EXHAUST SYSTEM FOR A LEAN-BURN INTERNAL COMBUSTION ENGINE INCLUDING SCR CATALYST

Abstract

An exhaust system 20 for an internal combustion engine comprises a) a first catalysed substrate monolith 12 comprising a first washcoat coating disposed in a first washcoat zone 16 of the substrate monolith and a second washcoat coating disposed in a second washcoat zone 18 of the substrate monolith, wherein the first washcoat coating comprises a catalyst composition comprising at least one platinum group metal (PGM) and at least one support material, wherein at least one PGM in the first washcoat coating is liable to volatilise when the first washcoat coating is exposed to relatively extreme conditions including relatively high temperatures, wherein the second washcoat coating comprises at least one material supporting copper for trapping volatilised PGM and wherein the second washcoat coating is oriented to contact exhaust gas that has contacted the first washcoat; and b) a second catalysed substrate monolith 14 comprising a catalyst for selectively catalysing the reduction of oxides of nitrogen to dinitrogen with a nitrogenous reductant disposed downstream from the first catalysed substrate monolith.

Claims

1.-18. (canceled)

19. A method of reducing or preventing a selective catalytic reduction (SCR) catalyst in an exhaust system of a lean-burn internal combustion engine from becoming poisoned with platinum group metal (PGM) which may volatilise from a catalyst composition of a first catalysed substrate monolith comprising at least one platinum group metal (PGM) supported on at least one support material and disposed on a substrate monolith upstream of the selective catalytic reduction (SCR) catalyst of a second catalysed substrate monolith when the catalyst composition comprising platinum group metal (PGM) is exposed to relatively extreme conditions including relatively high temperatures, which method comprising trapping volatilised platinum group metal (PGM) in a washcoat coating comprising at least one material supporting copper, which is disposed on the same substrate monolith as the catalyst composition comprising platinum group metal (PGM).

20. The method according to claim 19, wherein the exhaust system comprises an injector for injecting a nitrogenous reductant into exhaust gas between the first catalysed substrate monolith and the second catalysed substrate monolith.

21. The method according to claim 19, wherein the first catalysed substrate monolith comprises a first washcoat coating comprising the at least one platinum group metal (PGM), wherein the at least one platinum group metal (PGM) comprises platinum.

22. The method according to claim 19, wherein the first catalysed substrate monolith comprises a first washcoat coating comprising the at least one platinum group metal (PGM), wherein the at least one platinum group metal (PGM) comprises both platinum and palladium.

23. The method according to claim 22, wherein a weight ratio of Pt: Pd is 2.

24. The method according to claim 19, wherein the at least one support material is at least one metal oxide, a molecular sieve or a mixture of any two or more thereof.

25. The method according to claim 24, wherein the or each metal oxide support is selected from the group consisting of optionally stabilised alumina, amorphous silica-alumina, optionally stabilised zirconia, ceria, titania, an optionally stabilised ceria-zirconia mixed oxide and a mixture of any two or more thereof.

26. The method according to claim 24, wherein the molecular sieve is an aluminosilicate zeolite.

27. The method according to claim 19, wherein the first substrate monolith is a flow-through substrate monolith.

28. The method according to claim 19, wherein the first substrate monolith is a filtering substrate monolith having inlet surfaces and outlet surfaces, wherein the inlet surfaces are separated from the outlet surfaces by a porous structure and wherein the first washcoat coating of the first zone is applied to the inlet surfaces and the second washcoat coating of the second zone is applied to the outlet surfaces.

29. The method according to claim 28, wherein the filtering substrate monolith is a wall-flow filter, wherein inlet channels of the wall-flow filter comprise the first zone and wherein outlet channels of the wall-flow filter comprise the second zone.

30. The method according to claim 19, wherein the second substrate monolith is a flow-through substrate monolith.

31. The method according to claim 19, wherein the second substrate monolith is a filtering substrate monolith having inlet surfaces and outlet surfaces, wherein the inlet surfaces are separated from the outlet surfaces by a porous structure.

32. The method according to claim 32, wherein the filtering substrate monolith is a wall-flow filter.

33. The method according to claim 19, wherein the first washcoat comprises an oxidation catalyst or a NO.sub.x adsorber catalyst.

34. The method according to claim 19, comprising a third substrate monolith, wherein the third substrate monolith is a filtering substrate monolith, which third substrate monolith is disposed downstream of the second catalysed substrate monolith.

35. The method according to claim 34, wherein the third substrate monolith comprises an oxidation catalyst.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0034] In order that the invention may be more fully understood, reference is made to the following Examples by way of illustration only and with reference to the accompanying drawings.

[0035] FIG. 1 is a schematic drawing of a laboratory reactor used for testing platinum contamination on an Fe/Beta zeolite SCR catalyst or a Cu/CHA zeolite SCR catalyst.

[0036] FIG. 2 is a graph comparing the NO.sub.x conversion activity as a function of temperature of a two aged SCR catalyst cores each of which has been aged in a laboratory-scale exhaust system configuration containing core samples of Example 3 for use in the invention or Comparative Example 2. The results of the aged SCR activity are plotted against activity of a fresh, i.e. un-aged SCR catalyst.

[0037] FIG. 3 is a graph comparing the NO.sub.x conversion activity as a function of temperature of three aged SCR catalyst cores each of which has been aged in a laboratory-scale exhaust system configuration containing a catalysed wall-flow filter disposed upstream of the Fe/Beta zeolite SCR catalyst, one system comprising a filter coated on both inlet and outlet channels with Pt:Pd in a 1:1 weight ratio; a second system comprising a filter coated on both inlet and outlet channels with a Pt:Pd in a 5:1 weight ratio; and a third, comparative system comprising a filter coated on both inlet and outlet channels with a Pt-only catalyst. The results of the aged SCR activity are plotted against activity of a fresh, i.e. un-aged SCR catalyst.

[0038] FIG. 4 is a bar chart comparing the NO.sub.x conversion activity as a function of temperature of two aged SCR catalyst cores each of which has been aged in the laboratory-scale exhaust system shown in FIG. 1 containing core samples of the diesel oxidation catalyst of Example 8 heated in a tube furnace at 900 C. for 2 hours in a flowing synthetic exhaust gas with the Cu/CHA zeolite SCR catalyst core held at 300 C. located downstream.

[0039] FIG. 5 is a schematic drawing of an exhaust system embodiment according to the invention.

DETAILED DESCRIPTION OF THE INVENTION

[0040] Typically, the exhaust system according to the invention can comprise an injector for injecting a nitrogenous reductant into exhaust gas between the first catalysed substrate monolith and the second catalysed substrate monolith. Nitrogenous reductants and precursors thereof for use in the present invention include any of those mentioned hereinabove in connection with the background section. Thus, for example, the nitrogenous reductant is preferably ammonia or urea.

[0041] Alternatively, (i.e. without means for injecting ammonia or a precursor thereof such as urea being disposed between the first catalysed substrate monolith and the second catalysed substrate monolith), or in addition to the means for injecting ammonia or a precursor thereof, engine management means is preferably provided for enriching exhaust gas such that ammonia gas is generated in situ by reduction of NO.sub.x on the catalyst composition of the first washcoat coating and/or a DOC or NAC, typically a substrate monolith comprising a DOC composition or NAC composition, disposed upstream of the first substrate monolith or downstream of the first substrate monolith. Where the substrate monolith comprises a DOC composition or NAC composition or the NAC is disposed downstream of the filter, preferably it is disposed upstream of the means for injecting ammonia or a precursor thereof or between the first and the second catalysed substrate monoliths.

[0042] In combination with an appropriately designed and managed diesel compression ignition engine (upstream of substrate monolith, not shown), enriched exhaust gas, i.e. exhaust gas containing increased quantities of carbon monoxide and hydrocarbon relative to normal lean running mode, contacts the NAC. Components within a NAC or NAC composition such as PGM-promoted ceria or ceria-zirconia can promote the water-gas shift reaction, i.e. CO.sub.(g)+H.sub.2O.sub.(v).fwdarw.CO.sub.2(g)+H.sub.2(g) evolving H.sub.2. From the side reaction footnote to reactions (3) and (4) set out hereinabove, e.g. Ba(NO.sub.3).sub.2+8H.sub.2.fwdarw.BaO+2NH.sub.3+5H.sub.2O, NH.sub.3 can be generated in situ and stored for NO.sub.x reduction on the downstream SCR catalyst.

[0043] Nitrogenous reductants and precursors thereof for use in the present invention include any of those mentioned hereinabove in connection with the background section. Thus, for example, the nitrogenous reductant is preferably ammonia or urea.

[0044] In general, the first washcoat coating comprises platinum. When at least one PGM in the first washcoat coating is platinum, then the platinum is the PGM liable to volatilise when the first washcoat coating is exposed to relatively extreme conditions including relatively high temperatures. The relatively extreme conditions including relatively high temperatures are, for example, temperatures of 700 C., preferably 800 C., or more preferably 900 C.

[0045] Typically, the first washcoat coating comprises both platinum and palladium (i.e. the at least one PGM is both platinum and palladium). The platinum and/or the palladium can be the PGM liable to volatilise when the first washcoat coating is exposed to relatively extreme conditions including relatively high temperatures. However, when both platinum and palladium are present, then normally platinum is more likely to be the PGM liable to volatilise when the first washcoat coating is exposed to relatively extreme conditions including relatively high temperatures.

[0046] In an embodiment of the invention, the first washcoat coating does not comprise gold, especially a palladium-gold alloy.

[0047] Since the first catalysed substrate monolith comprises a measure to reduce or prevent volatilised platinum from migrating from the catalyst comprising platinum to a downstream SCR catalyst, it is possible for relatively high Pt:Pd weight ratios to be used in the catalyst comprising platinum for the purposes of, e.g. generating NO.sub.2 to promote downstream combustion of filtered particulate matter, such as 10:1, e.g. 8:1, 6:1, 5:1 or 4:1. It is possible to use such relatively high Pt:Pd weight ratios, even though PGM may volatilise therefrom because the design of the first catalysed substrate monolith of the invention substantially prevents volatilised PGM from contacting the downstream SCR catalyst.

[0048] However, the present inventors have found that by reducing the Pt:Pd weight ratio it is possible to further reduce the level of PGM volatilisation, which can reduce or prevent PGM poisoning of the downstream SCR catalyst. Where the at least one PGM in the first washcoat coating comprises both platinum and palladium, preferably the weight ratio of Pt:Pd is 2, such as 1.5:1, e.g. about 1:1. The significance of this feature is shown in the Examples: the inventors have found that the preferred Pt:Pd weight ratios volatilise less by empiric testing than a similar catalyst having a Pt:Pd weight ratio of 4:1. In layered catalyst arrangements, it is preferred that an outer layer has a Pt:Pd weight ratio of 2, or optionally that the overall Pt:Pd weight ratio of all layers combined is 2.

[0049] Typically, the weight ratio of Pt:Pd is 35:65 (e.g. 7:13). It is preferred that the weight ratio Pt:Pd is 40:60 (e.g. 2:3), more preferably 42.5:57.5 (e.g. 17:23), particularly 45:55 (e.g. 9:11), such as 50:50 (e.g. 1:1), and still more preferably 1.25:1. The weight ratio of Pt:Pd is typically 10:1 to 7:13. It is preferred that the weight ratio of Pt:Pd is 8:1 to 2:3, more preferably 6:1 to 17:23, even more preferably 5:1 to 9:11, such as 4:1 to 1:1, and still more preferably 2:1 to 1.25:1.

[0050] Generally, the total amount of the platinum group metal (PGM) (e.g. the total amount of Pt and/or Pd) is 1 to 500 g ft.sup.3. Preferably, the total amount of the PGM is 5 to 400 g ft.sup.3, more preferably 10 to 300 g ft.sup.3, still more preferably, 25 to 250 g ft.sup.3, and even more preferably 35 to 200 g ft.sup.3.

[0051] The support material in the first washcoat coating can be a metal oxide (i.e. at least one metal oxide), a molecular sieve (i.e. at least one molecular sieve) or a mixture of any two or more thereof. Preferably, the support material comprises at least one metal oxide. It is further preferred that the support material comprises at least one metal oxide, and that the first washcoat coating comprises at least one molecular sieve.

[0052] Generally, the at least one metal oxide support of the first washcoat coating may comprise a metal oxide selected from the group consisting of optionally stabilised alumina, amorphous silica-alumina, optionally stabilised zirconia, ceria, titania, an optionally stabilised ceria-zirconia mixed oxide and mixtures of any two or more thereof. Suitable stabilisers include one or more of silica and rare earth metals. The first washcoat coating preferably comprises optionally stabilised alumina or amorphous silica-alumina.

[0053] Typically, the support material in the second washcoat coating can be a metal oxide (i.e. at least one metal oxide), a molecular sieve (i.e. at least one molecular sieve) or a mixture of any two or more thereof. Thus, the at least one material supporting copper is copper supported on at least one support material, wherein the support material is as described herein.

[0054] The second washcoat coating may comprise a molecular sieve. It is appreciated that a molecular sieve supporting copper in the second washcoat coating may be formulated in such a way that it is active as a SCR catalyst for the reduction of oxides of nitrogen using a nitrogenous reductant. The combination of a copper/molecular sieve SCR catalyst and engine management means for enriching exhaust gas such that ammonia gas is generated in situ by reduction of NO.sub.x on the catalyst composition of the first washcoat is particularly preferred. In one embodiment, the second washcoat coating does not comprise a metal oxide, such as optionally stabilised alumina, amorphous silica-alumina, optionally stabilised zirconia, ceria, titania, an optionally stabilised ceria-zirconia mixed oxide and mixtures of any two or more thereof.

[0055] However, the at least one metal oxide support of the second washcoat coating typically comprises a metal oxide selected from the group consisting of optionally stabilised alumina, amorphous silica-alumina, optionally stabilised zirconia, ceria, titania, an optionally stabilised ceria-zirconia mixed oxide and mixtures of any two or more thereof. Suitable stabilisers include one or more of silica and rare earth metals.

[0056] When the second washcoat coating comprises a metal oxide, then preferably the metal oxide is selected from the group consisting of optionally stabilised alumina, amorphous silica-alumina, optionally stabilised zirconia, titania, an optionally stabilised ceria-zirconia mixed oxide and mixtures of any two or more thereof. More preferably, the metal oxide is optionally stabilised alumina.

[0057] In one embodiment, the second washcoat coating does not comprise ceria and/or a molecular sieve.

[0058] The second washcoat coating typically comprises copper in a total amount of from 10 to 350 g ft.sup.3. It is preferred that the total amount of copper in the second washcoat coating is 20 to 300 g ft.sup.3, more preferably 30 to 250 g ft.sup.3, still more preferably, 45 to 200 g ft.sup.3, and even more preferably 50 to 175 g ft.sup.3.

[0059] The first washcoat coating comprises a catalyst composition comprising at least one platinum group metal (PGM) and at least one support material for the at least one PGM. The catalyst is typically applied to the substrate monolith as a washcoat slurry comprising at least one PGM salt and one or more support materials in the finished catalyst coating, before the coated filter is dried and then calcined. The one or more support materials may be referred to as a washcoat component. It is also possible for at least one PGM to be pre-fixed to one or more support materials prior to it being slurried, or for a combination of support material particles to which PGM is pre-fixed to be slurried in a solution of PGM salt.

[0060] By at least one support material herein, we mean a metal oxide selected from the group consisting of optionally stabilised alumina, amorphous silica-alumina, optionally stabilised zirconia, ceria, titania and an optionally stabilised ceria-zirconia mixed oxide or a molecular sieve and mixtures of any two or more thereof.

[0061] The at least one support material may include one or more molecular sieve, e.g. an aluminosilicate zeolite. The primary duty of the molecular sieve in the PGM catalyst for use in the present invention is for improving hydrocarbon conversion over a duty cycle by storing hydrocarbon following cold start or during cold phases of a duty cycle and releasing stored hydrocarbon at higher temperatures when associated platinum group metal catalyst components are more active for HC conversion. See for example Applicant/Assignee's EP 0830201. Molecular sieves are typically used in catalyst compositions according to the invention for light-duty diesel vehicles, whereas they are rarely used in catalyst compositions for heavy duty diesel applications because the exhaust gas temperatures in heavy duty diesel engines mean that hydrocarbon trapping functionality is generally not required.

[0062] However, molecular sieves such as aluminosilicate zeolites are not particularly good supports for platinum group metals because they are mainly silica, particularly relatively higher silica-to-alumina molecular sieves, which are favoured for their increased thermal durability: they may thermally degrade during ageing so that a structure of the molecular sieve may collapse and/or the PGM may sinter, giving lower dispersion and consequently lower HC and/or CO conversion activity.

[0063] When the first washcoat coating and/or the second washcoat coating each comprise a molecular sieve, then preferably the first washcoat coating and/or the second washcoat coating comprise a molecular sieve at 30% by weight (such as 25% by weight, 20% by weight e.g. 15% by weight) of the individual washcoat coating layer. The remaining at least one support material of the first washcoat coating or the second washcoat coating may comprise a metal oxide selected from the group consisting of optionally stabilised alumina, amorphous silica-alumina, optionally stabilised zirconia, ceria, titania and an optionally stabilised ceria-zirconia mixed oxide and mixtures of any two or more thereof.

[0064] Preferred molecular sieves for use as support materials/hydrocarbon adsorbers are medium pore zeolites, preferably aluminosilicate zeolites, i.e. those having a maximum ring size of eight tetrahedral atoms, and large pore zeolites (maximum of ten tetrahedral atoms) preferably aluminosilicate zeolites, include natural or synthetic zeolites such as faujasite, clinoptilolite, mordenite, silicalite, ferrierite, zeolite X, zeolite Y, ultrastable zeolite Y, ZSM-5 zeolite, ZSM-12 zeolite, SSZ-3 zeolite, SAPO-5 zeolite, offretite or a beta zeolite, preferably ZSM-5, beta and Y zeolites. Preferred zeolite adsorbent materials have a high silica to alumina ratio, for improved hydrothermal stability. The zeolite may have a silica/alumina molar ratio of from at least about 25/1, preferably at least about 50/1, with useful ranges of from about 25/1 to 1000/1, 50/1 to 500/1 as well as about 25/1 to 100/1, 25/1 to 300/1, from about 100/1 to 250/1.

[0065] Substrate monoliths for use in the present invention can be ceramic, such as cordierite, aluminium titanate, silicon carbide or the like; or metallic, made e.g. of thin metal foils of ferritic iron-chromium-aluminium alloys.

[0066] The first substrate monolith may be a flow-through substrate monolith or a filtering substrate monolith. The second washcoat coating is generally oriented to contact exhaust gas that has contacted the first washcoat. This is to allow the first washcoat coating to come into contact with the exhaust gas first. The exhaust gas and any volatilised PGM from the first washcoat coating is then contacted with the second washcoat coating that includes copper for trapping the volatilised PGM.

[0067] When the first substrate monolith is a flow-through substrate monolith, then typically either the first washcoat zone or the first washcoat coating is disposed at an inlet end of the substrate monolith and the second washcoat zone or the second washcoat coating is disposed at an outlet end of the substrate monolith. The first washcoat coating and second washcoat coating may overlap (e.g. at a middle section of the substrate monolith). When the first washcoat coating and the second washcoat coating overlap (e.g. one washcoat coating on top of the other), then preferably the second washcoat coating is disposed on top of the first washcoat coating (e.g. in the region of overlap), and the first washcoat coating is disposed on the substrate monolith (i.e. the first washcoat coating is in contact with a surface of the substrate monolith). It is preferred that there is substantially no overlap between the first washcoat coating and the second washcoat coating or the first washcoat zone and the second washcoat zone.

[0068] Typically, a filtering substrate monolith has inlet surfaces and outlet surfaces, wherein the inlet surfaces are separated from the outlet surfaces by a porous structure and wherein the first washcoat coating of the first zone is applied to the inlet surfaces and the second washcoat coating of the second zone is applied to the outlet surfaces. When the first substrate monolith is a filtering substrate monolith, then preferably the filtering substrate monolith is a wall-flow filter, such as described in the background section hereinabove, wherein inlet channels of the wall-flow filter comprise the first zone and wherein outlet channels of the wall-flow filter comprise the second zone.

[0069] Methods of making catalysed substrate monoliths, including single layer washcoat coatings and dual layered arrangements (one washcoat coating layer above another washcoat coating layer) are known in the art and include Applicant/Assignee's WO 99/47260, i.e. comprising the steps of (a) locating a containment means on top, first end of a substrate monolith, (b) dosing a pre-determined quantity of a first washcoat coating component into said containment means, either in the order (a) then (b) or (b) then (a), and (c) by applying pressure or vacuum, drawing said first washcoat coating component into at least a portion of the substrate monolith, and retaining substantially all of said quantity within the substrate monolith. In a first step a coating from a first end of application can be dried and the dried substrate monolith can be flipped through 180 degrees and the same procedure can be done to a top, second end of the substrate monolith, with substantially no overlap in layers between applications from the first and second ends of the substrate monolith. The resulting coating product is then dried, and then calcined. The process is repeated with a second washcoat coating component, to provide a catalysed (bi-layered) substrate monolith according to the invention.

[0070] The filtering substrate monolith for use in the invention is preferably a wall-flow filter, i.e. a ceramic porous filter substrate comprising a plurality of inlet channels arranged in parallel with a plurality of outlet channels, wherein each inlet channel and each outlet channel is defined in part by a ceramic wall of porous structure, wherein each inlet channel is alternatingly separated from an outlet channel by a ceramic wall of porous structure and vice versa. In other words, the wall-flow filter is a honeycomb arrangement defining a plurality of first channels plugged at an upstream end and a plurality of second channels not plugged at the upstream end but plugged at a downstream end. Channels vertically and laterally adjacent to a first channel are plugged at a downstream end. When viewed from either end, the alternately plugged and open ends of the channels take on the appearance of a chessboard.

[0071] Catalysed filters, preferably wall-flow filters, can be coated using the method disclosed in Applicant/Assignee's WO 2011/080525. That is, a method of coating a honeycomb monolith substrate comprising a plurality of channels with a liquid comprising a catalyst component, which method comprising the steps of: (i) holding a honeycomb monolith substrate substantially vertically; (ii) introducing a pre-determined volume of the liquid into the substrate via open ends of the channels at a lower end of the substrate; (iii) sealingly retaining the introduced liquid within the substrate; (iv) inverting the substrate containing the retained liquid; and (v) applying a vacuum to open ends of the channels of the substrate at the inverted, lower end of the substrate to draw the liquid along the channels of the substrate. The catalyst composition may be coated on filter channels from a first end, following which the coated filter can be dried.

[0072] The second substrate monolith can be a flow-through substrate monolith or a filtering substrate monolith having inlet surfaces and outlet surfaces, wherein the inlet surfaces are separated from the outlet surfaces by a porous structure, preferably a wall-flow filter.

[0073] The first washcoat coating disposed in the first washcoat zone can comprise an oxidation catalyst or a NO.sub.x adsorber catalyst (i.e. an oxidation or NAC composition) as described in the background of the invention hereinabove. A NAC or an NAC composition contains significant quantities of alkaline earth metals and/or alkali metals relative to an oxidation catalyst. The NAC or NAC composition typically also includes ceria or a ceria-containing mixed oxide, e.g. a mixed oxide of cerium and zirconium, which mixed oxide optionally further including one or more additional lanthanide or rare earth elements. Where the first substrate monolith is a filtering substrate monolith and the first washcoat is an oxidation catalyst, this device is often referred to in the art as a catalysed soot filter or CSF.

[0074] The second catalysed substrate monolith comprises a catalyst for selectively catalysing the reduction of oxides of nitrogen to dinitrogen with a nitrogenous reductant, also known as a selective catalytic reduction (SCR) catalyst.

[0075] Typically, the SCR catalyst is coated as a coating onto a substrate monolith, such as described hereinabove.

[0076] Alternatively, the SCR catalyst is provided as an extrudate (also known as a catalyst body), i.e. the catalyst is mixed with components of the substrate monolith structure, which are both extruded, so the catalyst is part of the walls of the substrate monolith.

[0077] The SCR catalyst of the second substrate monolith can comprise a filtering substrate monolith or a flow-through substrate monolith. It is also possible to make a wall-flow filter from an extruded SCR catalyst (see Applicant/Assignee's WO 2009/093071 and WO 2011/092521). Selective Catalytic Reduction (SCR) catalysts for use in connection with the second catalysed substrate monolith can be 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, supported on a refractory oxide or molecular sieve. Suitable refractory oxides include Al.sub.2O.sub.3, TiO.sub.2, CeO.sub.2, SiO.sub.2, ZrO.sub.2 and mixed oxides containing two or more thereof. Non-zeolite catalyst can also include tungsten oxide, e.g. V.sub.2O.sub.5/WO.sub.3/TiO.sub.2. Preferred metals of particular interest are selected from the group consisting of Ce, Fe and Cu. Molecular sieves can be ion-exchanged with the above metals.

[0078] It is preferred that the at least one molecular sieve is an aluminosilicate zeolite or a SAPO. The at least one molecular sieve can be a small, a medium or a large pore molecular sieve, for example.

[0079] By small pore molecular sieve herein we mean a molecular sieves containing a maximum ring size of 8 tetrahedral atoms, such as CHA; by medium pore molecular sieve herein we mean a molecular sieve containing a maximum ring size of 10 tetrahedral atoms, such as ZSM-5; and by large pore molecular sieve herein we mean a molecular sieve having a maximum ring size of 12 tetrahedral atoms, such as beta. Small pore molecular sieves are potentially advantageous for use in SCR catalystssee for example WO 2008/132452. Molecular sieves for use in SCR catalysts according to the invention include one or more metals incorporated into a framework of the molecular sieve e.g. Fe in-framework Beta and Cu in-framework CHA.

[0080] Particular molecular sieves with application in the present invention are 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, with CHA molecular sieves, e.g. aluminosilicate CHA, currently preferred, particularly in combination with Cu as promoter, e.g. ion-exchanged.

[0081] It is preferred that an optionally catalysed filtering substrate monolith (i.e. a third catalysed substrate monolith) is disposed downstream from the second catalysed substrate, i.e. in the DOC/SCR/CSF arrangement discussed in connection with the background to the invention hereinabove. The filtering substrate monolith is preferably a wall-flow filter. Where catalysed, the catalyst for use in connection with the filtering substrate monolith is an oxidation catalyst, but in alternative embodiments it can be a NAC composition. Alternatively, the filtering substrate monolith can be uncatalysed.

[0082] An exhaust system according to the present invention is shown in FIG. 5. Exhaust system 20 comprises, in serial arrangement from upstream to downstream, a catalysed flow-through substrate monolith 12; a source of ammonia 13 comprising an injector for an ammonia precursor, urea; and a flow-through substrate monolith 14 coated with a Fe/Beta SCR catalyst. Each substrate monolith 12, 14 is disposed in a metal container or can including coned diffusers and they are linked by a series of conduits 3 of smaller cross sectional area than a cross sectional area of any of substrate monoliths 12, 14. The coned diffusers act to spread the flow of exhaust gas entering a housing of a canned substrate monolith so that the exhaust gas as a whole is directed across substantially the whole front face of each substrate monolith. Exhaust gas exiting substrate monolith 4 is emitted to atmosphere at tail pipe 5.

[0083] Catalysed flow-through substrate monolith 12 comprises a first zone 16 defined in part by an upstream end thereof coated with a 4:1 Pt:Pd weight ratio catalyst wherein the Pt and Pd are supported on a support material; and a second zone 18 of about 50% of a total length of the flow-through substrate monolith with substantially no overlap with first zone 16, which second zone 18 comprising a copper compound supported on a stabilised particulate alumina support material. The catalysed flow-through substrate monolith is designed for the purpose of promoting reaction (1) and thereby reaction (6) on the downstream SCR catalyst.

EXAMPLES

Example 1Preparation of Substrate Monolith Coated with 5 wt % Fe/Beta Zeolite

[0084] Commercially available Beta zeolite was added to an aqueous solution of Fe(NO.sub.3).sub.3 with stirring. After mixing, binders and rheology modifiers were added to form a washcoat composition.

[0085] A 400 cells per square inch cordierite flow-through substrate monolith was coated with an aqueous slurry of the 5 wt % Fe/Beta zeolite sample using the method disclosed in WO 99/47260, i.e. comprising the steps of (a) locating a containment means on top of a support, (b) dosing a pre-determined quantity of a liquid component into said containment means, either in the order (a) then (b) or (b) then (a), and (c) by applying pressure or vacuum, drawing said liquid component into at least a portion of the support, and retaining substantially all of said quantity within the support. This coated product (coated from one end only) is dried and then calcined and this process is repeated from the other end so that substantially the entire substrate monolith is coated, with a minor overlap in the axial direction at the join between the two coatings. A core of 1 inch (2.54 cm) diameter3 inches long was cut from the finished article.

Comparative Example 2Preparation of Pt-Only Catalysed Wall-Flow Filter

[0086] A washcoat composition comprising a mixture of alumina particles milled to a relatively high particle size distribution, platinum nitrate, binders and rheology modifiers in deionised water was prepared. An aluminium titanate wall-flow filter was coated with the catalyst composition at a washcoat loading of 0.2 g/in.sup.3 to a final total Pt loading of 501.sup.3 using the method and apparatus disclosed in the Applicant/Assignee's WO 2011/080525, wherein channels at a first end intended for orientation to an upstream side were coated for 75% of their total length with a washcoat comprising platinum nitrate and particulate alumina from the intended upstream end thereof; and channels at an opposite end and intended to be oriented to a downstream side are coated for 25% of their total length with the same washcoat as the inlet channels. That is, the method comprised the steps of: (i) holding a honeycomb monolith substrate substantially vertically; (ii) introducing a pre-determined volume of the liquid into the substrate via open ends of the channels at a lower end of the substrate; (iii) sealingly retaining the introduced liquid within the substrate; (iv) inverting the substrate containing the retained liquid; and (v) applying a vacuum to open ends of the channels of the substrate at the inverted, lower end of the substrate to draw the liquid along the channels of the substrate. The catalyst composition was coated on filter channels from a first end, following which the coated filter was dried. The dried filter coated from the first end was then turned and the method was repeated to coat the same catalyst to filter channels from the second end, followed by drying and calcining.

[0087] A core of 1 inch (2.54 cm) diameter3 inches (7.62 cm) long was cut from the finished article. The resulting part is described as fresh, i.e. unaged.

Example 3Preparation of Pt-Inlet/CuAl.SUB.2.O.SUB.3.-Outlet Containing Catalysed Wall-Flow Filter

[0088] A coated filter was prepared using the same method as Comparative Example 2, except in that 100% of the total channel length of channels intended for orientation towards the inlet side of gas contact was coated with a washcoat containing platinum nitrate and alumina before the coated filter was dried; and 35% of the total length of channels intended for orientation towards the outlet side were coated with a washcoat containing alumina and copper sulphate. The resulting coated filter was then dried, and then calcined. The total loading of Pt on inlet channels of the coated filter was 5 gft.sup.3. The total copper loading on the outlet was 66 gft.sup.3.

[0089] A core of 1 inch (2.54 cm) diameter3 inches long was cut from the finished article. The resulting part is described as fresh, i.e. unaged.

Example 4Preparation of 1:1 Weight % Pt:Pd Containing Catalysed Wall-Flow Filter

[0090] A coated filter was prepared using the same method as in Comparative Example 2, except in that the washcoat applied to both the inlet channels and the outlet channels of the filter included palladium nitrate in addition to the platinum nitrate. The washcoat loading in the inlet and outlet channels was conducted in such a way as to arrive at a 5 g/ft.sup.3 Pt, 5 g/ft.sup.3 Pd loading on both the inlet surfaces and the outlet surfaces, i.e. a total PGM loading of 10 g/ft.sup.3.

[0091] A core of 1 inch (2.54 cm) diameter3 inches long was cut from the finished article. The resulting part is described as fresh, i.e. unaged.

Example 5Preparation of 5:1 Weight % Pt:Pd Containing Catalysed Wall-Flow Filter

[0092] A coated filter was prepared using the same method as in Comparative Example 2, except in that the washcoat applied to both the inlet channels and the outlet channels of the filter included palladium nitrate in addition to the platinum nitrate. The washcoat loading in the inlet and outlet channels was conducted in such a way as to arrive at a 5 g/ft.sup.3 Pt, 1 g/ft.sup.3 Pd loading on both the inlet surfaces and the outlet surfaces, i.e. a total PGM loading of 6 g/ft.sup.3.

[0093] A core of 1 inch (2.54 cm) diameter3 inches long was cut from the finished article. The resulting part is described as fresh, i.e. unaged.

Example 6System Tests

[0094] The tests were performed on a first synthetic catalyst activity test (SCAT) laboratory reactor illustrated in FIG. 1, in which a fresh core of the coated Fe/Beta zeolite SCR catalyst of Example 1 is disposed in a conduit downstream of a core of either the catalysed wall-flow filter of Comparative Example 2 or of Example 3, 4 or 5. A synthetic gas mixture was passed through the conduit at a catalyst swept volume of 30,000 hr.sup.1. A furnace was used to heat (or age) the catalysed wall-flow filter sample at a steady-state temperature at a filter inlet temperature of 900 C. for 60 minutes, during which the inlet SCR catalyst temperature was 300 C. using. An air (heat exchanger) or water cooling mechanism was used to effect the temperature drop between the filter and the SCR catalyst. The gas mixture during the ageing was 10% O.sub.2, 6% H.sub.2O, 6% CO.sub.2, 100 ppm CO, 400 ppm NO, 100 ppm HC as Cl, balance N.sub.2.

[0095] Following ageing, the aged SCR catalysts were removed from the first SCAT reactor and inserted into a second SCAT reactor specifically to test NH.sub.3SCR activity of the aged samples. The aged SCR catalysts were then tested for SCR activity at 150, 200, 250, 300, 350, 450, 550 and 650 C. using a synthetic gas mixture (O.sub.2=14%; H.sub.2O=7%; CO.sub.2=5%; NH.sub.3=250 ppm; NO=250 ppm; NO.sub.2=0 ppm; N.sub.2=balance) and the resulting NO.sub.x conversion was plotted against temperature for each temperature data point in FIG. 2. This plot essentially measures competition between reaction (9) and reaction (5) and thus how much reaction (9) affects the NO.sub.x conversion by consumption of the available NH.sub.3 needed for the SCR reaction (reaction (5)).

[0096] The results are shown in FIG. 2. It can be seen from the results of testing Example 3 that the SCR catalyst in the exhaust system according to the present invention retains more activity than the SCR catalyst in Comparative Example 2, although it retains less SCR activity than a fresh catalyst. The inventors interpret this result as showing that the loss in SCR activity is caused in part by the deposition of low levels of Pt from the upstream catalysed wall-flow filter on the downstream SCR catalyst. Substantially no loss in activity was seen between a fresh Fe/Beta catalyst and a Fe/Beta catalyst aged at 300 C. for 1 hour without any catalyst present upstream (results not shown).

Example 7Preparation of Substrate Monolith Coated with 3 wt % Cu/CHA Zeolite

[0097] Commercially available aluminosilicate CHA zeolite was added to an aqueous solution of Cu(NO.sub.3).sub.2 with stirring. The slurry was filtered, then washed and dried. The procedure can be repeated to achieve a desired metal loading. The final product was calcined. After mixing, binders and rheology modifiers were added to form a washcoat composition.

[0098] A 400 cpsi cordierite flow-through substrate monolith was coated with an aqueous slurry of the 3 wt % Cu/CHA zeolite sample using the method disclosed in Applicant/Assignee's WO 99/47260 described in Example 1 hereinabove. The coated substrate monolith was aged in a furnace in air at 500 C. for 5 hours. A core of 1 inch (2.54 cm) diameter3 inches long (7.62 cm) was cut from the finished article.

Example 8Further Pt:Pd Weight Ratio Studies

[0099] Two diesel oxidation catalysts were prepared as follows:

Diesel Oxidation Catalyst A

[0100] A single layered DOC was prepared as follows. Platinum nitrate and palladium nitrate were added to a slurry of silica-alumina. Beta zeolite was added to the slurry such that it comprised <30% of the solids content as zeolite by mass. The washcoat slurry was dosed onto a 400 cpsi flow-through substrate using the method of Example 1 hereinabove. The dosed part was dried and then calcined at 500 C. The total platinum group metal loading in the washcoat coating was 60 gft.sup.3 and the total Pt:Pd weight ratio was 4:1. A core of 1 inch (2.54 cm) diameter3 inches (7.62 cm) long was cut from the finished article. The resulting part may be described as fresh, i.e. unaged.

Diesel Oxidation Catalyst B

[0101] A single layered DOC was prepared as follows. Platinum nitrate and palladium nitrate were added to a slurry of silica-alumina. Beta zeolite was added to the slurry such that it comprised <30% of the solids content as zeolite by mass. The washcoat slurry was dosed onto a 400 cpsi flow-through substrate using the same method as used for DOC A. The dosed part was dried and then calcined at 500 C. The total PGM loading in the single layer DOC was 120 g/ft.sup.3 and the Pt:Pd weight ratio was 2:1. A core of 1 inch (2.54 cm) diameter3 inches (7.62 cm) long was cut from the finished article. The resulting part may be described as fresh, i.e. unaged.

[0102] Both catalysts were tested according the protocols set out in Example 9. The results are set out in FIG. 3 with reference to a control (aged SCR catalyst that has not been further aged downstream of either DOC A or DOC B).

Example 9System Tests

[0103] The tests were performed on a first synthetic catalyst activity test (SCAT) laboratory reactor illustrated in FIG. 1, in which an aged core of the coated Cu/CHA zeolite SCR catalyst of Example 7 was disposed in a conduit downstream of a core of either the Diesel Oxidation Catalyst (DOC) A or B (according to Example 8). A synthetic gas mixture was passed through the conduit at a rate of 6 litres per minute. A furnace was used to heat (or age) the DOC samples at a steady-state temperature at a catalyst outlet temperature of 900 C. for 2 hours. The SCR catalyst was disposed downstream of the DOC sample and was held at a catalyst temperature of 300 C. during the ageing process by adjusting the length of tube between the furnace outlet and the SCR inlet, although a water cooled heat exchanger jacket could also be used as appropriate. Temperatures were determined using appropriately positioned thermocouples (T.sub.1 and T.sub.2). The gas mixture used during the ageing was 40% air, 50% N.sub.2, 10% H.sub.2O.

[0104] Following the DOC ageing, the SCR catalysts were removed from the first SCAT reactor and inserted into a second SCAT reactor specifically to test NH.sub.3SCR activity of the aged samples. The SCR catalysts were then tested for SCR activity at 500 C. using a synthetic gas mixture (O.sub.2=10%; H.sub.2O=5%; CO.sub.2=7.5%; CO=330 ppm; NH.sub.3=400 ppm; NO=500 ppm; NO.sub.2=0 ppm; N.sub.2=balance, i.e. an alpha value of 0.8 was used (ratio of NH.sub.3:NO.sub.x), so that the maximum possible NO.sub.x conversion available was 80%) and the resulting NO.sub.x conversion was plotted against temperature on the accompanying bar chart in FIG. 4. This plot essentially measures competition between reaction (9) and reaction (5) and thus how much reaction (9) affects the NO.sub.x conversion by consumption of the available NH.sub.3 needed for the SCR reaction (reaction (5)).

Pt:Pd weight Ratio StudyConclusions

[0105] Taken as a whole, the results of Example 6 shown in FIG. 3 in connection with Examples 4 and 5 and Comparative Example 2 indicate that a Pt:Pd weight ratio of between 1:1 and 5:1 is beneficial in reducing the problem of NO.sub.x conversion activity loss through volatilisation of platinum group metal, principally platinum, from a platinum group metal containing catalyst to a downstream SCR catalyst.

[0106] The results of Example 9 shown in FIG. 4 in connection with Diesel Oxidation Catalysts A and B show that for a SCR catalyst aged downstream of a DOC having a 2:1 Pt:Pd weight ratio overall, the loss of NO.sub.x conversion activity is relatively slight at 67% NO.sub.x conversion activity compared with the control at 72% NO.sub.x conversion activity (a SCR catalyst aged behind a 1:1 Pt:Pd weight ratio overall DOC (not described herein) using the same protocol had a NO.sub.x conversion activity of 69%). However, when the overall Pt:Pd weight ratio was increased to 4:1, SCR activity was significantly reduced to 48%.

[0107] The inventors conclude, therefore, that there exists a boundary at about 2:1 Pt:Pd weight ratio overall above which Pt volatilisation is more likely to occur. Hence, by limiting to an overall Pt:Pd weight ratio of 2:1 in the DOC as a whole, and to 2:1 Pt:Pd weight ratio in the second washcoat coating layer, Pt in the DOC is less likely to volatilise and migrate to a downstream SCR catalyst.

[0108] For the avoidance of any doubt, the entire content of any and all documents cited herein is incorporated by reference into the present application.