.082 g cm3 (1.35 g in-3) (Example 6); 0.0549 g cm3 (0.9 g in-3) (Example 7); 0.0411 g cm3 (0.675 g in-3) (Example 8). Palladium loading as a percentage of ceria loading is as follows: 2% by weight (Example 6); 3% by weight (Example 7); 4% by weight (Example 8). Each of the coated parts was hydrothermally aged at 750°C for 15 hours. Experimental Results
[00240] A 1 x 3" core sample from each of the catalysts of Examples 3, 6, 7 and 8 was taken and tested in a synthetic gas equipment. The method and gas mixture used to test the Examples 3 and 6 to 8 were the same as those used by examples 3 to 5 above. The results are shown in Figure 3.
[00241] Figure 4 shows that for a fixed Pd loading of 1667.19 g m3 (46.7 g ft-3) the amount of stored NOx storage increases with ceria loading. However, this trend is not linear and smaller increases in the amount of stored NOx storage were observed when the ceria loading was increased from 0.082 g cm-3 (1.35 g in-3) (•) to 0.1647 g cm3 (2.7 g in-3) (▲).
[00242] For the avoidance of doubt, the entire contents of any and all documents cited herein are incorporated by reference into this application.

权利要求:
Claims (11)
[0001]
1. Exhaust system for treating an exhaust gas from a compression ignition engine comprising an oxidation catalyst for use as a passive NOx absorber and a downstream emission control device in which the oxidation catalyst comprises: a substrate, which is a flow-through monolith, wherein the emission control device is a diesel particulate filter (DPF) coated with a catalyst formulation, wherein the catalyst formulation: (a) comprises platinum and/or palladium to oxidize particulate matter and carbon monoxide and hydrocarbons and the coated diesel particulate filter is a catalyzed soot filter (CSF); (b) is a NOx adsorber composition; or (c) is a selective catalytic reduction (SCR) catalyst and the coated diesel particulate filter is a selective catalytic reduction (SCRF) filter, characterized in that the substrate comprises: a first reactive coating region comprising palladium (Pd) directly supported on a first support material in an amount of 0.25 to 1.9% by weight of the first support material, wherein the first support material consists essentially of ceria; and a second reactive coating region comprising platinum (Pt), palladium (Pd) and a second support material, wherein a mass ratio of platinum (Pt) to palladium (Pd) is from 10:1 to 1.25: 1, and wherein the second support material comprises a refractory metal oxide, wherein the second reactive coating region is disposed or supported on the substrate downstream of the first reactive coating zone.
[0002]
2. Exhaust system according to claim 1, characterized in that it comprises a diesel oxidation catalyst (DOC) followed by the catalyzed soot filter (CSF).
[0003]
3. Exhaust system according to claim 1, characterized in that it comprises a diesel oxidation catalyst (DOC) followed by a selective catalytic reduction filter (SCRF) and a nitrogen reducer injector arranged between the diesel oxidation catalyst diesel (DOC) and the selective catalytic reduction filter (SCRF).
[0004]
4. Exhaust system according to any one of claims 1 to 3, characterized in that the mass of platinum (Pt) is greater than the mass of palladium (Pd) in the second reactive coating region.
[0005]
5. Exhaust system according to any one of claims 1 to 4, characterized in that the refractory metal oxide of the second support material is selected from the group consisting of alumina, silica, titania, zirconia, ceria and compound or mixed oxides of two or more of them.
[0006]
6. Exhaust system according to claim 5, characterized in that the refractory metal oxide is alumina.
[0007]
7. Exhaust system according to any one of claims 1 to 6, characterized in that the first reactive coating region comprises a hydrocarbon adsorbent, which is a zeolite.
[0008]
8. Exhaust system according to any one of claims 1 to 7, characterized in that the first reactive coating region is platinum-free.
[0009]
9. Exhaust system according to any one of claims 1 to 8, characterized in that the first reactive coating region of the oxidation catalyst is free of a NOx adsorbing material comprising an alkali metal, an alkaline earth metal and /or a rare earth metal except for the ceria of the first support material.
[0010]
10. Exhaust system according to any one of claims 1 to 9, characterized in that the first reactive coating region is rhodium-free.
[0011]
11. Exhaust system according to any one of claims 1 to 10, characterized in that the second reactive coating region of the oxidation catalyst comprises an amount of platinum (Pt) in the range of 0.2 to 15% by weight .

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法律状态:
2018-11-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-10-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-03-24| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2020-10-06| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-03-23| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-05-04| 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 16/05/2014, 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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GB1308909.9A|GB2514177A|2013-05-17|2013-05-17|Oxidation catalyst for a compression ignition engine|

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GB1308909.9|2013-05-17|

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PCT/GB2014/051499|WO2014184568A1|2013-05-17|2014-05-16|Oxidation catalyst for a compression ignition engine|

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