Patent Grant
11541379
The present invention relates to a catalyst and method of converting nitrogen oxides in a gas, such as an exhaust gas of a vehicular lean-burn internal combustion engine, to nitrogen by contacting the nitrogen oxides with a nitrogenous reducing agent in the presence of a transition metal-containing molecular sieve catalyst.
Selective catalytic reduction (SCR) of NOx by nitrogenous compounds, such as ammonia or urea, has been used in many applications, including industrial stationary applications. More recently, NOx reduction systems based on SCR technology are being developed for a number of vehicular (mobile) applications in Europe, Japan, and the USA, e.g. for treating diesel exhaust gas.
Several chemical reactions occur in an NH3 SCR system, most of which represent desirable reactions that reduce NOx, specifically NO and NO2, to nitrogen. The dominant reaction is represented by reaction (1).
4NO+4NH3+O2→4N2+6H2O (1)
Competing, non-selective reactions with oxygen can produce secondary emissions or may unproductively consume ammonia. One such non-selective reaction is the complete oxidation of ammonia, shown in reaction (2).
4NH3+5O2→4NO+6H2O (2)
Also, side reactions may lead to undesirable products such as N2O, as represented by reaction (3).
4NH3+5NO+3O2→4N2O+6H2O (3)
Molecular sieves, including aluminosilicate zeolites, may be used as catalysts for SCR of NOx with NH3. One application is to control NOx emissions from vehicular diesel engines, with the reductant obtainable from an ammonia precursor such as urea or by injecting ammonia per se. To promote the catalytic activity, transition metals may be incorporated into the aluminosilicate zeolites.
It is desired to prepare a catalyst composition for SCR of NOx with improved NOx conversion and reduced N2O production.
According to some aspects of the present invention, a catalyst composition for treating an exhaust gas comprises a molecular sieve, the molecular sieve comprising exchanged copper and exchanged manganese. In some aspects, the molecular sieve is an aluminosilicate molecular sieve. In some aspects, the molecular sieve comprises a zeolite. A suitable zeolite may have a silica to alumina molar ratio (SAR) of, for example, about 5 to about 200; about 10 to about 50; or about 10 to about 30. In some aspects, the molecular sieve comprises a small-pore zeolite. A suitable small-pore zeolite may have a crystal framework type selected from, for example, AEI, CHA, and combinations thereof. In some aspects, the molecular sieve comprises a medium- or large-pore zeolite. A suitable medium- or large-pore zeolite may have a crystal framework type selected from, for example, BEA, MFI, and combinations thereof.
In some aspects, a molecular sieve includes a weight ratio of copper to manganese of about 0.1 to about 50; about 0.2 to about 15; or about 0.3 to about 3. In some aspects, a molecular sieve includes copper and manganese present in a total amount of about 0.1 to about 10 wt %; about 1 to about 7 wt %; or about 2 to about 5 wt %, based on the weight of the molecular sieve. In some aspects, a molecular sieve includes copper present in an amount of about 0.05 to about 7 wt %; about 0.5 to about 5 wt %; or about 1 to about 4 wt %, based on the weight of the molecular sieve. In some aspects, a molecular sieve includes manganese present in an amount of about 0.05 to about 7 wt %; about 0.1 to about 5 wt %; or about 0.5 to about 2.5 wt %, based on the weight of the molecular sieve. In some aspects, a molecular sieve includes a transition metal to aluminum ratio of <1; <0.75; or <0.5.
In some aspects, the catalyst composition is effective to promote a reaction of NH3 with NOx to form nitrogen and water. In certain aspects, the catalyst composition produces about 20% to about 45% less N2O under standard SCR conditions compared to a Cu-exchanged molecular sieve. In some aspects, the catalyst composition converts about 30% to about 60% more total NOx under standard SCR conditions than a Mn-exchanged molecular sieve. In some aspects, the catalyst composition produces about 1% to about 15% less N2O under standard SCR conditions than a physical mixture of a Cu-exchanged molecular sieve and a Mn-exchanged molecular sieve. In some aspects, the catalyst composition converts about 1% to about 25% more total NOx under standard SCR conditions than a physical mixture of a Cu-exchanged molecular sieve and a Mn-exchanged molecular sieve. In some aspects, the catalyst composition produces about 25% to about 60% less N2O under fast SCR conditions compared to a Cu-exchanged molecular sieve. In some aspects, the catalyst composition converts about 1% to about 20% more total NOx under fast SCR conditions compared to a Cu-exchanged molecular sieve. In some aspects, the catalyst composition produces about 20% to about 45% less N2O under slow SCR conditions compared to a Cu-exchanged molecular sieve. In some aspects, the catalyst composition produces about 35% to about 65% less N2O under standard SCR conditions after 900° C. aging compared to a Cu-exchanged molecular sieve.
According to some aspects of the present invention, a catalyst article comprises a substrate coated with a catalyst composition comprising a molecular sieve, the molecular sieve comprising exchanged copper and exchanged manganese. In some aspects, a substrate may further include one or more additional catalysts, such as one or more Cu- or Fe-exchanged molecular sieve catalysts. In some aspects, the molecular sieve comprising exchanged copper and exchanged manganese is present upstream of the one or more additional catalyst compositions. In some aspects, the molecular sieve comprising exchanged copper and exchanged manganese is present in a top layer and the one or more additional catalyst compositions are present in a bottom layer. In some aspects, the catalyst article further comprises a catalyst composition comprising a platinum group metal.
According to some aspects of the present invention, a method of treating an exhaust gas containing nitrogen oxides comprises contacting the exhaust gas with a nitrogenous reductant in a presence of a catalyst composition, the catalyst composition comprising a molecular sieve, the molecular sieve comprising exchanged copper and exchanged manganese. In some aspects, the nitrogenous reductant comprises ammonia. In some aspects, the contacting occurs at a temperature of about 150° C. to about 750° C.
Compositions, methods, and systems of the present invention relate to catalysts for treating exhaust gas. Catalyst compositions of aspects of the present invention include a molecular sieve, wherein the molecular sieve includes exchanged copper and exchanged manganese. As explained herein, catalyst compositions of aspects of the present invention have been found to promote a reaction of NH3 with NOx to form nitrogen and water, i.e., selective catalytic reduction (SCR), with low N2O production. Such catalysts compositions may be useful for treating exhaust gas, for example, from internal combustion engines, including diesel engines.
Catalyst Composition
Catalyst compositions of the present invention include a molecular sieve with exchanged copper and exchanged manganese. In some aspects, the molecular sieve is free of, or essentially free of any additional transition metals. For example, in some aspects, the molecular sieve contains additional transition metals (i.e., further to the exchanged copper and exchanged manganese) in an amount less than about 1 wt %; less than about 0.7 wt %; less than about 0.5 wt %; less than about 0.3 wt %; less than about 0.1 wt %; less than about 0.07 wt %; less than about 0.05 wt %; or less than about 0.01 wt %, based on the weight of the molecular sieve. In some aspects, the molecular sieve may be described as bimetallic, as the molecular sieve includes two transition metals.
Molecular Sieves
Catalyst compositions of aspects of the present invention include a molecular sieve. In some aspects, the molecular sieve comprises, or consists essentially of, a molecular sieve having an aluminosilicate framework (e.g. zeolite) or a silicoaluminophosphate framework (e.g. SAPO). In some aspects, the molecular sieve comprises, or consists essentially of, a molecular sieve having an aluminosilicate framework (e.g. zeolite). In some aspects, preferred zeolites are synthetic zeolites.
When the molecular sieve has an aluminosilicate framework (e.g. the molecular sieve is a zeolite), then typically the molecular sieve has a silica to alumina molar ratio (SAR) of from 5 to 200 (e.g. 10 to 200); 10 to 100 (e.g. 10 to 30 or 20 to 80); 10 to 50; 10 to 30; 12 to 40; 15 to 30; 5 to 20; 5 to 15; 8 to 15; 8 to 13; 10 to 15; 10 to 20; 10 to 40; 10 to 60; 10 to 80; 10 to 100; 10 to 150; <30; <20; <15; or <13. In some aspects, a suitable molecular sieve has a SAR of >200; >600; or >1200. In some aspects, the molecular sieve has a SAR of from about 1500 to about 2100.
Typically, the molecular sieve is microporous. A microporous molecular sieve has pores with a diameter of less than 2 nm (e.g. in accordance with the IUPAC definition of “microporous” [see Pure & Appl. Chem., 66(8), (1994), 1739-1758)]).
The molecular sieve may be a small pore molecular sieve (e.g. a molecular sieve having a maximum ring size of eight tetrahedral atoms), a medium pore molecular sieve (e.g. a molecular sieve having a maximum ring size of ten tetrahedral atoms) or a large pore molecular sieve (e.g. a molecular sieve having a maximum ring size of twelve tetrahedral atoms) or a combination of two or more thereof.
In some aspects, the molecular sieve may be mesoporous. A mesoporous molecular sieve has pores with a diameter between 2 and 50 nm (e.g. in accordance with the IUPAC definition of “microporous”).
When the molecular sieve is a small pore molecular sieve, then the small pore molecular sieve may have a framework structure represented by a Framework Type Code (FTC) selected from the group consisting of ACO, AEI, AEN, AFN, AFT, AFX, ANA, APC, APD, ATT, CDO, CHA, DDR, DFT, EAB, EDI, EPI, ERI, GIS, GOO, IHW, ITE, ITW, LEV, LTA, KFI, MER, MON, NSI, OWE, PAU, PHI, RHO, RTH, SAT, SAV, SFW, SIV, THO, TSC, UEI, UFI, VNI, YUG and ZON, or a mixture and/or combination and/or an intergrowth of two or more thereof. In some aspects, the small pore molecular sieve has a framework structure represented by a FTC selected from the group consisting of CHA, LEV, AEI, AFX, ERI, LTA, SFW, KFI, DDR and ITE. In some aspects, the small pore molecular sieve has a framework structure represented by a FTC selected from the group consisting of CHA, AEI, and AFX. In some aspects, the small pore molecular sieve has a framework structure represented by a FTC selected from the group consisting of CHA and AEI. The small pore molecular sieve may have a framework structure represented by the FTC CHA. The small pore molecular sieve may have a framework structure represented by the FTC AEI.
When the molecular sieve is a medium pore molecular sieve, then the medium pore molecular sieve may have a framework structure represented by a Framework Type Code (FTC) selected from the group consisting of AEL, AFO, AHT, BOF, BOZ, CGF, CGS, CHI, DAC, EUO, FER, HEU, IMF, ITH, ITR, JRY, JSR, JST, LAU, LOV, MEL, MFI, MFS, MRE, MTT, MVY, MWW, NAB, NAT, NES, OBW, PAR, PCR, PON, PUN, RRO, RSN, SFF, SFG, STF, STI, STT, STW, SVR, SZR, TER, TON, TUN, UOS, VSV, WEI and WEN, or a mixture and/or an intergrowth of two or more thereof. In some aspects, the medium pore molecular sieve has a framework structure represented by a FTC selected from the group consisting of FER, MEL, MFI, and STT. In some aspects, the medium pore molecular sieve has a framework structure represented by a FTC selected from the group consisting of FER and MFI, particularly MFI. When the medium pore molecular sieve is a zeolite and has a framework represented by the FTC FER or MFI, then the zeolite may be ferrierite, silicalite or ZSM-5.
When the molecular sieve is a large pore molecular sieve, then the large pore molecular sieve may have a framework structure represented by a Framework Type Code (FTC) selected from the group consisting of AFI, AFR, AFS, AFY, ASV, ATO, ATS, BEA, BEC, BOG, BPH, BSV, CAN, CON, CZP, DFO, EMT, EON, EZT, FAU, GME, GON, IFR, ISV, ITG, IWR, IWS, IWV, IWW, JSR, LTF, LTL, MAZ, MEI, MOR, MOZ, MSE, MTW, NPO, OFF, OKO, OSI, RON, RWY, SAF, SAO, SBE, SBS, SBT, SEW, SFE, SFO, SFS, SFV, SOF, SOS, STO, SSF, SSY, USI, UWY, and VET, or a mixture and/or an intergrowth of two or more thereof. In some aspects, the large pore molecular sieve has a framework structure represented by a FTC selected from the group consisting of AFI, BEA, MAZ, MOR, and OFF. In some aspects, the large pore molecular sieve has a framework structure represented by a FTC selected from the group consisting of BEA, MOR and FAU. When the large pore molecular sieve is a zeolite and has a framework represented by the FTC BEA, FAU or MOR, then the zeolite may be a beta zeolite, faujasite, zeolite Y, zeolite X or mordenite.
In some aspects, a suitable molecular sieve includes a combination of small and large pore frameworks. In some aspects, a suitable molecular sieve includes ZSM-34 (ERI+OFF).
Transition Metals
In some aspects, a catalyst composition includes a molecular sieve with copper, manganese, and optionally one or more other metals such as exchanged period 4 transition metals and/or noble metals. Generally, suitable other metals may be selected from the group consisting of cobalt, iron, nickel, vanadium, palladium, platinum, ruthenium and rhenium. In some aspects, the two or more exchanged transition metals comprise copper and manganese. In some aspects, the exchanged transition metals consist essentially of copper and manganese. In some aspects, the exchanged transition metals consist of copper and manganese. In some aspects, the other metals do not include iron. In some aspects, the other metals do not include vanadium. In some aspects, the other metals do not include ruthenium. In some aspects, the other metals do not include nickel.
The transition metal(s) may be present on an extra-framework site on the external surface of the molecular sieve or within a channel, cavity or cage of the molecular sieve.
In some aspects, the transition metal exchanged molecular sieve comprises transition metals in an amount of about 0.10 to about 10% by weight of the transition metal exchanged molecular sieve; or an amount of about 0.2 to about 5% by weight of the transition metal exchanged molecular sieve.
Amounts Cu/Mn
In some aspects, a transition metal exchanged molecular sieve of the present invention comprises exchanged copper and exchanged manganese in a combined amount of about 0.10 to about 10% by weight of the transition metal exchanged molecular sieve; about 0.1 to about 7% by weight of the transition metal exchanged molecular sieve; about 0.2 to about 7% by weight of the transition metal exchanged molecular sieve; about 0.2 to about 5% by weight of the transition metal exchanged molecular sieve; about 0.5 to about 6% by weight of the transition metal exchanged molecular sieve; about 1 to about 7% by weight of the transition metal exchanged molecular sieve; about 1 to about 5% by weight of the transition metal exchanged molecular sieve; about 2 to about 5% by weight of the transition metal exchanged molecular sieve; about 1.5 to about 3% by weight of the transition metal exchanged molecular sieve; about 1.5 to 4% by weight of the transition metal exchanged molecular sieve; or about 2 to about 4% by weight of the transition metal exchanged molecular sieve.
In some aspects, a transition metal exchanged molecular sieve of the present invention comprises exchanged copper in an amount of about 0.05 to about 7% by weight of the transition metal exchanged molecular sieve; about 0.5 to about 5% by weight of the transition metal exchanged molecular sieve; about 0.05 to about 5% by weight of the transition metal exchanged molecular sieve; about 0.1 to about 4% by weight of the transition metal exchanged molecular sieve; about 0.1 to about 3% by weight of the transition metal exchanged molecular sieve; about 0.2 to about 3% by weight of the transition metal exchanged molecular sieve; about 0.5 to about 2.5% by weight of the transition metal exchanged molecular sieve; about 1 to about 4% by weight of the transition metal exchanged molecular sieve; or about 1 to about 2% by weight of the transition metal exchanged molecular sieve.
In some aspects, a transition metal exchanged molecular sieve of the present invention comprises exchanged manganese in an amount of about 0.05 to about 7% by weight of the transition metal exchanged molecular sieve, about 0.05 to about 5% by weight of the transition metal exchanged molecular sieve; about 0.1 to about 5% by weight of the transition metal exchanged molecular sieve; about 0.1 to about 4% by weight of the transition metal exchanged molecular sieve; about 0.1 to about 3% by weight of the transition metal exchanged molecular sieve; about 0.2 to about 3% by weight of the transition metal exchanged molecular sieve; about 0.5 to about 2.5% by weight of the transition metal exchanged molecular sieve; or about 1 to about 2% by weight of the transition metal exchanged molecular sieve.
Ratios Cu/Mn
In some aspects, a transition metal exchanged molecular sieve of the present invention comprises exchanged copper and exchanged manganese in a weight ratio of about 1:1. In some aspects, a transition metal exchanged molecular sieve of the present invention comprises exchanged copper and exchanged manganese in a weight ratio of about 0.1 to about 50; about 0.2 to about 15; or about 0.33 to about 3. In some aspects, in addition to utilizing the above-mentioned copper and manganese ratios, the exchange capacity of the molecular sieve in terms of metal ion to exchange site ratio should be <1; <0.75; or <0.5. In some aspects, a transition exchanged molecular sieve has a transition metal to aluminum ratio of <1; <0.75; or <0.5.
Catalysts of the present invention can be prepared by any suitable means known in the art, including, for example, one pot, prefixing, and spray drying.
Substrate
A catalyst article of the present invention may include a substrate and a catalyst composition. The substrate may be a flow-through substrate or a filtering substrate. The substrate may comprise the catalyst composition (i.e. the catalyst article is obtained by extrusion) or the catalyst composition may be disposed or supported on the substrate (i.e. the catalyst composition is applied onto the substrate by a washcoating method). The catalyst composition may coat the substrate entirely or partially, as desired. In some aspects, a catalyst article includes a Cu/Mn bimetallic molecular sieve extruded article which is coated with one or more additional catalysts. In some aspects, the extruded catalyst is coated with one or more additional SCR catalysts, which could include, for example, a Cu/Mn bimetallic molecular sieve.
In some aspects, the catalyst article may comprise the catalyst composition in a total concentration of about 0.5 to about 4.0 g in−3; about 1.0 to about 3.0 g in−3; or about 1.2 to about 2.5 g/in3.
When the catalyst article has a filtering substrate, then it is a selective catalytic reduction filter catalyst. The selective catalytic reduction filter comprises a filtering substrate and the catalyst composition. References to use of SCR catalysts throughout this application are understood to include use of selective catalytic reduction filter catalysts as well, where applicable.
The flow-through or filter substrate is a substrate that is capable of containing catalyst/adsorber components. The substrate is preferably a ceramic substrate or a metallic substrate. The ceramic substrate may include any suitable refractory material, e.g., alumina, silica, titania, ceria, zirconia, magnesia, zeolites, silicon nitride, silicon carbide, zirconium silicates, magnesium silicates, aluminosilicates, metallo aluminosilicates (such as cordierite and spudomene), or a mixture or mixed oxide of any two or more thereof. Cordierite, a magnesium aluminosilicate, and silicon carbide are particularly preferred.
The metallic substrates 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.
The flow-through substrate is preferably a flow-through monolith having a honeycomb structure with many small, parallel thin-walled channels running axially through the substrate and extending throughout from an inlet or an outlet of 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. The flow-through substrate may also be high porosity which allows the catalyst to penetrate into the substrate walls.
The filter substrate is preferably a wall-flow monolith filter. The channels of a wall-flow filter are alternately blocked, which allow the exhaust gas stream to enter a channel from the inlet, then flow through the channel walls, and exit the filter from a different channel leading to the outlet. Particulates in the exhaust gas stream are thus trapped in the filter.
The catalyst composition may be added to the flow-through or filter substrate by any known means, such as a washcoat procedure.
When the catalyst article is selective catalytic reduction filter, then the filtering substrate may preferably be a wall flow filter substrate monolith. The wall flow filter substrate monolith (e.g. of the SCR-DPF) typically has a cell density of 60 to 400 cells per square inch (cpsi). It is preferred that the wall flow filter substrate monolith has a cell density of 100 to 350 cpsi, more preferably 200 to 300 cpsi.
The wall flow filter substrate monolith may have a wall thickness (e.g. average internal wall thickness) of 0.20 to 0.50 mm, preferably 0.25 to 0.35 mm (e.g. about 0.30 mm).
Generally, the uncoated wall flow filter substrate monolith has a porosity of from 50 to 80%, preferably 55 to 75%, and more preferably 60 to 70%.
The uncoated wall flow filter substrate monolith typically has a mean pore size of at least 5 μm. It is preferred that the mean pore size is from 10 to 40 μm, such as 15 to 35 μm, more preferably 20 to 30 μm.
The wall flow filter substrate may have a symmetric cell design or an asymmetric cell design.
In general for a selective catalytic reduction filter, the catalyst composition is disposed within the wall of the wall-flow filter substrate monolith. Additionally, the catalyst composition may be disposed on the walls of the inlet channels and/or on the walls of the outlet channels.
Catalyst compositions of aspects of the present invention may be coated on a suitable monolith substrate. Washcoat compositions containing the catalyst compositions of the present invention for coating onto the monolith substrate or for manufacturing extruded type substrate monoliths can comprise a binder selected from the group consisting of alumina, silica, (non zeolite) silica-alumina, naturally occurring clays, TiO2, ZrO2, and SnO2. In general, catalytic articles comprising the catalyst composition in a desired loading level may be prepared by washcoating, extrusion, or other methods known in the art.
Methods and Systems
Methods of the present invention relate to treating exhaust gas containing nitrogen oxides, by contacting the exhaust gas with a reductant, such as a nitrogenous reductant or hydrocarbon reductant, in the presence of a catalyst composition as described herein. As such, catalyst compositions of the present invention may function as selective catalytic reduction catalysts.
In some aspects, the nitrogen oxides are reduced with the reducing agent at a temperature of at least 100° C. In some aspects, the catalysts as described herein are effective at reducing nitrogen oxides with the reducing agent over a wide temperature range (e.g., from about 150° C. to 750° C.) in addition to being hydrothermally stable at temperatures above 900° C. The latter characteristics may be particularly useful for treating exhaust gases from heavy and light duty diesel engines, particularly engines comprising exhaust systems comprising (optionally catalyzed) diesel particulate filters which are regenerated actively, e.g. by injecting hydrocarbon into the exhaust system upstream of the filter, wherein the zeolite catalyst for use in the present invention is located downstream of the filter.
In a particular aspect, the catalysts as described herein are effective at reducing nitrogen oxides with the reducing agent in a temperature range of from 175 to 550° C. In another aspect, the temperature range is from 175 to 400° C. in some aspects, the temperature range is from 275 to 500° C., or 250 to 550° C. When N2O is present in the gas stream, the temperature range may be wider, such as 150 to 650° C.; 175 to 625° C.; 200 to 600° C.; or 225 to 575° C.
In some aspects, the nitrogen oxides reduction is carried out in the presence of oxygen. In some aspects, the nitrogen oxides reduction is carried out in the absence of oxygen.
The nitrogenous reductant can be ammonia per se or the source of nitrogenous reductant can be hydrazine or any suitable ammonia precursor, such as urea ((NH2)2CO), ammonium carbonate, ammonium carbamate, ammonium hydrogen carbonate or ammonium formate. The reductant can be injected into the exhaust gas stream from an external source, such as reservoir or tank, supplied in-situ by a Nitrogen Storage Catalyst or NOx Adsorber Catalyst, so a combination of both. The reductant should be introduced into the exhaust gas upstream of the SCR catalyst.
The method can be performed on a gas derived from a combustion process, such as from an internal combustion engine (whether mobile or stationary), a gas turbine and coal or oil-fired power plants. The method may also be used to treat gas from industrial processes such as refining, from refinery heaters and boilers, furnaces, the chemical processing industry, coke ovens, municipal waste plants and incinerators, coffee roasting plants etc.
In a particular aspect, the method is used 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.
In some aspects, the invention provides an exhaust system for a vehicular lean burn internal combustion engine, which system comprising a conduit for carrying a flowing exhaust gas, a source of nitrogenous reductant, a catalyst composition comprising exchanged copper and exchanged manganese disposed in a flow path of the exhaust gas, and means for metering nitrogenous reductant into a flowing exhaust gas upstream of the catalyst composition.
A system can include means, when in use, for controlling the metering means so that nitrogenous reductant is metered into the flowing exhaust gas only when it is determined that the catalyst composition is capable of catalyzing NOx reduction at or above a desired efficiency, such as at a temperature of above 100° C., above 150° C., or above 175° C. The determination by the control means can be assisted by one or more suitable sensor inputs indicative of a condition of the engine selected from the group consisting of: exhaust gas temperature, catalyst bed temperature, accelerator position, mass flow of exhaust gas in the system, manifold vacuum, ignition timing, engine speed, lambda value of the exhaust gas, the quantity of fuel injected in the engine, the position of the exhaust gas recirculation (EGR) valve and thereby the amount of EGR and boost pressure.
In some aspects, metering is controlled in response to the quantity of nitrogen oxides in the exhaust gas determined either directly (using a suitable NOx sensor) or indirectly, such as using pre-correlated look-up tables or maps—stored in the control means13 correlating any one or more of the abovementioned inputs indicative of a condition of the engine with predicted NOx content of the exhaust gas.
The control means may comprise a pre-programmed processor such as an electronic control unit (ECU).
The metering of the nitrogenous reductant may be arranged such that 60% to 200% of theoretical ammonia is present in exhaust gas entering the SCR catalyst calculated at 1:1 NH3/NO and 4:3 NH3/NO2.
In some aspects, an oxidation catalyst for oxidizing nitrogen monoxide in the exhaust gas to nitrogen dioxide can be located upstream of a point of metering the nitrogenous reductant into the exhaust gas. In some aspects, the oxidation catalyst is adapted to yield a gas stream entering the SCR catalyst composition having a ratio of NO to NO2 of from about 4:1 to about 1:3 by volume, e.g. at an exhaust gas temperature at oxidation catalyst inlet of 200° C. to 450° C.; or 250° C. to 450° C. This concept is disclosed in S. Kasaoka et al. “Effect of Inlet NO/NO2 Molar Ratio and Contribution of Oxygen in the Catalytic Reduction of Nitrogen Oxides with Ammonia”, Nippon Kagaku Kaishi, 1978, No. 6, pp. 874-881 and WO 99/39809.
The oxidation catalyst can include at least one platinum group metal (or some combination of these), such as platinum, palladium or rhodium, coated on a flow-through monolith substrate. In one aspect, the at least one platinum group metal is platinum, palladium or a combination of both platinum and palladium. The platinum group metal can be supported on a high surface area washcoat component such as alumina, a zeolite such as an aluminosilicate zeolite, silica, non-zeolite silica alumina, ceria, zirconia, titania or a mixed or composite oxide containing both ceria and zirconia.
In some aspects, a suitable filter substrate is located between the oxidation catalyst and the zeolite catalyst. Filter substrates can be selected from any of those mentioned above, e.g. wall flow filters. Where the filter is catalyzed, e.g. with an oxidation catalyst of the kind discussed above, preferably the point of metering nitrogenous reductant is located between the filter and the zeolite catalyst. Alternatively, if the filter is uncatalyzed, the means for metering nitrogenous reductant can be located between the oxidation catalyst and the filter. It will be appreciated that this arrangement is disclosed in WO 99/39809.
In some aspects, the catalyst composition for use in the present invention is coated on a filter located downstream of the oxidation catalyst. Where the filter includes the catalyst composition for use in the present invention, the point of metering the nitrogenous reductant is preferably located between the oxidation catalyst and the filter.
In some aspects, a system configuration includes a NOx adsorber catalyst followed by a selective catalytic reduction filter, which may include, for example, a Cu/Mn bimetallic molecular sieve. In some aspects, a system configuration includes a first SCR followed by a second SCR. In some aspects, a system configuration includes a selective catalytic reduction filter followed by an SCR. In some aspects, a catalyst configuration includes an SCR followed by an ammonia oxidation catalyst. Where suitable, such catalysts may be included as different coatings on the same substrate. In some aspects, the SCR catalyst may include a Cu/Mn bimetallic molecular sieve.
In some aspects, there is provided a vehicular lean-burn engine comprising an exhaust system according to the present invention.
In some aspects, the vehicular lean burn internal combustion engine can be a diesel engine, a lean-burn gasoline engine or an engine powered by liquid petroleum gas or natural gas.
Zoning and Configurations
In some aspects, catalyst compositions including a molecular sieve with exchanged copper and exchanged manganese (Cu/Mn bimetallic molecular sieve) may be combined with one or more additional catalyst compositions. Such combinations may involve zoned and/or layered configurations on one or multiple substrates.
In some aspects, a Cu/Mn bimetallic molecular sieve may be combined with additional catalyst compositions formulated as SCR catalyst and/or oxidation catalysts such as ammonia oxidation catalysts. In some aspects, a Cu/Mn bimetallic molecular sieve may be combined with one or more additional SCR catalyst(s). In some aspects, a Cu/Mn bimetallic molecular sieve and the additional SCR catalyst(s) may be located on the same substrate. In some aspects, a Cu/Mn bimetallic molecular sieve and the additional SCR catalyst(s) may be located on different substrates. In some aspects, a catalyst configuration may include a Cu/Mn bimetallic molecular sieve with one or more additional SCR catalyst(s) on the same substrate and one or more additional SCR catalyst(s) on a separate substrate.
In some aspects, a catalyst configuration may include a Cu/Mn bimetallic molecular sieve with an additional catalyst composition, such as an SCR catalyst, located downstream. As used herein, the terms upstream and downstream are understood to indicate a location of the catalysts relative to each other in relation to the flow of exhaust gas. Similarly, inlet and outlet ends are understood to indicate the end of the catalyst substrate relative to the flow of exhaust gas. In some aspects, a Cu/Mn bimetallic molecular sieve is present in a first zone with an addition catalyst composition, such as an SCR catalyst, located in a second zone, where the first zone is upstream of the second zone. In some aspects, the first zone and the second zone are located on the same substrate. In some aspects, the first zone and the second zone are located on separate substrates.
In some aspects, a catalyst configuration may include a Cu/Mn bimetallic molecular sieve in a first upstream zone, with an additional catalyst such as an SCR catalyst located downstream in a second zone, on a separate substrate. For example,
In some aspects, a catalyst configuration may include a Cu/Mn bimetallic molecular sieve on an upstream portion of a substrate, with an additional catalyst such as an SCR catalyst located on a downstream portion of the same substrate. In some aspects, these catalyst compositions located on the upstream and downstream portions of the substrate may partially overlap. For example,
In some aspects, a catalyst configuration may include an additional catalyst such as an SCR catalyst located upstream, with a Cu/Mn bimetallic molecular sieve located downstream, on a separate substrate. In some aspects, the catalyst configuration may include a further catalyst located between the upstream additional catalyst and the downstream Cu/Mn bimetallic molecular sieve. For example,
In some aspects, a catalyst configuration may include an additional catalyst such as an SCR catalyst on an upstream portion of a substrate, with a Cu/Mn bimetallic molecular sieve located on a downstream portion of the same substrate. In some aspects, these catalyst compositions located on the upstream and downstream portions of the substrate may partially overlap. For example,
In some aspects, a catalyst configuration includes a first substrate with an additional catalyst such as an SCR catalyst on an upstream portion of the substrate, with a Cu/Mn bimetallic molecular sieve located on a downstream portion of the same substrate, followed by a second substrate having a further catalyst such as an SCR catalyst. In some aspects, these catalyst compositions located on the upstream and downstream portions of the first substrate may partially overlap. For example,
In some aspects, a catalyst configuration includes a first substrate with a Cu/Mn bimetallic molecular sieve, followed by a second substrate having one or more additional catalysts such as SCR catalysts. In some aspects, the second substrate includes an upstream catalyst located on an upstream portion of the second substrate and a downstream catalyst located on the downstream portion of the second substrate. In some aspects, these catalyst compositions located on the upstream and downstream portions of the second substrate may partially overlap.
In some aspects, any of the aforementioned catalyst configurations may further include a catalyst composition including platinum-group metal (“PGM catalyst”) applied in a bottom layer on one or more of the substrates in the configuration, from the outlet end of the substrate toward the inlet end, covering less than the entire length of the substrate. The catalyst composition including a platinum-group metal may comprise, for example, Pt.alumina, or a Pt.zeolite+Cu.zeolite blend.
For example, in some aspects, a catalyst configuration may include a Cu/Mn bimetallic molecular sieve in a first upstream zone, with an additional catalyst such as an SCR catalyst located downstream in a second zone, on a separate substrate, wherein the separate substrate includes a platinum-group metal applied in a bottom layer from the outlet end of the substrate toward the inlet end of the substrate. For example,
In some aspects, a catalyst configuration may include a Cu/Mn bimetallic molecular sieve on an upstream portion of a substrate, with an additional catalyst such as an SCR catalyst located on a downstream portion of the same substrate, and a PGM catalyst applied in a bottom layer from the outlet end of the substrate toward the inlet end of the substrate, covering less than the entire length of the substrate. In some aspects, these catalyst compositions located on the upstream and downstream portions of the substrate may partially overlap. For example,
In some aspects, a catalyst configuration may include an additional catalyst such as an SCR catalyst located upstream, with a Cu/Mn bimetallic molecular sieve located downstream, on a separate substrate, with a PGM catalyst applied in a bottom layer of either or both substrate(s), extending from the outlet end toward the inlet end and covering less than the entire length of the substrate. In some aspects, the catalyst configuration may include a further catalyst located between the upstream additional catalyst and the downstream Cu/Mn bimetallic molecular sieve. For example,
In some aspects, a catalyst configuration may include an additional catalyst such as an SCR catalyst on an upstream portion of a substrate, with a Cu/Mn bimetallic molecular sieve located on a downstream portion of the same substrate, with a PGM catalyst applied in a bottom layer, extending from the outlet end of the substrate toward the inlet end and covering less than the entire length of the substrate. In some aspects, these catalyst compositions located on the upstream and downstream portions of the substrate may partially overlap. For example,
In some aspects, a catalyst configuration includes a first substrate with an additional catalyst such as an SCR catalyst on an upstream portion of the substrate, with a Cu/Mn bimetallic molecular sieve located on a downstream portion of the same substrate, followed by a second substrate having a further catalyst such as an SCR catalyst, with a PGM catalyst applied in a bottom layer extending from the outlet end of either or both substrate(s) toward the inlet end, covering less than the entire length of the substrate. In some aspects, these catalyst compositions located on the upstream and downstream portions of the first substrate may partially overlap. For example,
In some aspects, a catalyst configuration includes a first substrate with a Cu/Mn bimetallic molecular sieve, followed by a second substrate having one or more additional catalysts such as SCR catalysts. In some aspects, the second substrate includes an upstream catalyst located on an upstream portion of the second substrate and a downstream catalyst located on the downstream portion of the second substrate, with a PGM catalyst applied in a bottom layer on either or both substrate(s), extending from the outlet end of the substrate toward the inlet end and covering less than the entire length of the substrate. In some aspects, these catalyst compositions located on the upstream and downstream portions of the second substrate may partially overlap.
In some aspects, a catalyst configuration includes a layered configuration, with a Cu/Mn bimetallic molecular sieve in a top layer, and an additional catalyst such as an SCR catalyst in a bottom layer. In some aspects, both the top and bottom layer extend the entire length of the substrate. For example,
In some aspects, a catalyst configuration includes a layered configuration, with a top layer including a catalyst such as an SCR catalyst and a bottom layer including a Cu/Mn bimetallic molecular sieve in an upstream portion of the bottom layer and another catalyst such as an SCR catalyst in a downstream portion of the bottom layer. For example,
In some aspects, a catalyst configuration may include a bottom layer having a catalyst such as an SCR catalyst, and a top layer with a catalyst such as an SCR catalyst in an upstream portion of the top layer and a Cu/Mn bimetallic molecular sieve in the downstream portion of the top layer. For example,
In some aspects, a catalyst configuration includes a layered configuration, with a top layer including a Cu/Mn bimetallic molecular sieve and a bottom layer including a catalyst such as an SCR catalyst in an upstream portion of the bottom layer and another catalyst such as an SCR catalyst in a downstream portion of the bottom layer. For example,
In some aspects, a catalyst configuration includes a layered configuration, with a PGM catalyst applied in a bottom layer, extending from the outlet end of the substrate toward the inlet end and covering less than the entire length of the substrate, a next layer with an additional catalyst such as an SCR catalyst covering the entire length of the substrate and covering the PGM catalyst, and a Cu/Mn bimetallic molecular sieve in a top layer. For example,
In some aspects, a catalyst configuration includes a layered configuration, with a PGM catalyst applied in a bottom layer, extending from the outlet end of the substrate toward the inlet end and covering less than the entire length of the substrate, a layer including a Cu/Mn bimetallic molecular sieve in an upstream portion of that layer and another catalyst such as an SCR catalyst in a downstream portion of that layer and covering the PGM catalyst, and with a top layer including a catalyst such as an SCR catalyst. For example,
In some aspects, a catalyst configuration may include a PGM catalyst applied in a bottom layer, extending from the outlet end of the substrate toward the inlet end and covering less than the entire length of the substrate, a next layer having a catalyst such as an SCR catalyst extending the entire length of the substrate and covering the PGM catalyst, and a top layer with a catalyst such as an SCR catalyst in an upstream portion of the top layer and a Cu/Mn bimetallic molecular sieve in the downstream portion of the top layer. For example,
In some aspects, a catalyst configuration includes a layered configuration, with a PGM catalyst applied in a bottom layer, extending from the outlet end of the substrate toward the inlet end and covering less than the entire length of the substrate, a layer including a catalyst such as an SCR catalyst in an upstream portion of that layer and another catalyst such as an SCR catalyst in a downstream portion of that layer and covering the PGM catalyst, and with a top layer including a Cu/Mn bimetallic molecular sieve. For example,
In some aspects, a catalyst configuration includes a layered configuration, with a Cu/Mn bimetallic molecular sieve in a top layer extending from the inlet end toward the outlet end of the substrate and covering less than the entire length of the substrate, and an additional catalyst such as an SCR catalyst in a bottom layer. In some aspects, both the top and bottom layer extend the entire length of the substrate. For example,
In some aspects, a catalyst configuration includes a layered configuration, with a top layer including a catalyst such as an SCR catalyst extending from the inlet end toward the outlet end of the substrate and covering less than the entire length of the substrate, and a bottom layer including a Cu/Mn bimetallic molecular sieve in an upstream portion of the bottom layer and another catalyst such as an SCR catalyst in a downstream portion of the bottom layer. For example,
In some aspects, a catalyst configuration includes a layered configuration, with a top layer including a Cu/Mn bimetallic molecular sieve extending from the inlet end toward the outlet end of the substrate and covering less than the entire length of the substrate, and a bottom layer including a catalyst such as an SCR catalyst in an upstream portion of the bottom layer and another catalyst such as an SCR catalyst in a downstream portion of the bottom layer. For example,
In some aspects, a catalyst configuration includes a layered configuration, with a PGM catalyst applied in a bottom layer, extending from the outlet end of the substrate toward the inlet end and covering less than the entire length of the substrate, a next layer with an additional catalyst such as an SCR catalyst covering the entire length of the substrate and covering the PGM catalyst, and a Cu/Mn bimetallic molecular sieve in a top layer extending from the inlet end toward the outlet end of the substrate and covering less than the entire length of the substrate. For example,
In some aspects, a catalyst configuration includes a layered configuration, with a PGM catalyst applied in a bottom layer, extending from the outlet end of the substrate toward the inlet end and covering less than the entire length of the substrate, a layer including a Cu/Mn bimetallic molecular sieve in an upstream portion of that layer and another catalyst such as an SCR catalyst in a downstream portion of that layer and covering the PGM catalyst, and with a top layer including a catalyst such as an SCR catalyst extending from the inlet end toward the outlet end of the substrate and covering less than the entire length of the substrate. For example,
In some aspects, a catalyst configuration includes a layered configuration, with a PGM catalyst applied in a bottom layer, extending from the outlet end of the substrate toward the inlet end and covering less than the entire length of the substrate, a layer including a catalyst such as an SCR catalyst in an upstream portion of that layer and another catalyst such as an SCR catalyst in a downstream portion of that layer and covering the PGM catalyst, and with a top layer including a Cu/Mn bimetallic molecular sieve extending from the inlet end toward the outlet end of the substrate and covering less than the entire length of the substrate. For example,
In some aspects, a catalyst configuration includes a layered configuration and multiple substrates, with first upstream substrate having a Cu/Mn bimetallic molecular sieve in a top layer, and an additional catalyst such as an SCR catalyst in a bottom layer, and a separate downstream substrate having an additional catalyst such as an SCR catalyst. In some aspects, a catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example,
In some aspects, a catalyst configuration includes a layered configuration and multiple substrates, with a first upstream substrate having a top layer including a catalyst such as an SCR catalyst and a bottom layer including a Cu/Mn bimetallic molecular sieve in an upstream portion of the bottom layer and another catalyst such as an SCR catalyst in a downstream portion of the bottom layer, and a separate downstream substrate having an additional catalyst such as an SCR catalyst. In some aspects, a catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example,
In some aspects, a catalyst configuration may include a first upstream substrate with a bottom layer having a catalyst such as an SCR catalyst, and a top layer with a catalyst such as an SCR catalyst in an upstream portion of the top layer and a Cu/Mn bimetallic molecular sieve in the downstream portion of the top layer, and a separate downstream substrate having an additional catalyst such as an SCR catalyst. In some aspects, a catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example,
In some aspects, a catalyst configuration includes a layered configuration with multiple substrates, with a first upstream substrate having a top layer including a Cu/Mn bimetallic molecular sieve and a bottom layer including a catalyst such as an SCR catalyst in an upstream portion of the bottom layer and another catalyst such as an SCR catalyst in a downstream portion of the bottom layer, and a separate downstream substrate having an additional catalyst such as an SCR catalyst. In some aspects, a catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example,
In some aspects, a catalyst configuration includes a layered configuration and multiple substrates, with first upstream substrate having a Cu/Mn bimetallic molecular sieve in a top layer, and an additional catalyst such as an SCR catalyst in a bottom layer, and a separate downstream substrate having an additional catalyst such as an SCR catalyst, and further having a PGM catalyst applied in a bottom layer extending from the outlet end toward the inlet end of one or both substrate(s), extending less than the entire length of the substrate. In some aspects, a catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example,
In some aspects, a catalyst configuration includes a layered configuration and multiple substrates, with a first upstream substrate having a top layer including a catalyst such as an SCR catalyst and a bottom layer including a Cu/Mn bimetallic molecular sieve in an upstream portion of the bottom layer and another catalyst such as an SCR catalyst in a downstream portion of the bottom layer, and a separate downstream substrate having an additional catalyst such as an SCR catalyst, and further having a PGM catalyst applied in a bottom layer extending from the outlet end toward the inlet end of one or both substrate(s), extending less than the entire length of the substrate. In some aspects, a catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example,
In some aspects, a catalyst configuration may include a first upstream substrate with a bottom layer having a catalyst such as an SCR catalyst, and a top layer with a catalyst such as an SCR catalyst in an upstream portion of the top layer and a Cu/Mn bimetallic molecular sieve in the downstream portion of the top layer, and a separate downstream substrate having an additional catalyst such as an SCR catalyst, and further having a PGM catalyst applied in a bottom layer extending from the outlet end toward the inlet end of one or both substrate(s), extending less than the entire length of the substrate. In some aspects, a catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example,
In some aspects, a catalyst configuration includes a layered configuration with multiple substrates, with a first upstream substrate having a top layer including a Cu/Mn bimetallic molecular sieve and a bottom layer including a catalyst such as an SCR catalyst in an upstream portion of the bottom layer and another catalyst such as an SCR catalyst in a downstream portion of the bottom layer, and a separate downstream substrate having an additional catalyst such as an SCR catalyst, and further having a PGM catalyst applied in a bottom layer extending from the outlet end toward the inlet end of one or both substrate(s), extending less than the entire length of the substrate. In some aspects, a catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example,
In some aspects, a catalyst configuration includes a layered configuration and multiple substrates, with first upstream substrate having a Cu/Mn bimetallic molecular sieve in a top layer extending from the inlet end of the substrate toward the outlet end and covering less than the entire length of the substrate, and an additional catalyst such as an SCR catalyst in a bottom layer, and a separate downstream substrate having an additional catalyst such as an SCR catalyst. In some aspects, a catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example,
In some aspects, a catalyst configuration includes a layered configuration and multiple substrates, with a first upstream substrate having a top layer including a catalyst such as an SCR catalyst, extending from the inlet end of the substrate toward the outlet end and covering less than the entire length of the substrate, and a bottom layer including a Cu/Mn bimetallic molecular sieve in an upstream portion of the bottom layer and another catalyst such as an SCR catalyst in a downstream portion of the bottom layer, and a separate downstream substrate having an additional catalyst such as an SCR catalyst. In some aspects, a catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example,
In some aspects, a catalyst configuration includes a layered configuration with multiple substrates, with a first upstream substrate having a top layer including a Cu/Mn bimetallic molecular sieve, extending from the inlet end of the substrate toward the outlet end and covering less than the entire length of the substrate, and a bottom layer including a catalyst such as an SCR catalyst in an upstream portion of the bottom layer and another catalyst such as an SCR catalyst in a downstream portion of the bottom layer, and a separate downstream substrate having an additional catalyst such as an SCR catalyst. In some aspects, a catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example,
In some aspects, a catalyst configuration includes a layered configuration and multiple substrates, with first upstream substrate having a Cu/Mn bimetallic molecular sieve in a top layer, extending from the inlet end of the substrate toward the outlet end and covering less than the entire length of the substrate, and an additional catalyst such as an SCR catalyst in a bottom layer, and a separate downstream substrate having an additional catalyst such as an SCR catalyst, and further having a PGM catalyst applied in a bottom layer extending from the outlet end toward the inlet end of one or both substrate(s), extending less than the entire length of the substrate. In some aspects, a catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example,
In some aspects, a catalyst configuration includes a layered configuration and multiple substrates, with a first upstream substrate having a top layer including a catalyst such as an SCR catalyst, extending from the inlet end of the substrate toward the outlet end and covering less than the entire length of the substrate, and a bottom layer including a Cu/Mn bimetallic molecular sieve in an upstream portion of the bottom layer and another catalyst such as an SCR catalyst in a downstream portion of the bottom layer, and a separate downstream substrate having an additional catalyst such as an SCR catalyst, and further having a PGM catalyst applied in a bottom layer extending from the outlet end toward the inlet end of one or both substrate(s), extending less than the entire length of the substrate. In some aspects, a catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example,
In some aspects, a catalyst configuration includes a layered configuration with multiple substrates, with a first upstream substrate having a top layer including a Cu/Mn bimetallic molecular sieve, extending from the inlet end of the substrate toward the outlet end and covering less than the entire length of the substrate, and a bottom layer including a catalyst such as an SCR catalyst in an upstream portion of the bottom layer and another catalyst such as an SCR catalyst in a downstream portion of the bottom layer, and a separate downstream substrate having an additional catalyst such as an SCR catalyst, and further having a PGM catalyst applied in a bottom layer extending from the outlet end toward the inlet end of one or both substrate(s), extending less than the entire length of the substrate. In some aspects, a catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example,
Benefits
It has surprisingly been discovered that catalyst compositions of aspects of the present invention, comprising a molecular sieve with exchanged copper and exchanged manganese, have distinct advantages for the selective catalytic reduction process. Such catalyst compositions have been found to promote a reaction of NH3 with NOx to form nitrogen and water, i.e., selective catalytic reduction (SCR), with low N2O production. Additionally, such catalyst compositions have been found to enhance light-off and lower N2O selectivity, and are stable to 900° C. aging while still retaining good NOx conversion and N2O selectivity; aging, for example, includes 5 hours at 4.5% H2O. For example, a bimetallic Cu/Mn molecular sieve was found to exhibit similar or improved activity and improved selectivity compared to a monometallic Cu molecular sieve, a monometallic Mn molecular sieve, and physically mixed Cu molecular sieve/Mn molecular sieve under typical SCR conditions. It is understood that such comparisons refer to molecular sieves containing the same or substantially the same total amount of transition metals. Such results may support a theory of balancing active sites in order to balance fundamental reaction steps to optimize performance.
In the below discussion, N2O selectivity is defined as the moles N2O formed divided by the moles of NOx (NOx defined as NO and NO2) converted, average N2O selectivity is defined as the N2O selectivity averaged across the tested temperature range of 150° C.-500° C., average N2O production is defined as the amount of N2O produced averaged across the tested temperature range of 150° C.-500° C., and total NOx conversion is defined as the average % NOx converted across the tested temperature range of 150° C.-500° C.
Standard SCR
It has been found that catalyst compositions of the present invention produce significantly less N2O and similar or higher NOx conversion when compared to monometallic molecular sieves, such as Cu-exchanged molecular sieves under standard SCR conditions. Standard SCR conditions may comprise, for example, 500 ppm NH3, 500 ppm NO, 0 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and a balance of N2 at a space velocity of 90 K h−1.
In some aspects, a catalyst composition of the present invention produces about 33% less N2O and similar total NOx conversion under standard SCR conditions compared to a Cu-exchanged molecular sieve. In some aspects, a catalyst composition of the present invention produces about 20% to about 45%; about 25% to about 40%; or about 30% to about 35% less N2O under standard SCR conditions compared to a Cu-exchanged molecular sieve.
In some aspects, a catalyst composition of the present invention produces about 65% less N2O and converts about 45% more total NOx under standard SCR conditions than a Mn-exchanged molecular sieve. In some aspects, a catalyst composition of the present invention produces about 50% to about 80%; about 55% to about 75%; or about 60% to about 70% less N2O under standard SCR conditions than a Mn-exchanged molecular sieve. In some aspects, a catalyst composition of the present invention converts about 30% to about 60%; about 35% to about 55%; or about 40% to about 50% more total NOx under standard SCR conditions than a Mn-exchanged molecular sieve.
In some aspects, a catalyst composition of the present invention produces about 4% less N2O and converts about 12% more total NOx under standard SCR conditions than a physical mixture of a Cu-exchanged molecular sieve and a Mn-exchanged molecular sieve. In some aspects, a catalyst composition of the present invention produces about 1% to about 15%; about 1% to about 10%; or about 2% to about 7% less N2O under standard SCR conditions than a physical mixture of a Cu-exchanged molecular sieve and a Mn-exchanged molecular sieve. In some aspects, a catalyst composition of the present invention converts about 1% to about 25%; about 5% to about 20%; or about 10% to about 15% more total NOx under standard SCR conditions than a physical mixture of a Cu-exchanged molecular sieve and a Mn-exchanged molecular sieve.
Fast SCR
It has been found that catalyst compositions of the present invention produce significantly less N2O and similar or higher NOx conversion when compared to monometallic molecular sieves, such as Cu-exchanged molecular sieves under fast SCR conditions. Fast SCR conditions may comprise, for example, 500 ppm NH3, 250 ppm NO, 250 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and a balance of N2 at a space velocity of 90 K h−1. Unlike Cu+Mn at “standard” conditions, which gives better N2O performance but slightly less NOx conversion, the Cu+Mn gives better NOx conversion performance and better N2O performance when NO2 is present—which may be more like real-world conditions. In some aspects, a catalyst composition of the present invention produces about 42% less N2O and converts about 5% more total NOx under fast SCR conditions compared to a Cu-exchanged molecular sieve. In some aspects, a catalyst composition of the present invention produces about 25% to about 60%; about 30% to about 50%; or about 35% to about 45% less N2O under fast SCR conditions compared to a Cu-exchanged molecular sieve. In some aspects, a catalyst composition of the present invention converts about 1% to about 20%; about 1% to about 15%; or about 1% to about 10% more total NOx under fast SCR conditions compared to a Cu-exchanged molecular sieve.
Slow SCR
It has been found that catalyst compositions of the present invention produce significantly less N2O and similar or higher NOx conversion when compared to monometallic molecular sieves, such as Cu-exchanged molecular sieves under slow SCR conditions. Slow SCR conditions may comprise, for example, 500 ppm NH3, 175 ppm NO, 325 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and a balance of N2 at a space velocity of 90 K h−1. In some aspects, a catalyst composition of the present invention produces about 33% less N2O and similar total NOx conversion under slow SCR conditions compared to a Cu-exchanged molecular sieve. In some aspects, a catalyst composition of the present invention produces about 20% to about 45%; about 25% to about 40%; or about 30% to about 35% less N2O under slow SCR conditions compared to a Cu-exchanged molecular sieve.
Aging
It has been found that catalyst compositions of the present invention may be stable to harsh 900° C. aging while still retaining good NOx conversion and N2O selectivity. After hydrothermal aging at 900° C. while under standard SCR conditions, it has been found that catalyst compositions of the present invention produce significantly less N2O and similar NOx conversion when compared to monometallic molecular sieves, such as Cu-exchanged molecular sieves. In some aspects, a catalyst composition of the present invention produces about 48% less N2O and similar total NOx conversion under standard SCR conditions after 900° C. aging compared to a Cu-exchanged molecular sieve. In some aspects, a catalyst composition of the present invention produces about 35% to about 65%; about 40% to about 60%; or about 45% to about 55% less N2O under standard SCR conditions after 900° C. aging compared to a Cu-exchanged molecular sieve.
Molecular sieves were impregnated with metals using the required amount of manganese (II) acetate and/or copper (II) acetate dissolved in de-mineralized water. The metal-impregnated samples were dried overnight at 80° C. and then calcined in air at 550° C. for 4 hours. Catalysts were prepared having the following formulations:
Pelletized samples of the powder catalysts were then tested for NOx conversion and N2O production in the following conditions: 500 ppm NH3, 500 ppm NO, 0 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and a balance of N2 at a space velocity of 90 K h−1. The samples were heated from room temperature to 150° C. under the above-mentioned gas mixture except for NH3. At 150° C., NH3 was added into the gas mixture and the samples were held under these conditions for 30 min. The temperature was then increased (ramped) from 150 to 500° C. at 5° C. min−1.
Results are shown in
The catalysts were also aged at 900° C. for 5 hours in 4.5% water in air. Samples of the powdered catalyst were pelletized and then heated at a rate of 10° C. min−1 to 250° C. in air only. The samples were then heated at a rate of 10° C. min−1 in 4.5% H2O in air to 900° C. After being held at a temperature of 900° C. for 5 hours, the samples were cooled in the steam/air mixture until the temperature was <250° C. The samples were then cooled from 250° C. to room temperature in an air only flow. Pelletized samples of the aged powder catalysts were then tested for NOx conversion and N2O production in the following conditions: 500 ppm NH3, 500 ppm NO, 0 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and a balance of N2 at a space velocity of 90 K h−1.
Results are shown in
Molecular sieves were impregnated with metals using the required amount of manganese (II) acetate and/or copper (II) acetate dissolved in de-mineralized water. The metal-impregnated samples were dried overnight at 80° C. and then calcined in air at 550° C. for 4 hours. Catalysts were prepared having the following formulations:
Pelletized samples of the powder catalysts were then tested for NOx conversion and N2O production in the following conditions: 500 ppm NH3, 250 ppm NO, 250 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and a balance of N2 at a space velocity of 90 K h−1. The samples were heated from room temperature to 150° C. under the above-mentioned gas mixture except for NH3. At 150° C., NH3 was added into the gas mixture and the samples were held under these conditions for 30 min. The temperature was then increased (ramped) from 150 to 500° C. at 5° C. min−1.
Results are shown in
Molecular sieves were impregnated with metals using the required amount of manganese (II) acetate and/or copper (II) acetate dissolved in de-mineralized water. The metal-impregnated samples were dried overnight at 80° C. and then calcined in air at 550° C. for 4 hours. Catalysts were prepared having the following formulations:
Pelletized samples of the powder catalysts were then tested for NOx conversion and N2O production in the following conditions: 500 ppm NH3, 175 ppm NO, 325 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and a balance of N2 at a space velocity of 90 K h−1. The samples were heated from room temperature to 150° C. under the above-mentioned gas mixture except for NH3. At 150° C., NH3 was added into the gas mixture and the samples were held under these conditions for 30 min. The temperature was then increased (ramped) from 150 to 500° C. at 5° C. min−1.
Results are shown in
Molecular sieves were impregnated with metals using the required amount of manganese (II) acetate and/or copper (II) acetate dissolved in de-mineralized water. The metal-impregnated samples were dried overnight at 80° C. and then calcined in air at 550° C. for 4 hours. Catalysts were prepared having the following formulations:
Pelletized samples of the powder catalysts were then tested for NOx conversion and N2O production in the following conditions: 500 ppm NH3, 500 ppm NO, 0 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and a balance of N2 at a space velocity of 90 K h−1. The samples were heated from room temperature to 150° C. under the above-mentioned gas mixture except for NH3. At 150° C., NH3 was added into the gas mixture and the samples were held under these conditions for 30 min. The temperature was then increased (ramped) from 150 to 500° C. at 5° C. min−1.
Results are shown in
Molecular sieves were impregnated with metals using the required amount of manganese (II) acetate and/or copper (II) acetate dissolved in de-mineralized water. The metal-impregnated samples were dried overnight at 80° C. and then calcined in air at 550° C. for 4 hours. Catalysts were prepared having the following formulations:
Pelletized samples of the powder catalysts were then tested for NOx conversion and N2O production in the following conditions: 500 ppm NH3, 500 ppm NO, 0 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and a balance of N2 at a space velocity of 90 K h−1. The samples were heated from room temperature to 150° C. under the above-mentioned gas mixture except for NH3. At 150° C., NH3 was added into the gas mixture and the samples were held under these conditions for 30 min. The temperature was then increased (ramped) from 150 to 500° C. at 5° C. min−1.
Results are shown in
Pelletized samples of the powder catalysts were then tested for NOx conversion and N2O production in the following conditions: 500 ppm NH3, 175 ppm NO, 325 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and a balance of N2 at a space velocity of 90 K h−1. The samples were heated from room temperature to 150° C. under the above-mentioned gas mixture except for NH3. At 150° C., NH3 was added into the gas mixture and the samples were held under these conditions for 30 min. The temperature was then increased (ramped) from 150 to 500° C. at 5° C. min−1.
Results are shown in
Molecular sieves were impregnated with metals using the required amount of manganese (II) acetate and/or copper (II) acetate dissolved in de-mineralized water. The metal-impregnated samples were dried overnight at 80° C. and then calcined in air at 550° C. for 4 hours. Catalysts were prepared having the following formulations:
Pelletized samples of the powder catalysts were then tested for NOx conversion and N2O production in the following conditions: 500 ppm NH3, 500 ppm NO, 0 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and a balance of N2 at a space velocity of 90 K h−1. The samples were heated from room temperature to 150° C. under the above-mentioned gas mixture except for NH3. At 150° C., NH3 was added into the gas mixture and the samples were held under these conditions for 30 min. The temperature was then increased (ramped) from 150 to 500° C. at 5° C. min−1.
Results are shown in
Molecular sieves were impregnated with metals using the required amount of manganese (II) acetate and/or copper (II) acetate dissolved in de-mineralized water. The metal-impregnated samples were dried overnight at 80° C. and then calcined in air at 550° C. for 4 hours. Catalysts were prepared having the following formulations:
Standard SCR: Pelletized samples of the powder catalysts were then tested for NOx conversion and N2O production in the following conditions: 500 ppm NH3, 500 ppm NO, 0 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and a balance of N2 at a space velocity of 90 K h−1. The samples were heated from room temperature to 150° C. under the above-mentioned gas mixture except for NH3. At 150° C., NH3 was added into the gas mixture and the samples were held under these conditions for 30 min. The temperature was then increased (ramped) from 150 to 500° C. at 5° C. min−1. Results are shown in
Fast SCR: Pelletized samples of the powder catalysts were then tested for NOx conversion and N2O production in the following conditions: 500 ppm NH3, 250 ppm NO, 250 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and a balance of N2 at a space velocity of 90 K h−1. The samples were heated from room temperature to 150° C. under the above-mentioned gas mixture except for NH3. At 150° C., NH3 was added into the gas mixture and the samples were held under these conditions for 30 min. The temperature was then increased (ramped) from 150 to 500° C. at 5° C. min−1. Results are shown in
Slow SCR: Pelletized samples of the powder catalysts were then tested for NOx conversion and N2O production in the following conditions: 500 ppm NH3, 175 ppm NO, 325 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and a balance of N2 at a space velocity of 90 K h−1. The samples were heated from room temperature to 150° C. under the above-mentioned gas mixture except for NH3. At 150° C., NH3 was added into the gas mixture and the samples were held under these conditions for 30 min. The temperature was then increased (ramped) from 150 to 500° C. at 5° C. min−1. Results are shown in
Molecular sieves were impregnated with metals using the required amount of manganese (II) acetate and/or copper (II) acetate dissolved in de-mineralized water. The metal-impregnated samples were dried overnight at 80° C. and then calcined in air at 550° C. for 4 hours. Catalysts were prepared having the following formulations:
The catalysts were then tested for NOx conversion and N2O selectivity in the following conditions: 500 ppm NH3, 500 ppm NO, 0 ppm NO2, SV=90 K h−1. Results are shown in
Molecular sieves were impregnated with metals using the required amount of manganese (II) acetate and/or copper (II) acetate dissolved in de-mineralized water. The metal-impregnated samples were dried overnight at 80° C. and then calcined in air at 550° C. for 4 hours. Catalysts were prepared having the following formulations:
Molecular sieves were impregnated with metals using the required amount of manganese (II) acetate and/or copper (II) acetate dissolved in de-mineralized water. The metal-impregnated samples were dried overnight at 80° C. and then calcined in air at 550° C. for 4 hours. Catalysts were prepared having the following formulations:
The Cu.zeolite and Mn—Cu.zeolite catalysts were prepared by known prior art ion-exchange techniques involving copper acetate and manganese acetate solutions. A washcoat was prepared by combining the exchanged Cu.zeolite or Mn—Cu.zeolite solution with an alumina binder and a hydroxyethyl cellulose rheology modifier. The washcoat was applied to a ceramic substrate, then the washcoat was pulled down the substrate using a vacuum. The article was dried and calcined at about 500° C. for about 1 hour.
Standard SCR: Coated monoliths were then tested for NOx conversion and N2O production in the following conditions: 550 ppm NH3, 500 ppm NO, 0 ppm NO2, 10% O2, 6.0% H2O, 6.0% CO2, and a balance of N2 at a space velocity of 60 K h−1. The samples were heated from room temperature to 150° C. under the above-mentioned gas mixture except for NH3. At 150° C., NH3 was added into the gas mixture and the samples were held under these conditions until both NOx and NH3 concentrations in the outlet gas reached steady state values. The NOx and NH3 streams were then turned off and the temperature was then ramped up to 450° C. and held for 10 min before being cooled to 200° C. At 200° C. the NOx and NH3 streams were turned on and conditions were held until both NOx and NH3 concentrations in the outlet gas reached steady state values. The entire process was then repeated for additional temperatures of 250, 350, 450, and 550° C.
Results are shown in Table 1. Under standard SCR conditions, it has been found that Cu—Mn.AEI and a 3 wt % Cu-exchanged molecular sieve both achieved similar total NOx conversions at 82% and 85%, respectively. However, the Cu—Mn.AEI exhibited an average N2O production of 1.1 ppm while a 3 wt % Cu-exchanged molecular sieve exhibited an average N2O production of 3.1 ppm. Thus, a catalyst of the present invention resulted in a significant reduction in N2O relative to a typical Cu-exchanged molecular sieve. Additionally, 1.5 wt % Cu-exchanged AEI exhibited a similar average N2O production value of 1.2 ppm, but could only achieve a total NOx conversion of 78%. Thus, a fully formulated monolith coated with Cu—Mn catalyst of the present invention exhibited significant advantages over monoliths containing only monometallic catalysts under standard SCR conditions.
The coated monoliths were also aged at 750° C. for 80 hours in 10% water in air. The samples were heated at a rate of 10° C. min−1 to 250° C. in air only. The monoliths were then heated at a rate of 10° C. min−1 in 10% H2O in air to 750° C. After being held at a temperature of 750° C. for 80 hours, the samples were cooled in the steam/air mixture until then temperature was <250° C. The samples were then cooled from 250° C. to room temperature in an air only flow. The aged monoliths were then tested for NOx conversion and N2O selectivity in the following conditions: 550 ppm NH3, 500 ppm NO, 0 ppm NO2, 10% O2, 6.0% H2O, 6.0% CO2, and a balance of N2 at a space velocity of 60 K h−1.
Results are shown in Table 1. After hydrothermal aging under standard SCR conditions, it has been found that Cu—Mn.AEI could achieve a total NOx conversion of 69% and maintained a low average N2O production of 2.6 ppm. A 3 wt % Cu-exchanged molecular sieve exhibited a total NOx conversion of 75%, however, it produced a large amount of N2O at an average value of 7.8 ppm. Additionally, 1.5 wt % Cu-exchanged AEI also exhibited a higher average N2O production at 3.4 ppm and could only achieve a total NOx conversion of 50%. Thus, a catalyst of the present invention resulted in a significant reduction in N2O relative to a typical Cu-exchanged molecular sieve.
Fast SCR: Coated monoliths were then tested for NOx conversion and N2O production in the following conditions: 550 ppm NH3, 250 ppm NO, 250 ppm NO2, 10% O2, 6.0% H2O, 6.0% CO2, and a balance of N2 at a space velocity of 60 K h−1. The samples were heated from room temperature to 150° C. under the above-mentioned gas mixture except for NH3. At 150° C., NH3 was added into the gas mixture and the samples were held under these conditions until both NOx and NH3 concentrations in the outlet gas reached steady state values. The NOx and NH3 streams were then turned off and the temperature was then ramped up to 450° C. and held for 10 min before being cooled to 200° C. At 200° C. the NOx and NH3 streams were turned on and conditions were held until both NOx and NH3 concentrations in the outlet gas reached steady state values. The entire process was then repeated for additional temperatures of 250, 350, 450, and 550° C.
Results are shown in Table 1. Under fast SCR conditions, it has been found that Cu—Mn.AEI could achieve a very high total NOx conversion of 88% and an average N2O production of 4.0 ppm. However, a 3 wt % Cu-exchanged molecular sieve and a 1.5 wt % Cu-exchanged molecular sieve could only achieve total NOx conversions of 83% and 86%, respectively, and average N2O productions of 8.9 ppm and 4.5 ppm, respectively. Thus, a fully formulated monolith coated with Cu—Mn catalyst of the present invention exhibited significant advantages over monoliths containing only monometallic catalysts under fast SCR conditions.
Slow SCR: Coated monoliths were then tested for NOx conversion and N2O production in the following conditions: 550 ppm NH3, 174 ppm NO, 325 ppm NO2, 10% O2, 6.0% H2O, 6.0% CO2, and a balance of N2 at a space velocity of 60 K h−1. The samples were heated from room temperature to 150° C. under the above-mentioned gas mixture except for NH3. At 150° C., NH3 was added into the gas mixture and the samples were held under these conditions until both NOx and NH3 concentrations in the outlet gas reached steady state values. The NOx and NH3 streams were then turned off and the temperature was then ramped up to 450° C. and held for 10 min before being cooled to 200° C. At 200° C. the NOx and NH3 streams were turned on and conditions were held until both NOx and NH3 concentrations in the outlet gas reached steady state values. The entire process was then repeated for additional temperatures of 250, 350, 450, and 550° C.
Results are shown in Table 1. Under slow conditions, it has been found that Cu—Mn.AEI could achieve a very high total NOx conversion of 81% and an average N2O production of 7.4 ppm. However, a 3 wt % Cu-exchanged molecular sieve and a 1.5 wt % Cu-exchanged molecular sieve could only achieve total NOx conversions of 75% and 72%, respectively, and average N2O productions of 12.2 ppm and 7.5 ppm, respectively. Thus, a fully formulated monolith coated with Cu—Mn catalyst of the present invention exhibited significant advantages over monoliths containing only monometallic catalysts under slow SCR conditions.
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| Number | Date | Country | |
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