Exhaust system having N2O catalyst in EGR circuit

Abstract

An exhaust system for an internal combustion engine is disclosed. The exhaust system comprises a particulate filter, one or more NO.sub.x reduction catalysts, and a low pressure exhaust gas recirculation (EGR) circuit for connecting the exhaust system downstream of the filter and the one or more NO.sub.x reduction catalysts to an intake of the engine. The EGR circuit comprises a N.sub.2O-producing catalyst.

Claims

1. An exhaust system for an internal combustion engine, the system comprising a particulate filter, one or more NO.sub.x reduction catalysts, and a low pressure exhaust gas recirculation (EGR) circuit for connecting the exhaust system downstream of the filter and the one or more NO.sub.x reduction catalysts to an intake of the engine, wherein the EGR circuit comprises a N.sub.2O-producing catalyst, and wherein the N.sub.2O-producing catalyst comprises manganese supported on an inorganic oxide.

2. The exhaust system of claim 1, wherein one or more NO.sub.x reduction catalysts is located on the filter.

3. The exhaust system of claim 1, wherein the one or more NO.sub.x reduction catalysts are a selective catalytic reduction catalyst.

4. The exhaust system of claim 3, wherein the selective catalytic reduction catalyst comprises a transition metal and molecular sieve.

5. The exhaust system of claim 3, further comprising a means for introducing a nitrogenous reductant into the exhaust system upstream of the selective catalytic reduction catalyst.

6. The exhaust system of claim 5, wherein the nitrogenous reductant is ammonia, hydrazine or an ammonia precursor selected from the group consisting of urea ((NH.sub.2).sub.2CO), ammonium carbonate, ammonium carbamate, ammonium hydrogen carbonate and ammonium formate.

7. The exhaust system of claim 1, wherein the one or more NO.sub.x reduction catalysts is a lean NO.sub.x trap.

8. The exhaust system of claim 1, wherein the N.sub.2O-producing catalyst is located in or on a flow-through monolith substrate.

9. The exhaust system of claim 1, further comprising a NO oxidation catalyst located upstream of the particulate filter.

10. The exhaust system of claim 1 further comprising an ammonia oxidation catalyst disposed downstream of the one or more NO.sub.x reduction catalysts and upstream of the EGR, relative to the direction of exhaust gas flow through the system.

11. The exhaust system of claim 10, wherein the NO.sub.x reduction catalyst and the ammonia oxidation catalyst are loaded onto the same substrate, wherein the front is loaded with the NO.sub.x reduction catalyst and the rear is loaded with the ammonia oxidation catalyst.

Description

BRIEF DESCRIPTION OF THE DRAWING

(1) FIG. 1 is a schematic flow diagram of one embodiment of the invention.

DETAILED DESCRIPTION OF THE INVENTION

(2) The exhaust system of the invention comprises a particulate filter, one or more NO.sub.x reduction catalysts, and a low pressure exhaust gas recirculation (EGR) circuit.

(3) Suitable NO.sub.x reduction catalysts include a lean NO.sub.x trap. NO.sub.x traps are devices that adsorb NO.sub.x under lean exhaust conditions, release the adsorbed NO.sub.x under rich conditions, and reduce the released NO.sub.x to form N.sub.2. A NO.sub.x trap typically includes a NO.sub.x adsorbent for the storage of NO.sub.x and an oxidation/reduction catalyst. Typically, nitric oxide reacts with oxygen to produce NO.sub.2 in the presence of the oxidation catalyst. Second, the NO.sub.2 is adsorbed by the NO.sub.x adsorbent in the form of an inorganic nitrate (for example, BaO or BaCO.sub.3 is converted to Ba(NO.sub.3).sub.2 on the NO.sub.x adsorbent). Lastly, when the engine runs under rich conditions, the stored inorganic nitrates decompose to form NO or NO.sub.2 which are then reduced to form N.sub.2 by reaction with carbon monoxide, hydrogen and/or hydrocarbons (or via NH.sub.x or NCO intermediates) 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.

(4) The NO.sub.x adsorbent component is preferably an alkaline earth metal (such as Ba, Ca, Sr, and Mg), an alkali metal (such as K, Na, Li, and Cs), a rare earth metal (such as La, Y, Pr, and Nd), or combinations thereof. These metals are typically found in the form of oxides. The oxidation/reduction catalyst is preferably one or more noble metals, more preferably platinum, palladium, and/or rhodium. Preferably, platinum is included to perform the oxidation function and rhodium is included to perform the reduction function. The oxidation/reduction catalyst and the NO.sub.x adsorbent are preferably loaded on a support material such as an inorganic oxide for use in the exhaust system.

(5) Suitable NO.sub.x reduction catalysts also include selective catalytic reduction (SCR) catalysts. A SCR catalyst is a catalyst that reduces NO.sub.x to N.sub.2 by reaction with nitrogen compounds (such as ammonia or urea) or hydrocarbons (lean NO.sub.x reduction). Preferably, the SCR catalyst is comprised of a vanadia-titania catalyst, a vanadia-tungsta-titania catalyst, or a transition metal/molecular sieve catalyst. The transition metal/molecular sieve catalyst comprises a transition metal and a molecular sieve, such as aluminosilicate zeolites and silicoaluminophosphates.

(6) Preferred transition metals include chromium, cerium manganese, iron, cobalt, nickel and copper, and mixtures of any two or more thereof. Iron and copper are particularly preferred. The molecular sieve is preferably a beta zeolite, a faujasite (such as an X-zeolite or a Y-zeolite, including NaY and USY), an L-zeolite, a ZSM zeolite (e.g., ZSM-5, ZSM-48), an SSZ-zeolite (e.g., SSZ-13, SSZ-41, SSZ-33), a ferrierite, a mordenite, a chabazite, an offretite, an erionite, a clinoptilolite, a silicalite, an aluminum phosphate zeolite (including metalloaluminophosphates such as SAPO-34), a mesoporous zeolite (e.g., MCM-41, MCM-49, SBA-15), or mixtures thereof; more preferably, the molecular sieve is a beta zeolite, a ferrierite, or a chabazite. Preferred SCR catalysts include Cu-CHA, such as Cu-SAPO-34, Cu-SSZ-13, and Fe-Beta zeolite.

(7) The NO.sub.x reduction catalyst is preferably an SCR catalyst.

(8) The NO.sub.x reduction catalyst is preferably coated on a ceramic or a metallic substrate. The substrate is typically designed to provide a number of channels through which vehicle exhaust passes, and the surface of the channels will be preferably be coated with the NO.sub.x reduction catalyst.

(9) A ceramic substrate 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, a magnesium aluminosilicate, and silicon carbide are particularly preferred. A metallic substrate 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 aluminum in addition to other trace metals.

(10) The substrate for the NO.sub.x reduction catalyst may be a filter substrate or a flow-through substrate. Preferably, the NO.sub.x reduction catalyst is coated onto a filter. When the NO.sub.x reduction catalyst is an SCR catalyst, the combination of an SCR catalyst and a filter is known as a selective catalytic reduction filter (SCRF). SCRFs are single-substrate devices that combine the functionality of an SCR and particulate filter.

(11) When the NO.sub.x reduction catalyst is an SCR catalyst, the exhaust system preferably comprises a means for introducing a nitrogenous reductant into the exhaust system upstream of the SCR catalyst. The reductant is added to the flowing exhaust gas by any suitable means for introducing the reductant into the exhaust gas. Suitable means include an injector, sprayer, or feeder, and is preferably an injector. Such means are well known in the art.

(12) The nitrogenous reductant for use in the system can be ammonia per se, hydrazine or an ammonia precursor selected from the group consisting of urea ((NH.sub.2).sub.2CO), ammonium carbonate, ammonium carbamate, ammonium hydrogen carbonate and ammonium formate. Urea is particularly preferred.

(13) The exhaust system may also comprise a means for controlling the introduction of reductant into the exhaust gas in order to reduce NO.sub.x therein. Preferred control means include an electronic control unit, optionally an engine control unit, and may additional comprise a NO.sub.x sensor located downstream of the NO reduction catalyst.

(14) The exhaust system of the invention also comprises a particulate filter. The particulate filter is preferably a wall-flow filter.

(15) The filter and NO.sub.x reduction catalyst can be arranged in any suitable configuration. For instance, the NO.sub.x reduction catalyst may be located downstream of the filter. If a means for introducing nitrogenous reductant is utilized when the NO.sub.x reduction catalyst is an SCR catalyst, the means for introducing reductant into a flowing exhaust gas is suitably located between the filter and the SCR catalyst.

(16) Preferably, the NO.sub.x reduction catalyst is located on the particulate filter, most preferably in the form of a selective catalytic reduction filter (SCRF). Where the filter is a wall-flow filter, the NO.sub.x reduction catalyst can be formulated as a washcoat that permeates the walls of the filter. This can be done, for example, by milling the catalyst to an average particle size of 5 m.

(17) Preferably, the exhaust system will comprise a NO oxidation catalyst (for example, a diesel oxidation catalyst) for oxidizing NO to nitrogen dioxide. The NO oxidation catalyst is preferably located upstream of the filter and/or the NO.sub.x reduction catalyst, relative to the direct of exhaust gas flow through the system. The NO oxidation catalyst preferably comprises a platinum group metal, most preferably platinum.

(18) The exhaust system may also comprise an ammonia oxidation catalyst (or ammonia slip catalyst) disposed downstream of the NO.sub.x reduction catalyst and upstream of the EGR, relative to the direct of exhaust gas flow through the system. Preferably, the ammonia oxidation catalyst includes platinum, palladium, or a combination thereof, with platinum or a platinum/palladium combination being preferred. Preferably, the ammonia oxidation catalyst comprises platinum and/or palladium supported on a metal oxide, more preferably a high surface area support, including but not limited to alumina.

(19) The ammonia oxidation catalyst may be applied to a flow-through monolith substrate, such as flow-through metallic or cordierite honeycombs, but is preferably loaded onto the same substrate as the NO.sub.x reduction catalyst, wherein the upstream zone is loaded with the NO.sub.x reduction catalyst and the downstream zone is loaded with the ammonia oxidation catalyst, relative to the direction of exhaust gas flow through the system.

(20) Preferred embodiments of the exhaust system, prior to the low pressure EGR circuit, may thus comprise a variety of different configurations, including: (1) a diesel oxidation catalyst (DOC), followed by a particulate filter, then a means for introducing a nitrogenous reductant, followed by an SCR catalyst; (2) a DOC, a means for introducing a nitrogenous reductant, then a SCRF, followed by a SCR catalyst; (3) a DOC, followed by a SCRF, then an ammonia oxidation catalyst; and other possible combinations.

(21) The system then comprises a low pressure exhaust gas recirculation (EGR) circuit for connecting the exhaust system downstream of the filter and the NO.sub.x reduction catalyst to an intake of the engine.

(22) The EGR circuit comprises an N.sub.2O-producing catalyst. The N.sub.2O-producing catalyst reacts NH.sub.3 with NO.sub.2 in the EGR circuit to produce N.sub.2O. Any catalyst that converts NH.sub.3 and NO.sub.2 to N.sub.2O is suitable. Preferred N.sub.2O-producing catalysts include manganese supported on an inorganic oxide, but may also include any other transition metal supported on an inorganic oxide.

(23) The inorganic oxide most commonly includes oxides of Groups 2, 3, 4, 5, 13 and 14 elements. Useful inorganic oxides preferably have surface areas in the range 10 to 700 m.sup.2/g, pore volumes in the range 0.1 to 4 mL/g, and pore diameters from about 10 to 1000 Angstroms. The inorganic oxide is preferably alumina, silica, titania, zirconia, niobia, tantalum oxides, molybdenum oxides, tungsten oxides, rare earth oxides (in particular ceria or neodymium oxide), or mixed oxides or composite oxides of any two or more thereof, e.g. silica-alumina, ceria-zirconia or alumina-ceria-zirconia, and can also be a zeolite.

(24) The N.sub.2O-producing catalyst is preferably prepared by adding a manganese compound (such as manganese acetate) to the inorganic oxide by any known means, the manner of addition is not considered to be particularly critical. For example, the manganese compound may be added to the inorganic oxide by impregnation, adsorption, ion-exchange, incipient wetness, precipitation, or the like to produce the N.sub.2O-producing catalyst.

(25) The N.sub.2O-producing catalyst is preferably located in or on a flow-through monolith substrate. The flow-through substrate is preferably a ceramic or metallic substrate. In particular, the flow-through substrate is a flow-through 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.

(26) The ceramic substrate 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, a magnesium aluminosilicate, and silicon carbide are particularly preferred. The metallic substrate 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 aluminum in addition to other trace metals.

(27) Preferably, the N.sub.2O-producing catalyst is coated onto the flow-through substrate by any known means, more preferably the N.sub.2O-producing catalyst is deposited on the substrate using washcoat procedures. The washcoating is preferably performed by first slurrying finely divided particles of the N.sub.2O-producing catalyst in an appropriate solvent, preferably water, to form the slurry. The slurry preferably contains between 5 to 70 weight percent solids, more preferably between 10 to 50 weight percent. Preferably, the N.sub.2O-producing catalyst 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. 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. 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 1 to 8 hours.

(28) FIG. 1 shows one embodiment of the invention, showing a cross section of the apparatus. The apparatus comprises an engine 10 and an exhaust system 12. The exhaust system comprises a conduit 14 linking the engine to an optional diesel oxidation catalyst (DOC) 16. The exhaust gas from the engine 10 flows to the optional DOC 16 then passes to a SCRF 20 before passing to an optional ammonia oxidation catalyst 22. The optional nitrogenous reductant means 18 is utilized to add a nitrogenous reductant such as urea to the exhaust gas flowing into the SCRF 20. The low pressure exhaust gas recirculation circuit 26 comprises an exhaust gas recirculation valve 24. Disposed within the EGR circuit 26, N.sub.2O-producing catalyst 28 is utilized to convert NH.sub.3 and NO.sub.2 in the EGR circuit to produce N.sub.2O, which is then fed back to an intake 30 of the engine 10.