Exhaust system comprising NO.SUB.x .storage catalyst and CSF

Abstract

An exhaust gas aftertreatment system for a diesel-engined vehicle, which system comprising a NO.sub.x Storage Catalyst (NSC) followed in a downstream direction by a Catalysed Soot Filter (CSF), wherein the CSF comprises an oxidative catalyst comprising a palladium-rich weight ratio of platinum and palladium.

Claims

1. An exhaust gas aftertreatment system for a diesel engine, the system comprising a NOx Storage Catalyst (NSC) followed in a downstream direction by a Catalyzed Soot Filter (CSF), wherein the CSF comprises a palladium rich oxidative catalyst composition comprising: (1) a palladium-rich platinum:palladium catalyst where the ratio of platinum:palladium is based on weight, (2) an oxygen storage component in an amount of 20-50 weight %, and (3) a washcoat component, where the oxygen storage component is present in a washcoat with the palladium-rich platinum:palladium catalyst and the washcoat component, and wherein the CSF comprises a wall flow filter comprising inlet channels and outlet channels, wherein the inlet channels comprise a platinum-based oxidative catalyst and the outlet channels comprise the palladium-rich oxidative catalyst composition.

2. The system according to claim 1, wherein the Pt:Pd weight ratio in the palladium rich oxidative catalyst composition is less than 1:2.

3. The system system according to claim 2, wherein the Pt:Pd weight ratio in the palladium rich oxidative catalyst composition is less than 1:10.

4. The system according to claim 1, wherein the oxygen storage component comprises ceria or a ceria-zirconia mixed oxide.

5. The system according to claim 1, wherein the platinum-based oxidative catalyst comprises palladium in a platinum-rich Pt:Pd weight ratio.

6. A vehicle comprising a diesel engine and an exhaust system according to claim 1.

7. A method of aftertreating the exhaust gases from a vehicular diesel engine during a NSC regeneration event, the method comprising passing the exhaust gases through an exhaust gas aftertreatment system of claim 1.

8. The method according to claim 7, wherein the method reduces total hydrocarbons in the exhaust gas.

9. The method according to claim 8, wherein the oxidative catalyst composition oxidises 20 to 90% by volume of methane present in the exhaust gases entering the CSF during the NSC regeneration event.

10. The method according to claim 7, wherein the oxidative catalyst composition oxidises 20 to 90% by volume of methane present in the exhaust gases entering the CSF during the NSC regeneration event.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) In order that the invention may be more fully understood, the following Example is provided by way of illustration only, with reference to the accompanying drawings, in which:

(2) FIG. 1 is a bar chart showing total HC slip as ppm in gas leaving oxidative catalyst samples at 300° C. inlet gas temperature following 8 second and 12 second exposure to a synthetic exhaust gas regeneration event; and

(3) FIG. 2 is a bar chart showing the results for the same oxidative catalyst samples at 350° C. inlet gas temperature.

DETAILED DESCRIPTION OF THE INVENTION

(4) Desirably, the oxidative catalyst is applied to the CSF as a partial, layered or zoned coating, although a coating applied throughout the CSF, for example to all of the outlet channels, is included within the invention. In the case of a zoned coating, it is desirable that the remainder of the coating is a conventional CSF catalyst capable of oxidising CO and HC under normal lean operating conditions, that is, not during a rich regeneration event.

(5) In preferred embodiments, the CSF comprises a wall flow filter comprising inlet channels and outlet channels. In one embodiment, the inlet channels comprise a platinum-based oxidative catalyst and the outlet channels comprise the palladium-rich Pt:Pd oxidative catalyst.

(6) Alternatively, the oxidative catalyst may be disposed in a downstream zone defined at a downstream end by an outlet end of the filter, wherein an inlet end of the filter comprises an upstream zone defined by an inlet end of the filter and wherein the upstream zone is a platinum-based oxidative catalyst. Such an arrangement can be used in combination with wall flow filters or any other filter arrangements.

(7) The arrangement of a conventional Pt-based CSF catalyst disposed in an inlet zone or coated on inlet channels of a wall flow filter upstream of the Pd-rich catalyst disposed in a zone or coated on outlet channels is advantageous in that it provides better thermal management and therefore increases the efficiency of the exhaust gas aftertreatment system. In particular, a rich regeneration event generates increased exhaust gas temperature. Accordingly, the location of the Pd-rich catalyst is not temperature limited, because the filter as a whole is contacted with exhaust gas at increased temperature. However, exhaust gas temperature during normal lean engine operation, i.e. between regeneration events, is cooler and so the activity of the Pt-based catalyst is temperature limited. Hence, it is preferred to dispose the Pt-based catalyst in a location where it can achieve carbon monoxide and hydrocarbon light-off as soon after cold start as possible and for treating exhaust gases emitted from high speed driving, e.g. the EUDC part of the MVEG-B drive cycle.

(8) In embodiments wherein the filter features a platinum-based oxidative catalyst, in preferred embodiments the platinum-based oxidative catalyst comprises palladium in a platinum-rich Pt:Pd weight ratio.

(9) The application of coatings to wall-flow filters and other filter substrates to achieve partial, layered or zoned coating may be achieved by methods known to the person skilled in the art, see for example our WO 99/47260 or our International patent application no. PCT/GB2011/050005 filed Jan. 4, 2011.

(10) The oxidative catalyst desirably comprises a Pt/Pd composition. A conventional CSF oxidative catalyst is based on Pt, but we have found that Pd is the best catalyst for oxidising methane. On the other hand, Pd-only catalysts are very susceptible to poisoning by the sulphur present in all diesel fuels, even ultra low sulphur fuels. A Pd-rich Pt:Pd weight ratio of down to approximately 1:10 is presently believed to be most effective in the present invention. The loading of active catalyst components may need to be established according to the specific engine and associated engine management, and will also vary according to the size and the number of cells per unit area of the filter substrate.

(11) The catalyst composition deposited generally comprises a washcoat component, as is conventional. We believe that the oxidation of methane is highly dependent on the air:fuel ratio, and that the conditions during a rich regeneration event do not assist the oxidation of methane. Accordingly, it is preferred to incorporate a relatively high amount of Oxygen Storage Component (OSC) component in the washcoat composition. The best-known OSC is ceria, often used in the form of ceria/zirconia mixed oxide. For example, suitable OSC component loadings for use in the present invention are 20-50% by weight. This compares to an OSC component loading in the conventional catalyst applied to a CSF of 0-15 wt %. It should be understood that this loading refers to the loading of OSC component, and if that is ceria/zirconia 50:50, the quantity of ceria will accordingly be halved.

(12) Desirably, the engine used in the present invention is of the common rail injector type, rather than a unit injector type (PD-type). Our initial tests indicate that unit injector engines can generate very high methane levels indeed (up to 90% methane in total HC) during a NSC regeneration. Nonetheless, it is believed that the present invention also offers the possibility of improvements in HC emissions with unit injector engines.

EXAMPLES

(13) To model CSFs, 1 inch×3 inch (2.5 cm×7.5 cm) ceramic flow-through substrates (not filter substrates) had 1.0 gin.sup.−3 of a variety of catalyst compositions, deposited using conventional technology. The samples were exposed to flowing gases in a synthetic catalytic activity test (SCAT) apparatus , to model lean conditions followed by a short (8 sec or 12 sec) rich excursion to represent regeneration.

(14) The catalyst compositions were all deposited at 60 gft.sup.−3 onto different washcoats which were deposited at 1 gin.sup.−3:

(15) Sample A: 2:1 Pt:Pd on an alumina washcoat (not according to the invention);

(16) Sample B: 1:2 Pt:Pd on an alumina washcoat;

(17) Sample C: 1:10 Pt:Pd on an alumina washcoat;

(18) Sample D: 1:2 Pt:Pd on a 50:50 alumina:ceria/zirconia mixed oxide washcoat; and

(19) Sample E: 1:10 Pt:Pd on a 50:50 alumina:ceria/zirconia mixed oxide washcoat.

(20) Lean condition gas composition was: 8% CO.sub.2, 12% O.sub.2 and 5% H.sub.2O.

(21) Rich condition gas composition was: 8% CO.sub.2, 0.5% O.sub.2, 5% H.sub.2O, 100 ppm NO, 500 ppm CO, 1000 ppm Cl methane and an equal amount of propene when measured as Cl carbon species.

(22) The SCAT apparatus was stabilised at inlet gas temperatures of 300° C. (equivalent to a light-duty diesel passenger vehicle fitted with a CSF in an underfloor location at fast motorway driving speeds) and 350° C. under lean conditions before either an 8 sec or 12 sec rich excursion (shown as black or grey bars respectively in the Figures). The total HC slip was measured as ppm in the gas leaving the samples, and the results are shown in FIG. 1 (at 300° C.) and FIG. 2 (at 350° C.).

(23) Examining the results, especially comparing Sample E with sample C in FIG. 1, it can be seen that the presence of ceria in Sample E slips significantly less HC during the rich regeneration, noticeably during the longer rich purge.

(24) FIG. 1 also demonstrates that the presence of ceria plays a useful role in the longer rich excursions, and no difference can be seen in HC slippage between 8 sec and 12 sec purges.

(25) At 350° C., it can easily be seen from FIG. 2 that samples containing more Pd than Pt, and OSC, convert most of the HC.