GB2510046A - Zoned catalysed substrate monolith - Google Patents

Abstract

A zoned catalysed substrate monolith comprises a first zone and a second zone, wherein the first zone and the second zone are arranged axially in series, wherein the first zone comprises a platinum group metal loaded in a support and a first base metal oxide selected from the group consisting of iron oxide, manganese oxide, copper oxide, zinc oxide, nickel oxide, and mixtures thereof or a first base metal selected from the group consisting of iron, manganese, copper, zinc, nickel, and mixtures thereof loaded on an inorganic oxide and the second zone comprises copper or iron loaded on a zeolite and a second base metal oxide selected from the group consisting of iron oxide, manganese oxide, copper oxide, zinc oxide, nickel oxide, and mixtures thereof or a second base metal selected from the group consisting of iron, manganese, copper, zinc, nickel, and mixtures thereof loaded on an inorganic oxide, wherein the second base metal is different from the first base metal.

Description

ZONED CATALYSED SUBSTRATE MONOLITH

The present invention relates to a zoned catalysed substrate monolith for controlling hydrogen sulphide gas formed in a lean NO trap during desulphation of the lean NO trap over an extended temperature range as compared to known hydrogen sulphide control mechanisms. The invention also relates to an exhaust system for an internal combustion engine comprising a lean NO trap and the zoned catalysed substrate monolith and to various methods of making the zoned catalysed substrate monolith and of treating an exhaust gas from an internal combustion engine.

Vehicular emissions which are the principle pollutants that have negative effects on public health and the natural environment are generally recognised to be carbon monoxide (CO), hydrocarbons (HC), nitrogen oxides (NO) and particulate matter.

Several solutions have been proposed to remove and/or control these principle pollutants, some of which focus on the engine design and some of which focus on control of emissions from exhaust systems.

Typical exhaust systems that exist to remove and/or control such emissions comprise a NO Trap, an oxidation catalyst to catalyse conversion of CO and HC, which are present as a result of incomplete combustion of the fuel in the engine, and a filter substrate to remove particulate matter, Lean NO traps (LNT) (also known as NO adsorber catalyst); such as disclosed in US5473887, use a trap, for example an alkaline earth metal oxide that adsorbs NO during the lean mode of operation. Exhaust gas is typically rich in NO which is converted to NO2 over a platinum group metal-containing oxidising catalyst, such as platinum or ruthenium, and the NO2 is trapped and stored on the alkaline earth metal oxide, such as barium carbonate, which is incorporated within the platinum group containing catalyst. The NO is then released from the barium under rich conditions, when the oxygen concentration in the exhaust emission is decreased, and reduced with a suitable reductant, for example diesel fuel for diesel engines, using a rhodium catalyst as a promoter. The rhodium catalyst may be incorporated on the platinum group containing catalyst or it may be located downstream of the LNT.

One mechanism commonly given for NO11 trapping from a lean exhaust gas for this formulation is: NO+0.502-'N02 (I); BaO+NCh+O.5 Ch-'Ba(NOi) (2), wherein in reaction (1), the NO reacts with oxygen on active oxidation sites on the platinum group metal catalyst to form NO2. Reaction (2) involves adsorption of the NCh by the storage material in the form of an inorganic nitrate.

At lower oxygen concentrations and/or at elevated temperatures, the nitrate species become thermodynamically unstable and decompose, producing NO or NO2 according to reaction (3) below. In the presence of a suitable reductant, these nitrogen oxides are subsequently reduced by carbon monoxide, hydrogen and hydrocarbons to N2, which can take place over the reduction catalyst (see reaction (4)).

Ba(N03)2 -BaO +2N0+ 1.502 orBa(NO -BaO+2NCh +0.502 (3); and NO + CO -0.5 N2 + CO2 (and other reactions) (4).

In the reactions of (1)-(4) above, the reactive barium species is given as the oxide.

However, it is understood that in the presence of air or lean engine exhaust gas most of the barium is in the form of the carbonate or possibly the hydroxide. The skilled person can adapt the above reaction schemes accordingly for species of barium other than the oxide.

A problem in the use of LNT, e.g. in both diesel and gasoline applications, is that the engine fuel also contains sulphur, and this is converted to sulphur dioxide (5(h) during fuel combustion. 502 is oxidised to sulphur trioxide (S02) by the oxidation catalyst component of the LNT and the SO3 is adsorbed on the NO11 adsorber by a similar mechanism to that of NO2. There are a finite number of active sites on the NO11 trapping component for adsorbing the NO11 and so the presence of sulphate on the NO11 trapping component reduces the capacity of the NO11 trapping n component as a whole to adsorb NO1, Therefore, in order to retain sufficient NO1 trapping capability, sulphur must be periodically removed from the LNT. However, suiphates of NO1 trapping components such as barium are more stable than nitrates in lean exhaust gas and generally higher temperatures and/or richer conditions for longer periods are required to remove SOx than for desorbing NO1.

Desulphation can be accomplished by a variety of techniques including by a series of short, rich pulses. A significant problem with desulphating a LNT using richer than normal exhaust gas compositions is that the sulphate is removed as hydrogen sulphide. This compound has a characteristic and unpleasant rotten egg odour, 0.0047 ppm is the recognition threshold, the concentration at which 50% of humans can detect the characteristic odour of hydrogen sulphide, and accordingly it is desirable to prevent/limit its emission to atmosphere, This problem has been reduced to a certain extent in recent years for diesel fuels because Ultra Low Sulphur Diesel (fuel of maximum sulphur content of 15 ppm (wt,)) is now available in the US. In Europe, diesel fuel with a maximum sulphur limit of 10 ppm has been available since the beginning of 2010. As a result, LNT desulphation procedures are required less often, However the extremely low odour threshold of hydrogen sulphide means that even a small emission to atmosphere is undesirable.

Particulate filters have been shown to be extremely effective at removal of particulate matter over the entire particle size range. However, these filters have limited capacity for trapping particulate matter before the pressure drop becomes excessive, Therefore it is necessary to periodically regenerate the particulate filter.

Passive regeneration may not readily take place as combustion of the retained particulate matter in the presence of oxygen requires higher temperatures than those typically provided by engine exhaust, particularly in the case of diesel passenger car exhausts. One effective method to lower the combustion temperature of the trapped particulate matter on the particulate filter is the addition of a catalysed washcoat to the filter substrate, Compositions of catalysed washcoats used are similar to those used in oxidation catalysts and typically comprise at least one platinum group metal supported on a suitable support material. Suitable support materials include alumina, silica-alumina, ceria or a mixed oxide or composite oxide of ceria and zirconia, and mixtures thereof Such filters are typically known as catalysed soot filters (C SF).

A diesel exhaust system comprising a LNT and a downstream CSF is known.

For example SAE 200 1-01-2065 entitled "Cummins Light Truck Diesel Engine Progress Report" discloses such a system. It is acknowledged by the authors in this report that there was no consideration of the effects of deterioration or contamination due to sulphur poisoning and no attempt was made to desulphate during any of the driving cycles.

W02008/075111 discloses an apparatus comprising a lean burn internal combustion engine which comprises an exhaust system for treating a flowing exhaust gas from the engine having a LNT, a CSF, a means for enriching the exhaust gas to provide an enriched exhaust gas intermittently during operation in order to remove sulphate that is adsorbed on the LNT and a compound located downstream of at least some of the LNT which is effective in removing andlor converting hydrogen sulphide that is produced during the sulphate removal process. The hydrogen sulphide removal and/or converting material is selected from the group consisting of oxides of nickel, calcium, iron and barium, The hydrogen sulphide removal and/or converting material may be located in a variety of positions in the exhaust system, which include between the LNT and CSF, on the CSF, between the CSF and the exhaust system exit. The only discussion about why the hydrogen sulphide removal and/or converting material is placed at the chosen position is with respect to any platinum group metal oxidation catalysts as nickel oxide can poison the hydrocarbon and carbon monoxide activity of the platinum group metal catalyst.

USS 196390 discloses a method of suppressing hydrogen sulphide formation by a three way catalyst by incorporating one or more of oxides of nickel, iron and manganese into an undercoat layer disposed on a monolith substrate. A topcoat overlying the undercoat comprises standard three way catalyst material. This structure avoids any interaction between the three way catalyst and the hydrogen sulphide suppressing material, SAE Paper 2005-01-1116 presented during the 2005 Society of Automotive Engineers (SAE) World Congress in Detroit, Michigan, USA (April 11-14, 2005) is entitled "H2S Suppression During the Desulfation of a Lean NO Trap with a Nickel-Containing Catalyst" -Three of the same authors are named as inventors on US patent publication no. US 2005/0160720.

JP 200 1-070754 addresses the problem of suppressing 112S emission amount from a lean burn internal occlusion engine without deteriorating the treatment capability ofaNO-occlusion type catalyst. The publication discloses an exhaust gas treatment apparatus comprising a three way catalyst downstream of a NO occlusion type catalyst, wherein the three way catalyst comprises nickel oxide at 10-35 g per I litre installed as a H2S emission suppressing catalytic apparatus or a nickel oxide together with other H2S emission suppressing agent is added to the three-way catalyst in 30-300% by mole ratio to Ba added as an occluding agent to the NO catalyst.

The European Parliament and of The Council Directive 94/27/EC of 30 June t994 (as subsequently amended by Commission Directive 2004/96/EC of 27 September 2004) restricts the use of nickel due to human sensitization, which may lead to allergic reactions. The Committee for Human Medicinal Products (CHMP) of the European Medicines Agency issued a Draft Guideline on the specification limits for residues of metal catalysts, including nickel catalysts, in January 2007. It is understood that there is currently a voluntary ban on the use of nickel in automotive catalysts amongst the automobile industry and its suppliers.

Applicant's WO 2012/175948 Al was filed earlier but published later than the current application. It discloses an exhaust system for internal combustion engines and a catalysed substrate for use in an exhaust system. The exhaust system comprises a lean NO trap and the catalysed substrate disposed downstream of the lean NO trap.

The catalysed substrate has a first zone and a second zone, wherein the first zone comprises a platinum group metal loaded on a support and the second zone comprises copper or iron loaded on a zeolite. The first zone or the second zone additionally comprises a base metal oxide or a base metal loaded on an inorganic oxide, wherein the base metal is preferably iron, manganese, copper, nickel or mixtures thereof The catalysed substrate can be oriented in the exhaust system so that the first zone is upstream of the second zone or vice versa. Preferably, however, the first zone is oriented so that the first zone is on the upstream side to receive exhaust gas from the NO1 trap prior to the second zone, The exhaust system is capable of storing NH3 generated in a rich purge, reacting the NH3 with slip NO1 from the NO1 trap, controlling H2S released from NO trap desulphation, and oxidizing slip hydrocarbons and carbon monoxide. When the catalysed substrate is a filter substrate, it is also capable of removing soot from exhaust system.

The different materials that are available to remove and/or convert the hydrogen sulphide each operate most efficiently over a defined temperature range.

For example oxides of iron are known to be effective at lower temperatures, typically 400-800°C, and oxides of manganese are known to be effective at higher temperatures, which in some cases can be in excess of 1000°C. Mixing together some of these different materials may not be enough to extend the temperature range for removal and/or conversion of the hydrogen sulphide as there may be negative interactions based on such combinations.

We have now identified a system which is capable of treating both NO1 and particulate matter emitted from the exhaust system of an internal combustion engine whilst also removing and/or converting unwanted hydrogen sulphide emissions over a broad temperature range. This is achieved by providing a catalysed substrate monolith downstream of an LNT, whose desulphation process leads to the formation of undesirable hydrogen sulphide, wherein separate zones within the catalysed substrate comprise different materials for removal and/or conversion of hydrogen sulphide emissions, Particulate matter can be trapped on a separate filter substrate or more preferably the catalysed substrate monolith is a catalytic soot filter.

Accordingly, in a first aspect, the invention provides a zoned catalysed substrate monolith comprising a first zone and a second zone, wherein the first zone and the second zone are arranged axially in series, wherein the first zone comprises a platinum group metal loaded in a support and a first base metal oxide selected from the group consisting of iron oxide, manganese oxide, copper oxide, zinc oxide, nickel oxide, and mixtures thereof or a first base metal selected from the group consisting of iron, manganese, copper, zinc, nickel, and mixtures thereof loaded on an inorganic oxide and the second zone comprises copper or iron loaded on a zeolite and a second base metal oxide selected from the group consisting of iron oxide, manganese oxide, copper oxide, zinc oxide, nickel oxide, and mixtures thereof or a second base metal selected from the group consisting of iron, manganese, copper, zinc, nickel, and mixtures thereof loaded on an inorganic oxide, wherein the second base metal is different from the first base metal.

Preferably, a washcoat loading of the copper or iron loaded on a zeolite in the second zone is 0.5«=3.Ogin3, preferaNy 1.O«=2.0gin.

Preferably, the first base metal or the second base metal is not nickel; and the first base metal oxide or the second base metal oxide is not nickel oxide. This is because of the voluntary European ban on including nickel in catalysts.

Preferred first base metals or second base metals are manganese and zinc; and preferred first base metal oxides or second base metal oxides are manganese oxide and zinc oxide, This is because the inventors have found that these base metals and base metal oxides are good 112S suppressants, but also they have a greater negative impact on CO oxidation at lower temperatures for the platinum group metal in the first zone compared with either copper (or copper oxide) or iron (or iron oxide); and a greater negative impact on selective catalytic NO conversion (using NH3 as reductant) over the Cu or Fe zeolite catalyst of the second zone than either (additional) Cu or CuO or (additional) Fe or Fe203. It is possible to use a Cu oxide or a Fe oxide as the H2S suppressants in the first zone (containing platinum group metals) but it is preferred that the Cu or Fe is physically separated from the platinum group metal loaded on a support (see below). It is preferred not to use Cu oxides or Fe oxides as the H2S suppressant in the second zone, because these materials (additional to Fe or Cu ion-exchanged with the zeolite framework) can undesirably competitively oxidise NH3, thereby reducing the efficiency of selective catalytic reduction reaction (i.e. 4NTJ5 + 4N0 + 02 -. 4N2 + 6H2O (i.e. 1:1 NH5:NO); 4NH3 + 2N0 + 2N02 4N2 + 6H2O (i.e. 1:1 NH3:NO); and 8NH5 + 6N02 7N2 + 12H20 (i.e. 4:3 NH3:NO) in preference to undesirable, non-selective side-reactions such as 2NH5 + 2N02 -. N2O + 31120 + N2) on the Cu or Fe zeolite catalysts.

The first zone may further comprise a platinum group metal loaded on a support. The platinum group metal is preferably platinum, palladium, rhodium, or mixtures thereof; most preferably, the platinum group metal is platinum, palladium, and mixtures thereof The support is preferably a zeolite, an inorganic oxide, or mixtures thereof More preferably, the support is an inorganic oxide such as alumina, silica, titania, zirconia, ceria, niobia, tantalum oxides, molybdenum oxides, tungsten oxides, mixed oxides or composite oxides of any two or more thereof (e.g. silica-alumina, ceria-zirconia or alumina-ceria-zirconia), and mixtures thereof Alumina and ceria-zirconia mixed oxide are particularly preferred.

When the first zone additionally comprises the platinum group metal loaded on a support it is preferred that the first base metal oxide or first base metal loaded on an inorganic oxide is physically separated from the platinum group metal loaded on a support. This can be achieved by preforming the supported platinum group metal powder, including calcination thereof to fix the platinum group metal on the support, prior to introducing the pre-formed powder into a washcoat, This is because the first base metal oxide may poison the hydrocarbon and carbon monoxide oxidising capability of the platinum group metal catalyst, Thus, separate particles of the supported platinum group metal and the first base metal oxide or first base metal loaded on an inorganic oxide are added to the first zone in order to physically segregate the two catalysts within the first zone.

In a preferred embodiment, wherein it is intended to orient the first zone in an exhaust system according to the second aspect of the invention to the upstream side, the first zone comprises a lean NO trap composition including a NO adsorbent for the storage/trapping of NO and an oxidation/reduction catalyst, as described hereinbelow, wherein the platinum group metal loaded on a support is the oxidation/reduction catalyst, The lean NO trap loading can be iOiO0gfi3, preferably 25<75gff3 or 3565gff3. Lean NO trap washcoat loadings can be -, .3 O.5<iOgrn, preferably 1O2.Ogin The zeolite in the second zone, i.e. loaded with copper or iron, is preferably a beta zeolite, a faujasite (such as an X-zeolite or a Y-zeolite, including NaY and IJSY), an L-zeolite, a ZSM zeolite (e.g., ZSM-5, ZSM-48), an SSZ-zeolite (e.g., SSZ-13 (a chabazite), SSZ-41, SSZ-33), a ferrierite, a mordenite, a chaba.zite, an ofiretite, an erionite, a clinoptilolite, a silicalite, an aluminium phosphate zeolite (including metalloaluminophosphates such as SAPO-34 (a chabazite)), a mesoporous zeolite (e.g., MCM-41, MCM-49, SBA-15), or mixtures thereof more preferably, the zeolite is a beta zeolite, a ferrierite, or a chabazite.

The first zone and the second zone each comprise a base metal oxide or a base metal loaded on an inorganic oxide. The inorganic oxide in each of the first zone and the second zone can be independently selected from the group consisting of alumina, silica, titania, zirconia, ceria, niobia, tantalum oxides, molybdenum oxides, tungsten oxides, any mixed oxide or composite oxide thereof and mixtures thereof Alumina is particularly preferred.

The zoned catalysed substrate is a substrate that contains catalyst components.

The substrate monolith is preferably a ceramic substrate monolith or a metallic substrate monolith, more preferably a ceramic substrate monolith. The ceramic substrate monolith may be made of any suitable refractory material, e.g. alumina, silica, titania, ceria, zirconia, magnesia, zeolites, silicon nitride, silicon carbide, zirconium silicates, magnesium silicates, aluminosilicates and metallo aluminosilicates (such as cordierite and spodumene), or a mixture or mixed oxide of any two or more thereof Cordierite, which is a magnesium aluminosilicate, and silicon carbide are particularly preferred ceramic substrate monoliths.

The metallic substrate monolith may be made of any suitable metal, and in particular heat-resistant metals and metal alloys such as titanium and stainless steel as well as ferritic alloys containing iron, nickel, chromium, and/or aluminium in addition to other trace metals.

The substrate monolith is preferably a filter substrate, but can also be a flow-through substrate monolith, Where the substrate monolith is a filter substrate, the washcoat loading of the (non-lean NO trap) platinum group metal loaded on a support in the first zone is preferably 0.il.O gin5, such as O.3O.7 gin3. In embodiments, where the (non-lean NO trap) first zone is oriented to the upstream side in the exhaust system according to the second aspect of the present invention and the substrate monolith is a filter substrate, the loading platinum group metal loading is preferably IO50gW3; or where the first zone is oriented to the downstream side, the platinum group metal loading is V2Ogf(3, such as 5115gfi3, or iEilUgff3.

Where the substrate monolith of the zoned catalysed substrate monolith is a filter substrate, in order to reduce backpressure in the exhaust system according to the present invention, it is preferred to locate a zone having a lower washcoat loading on the downstream side. In practice, the copper or iron loaded on a zeolite will be present at a higher washcoat loading and so it is preferred that the first zone is at a lower loading and is oriented to the downstream side. A lower washcoat loading also typically means a lower platinum group metal loading also. For on-board diagnostics purposes, modern exhaust systems are designed so that a filter regeneration process is conducted at intervals of about 5,000 km, thereby returning the system to a "base line" for onward diagnostic testing. Such regeneration processes can generate relatively high exhaust gas temperatures, which are beneficial for treating secondary emissions from soot combustion during a filter regeneration process even on relatively low loaded first zone oriented to the downstream side and copper and or iron can be used for the H2S suppressant. This is because, even though Cu or Fe can poison e.g. CO oxidation activity of the platinum group metal, a Cu-poisoned platinum group metal catalyst is able to light-off at the higher temperatures, thereby treating secondary emissions, during a filter regeneration process.

In a preferred embodiment of the first aspect of the invention, wherein the second zone is oriented to the upstream side in the exhaust system of the second aspect of the invention and the substrate monolith is a flow through substrate monolith or a filter substrate, and the first zone is a non-lean NO trap, the platinum group metal is preferably Pt or Pt and Pd at a relatively low loading, e.g. 515gfY3, or ViOgft.3 or i5gtI3, the first zone comprises a first layer coated on the substrate monolith and the first layer is coated with a second layer of copper or iron loaded on a zeolite of the second zone. This arrangement is particularly preferred as an oxidation catalyst for reducing or preventing slip of NH3 past the zoned catalysed substrate monolith of the invention (a so-called ammonia slip catalyst or If the substrate is a flow-through substrate monolith then the flow-through substrate monolith is a flow-through substrate monolith preferably having a honeycomb structure with many small, parallel thin-walled channels running axially through the substrate and extending throughout the substrate, The channel cross-section of the substrate may be any shape, but is preferably square, sinusoidal, triangular, rectangular, hexagonal, trapezoidal, circular, or oval.

If the substrate monolith is a filter substrate, it is preferably a wall-flow monolith filter, The wall-flow monolith filter comprises an inlet end, an outlet end, a substrate axial length extending between the inlet end and the outlet end, and a plurality of channels defined by internal walls of the wall flow substrate. The plurality of channels comprise inlet channels having an open inlet end and a closed outlet end and outlet channels having a closed inlet end and open outlet end.

Hence the channels of the wall-flow filter are alternately blocked, which allow the exhaust gas stream to enter a channel from the inlet end, then flow through the channel walls, and exit the filter from a different channel leading to the outlet end.

Particulates in the exhaust gas stream are thus trapped in the filter.

The substrate monolith comprises at least two catalytic zones, each zone containing a different catalyst composition deposited on the substrate monolith, In one embodiment there is substantially no overlap of the two zones on the substrate.

For instance, the first zone may cover from 10 to 90 percent of the total length of the substrate and the second zone would cover the rest of the length of the substrate (i.e. the remaining 90 to 10 percent which is not covered by the first zone). Preferably, the first zone covers from 20 to 80 percent of the total length of the substrate and the second zone covers from 80 to 20 percent of the total length of the substrate. More preferably the first zone covers from 30 to 70 percent of the total length of the substrate and the second zone covers from 70 to 30 percent of the total length of the substrate. More preferably the first zone covers from 40 to 60 percent of the total length of the substrate and the second zone covers from 60 to 40 percent of the total length of the substrate.

In a less preferred alternative embodiment there may be some overlap of the two zones on the substrate, For example there could be an overlap of up to 20% or greater.

When the substrate is a filter substrate it is preferably a wall-flow monolith filter. When such a wall-flow monolith filter is utilized, one zone may be deposited in/on the internal walls of the inlet channels and the other zone may be deposited in/on the internal walls of the outlet channels, thus effectively separating the first and second zones.

In certain instances, it may be preferable to add a small third zone to the substrate such that the third zone (preferably occupying less than 20 percent, and more preferably less than 10 percent, of the axial length of the substrate) is located after the second zone and at the opposite end of the substrate from the first zone. A third zone may be particularly useful when the substrate monolith is a filter substrate and the first zone is positioned in the exhaust system to contact the exhaust gas prior to the second zone, such that hydrocarbons and CO formed during burning of soot at high temperature may not be totally combusted over the second zone. If used, the third zone will contain supported platinum group metals, preferably platinum, palladium, and/or rhodium, to aid in the oxidation of any hydrocarbons and CO.

According to a second aspect, the invention provides an exhaust system for an internal combustion engine comprising: (a) a lean NO trap; and (b) a zoned catalysed substrate monolith, wherein the zoned catalysed substrate monolith is disposed downstream from the lean NO trap. Lean NO trap (a) is disposed on a substrate monolith such as a flow through substrate monolith or a filter substrate, such as a wall-flow filter substrate.

The catalysed substrate monolith removes/controls the H2S released from the NO trap desulphation by forming sulphide compounds in rich gas mixtures and oxidising suiphides to SO2 or 503 in lean gas mixtures. When present, the supported platinum group metal catalyst oxidises hydrocarbons and carbon monoxide that are not converted prior to contacting the catalysed substrate. When the catalysed substrate monolith is a filter substrate, it also removes soot from the exhaust gas.

The zoned catalysed substrate is located in the exhaust system such that it is downstream of the lean NO trap, so that the exhaust gas contacts the lean NO trap prior to contacting the catalysed substrate, Preferably, the two-zone catalysed substrate is positioned in the exhaust system such that there is an upstream (entrance) zone which is contacted by the exhaust gas after exiting the lean NO trap and a downstream (exit) zone following the upstream zone, The upstream zone that contacts the exhaust gas from the lean NO trap may be either the first zone or the second zone of the catalysed substrate. Thus, the first zone can be oriented to receive exhaust gas from the NO trap prior to the second zone; or the second zone can be oriented to receive exhaust gas from the NO trap prior to the first zone, In IL) In one embodiment, the first zone is oriented to the upstream side.

The copper or iron loaded zeolite catalyst of the second zone is active for catalysing the reduction of oxides of nitrogen with a nitrogenous reductant according to the following reactions: 4NH2 + 4N0 + 02 -* 4N2 + 6H20 (i.e. 1:1 NH3:N0); 4NH3 + 2N0 + 2N02 -4N2 + 6H20 (i.e. 1:1 NIH3:N0,J; and 8NH3 + 6N02 -, 7N2 + t2H7O (i.e. 4:3 NT-13:N01), in preference to undesirable, non-selective side-reactions such as 2NH3 + 2N02 -* N20 + 3fl20 + N2.

In embodiments of the second aspect according to the invention wherein the second zone is oriented to the upstream side, preferably the exhaust system comprises an injector for injecting a nitrogenous reductant, such as ammonia or an ammonia precursor such as urea or ammonium formate, preferably urea, into exhaust gas between the lean NO1 trap and the zoned catalysed substrate monolith according to the first aspect of the invention. Such injector is fluidly linked to a source of such nitrogenous reductant precursor, e.g. a tank thereof, and valve-controlled dosing of the precursor into the exhaust stream is regulated by suitably programmed engine management means and closed loop or open loop feedback provided by sensors monitoring 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.

Ammonia can also be generated in situ e.g. during rich regeneration of the lean NO1 trap with engine-derived rich exhaust gas, e.g. wherein barium is the NO1 adsorbent: Ba(N03)2 +8H2 -BaO +2NH2 +5H20. In this case, in situ NH3 generation can be used instead of a separate injector for nitrogenous reductant or in addition thereto. It will be appreciated that in the embodiment wherein the first zone comprises a lean NO1 trap and is oriented to the upstream side, the first zone lean NO1 trap can also contribute to in situ ammonia generation upstream of the copper or iron loaded on a zeolite catalyst of the second zone.

The lean NO1 trap typically includes a NO1 adsorbent for the storage/trapping of NO1 and an oxidation/reduction catalyst. The oxidation/reduction catalyst generally comprises one or more noble metals, preferably platinum, palladium, and/or rhodium. Typically, platinum is included to perform the oxidation fbnction and rhodium is included to perform the reduction function. The rhodium catalyst may be positioned downstream of the LNT.

The NO, adsorbent preferably comprises at least one alkaline earth metals (such as barium, calcium, strontium, and magnesium), at least one alkali metals (such as potassium, sodium, lithium, and caesium) or at least one rare earth metals (such as lanthanum, yttrium, praseodymium and neodymium), or combinations thereof These metals are typically found in the form of oxides. Most preferably the NO,. adsorbent comprises alkaline earth metals in the form of oxides. It is to be noted that although the alkaline earth metal species is disclosed as the oxide it is understood that in the presence of air or lean engine exhaust gas most of the alkaline earth metal species, for example barium, is in the form of the carbonate or possibly the hydroxide.

The oxidation/reduction catalyst and the NO,. adsorbent are preferably loaded on a support material such as an inorganic oxide for use in the exhaust system.

Inorganic oxides such as alumina, silica-alumina, ceria, titania, zirconia, alumina-zirconia, and combinations thereof are preferably utilised as the support material, The lean NO,. trap performs three functions. First, NO from the exhaust gas reacts with oxygen to produce NO2 in the presence of the oxidation catalyst. Second, the NO2 is adsorbed by the NO, adsorbent in the form of an inorganic nitrate (for example, BaO or BaCO3 is converted to Ba(NO3)2 on the NO,. adsorbent). Lastly, when the engine runs under rich conditions, the stored inorganic nitrates decompose to form NO or NO2 which are then reduced to form N2 by reaction with carbon monoxide, hydrogen and/or hydrocarbons in the presence of the reduction catalyst.

Typically, the nitrogen oxides are converted to nitrogen, carbon dioxide and water in the presence of heat, carbon monoxide and hydrocarbons in the exhaust stream.

In a NO, trap, the NO, adsorbent and the oxidation/reduction catalyst are preferably coated on a flow-through substrate monolith, preferably a honeycomb monolith. The flow-through substrate monolith may be made of a ceramic material (eg, cordierite) or a metallic material, e,g, FecralloyTM. The lean NO,. trap is typically designed to provide a number of channels through which the exhaust gases pass. The surface of the channels is loaded with the NO,. adsorbent and the oxidation/reduction catalyst(s).

The components of the lean NO trap may be added by any known means. For example, the support material, oxidation-reduction catalyst and the NO adsorbent material may preferably be applied and bonded to the substrate as a washcoat, a porous, high surface area layer bonded to the surface of the substrate. The washcoat is typically applied to the substrate from a water-based slurry, then dried and calcined at high temperature. The washcoat may alternatively comprise the support and NO adsorber, and the oxidation-reduction catalyst may be loaded onto the dried washcoat support layer (by impregnation, ion-exchange, or the like), then dried and calcined, The exhaust system may further comprise an oxidation catalyst positioned between the internal combustion engine and the lean NO trap to oxidise hydrocarbons and carbon monoxide in the exhaust gas. Such oxidation catalysts are well known in the prior art for both diesel and gasoline engines.

Furthermore, if the catalysed substrate monolith is a flow-through substrate monolith, the exhaust system of the invention preferably includes a particulate filter, more preferably a catalysed soot filter. Where present, the particulate filter is preferably capable of collecting soot without causing excessive back-pressure in the exhaust system. In general, ceramic, sintered metal or woven or non-woven wire filters are usable, and wall-flow honeycomb stmctures are particularly preferred. The stmctural material of the particulate filter is preferably a porous ceramic, silicon carbide, or sintered metal, The particulate filter can be catalysed, typically with a platinum group metal catalyst. The soot is generally carbon containing soluble organic fractions and/or volatile organic fractions and/or heavy hydrocarbons.

Combustion of the soot produces CO2 and H20.

If utilised, the particulate filter may be located upstream or downstream of the zoned catalysed substrate, Preferably, the particulate filter is upstream of the catalysed substrate and downstream of the lean NO trap such that the exhaust gas from the internal combustion engine passes through the lean NO trap, then the particulate filter, followed by the catalysed substrate before passing to atmosphere, According to a third aspect, the invention provides an apparatus comprising an internal combustion engine and an exhaust system according to the second aspect of the invention. The internal combustion engine is preferably a lean burn internal combustion engine.

"Lean-burn" refers to the use of lean mixtures in both a gasoline and diesel (compression-ignition) fuel powered internal combustion engine. The engine fuel can also include at least some biodiesel, bioethanol, components derived from a gas-to-liquid process, liquid petroleum gas or natural gas. The engine may be used in a mobile application, such as a vehicle, or a stationary application, such as a power generation unit. Preferably use of the lean mixtures is in a diesel internal combustion engine, more preferably a diesel internal combustion engine in a mobile application, especially in a vehicle. Vehicles include both light duty and heavy duty diesel, for example cars, trains and boats, with a preference for light duty vehicles, more preferably passenger cars (as opposed to heavy duty vehicle applications, such as trucks and buses).

According to a fourth aspect, the invention provides a vehicle comprising the apparatus according to the fourth aspect of the present invention.

Accordingly, in a fifth aspect, the invention provides a method of treating an exhaust gas from an internal combustion engine, in particular for treating exhaust gas from a vehicular lean burn internal combustion engine, such as a diesel engine, a lean-burn gasoline engine, or an engine powered by liquid petroleum gas or natural gas, which method comprising directing the exhaust gas through an exhaust emission system according to the second aspect of the present invention.

According to a sixth aspect, the invention provides a method of making a zoned catalysed substrate monolith according to the first aspect of the present invention, wherein the first and second zones are deposited on a substrate monolith using washcoating procedures, wherein the first zone is washcoated on the substrate monolith prior to the washcoating of the second zone.

The catalysed substrate monolith of the present invention may be prepared by processes well hiown in the prior art. Methods of zone coating are disclosed in, for example, WO 99/47260. Preferably, the catalytic zones are deposited on the substrate using washcoat procedures. A representative process for preparing the catalysed substrate monolith using a washcoat procedure is set forth below. It will be understood that the process below can be varied according to different embodiments of the invention. Also, the order of addition of the first zone and the second zone onto the substrate is not considered critical. Thus, the first zone can be washcoated on the substrate prior to washcoating the second zone or the second zone can be washcoated on the substrate prior to washcoating the first zone.

The first zone of the catalysed substrate monolith is preferably prepared using a washcoat procedure. If a base metal/inorganic oxide is utilised, the base metal is preferably loaded onto the inorganic oxide by, for example, supporting a base metal compound such as iron acetate on the inorganic oxide by impregnation, adsorption, ion-exchange, incipient wetness, precipitation, or the like prior to washcoating the first zone. Firstly the base metal compounds supported on the inorganic oxide are preferably milled or subject to another comminution process in order to ensure that substantially all of the solid particles have a particle size of less than 20 microns in an average diameter, Then the washcoating is preferably performed by slurrying these finely divided particles of the base metal compound supported on the inorganic oxide in an appropriate solvent, preferably water, to fonn the slurry. The slurry preferably contains between 4 to 40 weight percent solids, more preferably between 6 to 30 weight percent. Additional components, such as stabilizers or promoters may also be incorporated in the slurry as a mixture of water soluble or water-dispersible compounds or complexes. The substrate may then be coated one or more times with the slurry such that there will be deposited on the substrate the desired loading of catalytic materials.

If a base metal oxide is utilised then this can be applied to the substrate using similar washcoat preparation techniques described above. Additional binders may be used in the washcoat slurry to help adhesion of the base metal oxide to the substrate, When the first zone additionally comprises the supported platinum group metal, then the supported platinum group metal and the base metal oxide (or base metal/inorganic oxide) are preferably loaded onto the substrate such that the two catalysts are physically separated within the first zone. This may be accomplished by any known means, for example the base metal oxide (or base metal/inorganic oxide) is added to the first zone as a separate washcoat step from the addition of the platinum group metal.

For the washcoat step for the addition of the supported platinum group metal, the platinum group metal may be added to the support prior to the washcoating step or may be added to a support-coated substrate alier washcoating the support onto the substrate, If the platinum group metal is added to the support prior to washcoating the first zone of the substrate, it can be loaded onto the support by any known means, the manner of addition is not considered to be particularly critical. For example, a platinum compound (such as platinum nitrate) may be supported on the support by impregnation, adsorption, ion-exchange, incipient wetness, precipitation, or the like.

Firstly the support or the platinum group metal/support particles are milled or subject to another comminution process in order to ensure that substantially all of the solid particles have a particle size of less than 20 microns in an average diameter, prior to forming the slurry. The washcoating is preferably performed by first slurrying the finely divided particles of the supported platinum group metal (or just the support) in an appropriate solvent, preferably water, to form the slurry. The slurry preferably contains between 4 to 40 weight percent solids, more preferably between 6 to 30 weight percent. Preferably, additional components, such as stabilizers or promoters may also be incorporated in the slurry as a mixture of water soluble or water-dispersible compounds or complexes.

The substrate may then be coated one or more times with the slurry such that there will be deposited on the substrate monolith the desired loading of catalytic materials. If only the support is deposited on the substrate monolith, the platinum group metal may then be added to the support-coated substrate monolith by any known means, including impregnation, adsorption, or ion-exchange of a platinum compound (such as platinum nitrate).

Preferably, the substrate monolith is coated so that the first zone only occupies from 10 to 90 percent of the axial length of the substrate, more preferably from 20 to percent, especially from 40 to 60 percent of the axial length the substrate.

After the first zone of the substrate monolith has been coated the coated substrate is typically dried by heating at an elevated temperature of preferably 80 to 150°C. The substrate may also be calcined at higher temperatures (such as 400 to 600°C) but calcination is typically not required before the addition of the second zone.

Alternatively, the platinum group metal and the base metal may be added simultaneously by washcoating a slurry that contains distinct particles of the base metal oxide (or base metal/inorganic oxide) and the supported platinum group metal.

The second zone of the catalysed substrate monolith is preferably prepared using a washcoat procedure in the same manner as for the first zone. In one embodiment the substrate monolith is coated with the second zone washcoat so that the second zone and the first zone have substantially no overlap. For such an embodiment the second zone will preferably only occupy from 10 to 90 percent of the axial length of the substrate, more preferably from 20 to 80, especially from 40 to 60 percent of the axial length of the substrate monolith. In an alternative embodiment the substrate is coated with the second zone washcoat so that there is overlap of the two zones of up to 20% or greater.

After the substrate monolith has been coated with the second washcoat, the coated substrate is typically dried and then calcined by heating at an elevated temperature. Preferably, the calcination occurs at 400 to 600°C for approximately I to 8 hours.

The following Examples are provided by way of illustration only and with reference to the accompanyiug drawiugs iu which: Figure 1 is a histogram showing the hydrogen sulphide slip for a simulated rich exhaust gas passed through a catalysed substrate of the invention and a comparative catalysed substrate; and Figure 2 is a second histogram also showing the hydrogen sulphide slip for a simulated rich exhaust gas passed through a filter substrate catalysed with a catalyst corresponding to the first zone according to the present invention.

EXAMPLES

Example 1

A slurry was prepared using alumina and ceria-zirconia mixed oxide milled to a d90 particle size of <15 micron. Appropriate amounts of soluble Pt and Pd salts were added to give a final coated catalyst loading of 20 gIft5 with a Pt:Pd weight ratio of 2:1. Beta zeolite was added to the slurry followed by manganese dioxide (d90 < 10 micron) and the mixture stirred to homogenise. The coating slurry was applied to the inlet channels of a commercial wall-flow aluminium titanate filter substrate using established particulate filter coating techniques (see e.g. W0201 1/080525), such that the coating was to 50% of the total length of the substrate, This coating was dried at 100°C. The inlet coated filter had a manganese loading of 125 gIft3 in the inlet coated zone.

A second slurry was prepared using alumina and ceria-zirconia mixed oxide milled to a d90 particle size of<15 micron. Appropriate amounts of soluble Pt and Pd salts were added to give a final coated catalyst loading of 20 g/ft3 with a Pt:Pd weight ratio of 2:1, Beta zeolite was added to the slurry followed by iron oxide (d90 < 5 micron) and the mixture stirred to homogenise. The second coating slurry was applied to the outlet channels of the above wall flow aluminium titanate substrate using established particulate filter coating techniques, such that the coating was to 50% of the total length of the substrate. This coating was dried at 100°C and the part calcined at 500°C, The coated filter had an iron loading of 250 g/ft3 in the outlet zone.

Comparative Example 2 First Comparative Example An identical coated filter to Example I was prepared, except in that the inlet zone coating contained no manganese and the outlet zone coating contained no iron, but manganese at a loading of 125 glft°.

Second Comparative Example An identical coated filter to Example I was prepared, except in that the inlet zone coating contained no manganese and the outlet zone coating contained both iron at 250 gIft3 and manganese at a loading of 125 gIft3.

Example 3

The H2S controlling performance of the coated filters was determined using a laboratory reactor and a simulated exhaust gas. Lean and rich exhaust gas mixtures were used to represent those produced during the desulphation of a lean NO trap. All samples were previously aged under hydrothermal conditions of 800°C for 16 hours.

The reactor was heated to the first evaluation temperature and a lean gas mix was passed through the sample for 20 seconds. The gas mix was then switched to a rich gas mix for 20 seconds. This cycle of alternating lean and rich gas mixes was repeated during the test. Gas mix concentrations are given in Table 1, with the balance being nitrogen.

Table 1

Lean gas mix Rich gas mix CO2 14% 14% HC 120 ppm (Ci) 2000 ppm (Ci) 02 1.7% 0 H20 5% 5% H2 0 0.07% CO 0 0.24% H2S 0 500 ppm The concentration of H2S downstream of the filter sample was continuously measured and the peak concentration of I-T2S determined, This value is termed H2S slip. The average H2S slip measured over 5 cycles of lean/rich operation is shown in Figure 1.

Figure 1 illustrates the 112S slip for a simulated rich exhaust gas passed through a catalysed substrate monolith of the invention (according to Example 1) and exhaust gas passed through Comparative catalysed substrates (according to Example 2). Figure 1 clearly shows that the zoned catalysed substrate of the invention controls hydrogen sulphide emissions more effectively than a single base metal oxide or a mixture of base metal oxides in a single zone.

Example 4

A slurry was prepared using alumina and ceria-zirconia mixed oxide milled to a d90 particle size of <15 micron, Appropriate amounts of soluble Pt and Pd salts were added to give a final coated catalyst loading of 10 gIft3 with a Pt:Pd weight ratio of 21. Zinc oxide powder was added and the slurry was stirred to homogenise. The coating slurry was applied to the channels of a commercially available wall-flow silicon carbide filter substrate using established particulate filter coating techniques (see e.g. W020111080525). This coating was dried at 100°C, then calcined at 500°C.

The amount of zinc on the final catalyst was 250g ft*

Example S

A slurry was prepared using alumina and ceria-zirconia mixed oxide milled to a d90 particle size of <15 micron, Appropriate amounts of soluble Pt and Pd salts were added to give a final coated catalyst loading of 10 gIft3 with a Pt:Pd weight ratio of 2:1. Manganese dioxide powder was added and the slurry was stirred to homogenise. The coating slurry was applied to the channels of a commercially available wall-flow silicon carbide filter substrate using established particulate filter coating techniques (see e.g. W02011/080525). This coating was dried at 100°C, then calcined at 500°C. The amount of manganese on the final catalyst was 250g f15.

Example 6

A slurry was prepared using alumina and ceria-zirconia mixed oxide milled to a d90 particle size of <15 micron, Appropriate amounts of soluble Pt and Pd salts were added to give a final coated catalyst loading of 10 g/ft3 with a Pt:Pd weight ratio of 2:1, The slurry was stirred to homogenise. The coating slurry was applied to the channels of a commercially available wall-flow silicon carbide filter substrate using established particulate filter coating techniques (see e.g. W0201 1/080525). This coating was dried at 100°C, then calcined at 500°C.

Example 7

The H2S controlling performance of the coated filters was determined using a laboratory reactor and a simulated exhaust gas. Lean and rich exhaust gas mixtures were used to represent those produced during the desulphation of a lean NO trap. All samples were previously aged under hydrothermal conditions of 800°C for t6 hours, The reactor was heated to the first evaluation temperature and a lean gas mix was fin Li passed through the sample for 20 seconds. The gas mix was then switched to a rich gas mix for 20 seconds. This cycle of alternating lean and rich gas mixes was repeated during the test. Gas mix concentrations are given in Table 2, with the balance being nitrogen.

Table 2

Lean gas mix Rich gas mix CO2 14% 14% HC 120 ppm (Ci) 2000 ppm (C1) 02 1.7% 0 H20 5% 5% H2 0 0.07% CO 0 0.24% H2S 0 500 ppm The concentration of H2S downstream of the filter sample was continuously measured and the peak concentration of H2S determined, This value is termed H2S slip. The average H2S slip measured over 5 cycles of lean/rich operation is shown in Figure 2.

Figure 2 illustrates the 112S slip for a simulated rich exhaust gas passed through the catalysed substrate monoliths of Example 4, Example 5 and Example 6.

Figure 1 clearly shows that Example 4 which comprises zinc oxide and Example 2 which comprises manganese oxide both control hydrogen sulphide emissions more effectively than Example 3 which does not contain a base metal oxide for hydrogen sulphi de removal,

Example 8

The catalysed substrates monoliths of Example 4, Example 5 and Example 6 were tested for CO oxidation performance. The aged cores were tested in a simulated catalyst activity testing (SCAT) gas apparatus using the inlet gas mixtures in Table 3.

In each case the balance is nitrogen.

Table 3

Gas Component Quantity in Inlet Gas Mixture Composition CO 1500 ppm BC (as Ci) 430 ppm NO 100 ppm CO2 4% H20 4% 02 14% Space velocity 55000/hour Table 4 shows the T50 light-off temperatures for the catalysed substrate monoliths, Example 4 comprising zinc oxide shows a similar light off to Example 6, which does not contain a base metal oxide for hydrogen suiphide control. Example 5 which comprises manganese oxide shows a higher temperature light-off than both Example 4 and example 6. Table 4 shows the manganese oxide present in example 5 has a greater negative impact on CO oxidation performance than the zinc oxide present in Example 4.

Table 4

T50 temperature

Example 1 219°C

Example 2 248°C

Example 3 207°C

For the avoidance of any doubt, the entire contents of any and all prior art documents cited herein are incorporated herein by reference,