BIMETALLIC Cu / Mn CATALYSTS FOR SELECTIVE CATALYTIC REDUCTION

Abstract

To provide a catalyst composition for treating an exhaust gas, a catalyst article, and a method for treating an exhaust gas.SOLUTION: The present invention provides a catalyst composition for treating an exhaust gas, the catalyst composition comprising a molecular sieve, the molecular sieve comprising exchanged copper and exchanged manganese.SELECTED DRAWING: Figure 1

Description

[Background technology]

[0001] The present invention relates to a catalyst and method for converting nitrogen oxides in a gas, such as the exhaust gas of a lean-burn internal combustion engine for a vehicle, to nitrogen by contacting the nitrogen oxides with a nitrogenous reducing agent in the presence of a transition metal-containing molecular sieve catalyst.

[0002] NO from nitrogen compounds such as ammonia or urea x Selective catalytic reduction (SCR) of NO has been used in many applications, including stationary applications in industry. More recently, NO reductions based on SCR technology have been x Reduction systems have been developed in Europe, Japan, and the United States for many vehicle applications, for example to treat diesel exhaust gases.

[0003] Several chemical reactions occur in the NH3SCR system, most of which are x Specifically, the desired reactions for reducing NO and NO2 to nitrogen are shown. The dominant reaction is represented by reaction (1). 4NO+4NH3+O2→4N2+6H2O (1)

[0004] Competing, non-selective reactions with oxygen can produce secondary emissions or waste ammonia. One such non-selective reaction is the complete oxidation of ammonia, shown in reaction (2). 4NH3+5O2→4NO+6H2O (2)

[0005] Side reactions can also lead to undesirable products such as NO, as shown by reaction (3). 4NH3+5NO+3O2→4N2O+6H2O (3)

[0006] Molecular sieves containing aluminosilicate zeolites are xOne application is the reduction of NO from diesel engines for vehicles by injecting ammonia itself or by using a reductant that can be derived from ammonia precursors such as urea. x The primary objective of the present invention is to control emissions. Transition metals can be incorporated into the aluminosilicate zeolites to promote catalytic activity.

[0007] NO x Improved conversion and reduced N2O production, NO x It is desirable to prepare a catalyst composition for SCR of Summary of the Invention

[0008] According to some aspects of the present invention, a catalytic 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 embodiments, the molecular sieve comprises a zeolite. Suitable zeolites can 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 embodiments, the molecular sieve comprises a small pore zeolite. Suitable small pore zeolites can have a crystalline framework type selected from, for example, AEI, CHA, and combinations thereof. In some aspects, the molecular sieve comprises a medium pore zeolite or a large pore zeolite. Suitable medium pore zeolites or a large pore zeolites can have a crystalline framework type selected from, for example, BEA, MFI, and combinations thereof.

[0009] In some embodiments, the molecular sieve has a copper to manganese weight ratio of about 0.1 to about 50, about 0.2 to about 15, or about 0.3 to about 3. In some embodiments, the 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 embodiments, the 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 embodiments, the 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 embodiments, the molecular sieve has a transition metal to aluminum ratio of less than 1, less than 0.75, or less than 0.5.

[0010] In some embodiments, the catalyst composition comprises a mixture of NH3 and NO x The catalyst composition is effective in promoting the reaction of nitrous oxide with nitrous oxide to produce nitrogen and water. In certain embodiments, the catalyst composition produces about 20% to about 45% less NO under standard SCR conditions compared to Cu-exchanged molecular sieves. In some embodiments, the catalyst composition produces about 30% to about 60% more total NO than Mn-exchanged molecular sieves under standard SCR conditions. x In some embodiments, the catalyst composition produces about 1% to about 15% less NO under standard SCR conditions than a physical mixture of Cu-exchanged and Mn-exchanged molecular sieves. In some embodiments, the catalyst composition produces about 1% to about 25% more total NO under standard SCR conditions than a physical mixture of Cu-exchanged and Mn-exchanged molecular sieves. x In some embodiments, the catalyst composition produces about 25% to about 60% less NO under fast SCR conditions compared to Cu-exchanged molecular sieves. In some embodiments, the catalyst composition produces about 1% to about 20% more total NO under fast SCR conditions compared to Cu-exchanged molecular sieves. xIn some embodiments, the catalyst composition produces about 20% to about 45% less NO under slow SCR conditions compared to Cu-exchanged molecular sieves. In some embodiments, the catalyst composition produces about 35% to about 65% less NO under standard SCR conditions after aging at 900° C. compared to Cu-exchanged molecular sieves.

[0011] According to some embodiments of the present invention, the catalytic article comprises a substrate coated with a catalytic composition comprising a molecular sieve, the molecular sieve comprising exchanged copper and exchanged manganese. In some embodiments, the substrate may further comprise one or more additional catalysts, such as one or more Cu or Fe exchanged molecular sieve catalysts. In some embodiments, the molecular sieve comprising exchanged copper and exchanged manganese is upstream of the one or more additional catalytic compositions. In some embodiments, the molecular sieve comprising exchanged copper and exchanged manganese is in an upper layer and the one or more additional catalytic compositions is in a lower layer. In some embodiments, the catalytic article further comprises a catalytic composition comprising a platinum group metal.

[0012] According to some embodiments of the present invention, a method for treating an exhaust gas containing nitrogen oxides includes contacting the exhaust gas with a nitrogenous reductant in the presence of a catalyst composition, the catalyst composition including a molecular sieve, the molecular sieve including exchanged copper and exchanged manganese. In some embodiments, the nitrogenous reductant includes ammonia. In some embodiments, the contacting occurs at a temperature of about 150° C. to about 750° C. [Brief description of the drawings]

[0013] [Figure 1] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Diagram 2] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Diagram 3]Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 4] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Diagram 5] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 6] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 7] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 8] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 9] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 10] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 11] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 12] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 13] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 14] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 15] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 16] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 17] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 18] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 19] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 20] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 21] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 22] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 23] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 24] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Diagram 25] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 26] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 27] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 28] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 29] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Diagram 30] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Diagram 31] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Diagram 32] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Diagram 33] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Diagram 34] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Diagram 35] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Diagram 36] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 37] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 38] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Figure 39] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Diagram 40] Catalyst configurations of the catalysts and systems of the present invention are shown, which are described in more detail in the detailed description of the invention. [Diagram 41]1 shows NOx conversion under standard SCR conditions for unaged catalysts containing Cu-Mn.AEI and Cu.AEI. [Diagram 42] 1 shows the N2O selectivity of unaged catalysts containing Cu-Mn.AEI and Cu.AEI under standard SCR conditions. [Diagram 43] 1 shows NOx conversion under standard SCR conditions for aged catalysts containing Cu-Mn.AEI and Cu.AEI. [Diagram 44] 1 shows the N2O selectivity of aged catalysts containing Cu-Mn.AEI and Cu.AEI under standard SCR conditions. [Diagram 45] 1 shows NOx conversion under fast SCR conditions for catalysts containing Cu-Mn.AEI and Cu.AEI. [Figure 46] 1 shows N2O ppm under fast SCR conditions for catalysts containing Cu-Mn.AEI and Cu.AEI. [Figure 47] 1 shows NOx conversion under low speed SCR conditions for catalysts containing Cu-Mn.AEI and Cu.AEI. [Figure 48] 1 shows N2O ppm under slow SCR conditions for catalysts containing Cu-Mn.AEI and Cu.AEI. [Figure 49] 1 shows NOx conversion under standard SCR conditions for various bimetallic and monometallic catalysts. [Figure 50] Figure 1 shows the N2O selectivity of various bimetallic and monometallic catalysts under standard SCR conditions. [Figure 51] 4 shows the NOx conversion rate under standard SCR conditions for catalysts with varying Mn loading. [Figure 52] Figure 2 shows the N2O selectivity of catalysts with varying Mn loading under standard SCR conditions. [Figure 53] The NOx conversion rate of catalysts with different Mn loadings under low speed SCR conditions is shown. [Figure 54] Figure 2 shows N2O ppm under slow SCR conditions for catalysts with different Mn loadings. [Figure 55] The NOx conversion rate of catalysts with different Cu loadings under standard SCR conditions is shown. [Figure 56] N2O selectivity of catalysts with varying Cu loading under standard SCR conditions. [Figure 57] 1 shows NOx conversion under standard SCR conditions for different small pore zeolite catalysts. [Figure 58] Figure 1 shows the N2O selectivity of different small pore zeolite catalysts under standard SCR conditions. [Figure 59] Figure 2 shows NOx conversion under fast SCR conditions for different small pore zeolite catalysts. [Figure 60] 4 shows N2O ppm under fast SCR conditions for different small pore zeolite catalysts. [Figure 61] 4 shows NOx conversion under low speed SCR conditions for different small pore zeolite catalysts. [Figure 62] 4 shows N2O ppm under slow SCR conditions for different small pore zeolite catalysts. [Figure 63] Figure 2 shows NOx conversion under standard SCR conditions for different medium and large pore zeolite catalysts. [Figure 64] Figure 2 shows N2O ppm under standard SCR conditions for different medium / large pore zeolite catalysts. [Figure 65] The NOx conversion rates of catalysts with different SAR values ​​under standard SCR conditions are shown. [Figure 66] Figure 1 shows the N2O selectivity under standard SCR conditions for catalysts with different SAR values. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The compositions, methods, and systems of the present invention relate to catalysts for treating exhaust gases. The catalyst composition of the present invention includes a molecular sieve, the molecular sieve including exchanged copper and exchanged manganese. As described herein, the catalyst composition of the present invention is capable of converting NH3 and NO xIt has been found that the catalytic compositions promote the reaction of nitrous oxide with nitrous oxide to produce nitrogen and water, i.e., selective catalytic reduction (SCR) with reduced NO production. Such catalytic compositions may be useful, for example, for treating exhaust gases from internal combustion engines, including diesel engines.

[0015] catalyst composition The catalyst composition of the present invention comprises a molecular sieve having exchanged copper and exchanged manganese. In some embodiments, the molecular sieve does not contain or is essentially free of any additional transition metal. For example, in some embodiments, the molecular sieve contains an additional (i.e., in addition to exchanged copper and exchanged manganese) transition metal in an amount of 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 embodiments, the molecular sieve can be described as bimetallic because it contains two transition metals.

[0016] Molecular Sieves The catalyst composition of the present invention comprises a molecular sieve. In some embodiments, 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 embodiments, the molecular sieve comprises or consists essentially of a molecular sieve having an aluminosilicate framework (e.g., zeolite). In some embodiments, the preferred zeolite is a synthetic zeolite.

[0017] When the molecular sieve has an aluminosilicate framework (e.g., the molecular sieve is a zeolite), typically the molecular sieve has a silica to alumina molar ratio (SAR) of 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, less than 30, less than 20, less than 15, or less than 13. In some embodiments, suitable molecular sieves have a SAR greater than 200, greater than 600, or greater than 1200. In some embodiments, the molecular sieve has a SAR of about 1500 to about 2100.

[0018] Typically, the molecular sieve is microporous. A microporous molecular sieve has pores with a diameter of less than 2 nm (see, for example, the IUPAC definition of "microporous" [Pure & Appl. Chem., 66(8), (1994), 1739-1758]).

[0019] The molecular sieve may be a small pore molecular sieve (e.g., a molecular sieve having a maximum ring size of 8 tetrahedral atoms), a medium pore molecular sieve (e.g., a molecular sieve having a maximum ring size of 10 tetrahedral atoms) or a large pore molecular sieve (e.g., a molecular sieve having a maximum ring size of 12 tetrahedral atoms), or a combination of two or more thereof.

[0020] In some embodiments, the molecular sieve may be mesoporous. Mesoporous molecular sieves have pores with diameters between 2 and 50 nm (e.g., according to the IUPAC definition of "microporous").

[0021] When the molecular sieve is a small pore molecular sieve, the small pore molecular sieve can 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 mixtures and / or combinations of two or more thereof and / or intergrowth. In some embodiments, the small pore molecular sieve has a framework structure represented by an FTC selected from the group consisting of CHA, LEV, AEI, AFX, ERI, LTA, SFW, KFI, DDR and ITE. In some embodiments, the small pore molecular sieve has a framework structure represented by an FTC selected from the group consisting of CHA, AEI and AFX. In some embodiments, the small pore molecular sieve has a framework structure represented by an FTC selected from the group consisting of CHA and AEI. The small pore molecular sieve can have a framework structure represented by the CHA of the FTC. The small pore molecular sieve can have a framework structure represented by the AEI of the FTC.

[0022] When the molecular sieve is a medium pore molecular sieve, the medium pore molecular sieve can 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 mixtures of two or more thereof and / or intergrowth. In some embodiments, the medium pore molecular sieve has a framework structure represented by an FTC selected from the group consisting of FER, MEL, MFI, and STT. In some embodiments, the medium pore molecular sieve has a framework structure represented by an FTC selected from the group consisting of FER and MFI, and in particular MFI. When the medium pore molecular sieve is a zeolite and has a framework represented by the FER or MFI of the FTC, the zeolite may be ferrierite, silicalite, or ZSM-5.

[0023] When the molecular sieve is a large pore molecular sieve, 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 mixtures of two or more thereof and / or intergrowth. In some embodiments, the large pore molecular sieve has a framework structure represented by an FTC selected from the group consisting of AFI, BEA, MAZ, MOR, and OFF. In some embodiments, the large pore molecular sieve has a framework structure represented by an 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, the zeolite may be beta zeolite, faujasite, zeolite Y, zeolite X, or mordenite.

[0024] In some embodiments, suitable molecular sieves include a combination of small and large pore frameworks, hi some embodiments, suitable molecular sieves include ZSM-34(ERI+OFF).

[0025] transition metals In some embodiments, the catalyst composition comprises a molecular sieve with copper, manganese, and optionally one or more other metals, such as a fourth row transition metal and / or a noble metal, exchanged. In general, suitable other metals may be selected from the group consisting of cobalt, iron, nickel, vanadium, palladium, platinum, ruthenium, and rhenium. In some embodiments, the two or more exchanged transition metals comprise copper and manganese. In some embodiments, the exchanged transition metal consists essentially of copper and manganese. In some embodiments, the exchanged transition metal consists of copper and manganese. In some embodiments, the other metals do not comprise iron. In some embodiments, the other metals do not comprise vanadium. In some embodiments, the other metals do not comprise ruthenium. In some embodiments, the other metals do not comprise nickel.

[0026] The transition metal may be present at extraframework sites on the exterior surface of the molecular sieve or may be present within the channels, cavities, or cages of the molecular sieve.

[0027] In some embodiments, the transition metal exchanged molecular sieve comprises a transition metal in an amount from about 0.10 to about 10 weight percent of the transition metal exchanged molecular sieve, or from about 0.2 to about 5 weight percent of the transition metal exchanged molecular sieve.

[0028] Amount of Cu / Mn In some embodiments, the transition metal exchanged molecular sieve of the present invention contains exchanged copper and exchanged manganese in a total amount of about 0.10 to about 10 weight percent of the transition metal exchanged molecular sieve, about 0.1 to about 7 weight percent of the transition metal exchanged molecular sieve, about 0.2 to about 7 weight percent of the transition metal exchanged molecular sieve, about 0.2 to about 5 weight percent of the transition metal exchanged molecular sieve, about 0.5 to about 6 weight percent of the transition metal exchanged molecular sieve, about 1 to about 7 weight percent of the transition metal exchanged molecular sieve, about 1 to about 5 weight percent of the transition metal exchanged molecular sieve, about 2 to about 5 weight percent of the transition metal exchanged molecular sieve, about 1.5 to about 3 weight percent of the transition metal exchanged molecular sieve, about 1.5 to about 4 weight percent of the transition metal exchanged molecular sieve, or about 2 to about 4 weight percent of the transition metal exchanged molecular sieve.

[0029] In some embodiments, the transition metal exchanged molecular sieve of the present invention contains copper by exchange in an amount of about 0.05 to about 7 weight percent of the transition metal exchanged molecular sieve, about 0.5 to about 5 weight percent of the transition metal exchanged molecular sieve, about 0.05 to about 5 weight percent of the transition metal exchanged molecular sieve, about 0.1 to about 4 weight percent of the transition metal exchanged molecular sieve, about 0.1 to about 3 weight percent of the transition metal exchanged molecular sieve, about 0.2 to about 3 weight percent of the transition metal exchanged molecular sieve, about 0.5 to about 2.5 weight percent of the transition metal exchanged molecular sieve, about 1 to about 4 weight percent of the transition metal exchanged molecular sieve, or about 1 to about 2 weight percent of the transition metal exchanged molecular sieve.

[0030] In some embodiments, the transition metal exchanged molecular sieve of the present invention contains exchanged manganese in an amount of about 0.05 to about 7 weight percent of the transition metal exchanged molecular sieve, about 0.05 to about 5 weight percent of the transition metal exchanged molecular sieve, about 0.1 to about 5 weight percent of the transition metal exchanged molecular sieve, about 0.1 to about 4 weight percent of the transition metal exchanged molecular sieve, about 0.1 to about 3 weight percent of the transition metal exchanged molecular sieve, about 0.2 to about 3 weight percent of the transition metal exchanged molecular sieve, about 0.5 to about 2.5 weight percent of the transition metal exchanged molecular sieve, or about 1 to about 2 weight percent of the transition metal exchanged molecular sieve.

[0031] Cu / Mn ratio In some embodiments, the transition metal exchanged molecular sieves of the present invention comprise exchanged copper and exchanged manganese in a weight ratio of about 1:1. In some embodiments, the transition metal exchanged molecular sieves of the present invention comprise 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 embodiments, in addition to utilizing the above copper to manganese ratios, the exchange capacity of the molecular sieve should be less than 1, less than 0.75, or less than 0.5 in terms of the ratio of metal ions to exchange sites. In some embodiments, the transition metal exchanged molecular sieves have a transition metal to aluminum ratio of less than 1, less than 0.75, or less than 0.5.

[0032] The catalysts of the present invention can be prepared by any suitable means known in the art, including, for example, one-pot, pre-fixing, and spray drying.

[0033] Base material The catalytic article of the present invention may include a substrate and a catalytic composition. The substrate may be a flow-through substrate or a filter substrate. The substrate may include the catalytic composition (i.e., the catalytic article is obtained by extrusion), or the catalytic composition may be disposed or supported on the substrate (i.e., the catalytic composition is applied onto the substrate by a washcoating method). The catalytic composition may fully or partially coat the substrate, as desired. In some embodiments, the catalytic article includes a Cu / Mn bimetallic molecular sieve extruded article coated with one or more additional catalysts. In some embodiments, the extruded catalyst is coated with one or more additional SCR catalysts, which may include, for example, a Cu / Mn bimetallic molecular sieve.

[0034] In some embodiments, the catalyst article comprises a catalyst composition in an amount of from 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 / in 3may be contained in a total concentration of

[0035] When a catalyst article has a filter substrate, the catalyst article is a selective catalytic reduction filter catalyst. A selective catalytic reduction filter includes a filter substrate and a catalyst composition. Throughout this application, references to the use of an SCR catalyst are understood to also include the use of a selective catalytic reduction filter catalyst, where applicable.

[0036] The flow-through or filter substrate is a substrate that can contain catalyst / sorbent components. The substrate is preferably a ceramic substrate or a metal substrate. The ceramic substrate may comprise any suitable refractory material, such as alumina, silica, titania, ceria, zirconia, magnesia, zeolite, silicon nitride, silicon carbide, zirconium silicate, magnesium silicate, aluminosilicate, metalloaluminosilicate (such as cordierite and spodumene), or any two or more mixtures or mixed oxides thereof. Cordierite, magnesium aluminosilicate, and silicon carbide are particularly preferred.

[0037] The metal substrate may be made of any suitable metal, particularly heat-resistant metals and metal alloys such as titanium and stainless steel, and ferritic alloys containing iron, nickel, chromium, and / or aluminum in addition to other trace metals.

[0038] The flow-through substrate is preferably a flow-through monolith having a honeycomb structure with many small parallel thin-walled channels that are axially continuous through the substrate and extend entirely from the inlet or 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 elliptical. The flow-through substrate may also be highly porous, allowing the catalyst to penetrate the substrate wall.

[0039] The filter substrate is preferably a wall-flow monolith filter. The channels of the wall-flow filter are alternately blocked. This allows the exhaust gas flow to enter the channel through an inlet, then flow through the channel walls and exit the filter through a different channel that leads to an outlet. Thus, small particles in the exhaust gas flow are trapped within the filter.

[0040] The catalyst composition may be applied to the flow-through or filter substrate by any known means, such as a washcoat procedure.

[0041] When the catalyst article is a selective catalytic reduction filter, the filter substrate may preferably be a wall-flow filter substrate monolith. Wall-flow filter substrate monoliths (e.g., SCR-DPFs) typically have a cell density of 60 to 400 cells per square inch (cpsi). Wall-flow filter substrate monoliths preferably have a cell density of 100 to 350 cpsi, more preferably 200 to 300 cpsi.

[0042] The wall-flow filter substrate monolith can have a wall thickness (eg, average internal wall thickness) of 0.20 to 0.50 mm, preferably 0.25 to 0.35 mm (eg, about 0.30 mm).

[0043] Generally, uncoated wall-flow filter substrate monoliths have a porosity of 50-80%, preferably 55-75%, more preferably 60-70%.

[0044] Uncoated wall-flow filter substrate monoliths typically have an average pore size of at least 5 μm, preferably from 10 to 40 μm, for example from 15 to 35 μm, more preferably from 20 to 30 μm.

[0045] The wall-flow filter substrate may have a symmetric or asymmetric cell design.

[0046] In the case of selective catalytic reduction filters, the catalyst composition is generally disposed within the walls of the monolith of the wall-flow filter substrate. In addition, the catalyst composition may be disposed on the walls of the inlet channels and / or on the walls of the outlet channels.

[0047] The catalyst composition of the present invention may be coated onto a suitable monolith substrate. Washcoat compositions containing the catalyst composition of the present invention for coating onto monolith substrates or for producing extruded substrate monoliths may include a binder selected from the group consisting of alumina, silica, (non-zeolitic) silica-alumina, natural clay, TiO2, ZrO2, and SnO2. Generally, catalyst articles containing the catalyst composition at a desired loading level can be prepared by washcoating, extrusion, or other methods known in the art.

[0048] Methods and systems The method of the present invention involves treating an exhaust gas containing nitrogen oxides by contacting it with a reducing agent, such as a nitrogenous reducing agent or a hydrocarbon reducing agent, in the presence of the catalyst composition described herein, whereby the catalyst composition of the present invention can function as a selective catalytic reduction catalyst.

[0049] In some embodiments, the nitrogen oxides are reduced by the reducing agent at a temperature of at least 100° C. In some embodiments, the catalysts described herein are effective at reducing the nitrogen oxides by the reducing agent over a wide temperature range (e.g., about 150° C. to 750° C.), in addition to being hydrothermally stable at temperatures above 900° C. Hydrothermal stability may be particularly useful in treating exhaust gases from heavy and light duty diesel engines, particularly engines that include an exhaust system that includes an (optionally catalyzed) diesel particulate filter, where the filter is actively regenerated, for example, by injecting hydrocarbons into the exhaust system upstream of the filter, and the zeolite catalyst for use in the present invention is located downstream of the filter.

[0050] In certain embodiments, the catalysts described herein are effective for reducing nitrogen oxides with a reducing agent at a temperature range of 175-550° C. In other embodiments, the temperature range is 175-400° C. In some embodiments, the temperature range is 275-500° C., or 250-550° C. If NO is present in the gas stream, the temperature range may be broader, such as 150-650° C., 175-625° C., 200-600° C., or 225-575° C.

[0051] In some embodiments, the reduction of nitrogen oxides is carried out in the presence of oxygen. In some embodiments, the reduction of nitrogen oxides is carried out in the absence of oxygen.

[0052] The nitrogenous reductant may be ammonia itself, or the source of the nitrogenous reductant may be hydrazine or any suitable ammonia precursor, such as urea ((NH2)2CO), ammonium carbonate, ammonium carbamate, ammonium bicarbonate, or ammonium formate. The reductant may be injected into the exhaust gas stream from an external source, such as a reservoir or tank, or may be provided in situ by a nitrogen storage catalyst or a NOx adsorber catalyst, or a combination of both. The reductant must be introduced into the exhaust gas upstream of the SCR catalyst.

[0053] The method can be performed on gases originating from combustion processes, such as internal combustion engines (either mobile or stationary), gas turbines, and coal or oil fired power plants. The method can also be used to treat gases from industrial processes such as smelting heaters and boilers, furnaces, chemical processing industries, coke ovens, municipal waste plants, and incinerators, coffee roasting plants, etc.

[0054] In certain embodiments, the method is used to treat exhaust gas from a lean-burn internal combustion engine of a vehicle, such as a diesel engine, a lean-burn gasoline engine, or an engine powered by liquid petroleum gas or natural gas.

[0055] In some aspects, the present invention provides an exhaust system for a lean-burn internal combustion engine for a vehicle, the exhaust system including a conduit for carrying flowing exhaust gas, a source of nitrogenous reductant, a catalyst composition including exchanged copper and exchanged manganese disposed in the exhaust gas flow path, and means for metering the nitrogenous reductant into the flowing exhaust gas upstream of the catalyst composition.

[0056] The system may include means for controlling the metering means in use, whereby the catalyst composition provides catalytic NO production at or above a desired efficiency, for example at temperatures above 100°C, above 150°C, or above 175°C. x Only when reduction is determined to be possible is nitrogenous reductant metered into the flowing exhaust gas. The control means' determination may be assisted by one or more suitable sensor inputs indicative of engine conditions selected from the group consisting of exhaust gas temperature, catalyst bed temperature, promoter position, exhaust gas mass flow rate in the system, manifold vacuum, ignition timing, engine speed, exhaust gas lambda value, the amount of fuel injected into the engine, exhaust gas recirculation (EGR) valve position, and thus the magnitude of EGR and boost pressures.

[0057] In some embodiments, metering is controlled in response to the amount of nitrogen oxides in the exhaust gas, which is measured either directly (using a suitable sensor) or indirectly. Indirect determinations can be made, for example, based on predicted NOx in the exhaust gas. x A pre-correlated look-up table or map stored in the control means is used that correlates any one or more of the above mentioned inputs with their content to indicate engine condition.

[0058] The control means may comprise a pre-programmed processor such as an Electronic Control Unit (ECU).

[0059] The metering of nitrogenous reductant can be adjusted so that 60% to 200% of the theoretical ammonia is present in the exhaust gas entering the SCR catalyst, calculated at 1:1 NH3 / NO and 4:3 NH3 / NO2.

[0060] In some embodiments, an oxidation catalyst for oxidizing nitric oxide in the exhaust gas to nitrogen dioxide can be located upstream of where the nitrogenous reductant is metered into the exhaust gas. In some embodiments, the oxidation catalyst is adapted to produce a gas stream entering the SCR catalyst composition with a volume ratio of NO to NO2 of about 4:1 to about 1:3 at an exhaust gas temperature of, for example, 200°C to 450°C, or 250°C to 450°C at the oxidation catalyst inlet. 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.

[0061] The oxidation catalyst may include at least one platinum group metal (or some combination thereof), such as platinum, palladium, or rhodium, coated on a flow-through monolith substrate. In one embodiment, the at least one platinum group metal is platinum, palladium, or a combination of both platinum and palladium. The platinum group metal may be supported on a high surface area washcoat component, such as alumina, a zeolite, such as an aluminosilicate zeolite, silica, a non-zeolitic silica alumina, ceria, zirconia, titania, or a mixed or composite oxide containing both ceria and zirconia.

[0062] In some embodiments, a suitable filter substrate is located between the oxidation catalyst and the zeolite catalyst. The filter substrate may be selected from any of those described above, for example a wall-flow filter. If the filter is catalyzed, for example, with an oxidation catalyst of the type described above, then preferably the metering point for the nitrogenous reductant is located between the filter and the zeolite catalyst. Alternatively, if the filter is not catalyzed, the means for metering the nitrogenous reductant can be located between the oxidation catalyst and the filter, and this arrangement is understood to be disclosed in WO 99 / 39809.

[0063] In some embodiments, the catalyst composition for use in the present invention is coated on a filter located downstream of the oxidation catalyst. If the filter contains the catalyst composition for use in the present invention, the metering point for the nitrogenous reductant is preferably located between the oxidation catalyst and the filter.

[0064] In some embodiments, the system configuration includes x In some embodiments, the system configuration includes a first SCR followed by a second SCR. In some embodiments, the system configuration includes a selective catalytic reduction filter followed by an SCR. In some embodiments, the 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 embodiments, the SCR catalyst may include a Cu / Mn bimetallic molecular sieve.

[0065] In some aspects, a lean-burn engine for a vehicle is provided comprising an exhaust system according to the present invention.

[0066] In some aspects, the vehicle lean-burn internal combustion engine may be a diesel engine, a lean-burn gasoline engine, or an engine powered by liquid petroleum gas or natural gas.

[0067] Zoning and Configuration In some embodiments, the catalyst composition comprising a molecular sieve having exchanged copper and exchanged manganese (Cu / Mn bimetallic molecular sieve) can be combined with one or more additional catalyst compositions. Such combinations may involve zoned and / or layered configurations on one or more substrates.

[0068] In some embodiments, the Cu / Mn bimetallic molecular sieve can be combined with additional catalyst compositions formulated as an SCR catalyst and / or an oxidation catalyst, such as an ammonia oxidation catalyst. In some embodiments, the Cu / Mn bimetallic molecular sieve can be combined with one or more additional SCR catalysts. In some embodiments, the Cu / Mn bimetallic molecular sieve and the additional SCR catalyst can be located on the same substrate. In some embodiments, the Cu / Mn bimetallic molecular sieve and the additional SCR catalyst can be located on different substrates. In some embodiments, the catalyst configuration may include the Cu / Mn bimetallic molecular sieve with one or more additional SCR catalysts on the same substrate and one or more additional SCR catalysts on separate substrates.

[0069] In some embodiments, the catalyst configuration may include a Cu / Mn bimetallic molecular sieve and an additional catalyst composition, such as an SCR catalyst, located downstream. As used herein, the terms upstream and downstream are understood to indicate the location of the catalysts relative to one another in relation to the exhaust gas flow. Similarly, the inlet end and the outlet end are understood to indicate the ends of the catalyst substrate relative to the exhaust gas flow. In some embodiments, the Cu / Mn bimetallic molecular sieve is present in a first zone and the additional catalyst composition, such as an SCR catalyst, is located in a second zone, with the first zone being upstream of the second zone. In some embodiments, the first zone and the second zone are located on the same substrate. In some embodiments, the first zone and the second zone are located on separate substrates.

[0070] In some embodiments, the 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, Figure 1 shows a catalyst configuration having a Cu / Mn bimetallic molecular sieve on an upstream substrate and a Cu molecular sieve on a separate downstream substrate.

[0071] In some embodiments, the catalyst configuration may include a Cu / Mn bimetallic molecular sieve on an upstream portion of the substrate, and an additional catalyst, such as an SCR catalyst, on a downstream portion of the same substrate. In some embodiments, these catalyst compositions on the upstream and downstream portions of the substrate may overlap. For example, FIG. 2 shows a catalyst configuration having a Cu / Mn bimetallic molecular sieve on an upstream portion of the substrate, and a Cu molecular sieve on a downstream portion of the same substrate. As shown in FIG. 2, the upstream and downstream catalyst compositions overlap, with the Cu molecular sieve applied over less than 100% of the substrate's length from the downstream end of the substrate, and the Cu / Mn bimetallic molecular sieve applied over less than 100% of the substrate's length from the upstream end of the substrate.

[0072] In some embodiments, the catalyst configuration may include an additional catalyst, such as an SCR catalyst, located upstream and a Cu / Mn bimetallic molecular sieve on a separate substrate located downstream. In some embodiments, the catalyst configuration may include an additional catalyst located between the additional catalyst upstream and the Cu / Mn bimetallic molecular sieve downstream. For example, FIG. 3a shows a catalyst configuration having an Fe molecular sieve on an upstream substrate and a Cu / Mn bimetallic molecular sieve on a separate downstream substrate. FIG. 3b shows a catalyst configuration having an Fe molecular sieve on an upstream substrate and a Cu / Mn bimetallic molecular sieve on a separate downstream substrate with an additional catalyst located between the two.

[0073] In some embodiments, the catalyst configuration may include an additional catalyst, such as an SCR catalyst, on an upstream portion of the substrate, and a Cu / Mn bimetallic molecular sieve on a downstream portion of the same substrate. In some embodiments, these catalyst compositions on the upstream and downstream portions of the substrate may overlap. For example, FIG. 4 shows a catalyst configuration having an Fe molecular sieve on an upstream portion of the substrate and a Cu / Mn bimetallic molecular sieve on a downstream portion of the same substrate. As shown in FIG. 4, the upstream and downstream catalyst compositions overlap, with the Cu / Mn bimetallic molecular sieve applied from the downstream end of the substrate and covering less than 100% of the substrate's length, and the Fe molecular sieve applied from the upstream end of the substrate and covering less than 100% of the substrate's length.

[0074] In some embodiments, the catalyst configuration includes a first substrate having an additional catalyst, such as an SCR catalyst, on an upstream portion of the substrate and a Cu / Mn bimetallic molecular sieve on a downstream portion of the same substrate, followed by a second substrate having an additional catalyst, such as an SCR catalyst. In some embodiments, the catalyst compositions on the upstream and downstream portions of the first substrate may overlap. For example, FIG. 5a shows a catalyst configuration having a first substrate having an Fe molecular sieve on an upstream portion of the substrate and a Cu / Mn bimetallic molecular sieve on a downstream portion of the same substrate, followed by a separate substrate having a Cu molecular sieve downstream of the first substrate. As shown in Figure 5, the upstream and downstream catalyst compositions on the first substrate were partially overlapping, with the Cu / Mn bimetallic molecular sieve applied from the downstream end of the substrate and covering less than 100% of the substrate's length, and the Fe molecular sieve applied from the upstream end of the substrate and covering less than 100% of the substrate's length. Figure 5b shows a configuration that is the same as Figure 5a, but including an additional catalyst located between the first substrate and the downstream substrate.

[0075] In some embodiments, the catalyst configuration includes a first substrate having a Cu / Mn bimetallic molecular sieve, followed by a second substrate having one or more additional catalysts, such as an SCR catalyst. In some embodiments, the second substrate includes an upstream catalyst located on an upstream portion of the second substrate and a downstream catalyst located on a downstream portion of the second substrate. In some embodiments, the catalyst compositions located on the upstream and downstream portions of the second substrate may overlap. Figure 6a shows a catalyst configuration having a first upstream substrate having a Cu / Mn bimetallic substrate, followed by a second substrate having an Fe molecular sieve on the upstream portion of the substrate and a Cu molecular sieve on the downstream portion. As shown in Figure 6, the upstream and downstream catalyst compositions on the second substrate were partially overlapping, with the Cu molecular sieve applied from the downstream end of the substrate and covering less than 100% of the substrate's length, and the Fe molecular sieve applied from the upstream end of the substrate and covering less than 100% of the substrate's length. Figure 6b shows a catalyst configuration having a first upstream substrate with a Cu / Mn bimetallic substrate and a separate downstream substrate having an Fe molecular sieve on the upstream portion of the substrate and a Cu molecular sieve on the downstream portion, with an additional catalyst located between the first substrate and the downstream substrate.

[0076] In some embodiments, any of the foregoing catalyst configurations may further include a catalyst composition comprising a platinum group metal ("PGM catalyst") applied on one or more substrates in the configuration in an underlayer covering less than the entire length of the substrate from the outlet end to the inlet end of the substrate. The platinum group metal-containing catalyst composition may include, for example, Pt alumina, or a blend of Pt zeolite + Cu zeolite.

[0077] For example, in some embodiments, the catalyst configuration may include a Cu / Mn bimetallic molecular sieve in a first, upstream zone, and an additional catalyst, such as an SCR catalyst, in a second zone downstream on a separate substrate including a platinum group metal applied in an underlayer from the outlet end of the substrate toward the inlet end of the substrate. For example, Figure 7 shows a catalyst configuration having a Cu / Mn bimetallic molecular sieve on an upstream substrate and a Cu molecular sieve on a separate downstream substrate including a PGM catalyst applied in an underlayer covering less than the entire length of the substrate from the outlet end toward the inlet end of the downstream substrate.

[0078] In some embodiments, a catalyst configuration may include a Cu / Mn bimetallic molecular sieve on an upstream portion of a substrate, an additional catalyst, such as an SCR catalyst, on a downstream portion of the same substrate, and a PGM catalyst applied in an underlayer covering less than the full length of the substrate from the outlet end of the substrate toward the inlet end of the substrate. In some embodiments, these catalyst compositions on the upstream and downstream portions of the substrate may overlap. For example, FIG. 8 shows a catalyst configuration having a Cu / Mn bimetallic molecular sieve on an upstream portion of a substrate, a Cu molecular sieve on a downstream portion of the same substrate, and a PGM catalyst in an underlayer covering less than the full length of the substrate from the outlet end of the substrate toward the inlet end of the substrate. As shown in FIG. 8, the upstream and downstream catalyst compositions were partially overlapping, with the Cu molecular sieve applied from the downstream end of the substrate and covering less than 100% of the substrate's length, and the Cu / Mn bimetallic molecular sieve applied from the upstream end of the substrate and covering less than 100% of the substrate's length.

[0079] In some embodiments, the catalyst configuration may include an additional catalyst, such as an SCR catalyst, located upstream and a Cu / Mn bimetallic molecular sieve located downstream on a separate substrate, with a PGM catalyst applied in an underlayer extending from the outlet end toward the inlet end of either or both substrates and covering less than the full length of the substrate. In some embodiments, the catalyst configuration may include an additional catalyst located between the additional catalyst upstream and the Cu / Mn bimetallic molecular sieve downstream. For example, FIG. 9a shows a catalyst configuration having an Fe molecular sieve on an upstream substrate and a Cu / Mn bimetallic molecular sieve on a separate downstream substrate, with a PGM catalyst applied in an underlayer extending from the outlet end toward the inlet end of the downstream substrate and covering less than the full length of the substrate. FIG. 9b shows a catalyst configuration having an Fe molecular sieve on an upstream substrate and a Cu / Mn bimetallic molecular sieve on a separate downstream substrate with additional catalyst located between the two, with PGM catalyst applied in an underlayer extending from the outlet end of the upstream substrate towards the inlet end of the substrate covering less than the full length of the substrate, and with PGM catalyst applied in an underlayer extending from the outlet end of the downstream substrate towards the inlet end of the substrate covering less than the full length of the substrate.

[0080] In some embodiments, the catalyst configuration may include an additional catalyst, such as an SCR catalyst, on an upstream portion of the substrate, a Cu / Mn bimetallic molecular sieve on a downstream portion of the same substrate, and a PGM catalyst applied in an underlayer extending from the outlet end of the substrate toward the inlet end and covering less than the entire length of the substrate. In some embodiments, these catalyst compositions on the upstream and downstream portions of the substrate may overlap. For example, FIG. 10 shows a catalyst configuration having an Fe molecular sieve on an upstream portion of the substrate, a Cu / Mn bimetallic molecular sieve on a downstream portion of the same substrate, and a PGM catalyst applied in an underlayer extending from the outlet end of the substrate toward the inlet end and covering less than the entire length of the substrate. As shown in FIG. 10, the upstream and downstream catalyst compositions were partially overlapping, with the Cu / Mn bimetallic molecular sieve applied from the downstream end of the substrate and covering less than 100% of the substrate's length, and the Fe molecular sieve applied from the upstream end of the substrate and covering less than 100% of the substrate's length.

[0081] In some embodiments, the catalyst configuration includes a first substrate having an additional catalyst, such as an SCR catalyst, on an upstream portion of the substrate and a Cu / Mn bimetallic molecular sieve on a downstream portion of the same substrate, followed by a second substrate having an additional catalyst, such as an SCR catalyst, with a PGM catalyst applied to an underlayer extending from the outlet end toward the inlet end of either or both substrates and covering less than the entire length of the substrate. In some embodiments, the catalyst compositions on the upstream and downstream portions of the first substrate may overlap. For example, FIG. 11a shows a catalyst configuration including a first substrate having an Fe molecular sieve on an upstream portion of the substrate and a Cu / Mn bimetallic molecular sieve on a downstream portion of the same substrate, and a separate substrate having a Cu molecular sieve and a PGM catalyst in an underlayer extending from the outlet end toward the inlet end of the substrate and covering less than the entire length of the substrate, the separate substrate being downstream from the first substrate. As shown in Figure 11, the upstream and downstream catalyst compositions on the first substrate were partially overlapping, with the Cu / Mn bimetallic molecular sieve applied from the downstream end of the substrate and covering less than 100% of the substrate's length, and the Fe molecular sieve applied from the upstream end of the substrate and covering less than 100% of the substrate's length. Figure 11b shows a configuration similar to Figure 11a, but including an additional catalyst located between the first substrate and the downstream substrate, and also including a PGM catalyst applied in an underlayer extending from the outlet end of the upstream substrate towards the inlet end and covering less than the entire length of the substrate.

[0082] In some embodiments, the catalyst configuration includes a first substrate having a Cu / Mn bimetallic molecular sieve, followed by a second substrate having one or more additional catalysts, such as an SCR catalyst. In some embodiments, the second substrate includes an upstream catalyst located on an upstream portion of the second substrate and a downstream catalyst located on a downstream portion of the second substrate, with a PGM catalyst applied in an underlayer extending from the outlet end toward the inlet end of either or both substrates and covering less than the entire length of the substrate. In some embodiments, these catalyst compositions located on the upstream and downstream portions of the second substrate may overlap. Figure 12a shows a catalyst configuration having a first upstream substrate having a Cu / Mn bimetallic substrate, followed by a second substrate, with a Fe molecular sieve on the upstream portion of the second substrate and a Cu molecular sieve on the downstream portion of the second substrate, with a PGM catalyst applied in an underlayer extending from the outlet end toward the inlet end of the second substrate and covering less than the entire length of the substrate. As shown in Figure 12, the upstream and downstream catalyst compositions of the second substrate overlap, with the Cu molecular sieve applied from the downstream end of the substrate and covering less than 100% of the substrate's length, and the Fe molecular sieve applied from the upstream end of the substrate and covering less than 100% of the substrate's length. Figure 12b shows a catalyst configuration having a first upstream substrate with a Cu / Mn bimetallic substrate and a separate downstream substrate having an Fe molecular sieve on an upstream portion of the substrate and a Cu molecular sieve on a downstream portion of the substrate, with a PGM catalyst applied in an underlayer extending from the outlet end towards the inlet end of each of the upstream and downstream substrates and covering less than the entire length of the substrate, with an additional catalyst located between the first substrate and the downstream substrate.

[0083] In some embodiments, the catalyst configuration includes a layered configuration with a Cu / Mn bimetallic molecular sieve in an upper layer and an additional catalyst, such as an SCR catalyst, in a lower layer. In some embodiments, both the upper and lower layers extend the entire length of the substrate. For example, FIG. 13 shows a catalyst configuration with a Cu / Mn bimetallic molecular sieve in an upper layer that extends the entire length of the substrate and a Cu molecular sieve in a lower layer that extends the entire length of the substrate.

[0084] In some embodiments, the catalyst configuration includes a layered configuration having an upper layer including a catalyst such as an SCR catalyst, and a lower layer including a Cu / Mn bimetallic molecular sieve in an upstream portion and another catalyst such as an SCR catalyst in a downstream portion. For example, FIG. 14 shows a catalyst configuration having an upper layer including an Fe molecular sieve and a lower layer including a Cu / Mn bimetallic molecular sieve in an upstream portion that extends from the inlet end to the outlet end of the substrate covering less than the entire length of the substrate, and also including a Cu molecular sieve that extends from the outlet end to the inlet end of the substrate covering less than the entire length of the substrate. As shown in FIG. 14, the upstream and downstream catalyst compositions of the lower layer may overlap.

[0085] In some embodiments, the catalyst configuration may include a lower layer having a catalyst such as an SCR catalyst, and an upper layer having a catalyst such as an SCR catalyst in an upstream portion and a Cu / Mn bimetallic molecular sieve in a downstream portion. For example, Figure 15 shows a catalyst configuration having a lower layer including a Cu molecular sieve and an upper layer including an Fe molecular sieve in an upstream portion covering less than the full length of the substrate extending from the inlet end toward the outlet end, and also including a Cu / Mn bimetallic molecular sieve in a downstream portion covering less than the full length of the substrate extending from the outlet end toward the inlet end. As shown in Figure 15, the upstream and downstream catalyst compositions of the upper layer may overlap.

[0086] In some embodiments, the catalyst configuration includes a layered configuration including an upper layer including a Cu / Mn bimetallic molecular sieve and a lower layer including a catalyst such as an SCR catalyst in an upstream portion and another catalyst such as an SCR catalyst in a downstream portion. For example, FIG. 16 shows a catalyst configuration having an upper layer including a Cu / Mn bimetallic molecular sieve and a lower layer including an Fe molecular sieve in an upstream portion extending from the inlet end to the outlet end of the substrate covering less than the entire length of the substrate, and also including a Cu molecular sieve extending from the outlet end to the inlet end of the substrate covering less than the entire length of the substrate. As shown in FIG. 16, the upstream and downstream catalyst compositions of the lower layer may overlap.

[0087] In some embodiments, the catalyst configuration comprises a layered configuration including 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 full length of the substrate, a next layer covering the full length of the substrate and having an additional catalyst such as an SCR catalyst also covering the PGM catalyst, and a top layer including a Cu / Mn bimetallic molecular sieve. For example, Figure 17 shows a catalyst configuration having 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 full length of the substrate, a Cu molecular sieve extending the full length of the substrate and covering the PGM catalyst, and a Cu / Mn bimetallic molecular sieve in a top layer extending the full length of the substrate and covering the Cu molecular sieve.

[0088] In some embodiments, the catalyst configuration comprises a layered configuration having a PGM catalyst applied in a lower 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 and another catalyst such as an SCR catalyst covering the PGM catalyst in a downstream portion, and an upper layer including a catalyst such as an SCR catalyst. For example, Figure 18 shows a catalyst configuration having a PGM catalyst applied in a lower 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 including a Cu / Mn bimetallic molecular sieve in an upstream portion extending from the inlet end of the substrate toward the outlet end and covering less than the entire length of the substrate, and also including a Cu molecular sieve in a portion extending from the outlet end of the substrate toward the inlet end covering the PGM catalyst and covering less than the entire length of the substrate, and an upper layer including an Fe molecular sieve. As shown in FIG. 18, the Cu / Mn bimetallic molecular sieve and the Cu molecular sieve catalyst may be partially overlapped.

[0089] In some embodiments, the 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 having a catalyst such as an SCR catalyst in an upstream portion and a Cu / Mn bimetallic molecular sieve in a downstream portion. For example, Figure 19 shows a catalyst configuration having 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 extending the entire length of the substrate and covering the PGM catalyst and including a Cu molecular sieve, and a top layer including an Fe molecular sieve in an upstream portion extending from the inlet end toward the outlet end and covering less than the entire length of the substrate, and also including a Cu / Mn bimetallic molecular sieve in a downstream portion of the substrate extending from the outlet end toward the inlet end and covering less than the entire length of the substrate. As shown in FIG. 19, the upstream and downstream catalyst compositions of the upper layer may partially overlap.

[0090] In some embodiments, the catalyst configuration comprises a layered configuration having a PGM catalyst applied in a lower 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 the upstream portion and another catalyst such as an SCR catalyst in the downstream portion covering the PGM catalyst, and an upper layer including a Cu / Mn bimetallic molecular sieve. For example, Figure 20 shows a catalyst configuration having a PGM catalyst applied in a lower 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 including an Fe molecular sieve in the upstream portion extending from the inlet end of the substrate toward the outlet end and covering less than the entire length of the substrate, and a Cu molecular sieve in the portion extending from the outlet end of the substrate toward the inlet end covering the PGM catalyst and covering less than the entire length of the substrate, and an upper layer including a Cu / Mn bimetallic molecular sieve that extends the entire length of the substrate. As shown in FIG. 20, the Cu / Mn bimetallic molecular sieve and the Cu molecular sieve catalyst may be partially overlapped.

[0091] In some embodiments, the catalyst configuration includes a layered configuration having a Cu / Mn bimetallic molecular sieve in an upper layer that extends from the inlet end toward the outlet end of the substrate and covers less than the entire length of the substrate, and an additional catalyst, such as an SCR catalyst, in a lower layer. In some embodiments, both the upper and lower layers extend the entire length of the substrate. For example, Figure 21 shows a catalyst configuration having a Cu / Mn bimetallic molecular sieve in an upper layer that extends from the inlet end toward the outlet end of the substrate and covers less than the entire length of the substrate, and a Cu molecular sieve in a lower layer that extends the entire length of the substrate.

[0092] In some embodiments, the catalyst configuration includes a layered configuration having an upper layer that extends from the inlet end to the outlet end of the substrate and covers less than the entire length of the substrate and includes a catalyst such as an SCR catalyst, and a lower layer that includes a Cu / Mn bimetallic molecular sieve in an upstream portion and includes another catalyst such as an SCR catalyst in a downstream portion. For example, FIG. 22 shows a catalyst configuration having an upper layer that extends from the inlet end to the outlet end of the substrate and covers less than the entire length of the substrate and includes an Fe molecular sieve, and a lower layer that includes a Cu / Mn bimetallic molecular sieve in an upstream portion that extends from the inlet end to the outlet end of the substrate and covers less than the entire length of the substrate, and also includes a Cu molecular sieve that extends from the outlet end to the inlet end of the substrate and covers less than the entire length of the substrate. As shown in FIG. 22, the upstream and downstream catalyst compositions of the lower layer may overlap.

[0093] In some embodiments, the catalyst configuration includes a layered configuration having an upper layer including a Cu / Mn bimetallic molecular sieve extending from the inlet end to the outlet end of the substrate and covering less than the entire length of the substrate, and a lower layer including a catalyst such as an SCR catalyst in the upstream portion and another catalyst such as an SCR catalyst in the downstream portion. For example, FIG. 23 shows a catalyst configuration having an upper layer including a Cu / Mn bimetallic molecular sieve extending from the inlet end to the outlet end of the substrate and covering less than the entire length of the substrate, and a lower layer including an Fe molecular sieve in the upstream portion extending from the inlet end to the outlet end of the substrate covering less than the entire length of the substrate, and also including a Cu molecular sieve extending from the outlet end to the inlet end of the substrate covering less than the entire length of the substrate. As shown in FIG. 23, the upstream and downstream catalyst compositions of the lower layer may overlap.

[0094] In some embodiments, the catalyst configuration comprises a layered configuration having 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 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 included 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. For example, Figure 24 shows a catalyst configuration having 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 Cu molecular sieve extending the entire length of the substrate and covering the PGM catalyst, and a Cu / Mn bimetallic molecular sieve included 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.

[0095] In some embodiments, the catalyst configuration includes a layered configuration having a PGM catalyst applied in a lower 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 and another catalyst such as an SCR catalyst in a downstream portion covering the PGM catalyst, and an upper 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, FIG. 25 shows a catalyst configuration having a PGM catalyst applied in a lower 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 including a Cu / Mn bimetallic molecular sieve in an upstream portion extending from the inlet end toward the outlet end of the substrate and covering less than the entire length of the substrate, a Cu molecular sieve in a portion extending from the outlet end of the substrate toward the inlet end covering the PGM catalyst and covering less than the entire length of the substrate, and an upper layer including an Fe molecular sieve extending from the inlet end of the substrate toward the outlet end and covering less than the entire length of the substrate. As shown in FIG. 25, the Cu / Mn bimetallic molecular sieve and the Cu molecular sieve catalyst may be partially overlapped.

[0096] In some embodiments, the catalyst configuration comprises a layered configuration having a PGM catalyst applied in a lower layer extending from the outlet end towards the inlet end of the substrate and covering less than the entire length of the substrate, a layer including a catalyst such as an SCR catalyst in an upstream portion and another catalyst such as an SCR catalyst covering the PGM catalyst in a downstream portion, and an upper layer including a Cu / Mn bimetallic molecular sieve extending from the inlet end towards the outlet end of the substrate and covering less than the entire length of the substrate. For example, Figure 26 shows a catalyst configuration having 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 including an Fe molecular sieve in an upstream portion extending from the inlet end of the substrate toward the outlet end and covering less than the entire length, and a Cu molecular sieve in a portion extending from the outlet end of the substrate toward the inlet end covering the PGM catalyst and covering less than the entire length of the substrate, and 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 including a Cu / Mn bimetallic molecular sieve. As shown in Figure 26, the Cu / Mn bimetallic molecular sieve and the Cu molecular sieve catalyst may be partially overlapping.

[0097] In some embodiments, the catalyst configuration includes a layered configuration and multiple substrates, including a first upstream substrate having a Cu / Mn bimetallic molecular sieve in an upper layer and an additional catalyst such as an SCR catalyst in a lower layer, and a separate downstream substrate having an additional catalyst such as an SCR catalyst. In some embodiments, the catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example, FIG. 27a shows a catalyst configuration having a first upstream substrate having a Cu / Mn bimetallic molecular sieve in an upper layer that runs the entire length of the substrate and a Cu molecular sieve in a lower layer that runs the entire length of the substrate, and a downstream substrate that includes a Cu molecular sieve. FIG. 27b shows a catalyst configuration further including an additional catalyst between the first upstream substrate and the downstream substrate of FIG. 27a.

[0098] In some embodiments, the catalyst configuration includes a layered configuration and multiple substrates, including a first upstream substrate having an upper layer including a catalyst such as an SCR catalyst, and a lower layer including a Cu / Mn bimetallic molecular sieve in an upstream portion and another catalyst such as an SCR catalyst in a downstream portion, and a separate downstream substrate having an additional catalyst such as an SCR catalyst. In some embodiments, the catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example, FIG. 28a shows a catalyst configuration including a first upstream substrate having an upper layer including an Fe molecular sieve, and a lower layer including a Cu / Mn bimetallic molecular sieve in an upstream portion extending from the inlet end toward the outlet end of the substrate covering less than the entire length of the substrate, and a downstream substrate including a Cu molecular sieve. As shown in FIG. 28, the upstream and downstream catalyst compositions of the lower layer may overlap. FIG. 28b shows a catalyst configuration further including an additional catalyst between the first upstream substrate and the downstream substrate of FIG. 28a.

[0099] In some embodiments, the catalyst configuration may include a first upstream substrate having a lower layer with a catalyst such as an SCR catalyst, and an upper layer with a catalyst such as an SCR catalyst in an upstream portion and a Cu / Mn bimetallic molecular sieve in a downstream portion, and a separate downstream substrate with an additional catalyst such as an SCR catalyst. In some embodiments, the catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example, FIG. 29a shows a catalyst configuration having a first upstream substrate having a lower layer with a Cu molecular sieve, and an upper layer with an Fe molecular sieve in an upstream portion extending from the inlet end to the outlet end of the substrate and covering less than the entire length of the substrate, and a downstream substrate with a Cu molecular sieve. FIG. 29b shows a catalyst configuration further including an additional catalyst between the first upstream substrate and the downstream substrate of FIG. 29a.

[0100] In some embodiments, the catalyst configuration includes a layered configuration with multiple substrates, including a first upstream substrate having an upper layer including a Cu / Mn bimetallic molecular sieve and a lower layer including a catalyst such as an SCR catalyst in an upstream portion and another catalyst such as an SCR catalyst in a downstream portion, and a separate downstream substrate having an additional catalyst such as an SCR catalyst. In some embodiments, the catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example, FIG. 30a shows a catalyst configuration with a first upstream substrate having an upper layer including a Cu / Mn bimetallic molecular sieve and a lower layer including Fe in an upstream portion covering less than the entire length of the substrate extending from the inlet end toward the outlet end, and a downstream substrate including a Cu molecular sieve in a portion covering less than the entire length of the substrate extending from the outlet end toward the inlet end. FIG. 30b shows a catalyst configuration further including an additional catalyst between the first upstream substrate and the downstream substrate of FIG. 30a.

[0101] In some embodiments, the catalyst configuration includes a layered configuration and multiple substrates having a first upstream substrate having a Cu / Mn bimetallic molecular sieve in an upper layer and an additional catalyst such as an SCR catalyst in a lower layer, and a separate downstream substrate having an additional catalyst such as an SCR catalyst, and further having a PGM catalyst applied in the lower layer extending from the outlet end toward the inlet end of either or both substrates and extending less than the entire length of the substrate. In some embodiments, the catalyst configuration includes the additional catalyst between the first upstream substrate and the downstream substrate. For example, FIG. 31 a shows a catalyst configuration having a first upstream substrate having a Cu / Mn bimetallic molecular sieve in an upper layer extending the entire length of the substrate and a Cu molecular sieve in a lower layer extending the entire length of the substrate, and a downstream substrate including a PGM catalyst applied in a lower layer extending from the outlet end towards the inlet end of the substrate and extending less than the entire length of the substrate, and an upper layer including the PGM catalyst and Cu molecular sieve covering the entire length of the substrate. FIG. 31b shows a first upstream substrate including a catalyst configuration having a PGM catalyst applied in a lower layer extending from the outlet end towards the inlet end of the substrate and covering less than the full length of the substrate, a Cu molecular sieve extending the full length of the substrate and covering the PGM catalyst, and a Cu / Mn bimetallic molecular sieve included in an upper layer extending the full length of the substrate and covering the Cu molecular sieve, and a downstream substrate including a PGM catalyst applied in a lower layer extending from the outlet end towards the inlet end of the substrate and covering less than the full length of the substrate, and an upper layer including the Cu molecular sieve covering the PGM catalyst and the full length of the substrate, and an additional catalyst further included between the first upstream substrate and the downstream substrate.

[0102] In some embodiments, the catalyst configuration includes a first upstream substrate having an upper layer including a catalyst such as an SCR catalyst, and a lower layer including a Cu / Mn bimetallic molecular sieve in an upstream portion and another catalyst such as an SCR catalyst in a downstream portion, and a separate downstream substrate having an additional catalyst such as an SCR catalyst, and further having a PGM catalyst applied in the lower layer extending from the outlet end toward the inlet end of either or both substrates and extending less than the entire length of the substrate. In some embodiments, the catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example, FIG. 32a shows a catalyst configuration having a first upstream substrate having an upper layer comprising Fe molecular sieve, and a lower layer comprising Cu / Mn bimetallic molecular sieve in an upstream portion extending from the inlet end towards the outlet end of the substrate covering less than the entire length, and also comprising Cu molecular sieve in a portion extending from the outlet end towards the inlet end of the substrate covering less than the entire length of the substrate, and a downstream substrate including PGM catalyst applied in the lower layer extending from the outlet end towards the inlet end of the substrate covering less than the entire length of the substrate, and the upper layer comprising PGM catalyst and Cu molecular sieve covering the entire length of the substrate. FIG. 32b shows a first upstream substrate including a PGM catalyst applied in a lower layer extending from the outlet end of the substrate towards the inlet end and covering less than the entire length of the substrate, a Cu / Mn bimetallic molecular sieve in an upstream portion extending from the inlet end of the substrate towards the outlet end and covering less than the entire length of the substrate, a next layer including a Cu molecular sieve in a portion extending from the outlet end of the substrate towards the inlet end covering the PGM catalyst and covering less than the entire length of the substrate, and an upper layer including Fe molecular sieve; and a downstream substrate including a PGM catalyst applied in a lower layer extending from the outlet end of the substrate towards the inlet end and covering less than the entire length of the substrate, and an upper layer including a Cu molecular sieve covering the PGM catalyst and the entire length of the substrate, and an additional catalyst further included between the first upstream substrate and the downstream substrate.

[0103] In some embodiments, the catalyst configuration may include a first upstream substrate having a lower layer having a catalyst, such as an SCR catalyst, and an upper layer having a catalyst, such as an SCR catalyst, in an upstream portion and a Cu / Mn bimetallic molecular sieve in a downstream portion, as well as a separate downstream substrate having an additional catalyst, such as an SCR catalyst, and further a PGM catalyst applied in the lower layer extending from the outlet end toward the inlet end of either or both substrates and extending less than the entire length of the substrate. In some embodiments, the catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example, FIG. 33a shows a catalyst configuration having a first upstream substrate having a lower layer comprising a Cu molecular sieve and an upper layer comprising an Fe molecular sieve in an upstream portion extending from the inlet end towards the outlet end of the substrate covering less than the entire length, and a Cu / Mn bimetallic molecular sieve in a downstream portion extending from the outlet end towards the inlet end of the substrate covering less than the entire length of the substrate, and a downstream substrate comprising a PGM catalyst applied in the lower layer extending from the outlet end towards the inlet end of the substrate covering less than the entire length of the substrate, and the upper layer comprising the PGM catalyst and Cu molecular sieve covering the entire length of the substrate. FIG. 33b shows a first upstream substrate including a PGM catalyst applied in an underlayer extending from the outlet end of the substrate towards the inlet end and covering less than the entire length of the substrate, a next layer including a Cu molecular sieve extending the entire length of the substrate and covering the PGM catalyst, and an overlayer including an Fe molecular sieve in an upstream portion of the substrate extending from the inlet end of the substrate towards the outlet end and covering less than the entire length of the substrate, and also including a Cu / Mn bimetallic molecular sieve in a downstream portion of the substrate extending from the outlet end of the substrate towards the inlet end and covering less than the entire length of the substrate, and an additional catalyst further included between the first upstream substrate and the downstream substrate.

[0104] In some embodiments, the catalyst configuration includes a layered configuration having multiple substrates including a first upstream substrate having an upper layer including a Cu / Mn bimetallic molecular sieve and a lower layer including a catalyst such as an SCR catalyst in an upstream portion and another catalyst such as an SCR catalyst in a downstream portion, and a separate downstream substrate having an additional catalyst such as an SCR catalyst, and further having a PGM catalyst applied in the lower layer extending from the outlet end toward the inlet end of either or both substrates for less than the entire length of the substrate. In some embodiments, the catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example, FIG. 34a shows a catalyst configuration having a first upstream substrate having an upper layer comprising a Cu / Mn bimetallic molecular sieve, and a lower layer comprising an Fe molecular sieve in an upstream portion extending from the inlet end of the substrate toward the outlet end and covering less than the entire length, and also comprising a Cu molecular sieve in a portion extending from the outlet end of the substrate toward the inlet end and covering less than the entire length of the substrate, and a downstream substrate comprising a PGM catalyst applied in the lower layer extending from the outlet end of the substrate toward the inlet end and extending less than the entire length of the substrate, and an upper layer comprising the PGM catalyst and the Cu molecular sieve covering the entire length of the substrate. FIG. 34b shows a catalyst configuration having a first upstream substrate having a PGM catalyst applied in a lower layer extending from the outlet end of the substrate towards the inlet end and covering less than the entire length of the substrate, a next layer extending from the inlet end of the substrate towards the outlet end and covering less than the entire length of the substrate comprising Fe molecular sieve, a next layer extending from the outlet end of the substrate towards the inlet end covering the PGM catalyst and also comprising Cu molecular sieve in a portion covering less than the entire length of the substrate, and a top layer extending the entire length of the substrate and comprising Cu / Mn bimetallic molecular sieve, and a downstream substrate having a PGM catalyst applied in a lower layer extending from the outlet end of the substrate towards the inlet end and covering less than the entire length of the substrate, and a top layer comprising PGM catalyst and Cu molecular sieve covering the entire length of the substrate, and comprising an additional catalyst between the first upstream substrate and the downstream substrate.

[0105] In some embodiments, the catalyst configuration includes a layered configuration and multiple substrates, including a first upstream substrate having a Cu / Mn bimetallic molecular sieve in an upper layer covering less than the entire length of the substrate from the inlet end to the outlet end of the substrate, and an additional catalyst such as an SCR catalyst in a lower layer, and a separate downstream substrate having an additional catalyst such as an SCR catalyst. In some embodiments, the catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example, FIG. 35a shows a catalyst configuration including a first upstream substrate having a Cu / Mn bimetallic molecular sieve in an upper layer covering less than the entire length of the substrate from the inlet end to the outlet end of the substrate, and a Cu molecular sieve in a lower layer extending the entire length of the substrate, and a downstream substrate including a Cu molecular sieve. FIG. 35b shows a catalyst configuration further including an additional catalyst between the first upstream substrate and the downstream substrate of FIG. 35a.

[0106] In some embodiments, the catalyst configuration includes a layered configuration and multiple substrates including a first upstream substrate having an upper 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 lower layer including a Cu / Mn bimetallic molecular sieve in an upstream portion and another catalyst, such as an SCR catalyst, in a downstream portion, and a separate downstream substrate having an additional catalyst, such as an SCR catalyst. In some embodiments, the catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example, Figure 36a shows a catalyst configuration having a first upstream substrate with an upper layer including Fe molecular sieves extending from the inlet end to the outlet end of the substrate and covering less than the entire length of the substrate, and a lower layer including Cu / Mn bimetallic molecular sieves in an upstream portion extending from the inlet end to the outlet end of the substrate and covering less than the entire length of the substrate, and also including Cu molecular sieves in a portion extending from the outlet end to the inlet end of the substrate and covering less than the entire length of the substrate. As shown in Figure 36, the upstream and downstream catalyst compositions of the lower layer may overlap. Figure 36b shows a catalyst configuration further including an additional catalyst between the first upstream substrate and the downstream substrate of Figure 36a.

[0107] In some embodiments, the catalyst configuration includes a layered configuration having multiple substrates, including a first upstream substrate having an upper layer including a Cu / Mn bimetallic molecular sieve that extends from the inlet end toward the outlet end of the substrate and covers less than the entire length of the substrate, and a lower layer including a catalyst, such as an SCR catalyst, in an upstream portion and another catalyst, such as an SCR catalyst, in a downstream portion, and a separate downstream substrate having an additional catalyst, such as an SCR catalyst. In some embodiments, the catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example, Figure 37a shows a catalyst configuration having a first upstream substrate with an upper layer including a Cu / Mn bimetallic molecular sieve extending from the inlet end to the outlet end of the substrate and covering less than the entire length of the substrate, and a lower layer including an Fe molecular sieve in an upstream portion of the substrate extending from the inlet end to the outlet end and covering less than the entire length of the substrate, and also including a Cu molecular sieve in a portion of the substrate extending from the outlet end to the inlet end and covering less than the entire length of the substrate, and a downstream substrate including a Cu molecular sieve. Figure 37b shows a catalyst configuration further including an additional catalyst between the first upstream substrate and the downstream substrate of Figure 37a.

[0108] In some embodiments, the catalyst configuration includes a layered configuration and multiple substrates including a first upstream substrate having a Cu / Mn bimetallic molecular sieve in an upper layer extending from the inlet end toward the outlet end of the substrate covering less than the entire length of the substrate and an additional catalyst such as an SCR catalyst in a lower layer, and a separate downstream substrate having an additional catalyst such as an SCR catalyst, further having a PGM catalyst applied in a lower layer extending from the outlet end toward the inlet end of either or both substrates less than the entire length of the substrate. In some embodiments, the catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example, FIG. 38a shows a catalyst configuration having a first upstream substrate having a Cu / Mn bimetallic molecular sieve in an upper layer extending from the inlet end towards the outlet end of the substrate and covering less than the entire length of the substrate, and a Cu molecular sieve in a lower layer extending the entire length of the substrate, and a downstream substrate including a PGM catalyst applied in a lower layer extending from the outlet end towards the inlet end of the substrate and covering less than the entire length of the substrate, and an upper layer including the PGM catalyst and Cu molecular sieve covering the entire length of the substrate. FIG. 38b shows a first upstream substrate including a catalyst configuration having PGM catalyst applied in a lower layer extending from the outlet end towards the inlet end of the substrate and covering less than the entire length of the substrate, Cu molecular sieve extending the entire length of the substrate and covering the PGM catalyst, and Cu / Mn bimetallic molecular sieve included in an upper layer extending from the inlet end towards the outlet end of the substrate and covering less than the entire length of the substrate, and a downstream substrate including PGM catalyst applied in a lower layer extending from the outlet end towards the inlet end of the substrate and covering less than the entire length of the substrate, and an upper layer including the PGM catalyst and Cu molecular sieve covering the entire length of the substrate, and an additional catalyst further included between the first upstream substrate and the downstream substrate.

[0109] In some embodiments, the catalyst configuration includes a first upstream substrate having an upper 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 an underlayer including a Cu / Mn bimetallic molecular sieve in an upstream portion and another catalyst, such as an SCR catalyst, in a downstream portion, and a separate downstream substrate having an additional catalyst, such as an SCR catalyst, and further having a PGM catalyst applied in the underlayer extending from the outlet end toward the inlet end of either or both substrates, less than the entire length of the substrate. In some embodiments, the catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example, FIG. 39a shows a catalyst configuration having a first upstream substrate having an upper layer including Fe 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 lower layer including Cu / Mn bimetallic molecular sieve in an upstream portion extending from the inlet end toward the outlet end of the substrate and covering less than the entire length, and also including Cu molecular sieve in the lower layer extending from the outlet end toward the inlet end of the substrate and covering less than the entire length of the substrate, and a downstream substrate including PGM catalyst applied in the lower layer extending from the outlet end toward the inlet end of the substrate and extending less than the entire length of the substrate, and an upper layer including PGM catalyst and Cu molecular sieve covering the entire length of the substrate. FIG. 39b shows a first upstream substrate including a PGM catalyst applied in a lower layer extending from the outlet end towards the inlet end of the substrate and covering less than the entire length of the substrate, a next layer including a Cu / Mn bimetallic molecular sieve in an upstream portion extending from the inlet end towards the outlet end of the substrate and covering less than the entire length, and a top layer extending from the outlet end towards the inlet end of the substrate covering the PGM catalyst and also including a Cu molecular sieve in a portion of the substrate covering less than the entire length of the substrate, and an overlayer extending from the inlet end towards the outlet end of the substrate and covering less than the entire length of the substrate including a Fe molecular sieve, and a downstream substrate including a PGM catalyst applied in a lower layer extending from the outlet end towards the inlet end of the substrate and covering less than the entire length of the substrate, and an overlayer including a Cu molecular sieve covering the PGM catalyst and the entire length of the substrate, and an additional catalyst further included between the first upstream substrate and the downstream substrate.

[0110] In some embodiments, the catalyst configuration includes a layered configuration having multiple substrates, including a first upstream substrate having an upper layer having 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 lower layer including a catalyst such as an SCR catalyst in an upstream portion and another catalyst such as an SCR catalyst in a downstream portion, and a separate downstream substrate having an additional catalyst such as an SCR catalyst, and further having a PGM catalyst applied in the lower layer extending from the outlet end toward the inlet end of either or both substrates less than the entire length of the substrate. In some embodiments, the catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example, FIG. 40a shows a catalyst configuration having a first upstream substrate having an upper 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 lower layer including an Fe molecular sieve in an upstream portion extending from the inlet end toward the outlet end of the substrate and covering less than the entire length of the substrate, and also including a Cu molecular sieve extending from the outlet end toward the inlet end of the substrate and covering less than the entire length of the substrate, and a downstream substrate including a PGM catalyst applied in the lower layer extending from the outlet end toward the inlet end of the substrate and extending less than the entire length of the substrate, and an upper layer including the PGM catalyst and the Cu molecular sieve covering the entire length of the substrate. FIG. 40b shows a catalyst configuration having a first upstream substrate having a PGM catalyst applied in a lower layer extending from the outlet end of the substrate towards the inlet end and covering less than the entire length of the substrate, a next layer including Fe molecular sieve in an upstream portion extending from the inlet end of the substrate towards the outlet end and covering less than the entire length of the substrate, and a top layer including Cu / Mn bimetallic molecular sieve extending from the inlet end of the substrate towards the outlet end and covering less than the entire length of the substrate, and a downstream substrate having a PGM catalyst applied in a lower layer extending from the outlet end of the substrate towards the inlet end of the substrate and covering less than the entire length of the substrate, and a top layer including Cu / Mn bimetallic molecular sieve extending from the inlet end of the substrate towards the inlet end and covering less than the entire length of the substrate, and further including an additional catalyst between the first upstream substrate and the downstream substrate.

[0111] effect Surprisingly, it has been found that the catalyst composition according to the present invention, which comprises a molecular sieve having exchanged copper and exchanged manganese, has distinct advantages in selective catalytic reduction processes. Such catalyst composition can effectively reduce the amount of NH3 and NO x It has been found that such catalyst compositions promote the reaction of nitrogen with nitrogen oxides to produce nitrogen and water, i.e., selective catalytic reduction (SCR) with less NO production. In addition, such catalyst compositions have been shown to promote activation and reduce NO selectivity, as well as reduce NO oxidation upon aging at 900°C. x It has been found to be stable while still maintaining conversion and N2O selectivity. Aging includes, for example, 4.5% H2O for 5 hours. For example, bimetallic Cu / Mn molecular sieves have been found to exhibit similar or improved activity and improved selectivity under typical SCR conditions compared to monometallic Cu molecular sieves, monometallic Mn molecular sieves, and physically mixed Cu molecular sieves / Mn molecular sieves. Such comparisons are understood to refer to molecular sieves containing the same or substantially the same total amount of transition metals. Such results support the theory of balancing active sites to balance fundamental reaction steps and optimize performance.

[0112] In the following discussion, NO selectivity is calculated by dividing the moles of NO produced by the moles of NO converted. x (NO x The average NO selectivity is defined as the NO selectivity averaged over the test temperature range of 150°C to 500°C. The average NO production is defined as the average NO production over the test temperature range of 150°C to 500°C. The total NO x The conversion rate is the average NO x It is defined as the conversion rate (%).

[0113] standard SCR The catalyst composition of the present invention produces significantly less NO under standard SCR conditions, and produces similar or higher NO when compared to monometallic molecular sieves, such as Cu-exchanged molecular sieves. x Standard SCR conditions may include, for example, 500 ppm NH, 500 ppm NO, 0 ppm NO, 14% O, 4.6% H0, 5.0% CO, and balance N at a space velocity of 90 K / hr.

[0114] In some embodiments, the catalyst composition of the present invention produces about 33% less NO and similar total NO under standard SCR conditions compared to Cu-exchanged molecular sieves. x In some embodiments, the catalyst composition of the present invention produces about 20% to about 45%, about 25% to about 40%, or about 30% to about 35% less NO under standard SCR conditions compared to Cu-exchanged molecular sieves.

[0115] In some embodiments, the catalyst composition of the present invention produces about 65% less NO and about 45% more total NO under standard SCR conditions compared to Mn-exchanged molecular sieves. x In some embodiments, the catalyst composition of the present invention produces about 50% to about 80%, about 55% to about 75%, or about 60% to about 70% less NO than Mn-exchanged molecular sieves under standard SCR conditions. In some embodiments, the catalyst composition of the present invention produces about 30% to about 60%, about 35% to about 55%, or about 40% to about 50% more total NO than Mn-exchanged molecular sieves under standard SCR conditions. x Convert.

[0116] In some embodiments, the catalyst composition of the present invention produces about 4% less NO and about 12% more total NO under standard SCR conditions than a physical mixture of Cu-exchanged and Mn-exchanged molecular sieves. xIn some embodiments, the catalyst composition of the present invention produces about 1% to about 15%, about 1% to about 10%, or about 2% to about 7% less NO under standard SCR conditions than a physical mixture of Cu-exchanged and Mn-exchanged molecular sieves. In some embodiments, the catalyst composition of the present invention produces about 1% to about 25%, about 5% to about 20%, or about 10% to about 15% more total NO under standard SCR conditions than a physical mixture of Cu-exchanged and Mn-exchanged molecular sieves. x Convert.

[0117] Rapid SCR The catalyst composition of the present invention produces significantly less NO and similar or higher NO when compared to monometallic molecular sieves, such as Cu-exchanged molecular sieves, under fast SCR conditions. x Fast SCR conditions may include, for example, 500 ppm NH, 250 ppm NO, 250 ppm NO, 14% O, 4.6% H0, 5.0% CO, and balance N at a space velocity of 90 K / hr. x Unlike Cu+Mn under "standard" conditions, which have slightly lower conversions, Cu+Mn in the presence of NO2 (which may be closer to real-world conditions) has better NO x In some embodiments, the catalyst composition of the present invention produces about 42% less NO and about 5% more total NO under fast SCR conditions compared to Cu-exchanged molecular sieves. x In some embodiments, the catalyst composition of the present invention produces about 25% to about 60%, about 30% to about 50%, or about 35% to about 45% less NO under fast SCR conditions compared to Cu-exchanged molecular sieves. In some embodiments, the catalyst composition of the present invention produces about 1% to about 20%, about 1% to about 15%, or about 1% to about 10% more total NO under fast SCR conditions compared to Cu-exchanged molecular sieves. x Convert.

[0118] Low speed SCR The catalyst composition of the present invention produces significantly less NO and similar or higher NO when compared to monometallic molecular sieves, such as Cu-exchanged molecular sieves, under low-rate SCR conditions. x It has been found that the catalytic composition of the present invention produces about 33% less NO and a similar total NO conversion rate compared to Cu-exchanged molecular sieves under low-speed SCR conditions. Low-speed SCR conditions may, for example, include 500 ppm NH3, 175 ppm NO, 325 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and the balance N2 at a space velocity of 90 K / hr. In some embodiments, the catalytic composition of the present invention produces about 33% less NO and a similar total NO conversion rate compared to Cu-exchanged molecular sieves under low-speed SCR conditions. x In some embodiments, the catalyst composition of the present invention produces about 20% to about 45%, about 25% to about 40%, or about 30% to about 35% less NO under low-rate SCR conditions compared to Cu-exchanged molecular sieves.

[0119] aging The catalyst composition of the present invention is stable to severe aging at 900° C. and has good NO x It has been found that the conversion and N2O selectivity can still be maintained. After hydrothermal aging at 900°C under standard SCR conditions, the catalyst composition of the present invention produces significantly less N2O and similar NO2O when compared to monometallic molecular sieves such as Cu-exchanged molecular sieves. x It has been found that the catalyst composition of the present invention produces about 48% less NO and similar total NO conversion after aging at 900° C. under standard SCR conditions compared to Cu-exchanged molecular sieves. x In some embodiments, the catalyst compositions of the present invention produce about 35% to about 65%, about 40% to about 60%, or about 45% to about 55% less NO than Cu-exchanged molecular sieves under standard SCR conditions after aging at 900° C. EXAMPLES

[0120] Example 1. Standard SCR The molecular sieves were impregnated with metals using the required amount of manganese(II) acetate and / or copper(II) acetate dissolved in demineralized water. The metal impregnated samples were dried at 80°C overnight and then calcined in air at 550°C for 4 hours. Catalysts were prepared with the following formulation: AEI zeolite, 1.5 wt.% exchanged Cu and 1.5 wt.% exchanged Mn (1.5Cu-1.5Mn.AEI) AEI zeolite, 2 wt.% exchanged with Cu and 2 wt.% exchanged with Mn (2Cu-2Mn.AEI) AEI zeolite, with 3 wt% exchange of Cu (3Cu.AEI)

[0121] Then, the NO of the pelletized sample of the powder catalyst was x The conversion and N2O production were tested under the following conditions: 500 ppm NH3, 500 ppm NO, 0 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and balance N2, at a space velocity of 90 K / hr. The sample was heated from room temperature to 150°C under the gas mixture described above except for NH3. At 150°C, NH3 was added into the gas mixture and the sample was held under these conditions for 30 minutes. The temperature was then ramped (heated up) from 150°C to 500°C at 5°C / min.

[0122] The results are shown in Figures 41 and 42. Under standard SCR conditions, both the Cu-Mn.AEI molecular sieve and the 3 wt% Cu-exchanged molecular sieve showed similar total NO at 86% and 88%, respectively. x It was found that the conversion was achieved with the Cu-Mn.AEI catalyst. However, the Cu-Mn.AEI catalyst showed an average NO selectivity of 0.7%, whereas the 3 wt.% Cu-exchanged molecular sieve showed an average NO selectivity of 1.1%. Thus, the catalyst of the present invention provided a significant reduction in NO compared to the typical Cu-exchanged molecular sieve.

[0123] The catalyst was also aged at 900°C in 4.5% water in air for 5 hours. A sample of the powder catalyst was pelletized and then heated to 250°C at a rate of 10°C / min in air only. The sample was then heated to 900°C in 4.5% water in air at a rate of 10°C / min. After holding at a temperature of 900°C for 5 hours, the sample was cooled in a steam / air mixture until the temperature was below 250°C. The sample was then cooled from 250°C to room temperature in a flow of air only. The NO of the pelletized sample of the powder catalyst after aging was then measured. x Conversion and N2O production were tested under the following conditions: 500 ppm NH3, 500 ppm NO, 0 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and balance N2, at a space velocity of 90 K / hr.

[0124] The results are shown in Figures 43 and 44. Under standard SCR conditions, both 1.5Cu-1.5Mn.AEI and 3Cu.AEI produced similar total NO emissions at 82% and 83%, respectively. x It was found that the catalysts achieved a conversion of 0.8%. However, the Cu-Mn.AEI showed an average NO selectivity of 0.8%, whereas the 3 wt.% Cu-exchanged molecular sieves showed an average NO selectivity of 1.6%. These results indicate that the catalysts of the present invention are hydrothermally stable and maintain a significant effect after severe hydrothermal aging, more so than the monometallic molecular sieves.

[0125] Example 2. Rapid SCR The molecular sieves were impregnated with metals using the required amount of manganese(II) acetate and / or copper(II) acetate dissolved in demineralized water. The metal impregnated samples were dried at 80°C overnight and then calcined in air at 550°C for 4 hours. Catalysts were prepared with the following formulation: AEI zeolite, 1.5 wt% exchanged Cu and 1.5 wt% exchanged Mn, 1.5Cu-1.5Mn.AEI AEI zeolite, 3 wt% Cu exchanged, 3Cu.AEI

[0126] Then, the NO of the pelletized sample of the powder catalyst wasx The conversion and N2O production were tested under the following conditions: 500 ppm NH3, 250 ppm NO, 250 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and balance N2, at a space velocity of 90 K / hr. The sample was heated from room temperature to 150°C under the gas mixture described above except for NH3. At 150°C, NH3 was added into the gas mixture and the sample was held under these conditions for 30 minutes. The temperature was then ramped (heated up) from 150°C to 500°C at 5°C / min.

[0127] The results are shown in Figures 45 and 46. Under fast SCR conditions, Cu-Mn.AEI reduced the average NO production by 8.4 ppm and the total NO x The 3 wt.% Cu exchanged molecular sieve showed an average NO production of 14.5 and a total NO conversion of 77%. x It was found that the bimetallic catalysts thus exhibited significantly lower average NO production and higher total NO than the monometallic Cu-exchanged molecular sieves. x Conversion rate achieved.

[0128] Example 3. Low Speed ​​SCR The molecular sieves were impregnated with metals using the required amount of manganese(II) acetate and / or copper(II) acetate dissolved in demineralized water. The metal impregnated samples were dried at 80°C overnight and then calcined in air at 550°C for 4 hours. Catalysts were prepared with the following formulation: AEI zeolite, 1.5 wt% exchanged Cu and 1.5 wt% exchanged Mn, 1.5Cu-1.5Mn.AEI AEI zeolite, 3 wt% Cu exchanged, 3Cu.AEI

[0129] Then, the NO of the pelletized sample of the powder catalyst was xThe conversion and N2O production were tested under the following conditions: 500 ppm NH3, 175 ppm NO, 325 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and balance N2, at a space velocity of 90 K / hr. The sample was heated from room temperature to 150°C under the gas mixture described above except for NH3. At 150°C, NH3 was added to the gas mixture and the sample was held under these conditions for 30 minutes. The temperature was then ramped (heated up) from 150°C to 500°C at 5°C / min.

[0130] The results are shown in Figures 47 and 48. Under slow SCR conditions, Cu-Mn.AEI reduced the average NO production by 14.4 ppm and the total NO x The 3 wt.% Cu exchanged molecular sieve showed an average NO production of 21.4 and a total NO conversion of 74%. x Thus, the bimetallic catalysts were found to produce significantly less average NO and similar total NO compared to the monometallic Cu-exchanged molecular sieves. x Conversion rate achieved.

[0131] Example 4. Control study The molecular sieves were impregnated with metals using the required amount of manganese(II) acetate and / or copper(II) acetate dissolved in demineralized water. The metal impregnated samples were dried at 80°C overnight and then calcined in air at 550°C for 4 hours. Catalysts were prepared with the following formulation: AEI zeolite, 1.5 wt% exchanged Cu and 1.5 wt% exchanged Mn, 1.5Cu-1.5Mn.AEI AEI zeolite, 1.5 wt% Mn exchanged, 1.5Mn.AEI AEI zeolite, 1.5 wt% Cu exchanged, 1.5Cu.AEI A physical mixture of AEI zeolite with 1.5 wt. % exchange of Cu and AEI zeolite with 1.5 wt. % exchange of Mn, a physical mixture

[0132] Then, the NO of the pelletized sample of the powder catalyst was xThe conversion and N2O production were tested under the following conditions: 500 ppm NH3, 500 ppm NO, 0 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and balance N2, at a space velocity of 90 K / hr. The sample was heated from room temperature to 150°C under the gas mixture described above except for NH3. At 150°C, NH3 was added into the gas mixture and the sample was held under these conditions for 30 minutes. The temperature was then ramped (heated up) from 150°C to 500°C at 5°C / min.

[0133] The results are shown in Figures 49 and 50. Under standard SCR conditions, Cu-Mn.AEI had an average NO selectivity of 0.7% and total NO selectivity of 86%. x It was found that the 1.5 wt. % Cu exchanged molecular sieve achieved an average NO selectivity of 0.6%, but a total NO conversion of 79%. x Thus, the bimetallic Cu-Mn molecular sieve achieved a significantly higher NO conversion than the monometallic Cu-exchanged molecular sieve. x The Mn-exchanged molecular sieve showed an average NO selectivity of 2.1% and a total NO conversion of 41%. x Thus, the Cu / Mn exchanged catalyst provided significant improvements in selectivity and activity over the equivalent Mn-loaded monometallic molecular sieve. Furthermore, a physical mixture of 1.5 wt. % Cu exchanged molecular sieve and 1.5 wt. % Mn exchanged molecular sieve achieved an average NO selectivity of 0.8% and a total NO selectivity of 74%. x The results also demonstrated that the catalyst of the present invention exhibits a significant selectivity and activity advantage over the monometallic analogues. The results showed that when utilizing bimetallic Cu / Mn exchanged molecular sieves, NO 3 was significantly reduced compared to the separate mixed monometallic molecular sieves. x It shows that the conversion rate is obviously improved.

[0134] Example 5. Mn loading The molecular sieves were impregnated with metals using the required amount of manganese(II) acetate and / or copper(II) acetate dissolved in demineralized water. The metal impregnated samples were dried at 80°C overnight and then calcined in air at 550°C for 4 hours. Catalysts were prepared with the following formulation: AEI zeolite, 3 wt% Cu exchanged, 3Cu.AEI AEI zeolite, 1.5 wt% Cu exchanged, 1.5Cu.AEI AEI zeolite, 1.5 wt% Cu exchanged and 0.1 wt% Mn exchanged, 1.5Cu-0.1Mn.AEI AEI zeolite, 1.5 wt% exchanged Cu and 0.25 wt% exchanged Mn, 1.5Cu-0.25Mn.AEI AEI zeolite, 1.5 wt% exchanged Cu and 0.5 wt% exchanged Mn, 1.5Cu-0.5Mn.AEI AEI zeolite, 1.5 wt% exchanged Cu and 1.5 wt% exchanged Mn, 1.5Cu-1.5Mn.AEI AEI zeolite, 1.5 wt% exchanged Cu and 2.5 wt% exchanged Mn, 1.5Cu-2.5Mn.AEI

[0135] Then, the NO of the pelletized sample of the powder catalyst was x The conversion and N2O production were tested under the following conditions: 500 ppm NH3, 500 ppm NO, 0 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and balance N2, at a space velocity of 90 K / hr. The sample was heated from room temperature to 150°C under the gas mixture described above except for NH3. At 150°C, NH3 was added into the gas mixture and the sample was held under these conditions for 30 minutes. The temperature was then ramped (heated up) from 150°C to 500°C at 5°C / min.

[0136] The results are shown in Figures 51 and 52. The addition of 0.1 wt% Mn (Cu:Mn=15) resulted in a significant improvement in activation temperature compared to the monometallic 1.5 wt% Cu molecular sieve. Further addition of up to 1.5 wt% Mn (Cu:Mn=1) resulted in further improvement in activation temperature without significant increase in NO selectivity. The results show that at constant Cu loading, the addition of Mn to 1.5 wt% Cu catalyst significantly improved NO selectivity of the Cu-SCR catalyst without significant change in NO selectivity. x This shows a dramatic improvement in conversion rates.

[0137] Then, the NO of the pelletized sample of the powder catalyst was x The conversion and N2O production were tested under the following conditions: 500 ppm NH3, 175 ppm NO, 325 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and balance N2, at a space velocity of 90 K / hr. The sample was heated from room temperature to 150°C under the gas mixture described above except for NH3. At 150°C, NH3 was added to the gas mixture and the sample was held under these conditions for 30 minutes. The temperature was then ramped (heated up) from 150°C to 500°C at 5°C / min.

[0138] The results are shown in Figures 53 and 54. At a constant Cu loading of 1.5 wt%, the addition of 0.1 wt% Mn (Cu:Mn=15) resulted in a reduction in NO production without significant change in activation temperature compared to the monometallic 1.5 wt% Cu molecular sieve. Further additions of 0.5 wt% Mn (Cu:Mn=3), 1.0 wt% Mn (Cu:Mn=1.5), and 1.5 wt% Mn (Cu:Mn=1) resulted in improved activation temperature and lower NO production values. However, all embodiments of the Cu-Mn.AEI produced less NO than the monometallic Cu.AEI analog. Thus, the activity and selectivity of Cu-Mn can be tailored to specific applications by varying the Cu to Mn ratio and total metal content.

[0139] Example 6. Cu loading The molecular sieves were impregnated with metals using the required amount of manganese(II) acetate and / or copper(II) acetate dissolved in demineralized water. The metal impregnated samples were dried at 80°C overnight and then calcined in air at 550°C for 4 hours. Catalysts were prepared with the following formulation: AEI zeolite, 3 wt% Cu exchanged, 3Cu.AEI AEI zeolite, 1.5 wt% Mn exchanged, 1.5Mn.AEI AEI zeolite, 1.5 wt% exchanged Mn and 0.5 wt% exchanged Cu, 0.5Cu-1.5Mn.AEI AEI zeolite, 1.5 wt% exchanged Mn and 1.0 wt% exchanged Cu, 1Cu-1.5Mn.AEI AEI zeolite, 1.5 wt% exchanged Mn and 1.5 wt% exchanged Cu, 1.5Cu-1.5Mn.AEI AEI zeolite, 1.5 wt% exchanged Mn and 2.0 wt% exchanged Cu, 1.5Cu-2Mn.AEI AEI zeolite, 1.5 wt% exchanged Mn and 2.5 wt% exchanged Cu, 1.5Cu-2.5Mn.AEI AEI zeolite, 1.5 wt% exchanged Mn and 3 wt% exchanged Cu, 3Cu-1.5Mn.AEI

[0140] Then, the NO of the pelletized sample of the powder catalyst was x The conversion and N2O production were tested under the following conditions: 500 ppm NH3, 500 ppm NO, 0 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and balance N2, at a space velocity of 90 K / hr. The sample was heated from room temperature to 150°C under the gas mixture described above except for NH3. At 150°C, NH3 was added into the gas mixture and the sample was held under these conditions for 30 minutes. The temperature was then ramped (heated up) from 150°C to 500°C at 5°C / min.

[0141] The results are shown in Figures 55 and 56. At a constant Mn loading of 1.5 wt%, the addition of only 0.5 wt% Cu (Cu:Mn=0.33) significantly reduced NO compared to the monometallic 1.5 wt% Mn catalyst. x A dramatic improvement in conversion and a significant decrease in NO selectivity were observed. As the Cu content was successively increased to 1 wt% (Cu:Mn=0.67), 1.5 wt% (Cu:Mn=1), and 3.0 wt% (Cu:Mn=2), NO was observed at the expense of increased NO selectivity. x The conversion rate increases sequentially. Furthermore, the 1Cu-1.5Mn.AEI and 1.5Cu-1.5Mn.AEI catalysts showed a significant decrease in NO selectivity compared to monometallic Cu or Mn molecular sieves. However, as shown in the case of Cu:Mn, when the Cu:Mn ratio is increased excessively, most of the NO benefit is lost. The results show that at a constant Mn loading of 1.5 wt%, increasing the Cu content reduces the NO x It shows that the conversion is improved, but the selectivity to N2O increases when the Cu content is higher than the Mn content.

[0142] Example 7. Small pore zeolite The molecular sieves were impregnated with metals using the required amount of manganese(II) acetate and / or copper(II) acetate dissolved in demineralized water. The metal impregnated samples were dried at 80°C overnight and then calcined in air at 550°C for 4 hours. Catalysts were prepared with the following formulation: AEI zeolite, 1.5 wt% exchanged Mn and 1.5 wt% exchanged Cu, 1.5Cu-1.5Mn.AEI CHA zeolite, 1.5 wt% exchanged Mn and 1.5 wt% exchanged Cu, 1.5Cu-1.5Mn.CHA

[0143] Standard SCR: NO of pelletized samples of powder catalyst was then xThe conversion and N2O production were tested under the following conditions: 500 ppm NH3, 500 ppm NO, 0 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and balance N2, at a space velocity of 90 K / hr. The sample was heated from room temperature to 150°C under the gas mixture mentioned above except for NH3. At 150°C, NH3 was added into the gas mixture and the sample was held under these conditions for 30 minutes. The temperature was then ramped from 150°C to 500°C at 5°C / min (ramp up). The results are shown in Figures 57 and 58. The results show that Cu-Mn.CHA performs similarly to Cu-Mn.AEI, indicating that this strategy is effective for small pore zeolites.

[0144] Rapid SCR: NO from pelletized samples of powder catalyst x The conversion and N2O production were tested under the following conditions: 500 ppm NH3, 250 ppm NO, 250 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and balance N2, at a space velocity of 90 K / hr. The sample was heated from room temperature to 150°C under the gas mixture mentioned above except for NH3. At 150°C, NH3 was added into the gas mixture and the sample was held under these conditions for 30 minutes. The temperature was then ramped from 150°C to 500°C at 5°C / min (ramp up). The results are shown in Figures 59 and 60. The results show that both Cu-Mn.CHA and Cu-Mn.AEI produced similar total NO2O production at 82%. x However, Cu-Mn.AEI produced less N2O than the Cu-Mn.CHA, which produced an average of 11.8 ppm N2O.

[0145] Low-SCR: NO from pelletized samples of powder catalyst was then xThe conversion and N2O production were tested under the following conditions: 500 ppm NH3, 175 ppm NO, 325 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and balance N2, at a space velocity of 90 K / hr. The sample was heated from room temperature to 150°C under the gas mixture mentioned above except for NH3. At 150°C, NH3 was added into the gas mixture and the sample was held under these conditions for 30 minutes. The temperature was then ramped from 150°C to 500°C at 5°C / min (ramp up). The results are shown in Figures 61 and 62. The results show that both Cu-Mn.CHA and Cu-Mn.AEI produced similar total NO2O production at 76%. x However, Cu-Mn.AEI produced less N2O than the Cu-Mn.CHA, which produced an average of 17.1 ppm N2O.

[0146] Example 8. Medium pore zeolite / large pore zeolite The molecular sieves were impregnated with metals using the required amount of manganese(II) acetate and / or copper(II) acetate dissolved in demineralized water. The metal impregnated samples were dried at 80°C overnight and then calcined in air at 550°C for 4 hours. Catalysts were prepared with the following formulation: BEA zeolite, 3 wt% Cu exchanged, 3Cu.BEA BEA zeolite, 1.5 wt% exchanged Mn and 1.5 wt% exchanged Cu, 1.5Cu-1.5Mn.BEA MFI zeolite, 3 wt% Cu exchanged, 3Cu.MFI MFI zeolite, 1.5 wt% exchanged Mn and 1.5 wt% exchanged Cu, 1.5Cu-1.5Mn.MFI

[0147] Then, the catalytic NO x Conversion and N2O selectivity were tested under the following conditions: 500 ppm NH3, 500 ppm NO, 0 ppm NO2, SV=90K / hr. The results are shown in Figures 63 and 64. Under standard SCR conditions, both Cu-Mn.BEA and Cu.BEA showed similar total NO2 conversion at 82% and 85%, respectively. xIt was found that the Cu-Mn.BEA achieved a conversion rate of 72% compared to 5.9% for the Cu-Mn.BEA. However, the Cu-Mn.BEA showed an average NO selectivity of 0.8%, whereas the Cu.BEA showed an average NO selectivity of 5.9%. Thus, the Cu-Mn.BEA provided a significant reduction in NO compared to the typical Cu-exchanged BEA. Under standard SCR conditions, the Cu-Mn.MFI reduced the total NO by 72%. x It was found to achieve a conversion rate and an average NO selectivity of 1.5%. However, the monometallic Cu.MFI achieved a higher NO conversion rate of 79%. x Conversion could be achieved, but with a higher average NO selectivity at 2.9%. Thus, Cu-Mn.BEA provided a significant reduction in NO compared to the typical Cu-exchanged BEA. The results show that Cu-Mn.BEA and Cu-Mn.MFI provided a significant reduction in NO selectivity compared to Cu.BEA and Cu.MFI, respectively. Thus, the strategy of utilizing dual Cu and Mn exchanged molecular sieves is effective for both medium and large pore zeolites.

[0148] Example 9. SAR range The molecular sieves were impregnated with metals using the required amount of manganese(II) acetate and / or copper(II) acetate dissolved in demineralized water. The metal impregnated samples were dried at 80°C overnight and then calcined in air at 550°C for 4 hours. Catalysts were prepared with the following formulation: CHA zeolite, SAR=22, 1.5 wt% Mn exchanged and 1.5 wt% Cu exchanged, SAR22 CHA zeolite, SAR=13, 1.5 wt% Mn exchanged and 1.5 wt% Cu exchanged, SAR 13

[0149] Standard SCR: NO of pelletized samples of powder catalyst was then xThe conversion and N2O production were tested under the following conditions: 500 ppm NH3, 500 ppm NO, 0 ppm NO2, 14% O2, 4.6% H2O, 5.0% CO2, and balance N2, at a space velocity of 90 K / hr. The sample was heated from room temperature to 150°C under the gas mixture described above except for NH3. At 150°C, NH3 was added to the gas mixture and the sample was held under these conditions for 30 minutes. The temperature was then ramped from 150°C to 500°C at 5°C / min. The results are shown in Figures 65 and 66. The results show that Cu-Mn.CHA at SAR13 reduced 92% of the total NO x The Cu-Mn.CHA at SAR22 achieved an average NO conversion and selectivity of 0.5%, whereas the Cu-Mn.CHA at SAR22 achieved 89% of the total NO x The results show that the conversion and average NO selectivity of 0.7% were achieved. These results indicate that the use of the Cu-Mn bimetallic molecular sieve strategy is effective over a wide range of SAR. In addition, the lower SAR materials show a decrease in NO selectivity.

[0150] Example 10. Coated monoliths The molecular sieves were impregnated with metals using the required amount of manganese(II) acetate and / or copper(II) acetate dissolved in demineralized water. The metal impregnated samples were dried at 80°C overnight and then calcined in air at 550°C for 4 hours. Catalysts were prepared with the following formulation: AEI zeolite, 3 wt% Cu exchanged, 3Cu.AEI AEI zeolite, 1.5 wt% Cu exchanged, 1.5Cu.AEI AEI zeolite, 1.5 wt% exchanged Mn and 1.5 wt% exchanged Cu, 1.5Cu-1.5Mn.AEI

[0151] Cu.zeolite catalysts and Mn-Cu.zeolite catalysts were prepared by known prior art ion exchange techniques using copper acetate and manganese acetate solutions. Washcoats were prepared by combining the exchanged Cu.zeolite or Mn-Cu.zeolite solutions with an alumina binder and a hydroxyethyl cellulose rheology modifier. The washcoats were applied to a ceramic substrate and then negative pressure was used to draw the washcoat down onto the substrate. The articles were dried and calcined at about 500°C for about 1 hour.

[0152] Standard SCR: Next, the NO of the coated monolith x The conversion and N2O production were tested under the following conditions: 550 ppm NH3, 500 ppm NO, 0 ppm NO2, 10% O2, 6.0% H2O, 6.0% CO2, and balance N2, at a space velocity of 60 K / h. The sample was heated from room temperature to 150°C under the gas mixture described above except for NH3. At 150°C, NH3 was added to the gas mixture and under these conditions, the NO2O production in the outlet gas was 100%. x The samples were then held until both NO and NH3 concentrations reached steady state values. x The flow of NO and NH3 was stopped, and the temperature was then increased to 450°C, held for 10 minutes, and then cooled to 200°C. x and NH3 flow, and NO in the outlet gas x The conditions were held until both the H and NH concentrations reached steady-state values. The entire process was then repeated for additional temperatures of 250°C, 350°C, 450°C, and 550°C.

[0153] [Table 1]

[0154] The results are shown in Table 1. Under standard SCR conditions, both the Cu-Mn.AEI and the 3 wt.% Cu-exchanged molecular sieve produced similar total NO at 82% and 85%, respectively. x It was found that the 3 wt% Cu-exchanged molecular sieve achieved a conversion of 3.1 ppm average NO production, whereas the Cu-Mn.AEI showed an average NO production of 1.1 ppm. Thus, the catalyst of the present invention provided a significant reduction in NO production compared to the typical Cu-exchanged molecular sieve. In addition, the 1.5 wt% Cu-exchanged AEI achieved a similar average NO production of 1.2 ppm, but with 78% less total NO production. x Thus, the fully loaded monolith coated with the Cu-Mn catalyst of the present invention showed a significant advantage over the monolith containing only the monometallic catalyst under standard SCR conditions.

[0155] The coated monolith was also aged at 750°C in 10% water in air for 80 hours. The sample was heated to 250°C in air only at a rate of 10°C / min. The monolith was then heated to 750°C in air with 10% H2O at a rate of 10°C / min. After holding at 750°C for 80 hours, the sample was cooled in a steam / air mixture until the temperature was below 250°C. The sample was then cooled from 250°C to room temperature in an air-only stream. The NO of the aged monolith was then measured. x Conversion and N2O selectivity were tested under the following conditions: 550 ppm NH3, 500 ppm NO, 0 ppm NO2, 10% O2, 6.0% H2O, 6.0% CO2, and balance N2 at a space velocity of 60 K / hr.

[0156] The results are shown in Table 1. After hydrothermal aging under standard SCR conditions, the Cu-Mn.AEI reduced the total NO x It was found that the conversion could be achieved while maintaining an average NO production as low as 2.6 ppm. The 3 wt. % Cu exchanged molecular sieve reduced the total NO by 75%. xThe results showed that the conversion of the 1.5 wt. % Cu-exchanged AEI also achieved a higher average NO production of 3.4 ppm, and a 50% reduction in the total NO x Only a small conversion could be achieved. Thus, the catalyst of the present invention provided a significant reduction in N2O compared to the typical Cu-exchanged molecular sieve.

[0157] Rapid SCR: Then, the coating monolith NO x The conversion and N2O production were tested under the following conditions: 550 ppm NH3, 250 ppm NO, 250 ppm NO2, 10% O2, 6.0% H2O, 6.0% CO2, and balance N2, at a space velocity of 60 K / h. The sample was heated from room temperature to 150°C under the gas mixture described above except for NH3. At 150°C, NH3 was added to the gas mixture and under these conditions, the NO2O production in the outlet gas was reduced by 10%. x The samples were then held until both NO and NH3 concentrations reached steady state values. x The flow of NO and NH3 was stopped, and the temperature was then increased to 450°C, held for 10 minutes, and then cooled to 200°C. x and NH3 flow, and NO in the outlet gas x The conditions were held until both the H and NH concentrations reached steady-state values. The entire process was then repeated for additional temperatures of 250°C, 350°C, 450°C, and 550°C.

[0158] The results are shown in Table 1. Under fast SCR conditions, Cu-Mn.AEI reduced the total NO x It was found that the 3 wt. % Cu-exchanged molecular sieve and the 1.5 wt. % Cu-exchanged molecular sieve were able to achieve a conversion of 83% and 86%, respectively, of the total NO2O production. xConversion and average NO production of only 8.9 ppm and 4.5 ppm, respectively, could be achieved. Thus, the fully loaded monolith coated with the Cu-Mn catalyst of the present invention showed a significant advantage over the monolith containing only the monometallic catalyst under fast SCR conditions.

[0159] Low-speed SCR: NO of the coated monolith x The conversion and N2O production were tested under the following conditions: 550 ppm NH3, 174 ppm NO, 325 ppm NO2, 10% O2, 6.0% H2O, 6.0% CO2, and balance N2, at a space velocity of 60 K / h. The sample was heated from room temperature to 150°C under the gas mixture described above except for NH3. At 150°C, NH3 was added to the gas mixture and under these conditions, the NO2O production in the outlet gas was 1.0 ppm. x The samples were then held until both NO and NH3 concentrations reached steady state values. x The flow of NO and NH3 was stopped, and the temperature was then increased to 450°C, held for 10 minutes, and then cooled to 200°C. x and NH3 flow, and NO in the outlet gas x The conditions were held until both the H and NH concentrations reached steady-state values. The entire process was then repeated for additional temperatures of 250°C, 350°C, 450°C, and 550°C.

[0160] The results are shown in Table 1. Under low-rate conditions, Cu-Mn.AEI produced a very high 81% total NO x It was found that the 3 wt. % Cu-exchanged molecular sieve and the 1.5 wt. % Cu-exchanged molecular sieve achieved a conversion of 75% and 72%, respectively, of the total NO2O production. x Conversions and average NO production of only 12.2 ppm and 7.5 ppm, respectively, could be achieved. Thus, the fully loaded monolith coated with the Cu-Mn catalyst of the present invention showed a significant advantage over the monolith containing only the monometallic catalyst under low-rate SCR conditions.

Claims

1. A catalytic composition for treating exhaust gas, said catalytic composition comprising a molecular sieve, said molecular sieve comprising exchanged copper and exchanged manganese.

2. 2. The catalyst composition of claim 1, wherein the molecular sieve is an aluminosilicate molecular sieve.

3. 3. The catalyst composition of claim 1 or 2, wherein the molecular sieve comprises a zeolite.

4. 4. The catalyst composition of claim 3, wherein the zeolite has an SAR of about 5 to about 200.

5. 5. The catalyst composition of claim 3, wherein the zeolite has an SAR of about 10 to about 50.

6. 6. The catalyst composition of claim 3 or 5, wherein the zeolite has an SAR of about 10 to about 30.

7. The catalyst composition of any one of claims 3 to 6, wherein the molecular sieve comprises a small pore zeolite.

8. 8. The catalyst composition of claim 7, wherein the small pore zeolite has a crystalline framework type selected from AEI, CHA, and combinations thereof.

9. 9. The catalyst composition of claim 3, wherein the molecular sieve comprises a medium pore zeolite or a large pore zeolite.

10. 10. The catalyst composition of claim 9, wherein the zeolite has a crystalline framework type selected from BEA, MFI, and combinations thereof.

11. 11. The catalyst composition of any one of claims 1 to 10, wherein the weight ratio of copper to manganese is from about 0.1 to about 50.

12. 12. The catalyst composition of any one of claims 1 to 11, wherein the weight ratio of copper to manganese is from about 0.2 to about 15.

13. 13. The catalyst composition of any one of claims 1 to 12, wherein the weight ratio of copper to manganese is from about 0.3 to about 3.

14. 14. The catalyst composition of any one of claims 1 to 13, wherein the copper and manganese are present in a total amount of about 0.1 to about 10 weight percent, based on the weight of the molecular sieve.

15. 15. The catalyst composition of any one of claims 1 to 14, wherein the copper and manganese are present in a total amount of about 1 to about 7 weight percent, based on the weight of the molecular sieve.

16. 16. The catalyst composition of any one of claims 1 to 15, wherein the copper and manganese are present in a total amount of about 2 to about 5 weight percent, based on the weight of the molecular sieve.

17. 17. The catalyst composition of any one of claims 1 to 16, wherein the copper is present in an amount of about 0.05 to about 7 weight percent based on the weight of the molecular sieve.

18. 18. The catalyst composition of any one of claims 1 to 17, wherein the copper is present in an amount of about 0.5 to about 5 weight percent based on the weight of the molecular sieve.

19. 19. The catalyst composition of any one of claims 1 to 18, wherein the copper is present in an amount of about 1 to about 4 weight percent based on the weight of the molecular sieve.

20. 20. The catalyst composition of any one of claims 1 to 19, wherein the manganese is present in an amount of about 0.05 to about 7 weight percent based on the weight of the molecular sieve.

21. 21. The catalyst composition of any one of claims 1 to 20, wherein the manganese is present in an amount of about 0.1 to about 5 weight percent based on the weight of the molecular sieve.

22. 22. The catalyst composition of any one of claims 1 to 21, wherein the manganese is present in an amount of about 0.5 to about 2.5 wt. %, based on the weight of the molecular sieve.

23. 23. The catalyst composition according to any one of claims 1 to 22, wherein the molecular sieve has a transition metal to aluminium ratio of less than 1.

24. Catalyst composition according to any one of claims 1 to 23, wherein the molecular sieve has a transition metal to aluminium ratio of less than 0.

75.

25. Catalyst composition according to any one of claims 1 to 24, wherein the molecular sieve has a transition metal to aluminium ratio of less than 0.

5.

26. N.H. ３ And NO ｘ 26. The catalyst composition of any one of claims 1 to 25, which is effective to promote a reaction with to produce nitrogen and water.

27. About 20% to about 45% less N compared to Cu-exchanged molecular sieves under standard SCR conditions. ２ The catalyst composition according to any one of claims 1 to 26, which produces O.

28. Under standard SCR conditions, it produces about 30% to about 60% more total NO than Mn-exchanged molecular sieves. ｘ The catalytic composition according to any one of claims 1 to 27,

29. Under standard SCR conditions, it produces about 1% to about 15% less N than a physical mixture of Cu-exchanged and Mn-exchanged molecular sieves. ２ The catalyst composition of any one of claims 1 to 28, which produces O.

30. Under standard SCR conditions, it produces about 1% to about 25% more total NO than a physical mixture of Cu-exchanged and Mn-exchanged molecular sieves. ｘ The catalytic composition according to any one of claims 1 to 29,

31. About 25% to about 60% less N compared to Cu-exchanged molecular sieves under fast SCR conditions. ２ The catalyst composition according to any one of claims 1 to 30, which produces O.

32. Under fast SCR conditions, about 1% to about 20% more total NO compared to Cu-exchanged molecular sieves. ｘ The catalytic composition according to any one of claims 1 to 31,

33. About 20% to about 45% less N compared to Cu-exchanged molecular sieves under slow SCR conditions. ２ The catalyst composition according to any one of claims 1 to 32, which produces O.

34. After aging at 900° C., under standard SCR conditions, the Cu-exchanged molecular sieve produces about 35% to about 65% less N. ２ The catalyst composition of any one of claims 1 to 33, which produces O.

35. A catalytic article comprising a substrate coated with the catalytic composition of any one of claims 1 to 34.

36. 36. The catalytic article of claim 35, further comprising one or more additional catalytic compositions.

37. 37. The catalytic article of claim 36, wherein the one or more additional catalyst compositions comprise a Cu or Fe exchanged molecular sieve catalyst.

38. 38. The catalytic article of claim 36 or 37, wherein the exchanged copper and exchanged manganese containing molecular sieve is upstream of the one or more additional catalytic compositions.

39. 38. The catalytic article of claim 36 or 37, wherein the exchanged copper and exchanged manganese containing molecular sieve is in an upper layer and the one or more additional catalytic compositions are in a lower layer.

40. The catalytic article of any one of claims 35 to 39, further comprising a catalytic composition comprising a platinum group metal.

41. 1. A method for treating an exhaust gas containing nitrogen oxides, comprising contacting the exhaust gas with a nitrogenous reducing agent in the presence of a catalytic composition, the catalytic composition comprising a molecular sieve, the molecular sieve comprising exchanged copper and exchanged manganese.

42. 42. The method of claim 41 , wherein the nitrogenous reductant comprises ammonia.

43. 43. The method of claim 41 or 42, wherein the contacting occurs at a temperature of about 150°C to about 750°C.

44. 44. The method of any one of claims 41 to 43, wherein the molecular sieve is an aluminosilicate molecular sieve.

45. 45. The method of any one of claims 41 to 44, wherein the molecular sieve comprises a zeolite.

46. 46. ​​The method of claim 45, wherein the zeolite has an SAR of from about 5 to about 200.

47. 46. ​​The method of claim 45, wherein the zeolite has an SAR of about 10 to about 50.

48. 46. ​​The method of claim 45, wherein the zeolite has an SAR of about 10 to about 30.

49. The method of any one of claims 41 to 48, wherein the molecular sieve comprises a small pore zeolite.

50. 50. The method of claim 49, wherein the small pore zeolite has a crystalline framework type selected from AEI, CHA, and combinations thereof.

51. 49. The method of any one of claims 41 to 48, wherein the molecular sieve comprises a medium pore zeolite or a large pore zeolite.

52. 52. The method of claim 51, wherein the zeolite has a crystalline framework type selected from BEA, MFI, and combinations thereof.

53. 53. The method of any one of claims 41 to 52, wherein the weight ratio of copper to manganese is from about 0.1 to about 50.

54. 53. The method of any one of claims 41 to 52, wherein the weight ratio of copper to manganese is from about 0.2 to about 15.

55. 53. The method of any one of claims 41 to 52, wherein the weight ratio of copper to manganese is from about 0.3 to about 3.

56. 56. The method of any one of claims 41 to 55, wherein the copper and manganese are present in a total amount of about 0.1 to about 10 weight percent, based on the weight of the molecular sieve.

57. 56. The method of any one of claims 41 to 55, wherein the copper and manganese are present in a total amount of about 1 to about 7 weight percent, based on the weight of the molecular sieve.

58. 56. The method of any one of claims 41 to 55, wherein the copper and manganese are present in a total amount of about 2 to about 5 weight percent, based on the weight of the molecular sieve.

59. 59. The method of any one of claims 41 to 58, wherein the copper is present in an amount of about 0.05 to about 7 weight percent based on the weight of the molecular sieve.

60. 59. The method of any one of claims 41 to 58, wherein the copper is present in an amount of about 0.5 to about 5 weight percent based on the weight of the molecular sieve.

61. 59. The method of any one of claims 41 to 58, wherein the copper is present in an amount of about 1 to about 4 weight percent based on the weight of the molecular sieve.

62. 62. The method of any one of claims 41 to 61, wherein the manganese is present in an amount of about 0.05 to about 7 weight percent based on the weight of the molecular sieve.

63. 62. The method of any one of claims 41 to 61, wherein the manganese is present in an amount of about 0.1 to about 5 wt. %, based on the weight of the molecular sieve.

64. 62. The method of any one of claims 41 to 61, wherein the manganese is present in an amount of about 0.5 to about 2.5 wt. %, based on the weight of the molecular sieve.

65. 65. The method of any one of claims 41 to 64, wherein the molecular sieve has a transition metal to aluminum ratio of less than 1.

66. 65. The method of any one of claims 41 to 64, wherein the molecular sieve has a transition metal to aluminum ratio of less than 0.

75.

67. 65. The method of any one of claims 41 to 64, wherein the molecular sieve has a transition metal to aluminum ratio of less than 0.

5.

68. The catalyst composition comprises NH ３ And NO ｘ 68. The method of any one of claims 41 to 67, effective to promote a reaction with to produce nitrogen and water.

69. The catalyst composition produces about 20% to about 45% less N under standard SCR conditions compared to Cu-exchanged molecular sieves. ２ The method of any one of claims 41 to 68, wherein O is produced.

70. The catalyst composition produces about 30% to about 60% more total NO than Mn-exchanged molecular sieves under standard SCR conditions. ｘ The method according to any one of claims 41 to 69, wherein

71. The catalyst composition has about 1% to about 15% less N than a physical mixture of Cu-exchanged and Mn-exchanged molecular sieves under standard SCR conditions. ２ The method of any one of claims 41 to 70, wherein O is produced.

72. The catalyst composition produces about 1% to about 25% more total NO than a physical mixture of Cu-exchanged and Mn-exchanged molecular sieves under standard SCR conditions. ｘ The method according to any one of claims 41 to 71, wherein

73. The catalyst composition produces about 25% to about 60% less N under fast SCR conditions compared to Cu-exchanged molecular sieves. ２ The method of any one of claims 41 to 72, wherein O is produced.

74. The catalyst composition produces about 1% to about 20% more NO under fast SCR conditions compared to a Cu-exchanged molecular sieve. ｘ The method according to any one of claims 41 to 73, wherein

75. The catalyst composition produces about 20% to about 45% less N under slow SCR conditions compared to Cu-exchanged molecular sieves. ２ The method of any one of claims 41 to 74, wherein O is produced.

76. The catalyst composition produces about 35% to about 65% less N than a Cu-exchanged molecular sieve under standard SCR conditions after aging at 900° C. ２ The method of any one of claims 41 to 75, wherein O is produced.

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