Bimetallic Cu / Mn catalysts for selective catalytic reduction

Abstract

The present invention provides a catalyst composition for treating an exhaust gas, the catalyst composition comprising a molecular sieve comprising exchanged copper and exchanged manganese.

Description

[0001] This application is a divisional application of a Chinese patent application with the application number 201980053259.3, the filing date of August 30, 2019, and the invention title of "Bimetallic Cu / Mn Catalysts for Selective Catalytic Reduction". Background Art

[0002] The present invention relates to catalysts and a method for converting nitrogen oxides in a gas (such as the exhaust gas of a lean-burning vehicle internal combustion engine) into nitrogen by contacting the nitrogen oxides with a nitrogen-containing reducing agent in the presence of a molecular sieve catalyst containing a transition metal.

[0003] The selective catalytic reduction (SCR) of NO by nitrogen-containing compounds such as ammonia or urea x has been used in many applications, including industrial stationary applications. Recently, SCR-based NO x reduction systems are being developed in Europe, Japan, and the United States for many vehicle (mobile) applications, such as for treating diesel exhaust gases.

[0004] In the NH 3 SCR system, several chemical reactions occur, most of which represent the desired reactions for reducing NO x , especially NO and NO 2 to nitrogen. The main reaction is represented by reaction (1).

[0005] 4NO + 4NH 3 + O 2 → 4N 2 + 6H 2 O (1)

[0006] Competitive non-selective reactions with oxygen can produce secondary emissions or can non-productively consume ammonia. One such non-selective reaction is the complete oxidation of ammonia, as shown in reaction (2).

[0007] 4NH 3 + 5O 2 → 4NO + 6H 2 O (2)

[0008] In addition, side reactions can lead to undesirable products such as N 2 O, as represented by reaction (3).

[0009] 4NH 3 + 5NO + 3O 2 → 4N 2 O + 6H 2 O (3)

[0010] Molecular sieves, including aluminosilicate zeolites, can be used as NO x with NH 3The catalyst of the SCR. One application is to control NO from a vehicle diesel engine with a reducing agent obtainable from an ammonia precursor such as urea or by injecting ammonia itself. x Emissions. To promote catalytic activity, transition metals can be incorporated into aluminosilicate zeolites.

[0011] It is desired to prepare a catalyst composition for SCR of NOx, which has improved NOx conversion and reduced N 2 O production. SUMMARY OF THE INVENTION

[0012] According to some aspects of the present invention, a catalyst composition for treating exhaust gas comprises a molecular sieve containing exchanged copper and exchanged manganese. In some aspects, the molecular sieve is an aluminosilicate molecular sieve. In some aspects, the molecular sieve includes zeolite. Suitable zeolites can have, for example, a silica to alumina molar ratio (SAR) of about 5 to about 200, about 10 to about 50, or about 10 to about 30. In some aspects, the molecular sieve includes small pore zeolites. Suitable small pore zeolites can have a crystal framework type selected from, for example, AEI, CHA, and combinations thereof. In some aspects, the molecular sieve includes mesoporous or macroporous zeolites. Suitable mesoporous or macroporous zeolites can have a crystal framework type selected from, for example, BEA, MFI, and combinations thereof.

[0013] In some aspects, the molecular sieve includes a weight ratio of copper to manganese of about 0.1 to about 50, about 0.2 to about 15, or about 0.3 to about 3. In some aspects, based on the weight of the molecular sieve, the molecular sieve contains copper and manganese present in a total amount of about 0.1 wt% to about 10 wt%, about 1 wt% to about 7 wt%, or about 2 wt% to about 5 wt%. In some aspects, based on the weight of the molecular sieve, the molecular sieve contains copper in an amount of about 0.05 wt% to about 7 wt%, about 0.5 wt% to about 5 wt%, or about 1 wt% to about 4 wt%. In some aspects, based on the weight of the molecular sieve, the molecular sieve contains manganese in an amount of about 0.05 wt% to about 7 wt%, about 0.1 wt% to about 5 wt%, or about 0.5 wt% to about 2.5 wt%. In some aspects, the molecular sieve includes a transition metal to aluminum ratio of <1, <0.75, or <0.5.

[0014] In some aspects, the catalyst composition effectively promotes the reaction of NH 3 with NOx to form nitrogen and water. In certain aspects, the catalyst composition produces about 20% to about 45% less N 2 O than the Cu-exchanged molecular sieve under standard SCR conditions. In some aspects, the catalyst composition converts about 30% to about 60% more total NO x. In some aspects, the catalyst composition produces about 1% to about 15% less N 2 O than a physical mixture of a Cu-exchanged molecular sieve and an Mn-exchanged molecular sieve under standard SCR conditions. In some aspects, the catalyst composition converts about 1% to about 25% more total NO x than a physical mixture of a Cu-exchanged molecular sieve and an Mn-exchanged molecular sieve under standard SCR conditions. In some aspects, the catalyst composition produces about 25% to about 60% less N 2 O than a Cu-exchanged molecular sieve under fast SCR conditions. In some aspects, the catalyst composition converts about 1% to about 20% more total NO than a Cu-exchanged molecular sieve under fast SCR conditions. In some aspects, the catalyst composition produces about 20% to about 45% less N x O than a Cu-exchanged molecular sieve under slow SCR conditions. In some aspects, the catalyst composition produces about 35% to about 65% less N 2 O than a Cu-exchanged molecular sieve under standard SCR conditions after aging at 900 °C. 2 .

[0015] According to some aspects of the present invention, a catalyst article includes a substrate coated with a catalyst composition that includes a molecular sieve that includes exchanged copper and exchanged manganese. In some aspects, the substrate may further include one or more additional catalysts, such as one or more Cu-exchanged or Fe-exchanged molecular sieve catalysts. In some aspects, the molecular sieve that includes exchanged copper and exchanged manganese is upstream of one or more additional catalyst compositions. In some aspects, the molecular sieve that includes exchanged copper and exchanged manganese is in a top layer and one or more additional catalyst compositions are in a bottom layer. In some aspects, the catalyst article further includes a catalyst composition that contains a platinum group metal.

[0016] According to some aspects of the present invention, a method of treating an exhaust gas containing nitrogen oxides includes contacting the exhaust gas with a nitrogen-containing reducing agent in the presence of a catalyst composition that includes a molecular sieve that includes exchanged copper and exchanged manganese. In some aspects, the nitrogen-containing reducing agent includes ammonia. In some aspects, the contacting occurs at a temperature of about 150 °C to about 750 °C.

[0017] Embodiments of the present invention include:

[0018] 1) A catalyst composition for treating an exhaust gas, the catalyst composition including a molecular sieve that includes exchanged copper and exchanged manganese.

[0019] 2) The catalyst composition according to embodiment 1, wherein the molecular sieve is an aluminosilicate molecular sieve.

[0020] 3) The catalyst composition according to embodiment 1 or 2, wherein the molecular sieve comprises zeolite.

[0021] 4) The catalyst composition according to embodiment 3, wherein the zeolite has a SAR of about 5 to about 200.

[0022] 5) The catalyst composition according to embodiment 3 or 4, wherein the zeolite has a SAR of about 10 to about 50.

[0023] 6) The catalyst composition according to embodiment 3 or 5, wherein the zeolite has a SAR of about 10 to about 30.

[0024] 7) The catalyst composition according to any one of embodiments 3 to 6, wherein the molecular sieve comprises small-pore zeolite.

[0025] 8) The catalyst composition according to embodiment 7, wherein the small-pore zeolite has a crystal framework type selected from AEI, CHA, and combinations thereof.

[0026] 9) The catalyst composition according to any one of embodiments 3 to 8, wherein the molecular sieve comprises mesoporous or macroporous zeolite.

[0027] 10) The catalyst composition according to embodiment 9, wherein the zeolite has a crystal framework type selected from BEA, MFI, and combinations thereof.

[0028] 11) The catalyst composition according to any one of the foregoing embodiments, wherein the weight ratio of copper to manganese is about 0.1 to about 50.

[0029] 12) The catalyst composition according to any one of the foregoing embodiments, wherein the weight ratio of copper to manganese is about 0.2 to about 15.

[0030] 13) The catalyst composition according to any one of the foregoing embodiments, wherein the weight ratio of copper to manganese is about 0.3 to about 3.

[0031] 14) The catalyst composition according to any one of the foregoing embodiments, wherein the copper and the manganese are present in a total amount of about 0.1 wt% to about 10 wt% based on the weight of the molecular sieve.

[0032] 15) The catalyst composition according to any one of the foregoing embodiments, wherein the copper and the manganese are present in a total amount of about 1 wt% to about 7 wt% based on the weight of the molecular sieve.

[0033] 16) The catalyst composition according to any one of the foregoing embodiments, wherein the copper and the manganese are present in a total amount of about 2 wt% to about 5 wt% based on the weight of the molecular sieve.

[0034] 17) The catalyst composition according to any one of the foregoing embodiments, wherein the copper is present in an amount of from about 0.05 wt% to about 7 wt% based on the weight of the molecular sieve.

[0035] 18) The catalyst composition according to any one of the foregoing embodiments, wherein the copper is present in an amount of from about 0.5 wt% to about 5 wt% based on the weight of the molecular sieve.

[0036] 19) The catalyst composition according to any one of the foregoing embodiments, wherein the copper is present in an amount of from about 1 wt% to about 4 wt% based on the weight of the molecular sieve.

[0037] 20) The catalyst composition according to any one of the foregoing embodiments, wherein the manganese is present in an amount of from about 0.05 wt% to about 7 wt% based on the weight of the molecular sieve.

[0038] 21) The catalyst composition according to any one of the foregoing embodiments, wherein the manganese is present in an amount of from about 0.1 wt% to about 5 wt% based on the weight of the molecular sieve.

[0039] 22) The catalyst composition according to any one of the foregoing embodiments, wherein the manganese is present in an amount of from about 0.5 wt% to about 2.5 wt% based on the weight of the molecular sieve.

[0040] 23) The catalyst composition according to any one of the foregoing embodiments, wherein the molecular sieve has a transition metal to aluminum ratio of <1.

[0041] 24) The catalyst composition according to any one of the foregoing embodiments, wherein the molecular sieve has a transition metal to aluminum ratio of <0.75.

[0042] 25) The catalyst composition according to any one of the foregoing embodiments, wherein the molecular sieve has a transition metal to aluminum ratio of <0.5.

[0043] 26) The catalyst composition according to any one of the foregoing embodiments, wherein the catalyst composition effectively promotes the reaction of NH 3 with NOx to form nitrogen and water.

[0044] 27) The catalyst composition according to any one of the foregoing embodiments, wherein the catalyst composition produces about 20% to about 45% less N 2 O under standard SCR conditions than a Cu-exchanged molecular sieve.

[0045] 28) The catalyst composition according to any one of the preceding embodiments, wherein the catalyst composition converts approximately 30% to approximately 60% more total NO than an Mn-exchanged molecular sieve under standard SCR conditions x 。

[0046] 29) The catalyst composition according to any one of the preceding embodiments, wherein the catalyst composition produces approximately 1% to approximately 15% less N 2 O than a physical mixture of a Cu-exchanged molecular sieve and an Mn-exchanged molecular sieve under standard SCR conditions

[0047] 30) The catalyst composition according to any one of the preceding embodiments, wherein the catalyst composition converts approximately 1% to approximately 25% more total NO than a physical mixture of a Cu-exchanged molecular sieve and an Mn-exchanged molecular sieve under standard SCR conditions x 。

[0048] 31) The catalyst composition according to any one of the preceding embodiments, wherein the catalyst composition produces approximately 25% to approximately 60% less N 2 O than a Cu-exchanged molecular sieve under fast SCR conditions

[0049] 32) The catalyst composition according to any one of the preceding embodiments, wherein the catalyst composition converts approximately 1% to approximately 20% more total NO than a Cu-exchanged molecular sieve under fast SCR conditions x 。

[0050] 33) The catalyst composition according to any one of the preceding embodiments, wherein the catalyst composition produces approximately 20% to approximately 45% less N 2 O than a Cu-exchanged molecular sieve under slow SCR conditions

[0051] 34) The catalyst composition according to any one of the preceding embodiments, wherein the catalyst composition produces approximately 35% to approximately 65% less N 2 O than a Cu-exchanged molecular sieve under standard SCR conditions after aging at 900 °C

[0052] 35) A catalyst article comprising a substrate coated with the catalyst composition according to any one of embodiments 1 to 34

[0053] 36) The catalyst article according to embodiment 35, further comprising one or more additional catalyst compositions

[0054] 37) The catalyst article according to embodiment 36, wherein the one or more additional catalyst compositions comprise a Cu-exchanged molecular sieve catalyst or an Fe-exchanged molecular sieve catalyst

[0055] 38) The catalyst article according to embodiment 36 or 37, wherein the molecular sieve containing the exchanged copper and the exchanged manganese is present upstream of the one or more additional catalyst compositions.

[0056] 39) The catalyst article according to embodiment 36 or 37, wherein the molecular sieve containing the exchanged copper and the exchanged manganese is present in the top layer, and the one or more additional catalyst compositions are present in the bottom layer.

[0057] 40) The catalyst article according to embodiments 35 to 39, further comprising a catalyst composition containing a platinum group metal.

[0058] 41) A method for treating an exhaust gas containing nitrogen oxides, comprising contacting the exhaust gas with a nitrogen-containing reducing agent in the presence of a catalyst composition, the catalyst composition comprising a molecular sieve containing exchanged copper and exchanged manganese.

[0059] 42) The method according to embodiment 41, wherein the nitrogen-containing reducing agent comprises ammonia.

[0060] 43) The method according to embodiment 41 or embodiment 42, wherein the contacting occurs at a temperature of about 150 °C to about 750 °C.

[0061] 44) The method according to any one of embodiments 41 to 43, wherein the molecular sieve is an aluminosilicate molecular sieve.

[0062] 45) The method according to any one of embodiments 41 to 44, wherein the molecular sieve comprises a zeolite.

[0063] 46) The method according to embodiment 45, wherein the zeolite has a SAR of about 5 to about 200.

[0064] 47) The method according to embodiment 45, wherein the zeolite has a SAR of about 10 to about 50.

[0065] 48) The method according to embodiment 45, wherein the zeolite has a SAR of about 10 to about 30.

[0066] 49) The method according to any one of embodiments 41 to 48, wherein the molecular sieve comprises a small-pore zeolite.

[0067] 50) The method according to embodiment 49, wherein the small-pore zeolite has a crystal framework type selected from AEI, CHA, and combinations thereof.

[0068] 51) The method according to any one of embodiments 41 to 48, wherein the molecular sieve comprises a mesoporous or macroporous zeolite.

[0069] 52) The method according to embodiment 51, wherein the zeolite has a crystal framework type selected from BEA, MFI, and combinations thereof.

[0070] 53) The method according to any one of embodiments 41 to 52, wherein the weight ratio of copper to manganese is from about 0.1 to about 50.

[0071] 54) The method according to any one of embodiments 41 to 52, wherein the weight ratio of copper to manganese is from about 0.2 to about 15.

[0072] 55) The method according to any one of embodiments 41 to 52, wherein the weight ratio of copper to manganese is from about 0.3 to about 3.

[0073] 56) The method according to any one of embodiments 41 to 55, wherein the copper and the manganese are present in a total amount of from about 0.1 wt% to about 10 wt% based on the weight of the molecular sieve.

[0074] 57) The method according to any one of embodiments 41 to 55, wherein the copper and the manganese are present in a total amount of from about 1 wt% to about 7 wt% based on the weight of the molecular sieve.

[0075] 58) The method according to any one of embodiments 41 to 55, wherein the copper and the manganese are present in a total amount of from about 2 wt% to about 5 wt% based on the weight of the molecular sieve.

[0076] 59) The method according to any one of embodiments 41 to 58, wherein the copper is present in an amount of from about 0.05 wt% to about 7 wt% based on the weight of the molecular sieve.

[0077] 60) The method according to any one of embodiments 41 to 58, wherein the copper is present in an amount of from about 0.5 wt% to about 5 wt% based on the weight of the molecular sieve.

[0078] 61) The method according to any one of embodiments 41 to 58, wherein the copper is present in an amount of from about 1 wt% to about 4 wt% based on the weight of the molecular sieve.

[0079] 62) The method according to any one of embodiments 41 to 61, wherein the manganese is present in an amount of from about 0.05 wt% to about 7 wt% based on the weight of the molecular sieve.

[0080] 63) The method according to any one of embodiments 41 to 61, wherein the manganese is present in an amount of about 0.1 wt% to about 5 wt% based on the weight of the molecular sieve.

[0081] 64) The method according to any one of embodiments 41 to 61, wherein the manganese is present in an amount of about 0.5 wt% to about 2.5 wt% based on the weight of the molecular sieve.

[0082] 65) The method according to any one of embodiments 41 to 64, wherein the molecular sieve has a transition metal to aluminum ratio of <1.

[0083] 66) The method according to any one of embodiments 41 to 64, wherein the molecular sieve has a transition metal to aluminum ratio of <0.75.

[0084] 67) The method according to any one of embodiments 41 to 64, wherein the molecular sieve has a transition metal to aluminum ratio of <0.5.

[0085] 68) The method according to any one of embodiments 41 to 67, wherein the catalyst composition effectively promotes the reaction of NH 3 with NOx to form nitrogen and water.

[0086] 69) The method according to any one of embodiments 41 to 68, wherein the catalyst composition produces about 20% to about 45% less N 2 O than a Cu-exchanged molecular sieve under standard SCR conditions.

[0087] 70) The method according to any one of embodiments 41 to 69, wherein the catalyst composition converts about 30% to about 60% more total NO x than a Mn-exchanged molecular sieve under standard SCR conditions.

[0088] 71) The method according to any one of embodiments 41 to 70, wherein the catalyst composition produces about 1% to about 15% less N 2 O than a physical mixture of a Cu-exchanged molecular sieve and a Mn-exchanged molecular sieve under standard SCR conditions.

[0089] 72) The method according to any one of embodiments 41 to 71, wherein the catalyst composition converts about 1% to about 25% more total NO x than a physical mixture of a Cu-exchanged molecular sieve and a Mn-exchanged molecular sieve under standard SCR conditions.

[0090] 73) The method according to any one of embodiments 41 to 72, wherein the catalyst composition produces about 25% to about 60% less N 2 O than a Cu-exchanged molecular sieve under fast SCR conditions.

[0091] 74) The method according to any one of embodiments 41 to 73, wherein the catalyst composition converts about 1% to about 20% more total NO than a Cu-exchanged molecular sieve under fast SCR conditions. x

[0092] 75) The method according to any one of embodiments 41 to 74, wherein the catalyst composition produces about 20% to about 45% less N 2 O than a Cu-exchanged molecular sieve under slow SCR conditions.

[0093] 76) The method according to any one of embodiments 41 to 75, wherein the catalyst composition produces about 35% to about 65% less N 2 O than a Cu-exchanged molecular sieve under standard SCR conditions after aging at 900 °C. BRIEF DESCRIPTION OF THE DRAWINGS

[0094] Figures 1 - 40 Catalyst configurations and systems of catalysts showing aspects of the present invention are shown. They are described in more detail in the detailed description.

[0095] Figure 41 Shows the NOx conversion of fresh catalysts containing Cu-Mn.AEI and Cu.AEI under standard SCR conditions.

[0096] Figure 42 Shows the N 2 O selectivity of fresh catalysts containing Cu-Mn.AEI and Cu.AEI under standard SCR conditions.

[0097] Figure 43 Shows the NOx conversion of aged catalysts containing Cu-Mn.AEI and Cu.AEI under standard SCR conditions.

[0098] Figure 44 Shows the N 2 O selectivity of aged catalysts containing Cu-Mn.AEI and Cu.AEI under standard SCR conditions.

[0099] Figure 45 Shows the NOx conversion of catalysts containing Cu-Mn.AEI and Cu.AEI under fast SCR conditions.

[0100] Figure 46Shows the N of catalysts containing Cu-Mn.AEI and Cu.AEI under fast SCR conditions 2 O ppm.

[0101] Figure 47 Shows the NOx conversion rate of catalysts containing Cu-Mn.AEI and Cu.AEI under slow SCR conditions.

[0102] Figure 48 Shows the N of catalysts containing Cu-Mn.AEI and Cu.AEI under slow SCR conditions 2 O ppm.

[0103] Figure 49 Shows the NOx conversion rate of various bimetallic and monometallic catalysts under standard SCR conditions.

[0104] Figure 50 Shows the N of various bimetallic and monometallic catalysts under standard SCR conditions 2 O selectivity.

[0105] Figure 51 Shows the NOx conversion rate of catalysts with different Mn loadings under standard SCR conditions.

[0106] Figure 52 Shows the N of catalysts with different Mn loadings under standard SCR conditions 2 O selectivity.

[0107] Figure 53 Shows the NOx conversion rate of catalysts with different Mn loadings under slow SCR conditions.

[0108] Figure 54 Shows the N of catalysts with different Mn loadings under slow SCR conditions 2 O ppm.

[0109] Figure 55 Shows the NOx conversion rate of catalysts with different Cu loadings under standard SCR conditions.

[0110] Figure 56 Shows the N of catalysts with different Cu loadings under standard SCR conditions 2 O selectivity.

[0111] Figure 57 Shows the NOx conversion rate of catalysts with different small pore zeolites under standard SCR conditions.

[0112] Figure 58 Shows the N of catalysts with different small pore zeolites under standard SCR conditions 2 O selectivity.

[0113] Figure 59 Shows the NOx conversion of catalysts with different small-pore zeolites under fast SCR conditions.

[0114] Figure 60 Shows the N of catalysts with different small-pore zeolites under fast SCR conditions 2 O ppm.

[0115] Figure 61 Shows the NOx conversion of catalysts with different small-pore zeolites under slow SCR conditions.

[0116] Figure 62 Shows the N of catalysts with different small-pore zeolites under slow SCR conditions 2 O ppm.

[0117] Figure 63 Shows the NOx conversion of catalysts with different medium / large-pore zeolites under standard SCR conditions.

[0118] Figure 64 Shows the N of catalysts with different medium / large-pore zeolites under standard SCR conditions 2 Oppm.

[0119] Figure 65 Shows the NOx conversion of catalysts with different SAR values under standard SCR conditions.

[0120] Figure 66 Shows the N of catalysts with different SAR values under standard SCR conditions 2 O selectivity. Detailed Description

[0121] The compositions, methods, and systems of the present invention relate to catalysts for treating exhaust gases. The catalyst compositions of various aspects of the present invention comprise a molecular sieve, wherein the molecular sieve comprises exchanged copper and exchanged manganese. As described herein, it has been found that the catalyst compositions of various aspects of the present invention promote the reaction of NH 3 with NOx to form nitrogen and water, i.e., selective catalytic reduction (SCR), while producing low N 2 O. Such catalyst compositions can be used to treat exhaust gases from, for example, internal combustion engines (including diesel engines).

[0122] Catalyst Composition

[0123] The catalyst composition of the present invention comprises a molecular sieve having exchanged copper and exchanged manganese. In some aspects, the molecular sieve contains no or substantially no additional transition metals. For example, in some aspects, based on the weight of the molecular sieve, the molecular sieve contains 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% of additional transition metals (i.e., other than exchanged copper and exchanged manganese). In some aspects, the molecular sieve can be described as bimetallic because the molecular sieve contains two transition metals.

[0124] Molecular Sieve

[0125] The catalyst compositions of various aspects of the present invention comprise a molecular sieve. In some aspects, the molecular sieve comprises or consists essentially of a molecular sieve having an aluminosilicate framework (such as zeolite) or a silicoaluminophosphate framework (such as SAPO). In some aspects, the molecular sieve comprises or consists essentially of a molecular sieve having an aluminosilicate framework (such as zeolite). In some aspects, the preferred zeolite is a synthetic zeolite.

[0126] When the molecular sieve has an aluminosilicate framework (such as when the molecular sieve is a zeolite), the molecular sieve typically has a silica to alumina molar ratio (SAR) of 5 to 200 (such as 10 to 200), 10 to 100 (such as 10 to 30 or 20 to 80), 10 to 50, 10 to 30, 12 to 40, 15 to 30, 5 to 20, 5 to 15, 8 to 15, 8 to 13, 10 to 15, 10 to 20, 10 to 40, 10 to 60, 10 to 80, 10 to 100, 10 to 150, <30, <20, <15 or <13. In some aspects, suitable molecular sieves have an SAR >200, >600, or >1200. In some aspects, the molecular sieve has an SAR of about 1500 to about 2100.

[0127] Typically, the molecular sieve is microporous. A microporous molecular sieve has pores with a diameter less than 2 nm (e.g., according to the IUPAC definition of "microporous" [see Pure & Appl. Chem., 66(8), (1994), 1739 - 1758]).

[0128] The molecular sieve can be a small - pore molecular sieve (such as a molecular sieve having a maximum ring size of eight tetrahedral atoms), a mesoporous molecular sieve (such as a molecular sieve having a maximum ring size of ten tetrahedral atoms), or a macroporous molecular sieve (such as a molecular sieve having a maximum ring size of twelve tetrahedral atoms) or a combination of two or more thereof.

[0129] In some aspects, the molecular sieve can be mesoporous. A mesoporous molecular sieve has pores with diameters between 2 nm and 50 nm (e.g., according to the IUPAC definition of "micropore").

[0130] 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 a mixture and / or combination and / or coproduction of two or more of them. In some aspects, 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 aspects, 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 aspects, 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 FTC CHA. The small pore molecular sieve can have a framework structure represented by the FTC AEI.

[0131] When the molecular sieve is a mesoporous molecular sieve, the mesoporous molecular sieve may have a framework structure represented by a framework type code (FTC) selected from the group consisting of: AEL, AFO, AHT, BOF, BOZ, CGF, CGS, CHI, DAC, EUO, FER, HEU, IMF, ITH, ITR, JRY, JSR, JST, LAU, LOV, MEL, MFI, MFS, MRE, MTT, MVY, MWW, NAB, NAT, NES, OBW, -PAR, PCR, PON, PUN, RRO, RSN, SFF, SFG, STF, STI, STT, STW, -SVR, SZR, TER, TON, TUN, UOS, VSV, WEI, and WEN, or a mixture and / or copolymer of two or more of them. In some aspects, the mesoporous molecular sieve has a framework structure represented by an FTC selected from the group consisting of: FER, MEL, MFI, and STT. In some aspects, the mesoporous molecular sieve has a framework structure represented by an FTC selected from the group consisting of: FER and MFI, specifically MFI. When the mesoporous molecular sieve is a zeolite and has a framework represented by FTC FER or MFI, the zeolite may be ferrierite, silicalite, or ZSM-5.

[0132] When the molecular sieve is a macroporous molecular sieve, the macroporous molecular sieve may have a framework structure represented by a framework type code (FTC) selected from the group consisting of: AFI, AFR, AFS, AFY, ASV, ATO, ATS, BEA, BEC, BOG, BPH, BSV, CAN, CON, CZP, DFO, EMT, EON, EZT, FAU, GME, GON, IFR, ISV, ITG, IWR, IWS, IWV, IWW, JSR, LTF, LTL, MAZ, MEI, MOR, MOZ, MSE, MTW, NPO, OFF, OKO, OSI, -RON, RWY, SAF, SAO, SBE, SBS, SBT, SEW, SFE, SFO, SFS, SFV, SOF, SOS, STO, SSF, SSY, USI, UWY, and VET, or a mixture and / or copolymer of two or more of them. In some aspects, the macroporous molecular sieve has a framework structure represented by an FTC selected from the group consisting of: AFI, BEA, MAZ, MOR, and OFF. In some aspects, the macroporous molecular sieve has a framework structure represented by an FTC selected from the group consisting of: BEA, MOR, and FAU. When the macroporous molecular sieve is a zeolite and has a framework represented by FTC BEA, FAU, or MOR, the zeolite may be beta zeolite, faujasite, zeolite Y, zeolite X, or mordenite.

[0133] In some aspects, suitable molecular sieves include a combination of small pore frameworks and large pore frameworks. In some aspects, suitable molecular sieves include ZSM-34 (ERI+OFF).

[0134] Transition Metal

[0135] In some aspects, the catalyst composition comprises a molecular sieve having copper, manganese and optionally one or more other metals such as an exchanged Period 4 transition metal and / or a noble metal. Generally, suitable other metals may be selected from the group consisting of: cobalt, iron, nickel, vanadium, palladium, platinum, ruthenium and rhenium. In some aspects, the two or more exchanged transition metals include copper and manganese. In some aspects, the exchanged transition metals consist essentially of copper and manganese. In some aspects, the exchanged transition metals consist of copper and manganese. In some aspects, the other metal does not include iron. In some aspects, the other metal does not include vanadium. In some aspects, the other metal does not include ruthenium. In some aspects, the other metal does not include nickel.

[0136] The transition metal may be present at extraframework sites on the outer surface of the molecular sieve or within the channels, cavities or cages of the molecular sieve.

[0137] In some aspects, the transition metal-exchanged molecular sieve comprises a transition metal in an amount of from about 0.10 wt% to about 10 wt% of the transition metal-exchanged molecular sieve, or from about 0.2 wt% to about 5 wt% of the transition metal-exchanged molecular sieve.

[0138] Cu / Mn Amount

[0139] In some aspects, the transition metal-exchanged molecular sieve of the present invention comprises exchanged copper and exchanged manganese in a combined amount of from about 0.10 wt% to about 10 wt% of the transition metal-exchanged molecular sieve; from about 0.1 wt% to about 7 wt% of the transition metal-exchanged molecular sieve; from about 0.2 wt% to about 7 wt% of the transition metal-exchanged molecular sieve; from about 0.2 wt% to about 5 wt% of the transition metal-exchanged molecular sieve; from about 0.5 wt% to about 6 wt% of the transition metal-exchanged molecular sieve; from about 1 wt% to about 7 wt% of the transition metal-exchanged molecular sieve; from about 1 wt% to about 5 wt% of the transition metal-exchanged molecular sieve; from about 2 wt% to about 5 wt% of the transition metal-exchanged molecular sieve; from about 1.5 wt% to about 3 wt% of the transition metal-exchanged molecular sieve; from about 1.5 wt% to 4 wt% of the transition metal-exchanged molecular sieve; or from about 2 wt% to about 4 wt% of the transition metal-exchanged molecular sieve.

[0140] In some aspects, the transition metal-exchanged molecular sieve of the present invention comprises exchanged copper in an amount of from about 0.05 wt% to about 7 wt% of the transition metal-exchanged molecular sieve; from about 0.5 wt% to about 5 wt% of the transition metal-exchanged molecular sieve; from about 0.05 wt% to about 5 wt% of the transition metal-exchanged molecular sieve; from about 0.1 wt% to about 4 wt% of the transition metal-exchanged molecular sieve; from about 0.1 wt% to about 3 wt% of the transition metal-exchanged molecular sieve; from about 0.2 wt% to about 3 wt% of the transition metal-exchanged molecular sieve; from about 0.5 wt% to about 2.5 wt% of the transition metal-exchanged molecular sieve; from about 1 wt% to about 4 wt% of the transition metal-exchanged molecular sieve; or from about 1 wt% to about 2 wt% of the transition metal-exchanged molecular sieve.

[0141] In some aspects, the transition metal-exchanged molecular sieve of the present invention comprises exchanged manganese in an amount of from about 0.05 wt% to about 7 wt%, from about 0.05 wt% to about 5 wt% of the transition metal-exchanged molecular sieve; from about 0.1 wt% to about 5 wt% of the transition metal-exchanged molecular sieve; from about 0.1 wt% to about 4 wt% of the transition metal-exchanged molecular sieve; from about 0.1 wt% to about 3 wt% of the transition metal-exchanged molecular sieve; from about 0.2 wt% to about 3 wt% of the transition metal-exchanged molecular sieve; from about 0.5 wt% to about 2.5 wt% of the transition metal-exchanged molecular sieve; or from about 1 wt% to about 2 wt% of the transition metal-exchanged molecular sieve.

[0142] Cu / Mn Ratio

[0143] In some aspects, the transition metal-exchanged molecular sieve of the present invention comprises exchanged copper and exchanged manganese in a weight ratio of about 1:1. In some aspects, the transition metal-exchanged molecular sieve of the present invention comprises exchanged copper and exchanged manganese in a weight ratio of from about 0.1 to about 50, from about 0.2 to about 15, or from about 0.33 to about 3. In some aspects, in addition to using the above copper and manganese ratios, the exchange capacity of the molecular sieve should be <1, less than 0.75, or <0.5 based on the metal ion to exchange site ratio. In some aspects, the transition metal-exchanged molecular sieve has a transition metal to aluminum ratio of <1, <0.75, or <0.5.

[0144] The catalyst of the present invention can be prepared by any suitable method known in the art (including, for example, the one-pot method, pre-fixation, and spray drying).

[0145] Substrate

[0146] The catalyst article of the present invention may include a substrate and a catalyst composition. The substrate can be a flow-through substrate or a filter substrate. The substrate may contain the catalyst composition (i.e., the catalyst article is obtained by extrusion), or the catalyst composition may be disposed or supported on the substrate (i.e., the catalyst composition is applied to the substrate by a washcoat method). The catalyst composition may coat the substrate completely or partially as needed. In some aspects, the catalyst article includes a Cu / Mn bimetallic zeolite extruded article coated with one or more additional catalysts. In some aspects, the extruded catalyst is coated with one or more additional SCR catalysts, which may include, for example, a Cu / Mn bimetallic zeolite.

[0147] In some aspects, the catalyst article may contain a catalyst composition having a total concentration of about 0.5 to about 4.0 g in -3 , about 1.0 to about 3.0 g in -3 , or about 1.2 to about 2.5 g / in -3 .

[0148] When the catalyst article has a filter substrate, it is a selective catalytic reduction filter catalyst. The selective catalytic reduction filter includes a filter substrate and a catalyst composition. References to the use of SCR catalysts throughout this application should be understood to also include the use of selective catalytic reduction filter catalysts where applicable.

[0149] A flow-through substrate or a filter substrate is a substrate capable of accommodating catalyst / adsorbent components. The substrate is preferably a ceramic substrate or a metal substrate. The ceramic substrate may include any suitable refractory material, such as alumina, silica, titanium dioxide, cerium dioxide, zirconia, magnesia, zeolite, silicon nitride, silicon carbide, zirconium silicate, magnesium silicate, aluminosilicate, metal aluminosilicate (such as cordierite and spodumene), or a mixture or mixed oxide of any two or more of them. Cordierite, magnesium aluminosilicate, and silicon carbide are particularly preferred.

[0150] The metal substrate may be made of any suitable metal, and specifically made of 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.

[0151] The flow-through substrate is preferably a flow-through monolith having a honeycomb structure with many small parallel thin-walled channels that axially extend through the substrate and extend through from the inlet or outlet of the substrate. The cross-section of the channels of the substrate can be any shape, but is preferably square, sinusoidal, triangular, rectangular, hexagonal, trapezoidal, circular, or elliptical. The flow-through substrate can also have a high porosity such that the catalyst penetrates into the substrate walls.

[0152] The filter substrate is preferably a wall-flow monolithic filter. The channels of the wall-flow filter are alternately blocked, which causes the waste gas stream to enter the channels from the inlet, then flow through the channel walls, and leave the filter through different channels leading to the outlet. Thus, the particles in the waste gas stream are trapped in the filter.

[0153] The catalyst composition can be added to the flow-through substrate or the filter substrate by any known means, such as a washcoat procedure.

[0154] When the catalyst article is a selective catalytic reduction filter, the filter substrate can preferably be a wall-flow filter substrate monolith. A wall-flow filter substrate monolith (e.g., the wall-flow filter substrate monolith of an SCR-DPF) typically has a pore density of 60 to 400 cells per square inch (cpsi). Preferably, the wall-flow filter substrate monolith has a pore density of 100 cpsi to 350 cpsi, and more preferably 200 cpsi to 300 cpsi.

[0155] The wall-flow filter substrate monolith can have a wall thickness (e.g., average inner wall thickness) of 0.20 mm to 0.50 mm, preferably 0.25 mm to 0.35 mm (e.g., about 0.30 mm).

[0156] Generally speaking, an uncoated wall-flow filter substrate monolith has a porosity of 50% to 80%, preferably 55% to 75%, and more preferably 60% to 70%.

[0157] An uncoated wall-flow filter substrate monolith typically has an average pore diameter of at least 5 μm. Preferably, the average pore diameter is 10 μm to 40 μm, such as 15 μm to 35 μm, and more preferably 20 μm to 30 μm.

[0158] The wall-flow filter substrate can have a symmetric pore design or an asymmetric pore design.

[0159] Generally for a selective catalytic reduction filter, the catalyst composition is disposed within the walls of the wall-flow filter substrate monolith. Additionally, the catalyst composition can be disposed on the walls of the inlet channels and / or the walls of the outlet channels.

[0160] The catalyst compositions of various aspects of the present invention can be coated on a suitable monolithic substrate. A carrier coating composition comprising the catalyst composition of the present invention for coating onto a monolithic substrate or for manufacturing an extruded substrate monolith can comprise a binder selected from the group consisting of: alumina, silica, (non-zeolite) silica-alumina, naturally occurring clays, TiO 2 、ZrO 2 and SnO 2Typically, a catalytic article containing a catalyst composition at a desired loading level can be prepared by washcoating, extrusion, or other methods known in the art.

[0161] Method and System

[0162] The method of the present invention involves treating an exhaust gas containing nitrogen oxides by contacting the exhaust gas with a reducing agent such as a nitrogen-containing reducing agent or a hydrocarbon reducing agent in the presence of a catalyst composition as described herein. Accordingly, the catalyst composition of the present invention can be used as a selective catalytic reduction catalyst.

[0163] In some aspects, nitrogen oxides are reduced by the reducing agent at a temperature of at least 100 °C. In some aspects, in addition to being hydrothermally stable at temperatures above 900 °C, the catalysts as described herein effectively reduce nitrogen oxides with a reducing agent over a wide temperature range (e.g., about 150 °C to 750 °C). The latter feature is particularly useful for treating exhaust gases from heavy-duty and light-duty diesel engines, especially engines including an exhaust gas system comprising (optionally catalytic) diesel particulate filters that are actively regenerated, for example, by injecting hydrocarbons into the exhaust gas system upstream of the filter, wherein the zeolite catalyst for use in the present invention is located downstream of the filter.

[0164] In a specific aspect, the catalysts as described herein effectively reduce nitrogen oxides with a reducing agent in a temperature range of 175 °C to 550 °C. In another aspect, the temperature range is 175 °C to 400 °C. In some aspects, the temperature range is 275 °C to 500 °C, or 250 °C to 550 °C. When NO is present in the gas stream, the temperature range can be wider, such as 150 °C to 650 °C, 175 °C to 625 °C, 200 °C to 600 °C, or 225 °C to 575 °C. 2 O exists in the gas stream, the temperature range can be wider, such as 150 °C to 650 °C, 175 °C to 625 °C, 200 °C to 600 °C, or 225 °C to 575 °C.

[0165] In some aspects, the reduction of nitrogen oxides is carried out in the presence of oxygen. In some aspects, the reduction of nitrogen oxides is carried out in the absence of oxygen.

[0166] The nitrogen-containing reducing agent can be ammonia itself, or the source of the nitrogen-containing reducing agent can be hydrazine or any suitable ammonia precursor, such as urea ((NH 2 ) 2 CO), ammonium carbonate, ammonium carbamate, ammonium bicarbonate, or ammonium formate. The reducing agent can be injected into the exhaust gas stream from an external source such as a reservoir or tank, provided in situ by a nitrogen storage catalyst or a NOx adsorbent catalyst, or a combination of both. The reducing agent should be introduced into the exhaust gas upstream of the SCR catalyst.

[0167] The method can be carried out on gases originating from combustion processes such as those from internal combustion engines (whether 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 refining, from refinery heaters and boilers, heating furnaces, the chemical processing industry, coke ovens, municipal waste plants, and incinerators, coffee roasting plants, etc.

[0168] In a specific aspect, the method is used to treat the exhaust gases 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 liquefied petroleum gas or natural gas.

[0169] In some aspects, the present invention provides an exhaust system for a lean-burn internal combustion engine of a vehicle, the system comprising a duct for carrying the flowing exhaust gases, a source of nitrogen-containing reducing agent, a catalyst composition comprising exchanged copper and exchanged manganese disposed in the flow path of the exhaust gases, and means for metering the nitrogen-containing reducing agent into the flowing exhaust gases upstream of the catalyst composition.

[0170] The system may include means for controlling the metering means in use such that the nitrogen-containing reducing agent is metered into the flowing exhaust gases only when it is determined that the catalyst composition is capable of catalyzing the reduction of NO, for example, at a temperature higher than 100 °C, higher than 150 °C, or higher than 175 °C, at an efficiency equal to or higher than the desired efficiency. The determination by the control means may be assisted by one or more suitable sensor inputs indicating the engine conditions, which are selected from the group consisting of: exhaust gas temperature, catalyst bed temperature, accelerator position, exhaust gas mass flow rate in the system, manifold vacuum, ignition timing, engine speed, exhaust gas lambda value, amount of fuel injected into the engine, position of the exhaust gas recirculation (EGR) valve, and thus the amount of EGR and boost pressure. x In some aspects, the metering is controlled in response to the amount of nitrogen oxides in the exhaust gases determined directly (using a suitable NO sensor) or indirectly (such as using a pre-associated look-up table or map stored in the control means), correlating any one or more of the above inputs indicating the engine conditions with the predicted NO content in the exhaust gases.

[0171] In some aspects, in response to the amount of nitrogen oxides in the exhaust gases determined directly (using a suitable NO sensor) or indirectly (such as using a pre-associated look-up table or map stored in the control means), the metering is controlled, correlating any one or more of the above inputs indicating the engine conditions with the predicted NO content in the exhaust gases. x sensor) or indirectly (such as using a pre-associated look-up table or map stored in the control means), correlating any one or more of the above inputs indicating the engine conditions with the predicted NO x content in the exhaust gases.

[0172] The control means may include a pre-programmed processor, such as an electronic control unit (ECU).

[0173] The metering of the nitrogen-containing reducing agent may be arranged such that 60% to 200% of the theoretical ammonia is present in the exhaust gases entering the SCR catalyst, calculated on a 1:1 NH / NO and 4:3 NH / NO basis. 3 / NO and 4:3 NH 3 / NO 2 basis.

[0174] In some aspects, an oxidation catalyst for oxidizing nitric oxide in the exhaust gas to nitrogen dioxide can be located upstream of the point where the nitrogen-containing reductant is metered into the exhaust gas. In some aspects, the oxidation catalyst is adapted to produce a gas stream entering the SCR catalyst composition that has a ratio of NO to NO 2 at the oxidation catalyst inlet, for example, at an exhaust gas temperature of 200 °C to 450 °C, or 250 °C to 450 °C, of about 4:1 to about 1:3 by volume. This concept is disclosed in S. Kasaoka et al., “Effect of Inlet NO / NO 2 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.

[0175] The oxidation catalyst can include at least one platinum group metal (or some combination thereof), such as platinum, palladium, or rhodium, coated on a flow-through monolithic substrate. In one aspect, the at least one platinum group metal is platinum, palladium, or a combination of both platinum and palladium. The platinum group metal can be supported on a high-surface area carrier coating component such as alumina, a zeolite such as an aluminosilicate zeolite, silica, non-zeolite silica-alumina, cerium dioxide, zirconia, titanium dioxide, or a mixed or composite oxide containing both cerium dioxide and zirconia.

[0176] In some aspects, a suitable filter substrate is located between the oxidation catalyst and the zeolite catalyst. The filter substrate can be selected from any of those described above, such as a wall-flow filter. In the case where the filter is catalyzed, for example, with an oxidation catalyst of the above type, the point for metering the nitrogen-containing reductant is preferably located between the filter and the zeolite catalyst. Alternatively, if the filter is not catalyzed, the means for metering the nitrogen-containing reductant can be located between the oxidation catalyst and the filter, it being understood that this arrangement is disclosed in WO 99 / 39809.

[0177] In some aspects, the catalyst composition for the present invention is coated on a filter located downstream of the oxidation catalyst. In the case where the filter contains the catalyst composition for the present invention, the point for metering the nitrogen-containing reductant is preferably located between the oxidation catalyst and the filter.

[0178] In some aspects, the system configuration includes a NOx adsorbent catalyst, followed by a selective catalytic reduction filter, which may include, for example, a Cu / Mn bimetallic molecular sieve. In some aspects, the system configuration includes a first SCR, followed by a second SCR. In some aspects, the system configuration includes a selective catalytic reduction filter, followed by an SCR. In some aspects, the catalyst configuration includes an SCR, followed by an ammonia oxidation catalyst. Where appropriate, such catalysts may be included as different coatings on the same substrate. In some aspects, the SCR catalyst may include a Cu / Mn bimetallic molecular sieve.

[0179] In some aspects, a lean burn engine vehicle is provided that includes an exhaust system according to the present invention.

[0180] In some aspects, the lean burn internal combustion engine of the vehicle can be a diesel engine, a lean burn gasoline engine, or an engine powered by liquefied petroleum gas or natural gas.

[0181] Partitioning and Structure

[0182] In some aspects, a 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 can involve zoned and / or layered configurations on one or more substrates.

[0183] In some aspects, the Cu / Mn bimetallic molecular sieve can be combined with additional catalyst compositions formulated as SCR catalysts and / or oxidation catalysts such as ammonia oxidation catalysts. In some aspects, the Cu / Mn bimetallic molecular sieve can be combined with one or more additional SCR catalysts. In some aspects, the Cu / Mn bimetallic molecular sieve and the additional SCR catalysts can be located on the same substrate. In some aspects, the Cu / Mn bimetallic molecular sieve and the additional SCR catalysts can be located on different substrates. In some aspects, the catalyst configuration can include a Cu / Mn bimetallic molecular sieve, where one or more additional SCR catalysts are located on the same substrate and one or more additional SCR catalysts are located on a separate substrate.

[0184] In some aspects, the catalyst configuration can include a Cu / Mn bimetallic molecular sieve, where additional catalyst compositions such as SCR catalysts are located downstream. As used herein, the terms upstream and downstream should be understood to indicate the relative positions of the catalysts with respect to the flow of the exhaust gas. Similarly, the inlet end and the outlet end should be understood to indicate the ends of the catalyst substrate with respect to the flow of the exhaust gas. In some aspects, the Cu / Mn bimetallic molecular sieve is present in a first zone, where an additional catalyst composition such as an SCR catalyst is located in a second zone, where the first zone is upstream of the second zone. In some aspects, the first zone and the second zone are located on the same substrate. In some aspects, the first zone and the second zone are located on separate substrates.

[0185] In some aspects, the catalyst configuration may include a Cu / Mn bimetallic molecular sieve in a first upstream zone, where additional catalysts such as SCR catalysts are located downstream of a second zone on a separate substrate. For example, Figure 1 A catalyst configuration is shown having a Cu / Mn bimetallic molecular sieve on an upstream substrate and a Cu molecular sieve on a separate downstream substrate.

[0186] In some aspects, the catalyst configuration may include a Cu / Mn bimetallic molecular sieve on an upstream portion of a substrate, where additional catalysts such as SCR catalysts are located on a downstream portion of the same substrate. In some aspects, these catalyst compositions located on the upstream and downstream portions of the substrate may partially overlap. For example, Figure 2 A catalyst configuration is shown having a Cu / Mn bimetallic molecular sieve on an upstream portion of a substrate and a Cu molecular sieve on a downstream portion of the same substrate. As Figure 2 shown, the upstream catalyst composition and the downstream catalyst composition partially overlap - the Cu molecular sieve is applied from the downstream end of the substrate to cover less than 100% of the substrate length and the Cu / Mn bimetallic molecular sieve is applied from the upstream end of the substrate to cover less than 100% of the substrate length.

[0187] In some aspects, the catalyst configuration may include additional catalysts such as SCR catalysts located upstream, where the Cu / Mn bimetallic molecular sieve is located downstream on a separate substrate. In some aspects, the catalyst configuration may include additional catalysts between the upstream additional catalyst and the downstream Cu / Mn bimetallic molecular sieve. For example, Figure 3 a 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. Figure 3 b 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, where additional catalysts are located therebetween.

[0188] In some aspects, the catalyst configuration may include additional catalysts such as SCR catalysts on an upstream portion of a substrate, where the Cu / Mn bimetallic molecular sieve is located on a downstream portion of the same substrate. In some aspects, these catalyst compositions located on the upstream and downstream portions of the substrate may partially overlap. For example, Figure 4 A catalyst configuration is shown having an Fe molecular sieve on an upstream portion of a substrate and a Cu / Mn bimetallic molecular sieve on a downstream portion of the same substrate. As Figure 4As shown, the upstream catalyst composition and the downstream catalyst composition partially overlap - the Cu / Mn bimetallic molecular sieve is applied from the downstream end of the substrate to cover less than 100% of the substrate length and the Fe molecular sieve is applied from the upstream end of the substrate to cover less than 100% of the substrate length.

[0189] In some aspects, the catalyst configuration includes: a first substrate having an additional catalyst such as an SCR catalyst on the upstream portion of the substrate and a Cu / Mn bimetallic molecular sieve on the downstream portion of the same substrate, followed by a second substrate having an additional catalyst such as an SCR catalyst. In some aspects, these catalyst compositions on the upstream and downstream portions of the first substrate may partially overlap. For example, Figure 5 a shows a catalyst configuration having a first substrate, followed by a separate substrate, the first substrate having an Fe molecular sieve on the upstream portion of the substrate and a Cu / Mn bimetallic molecular sieve on the downstream portion of the same substrate, the separate substrate having a Cu molecular sieve, downstream of the first substrate. As Figure 5 shown, the upstream catalyst composition and the downstream catalyst composition on the first substrate partially overlap - the Cu / Mn bimetallic molecular sieve is applied from the downstream end of the substrate to cover less than 100% of the substrate length and the Fe molecular sieve is applied from the upstream end of the substrate to cover less than 100% of the substrate length. Figure 5 b shows the same configuration as Figure 5 a but includes an additional catalyst between the first substrate and the downstream substrate.

[0190] In some aspects, 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 aspects, the second substrate includes an upstream catalyst on the upstream portion of the second substrate and a downstream catalyst on the downstream portion of the second substrate. In some aspects, these catalyst compositions on the upstream and downstream portions of the second substrate may partially overlap. Figure 6 a shows a catalyst configuration having a first upstream substrate, followed by a second substrate, the first upstream substrate having a Cu / Mn bimetallic substrate, the second substrate having an Fe molecular sieve on the upstream portion of the second substrate and a Cu molecular sieve on the downstream portion of the second substrate. As Figure 6 shown, the upstream catalyst composition and the downstream catalyst composition on the second substrate partially overlap - the Cu molecular sieve is applied from the downstream end of the substrate to cover less than 100% of the substrate length and the Fe molecular sieve is applied from the upstream end of the substrate to cover less than 100% of the substrate length. Figure 6b shows a catalyst configuration having a first upstream substrate and a separate downstream substrate, the first upstream substrate having a Cu / Mn bimetallic substrate, the downstream substrate having an Fe zeolite on an upstream portion of the substrate and a Cu zeolite on a downstream portion of the substrate, wherein an additional catalyst is located between the first substrate and the downstream substrate.

[0191] In some aspects, any of the above catalyst configurations may further include a catalyst composition comprising a platinum group metal (“PGM catalyst”), the catalyst composition being applied in an underlayer on one or more of the substrates in the configuration, extending from an outlet end of the substrate toward an inlet end and covering less than the entire length of the substrate. The catalyst composition comprising a platinum group metal may include, for example, Pt. alumina or Pt. zeolite + Cu. zeolite blend.

[0192] For example, in some aspects, the catalyst configuration may include a Cu / Mn bimetallic zeolite in a first upstream zone and an additional catalyst such as an SCR catalyst downstream of a second zone on a separate substrate, wherein the separate substrate includes a platinum group metal applied in an underlayer from an outlet end of the substrate toward an inlet end of the substrate. For example, Figure 7 shows a catalyst configuration having a Cu / Mn bimetallic zeolite on an upstream substrate and a Cu zeolite on a separate downstream substrate, wherein the separate substrate includes a PGM catalyst applied in an underlayer from an outlet end of the downstream substrate toward an inlet end and covering less than the entire length of the substrate.

[0193] In some aspects, the catalyst configuration may include a Cu / Mn bimetallic zeolite on an upstream portion of the substrate and an additional catalyst such as an SCR catalyst on a downstream portion of the same substrate, and a PGM catalyst applied in an underlayer from an outlet end of the substrate toward an inlet end of the substrate and covering less than the entire length of the substrate. In some aspects, these catalyst compositions on the upstream portion and the downstream portion of the substrate may partially overlap. For example, Figure 8 shows a catalyst configuration having a Cu / Mn bimetallic zeolite on an upstream portion of the substrate and a Cu zeolite on a downstream portion of the same substrate, and a PGM catalyst extending in an underlayer from an outlet end of the substrate toward an inlet end of the substrate and covering less than the entire length of the substrate. As Figure 8 shown, the upstream catalyst composition and the downstream catalyst composition partially overlap - the Cu zeolite is applied from the downstream end of the substrate to cover less than 100% of the substrate length and the Cu / Mn bimetallic zeolite is applied from the upstream end of the substrate to cover less than 100% of the substrate length.

[0194] In some aspects, the catalyst configuration may include an additional upstream catalyst such as an SCR catalyst and a Cu / Mn bimetallic zeolite located downstream on a separate substrate, and a PGM catalyst applied in the underlayer of either or both substrates that extends from the outlet end towards the inlet end and covers less than the entire length of the substrate. In some aspects, the catalyst configuration may include an additional catalyst between the upstream additional catalyst and the downstream Cu / Mn bimetallic zeolite. For example, Figure 9 a shows a catalyst configuration having an Fe zeolite on an upstream substrate and a Cu / Mn bimetallic zeolite on a separate downstream substrate, and a PGM catalyst applied in the underlayer that extends from the outlet end of the downstream substrate towards the inlet end and covers less than the entire length of the substrate. Figure 9 b shows a catalyst configuration having an Fe zeolite on an upstream substrate and a Cu / Mn bimetallic zeolite on a separate downstream substrate, and an additional catalyst between them, and having a PGM catalyst applied in the underlayer of the upstream substrate that extends from the outlet end of the substrate towards the inlet end of the substrate and covers less than the entire length of the substrate, and having a PGM catalyst applied in the underlayer of the downstream substrate that extends from the outlet end of the substrate towards the inlet end of the substrate and covers less than the entire length of the substrate.

[0195] In some aspects, the catalyst configuration may include an additional catalyst such as an SCR catalyst on the upstream portion of the substrate and a Cu / Mn bimetallic zeolite on the downstream portion of the same substrate, and a PGM catalyst applied in the underlayer that extends from the outlet end of the substrate towards the inlet end and covers less than the entire length of the substrate. In some aspects, these catalyst compositions on the upstream and downstream portions of the substrate may partially overlap. For example, Figure 10 shows a catalyst configuration having an Fe zeolite on the upstream portion of the substrate and a Cu / Mn bimetallic zeolite on the downstream portion of the same substrate, and a PGM catalyst applied in the underlayer that extends from the outlet end of the substrate towards the inlet end and covers less than the entire length of the substrate. As Figure 10 shown, the upstream catalyst composition and the downstream catalyst composition partially overlap - the Cu / Mn bimetallic zeolite is applied from the downstream end of the substrate to cover less than 100% of the substrate length and the Fe zeolite is applied from the upstream end of the substrate to cover less than 100% of the substrate length.

[0196] In some aspects, the catalyst configuration includes: a first substrate having additional catalysts such as SCR catalysts on the upstream portion of the substrate and a Cu / Mn bimetallic zeolite on the downstream portion of the same substrate, followed by a second substrate having additional catalysts such as SCR catalysts, and a PGM catalyst applied in the underlayer extending from the outlet end of either or both substrates toward the inlet end and covering less than the entire length of the substrate. In some aspects, these catalyst compositions on the upstream and downstream portions of the first substrate may partially overlap. For example, Figure 11 a shows a catalyst configuration having a first substrate, followed by a separate substrate, the first substrate having an Fe zeolite on the upstream portion of the substrate and a Cu / Mn bimetallic zeolite on the downstream portion of the same substrate, the separate substrate having a Cu zeolite and an underlayer including a PGM catalyst extending from the outlet end of the substrate toward the inlet end and covering less than the entire length of the substrate, the substrate being downstream of the first substrate. As Figure 11 shown, the upstream and downstream catalyst compositions on the first substrate partially overlap - the Cu / Mn bimetallic zeolite is applied from the downstream end of the substrate to cover less than 100% of the substrate length and the Fe zeolite is applied from the upstream end of the substrate to cover less than 100% of the substrate length. Figure 11 b shows the same configuration as Figure 11 a, but includes additional catalysts located between the first substrate and the downstream substrate, and also includes a PGM catalyst applied in the underlayer extending from the outlet end of the upstream substrate toward the inlet end and covering less than the entire length of the substrate.

[0197] In some aspects, the catalyst configuration includes a first substrate having a Cu / Mn bimetallic zeolite, followed by a second substrate having one or more additional catalysts such as SCR catalysts. In some aspects, the second substrate includes an upstream catalyst on the upstream portion of the second substrate and a downstream catalyst on the downstream portion of the second substrate, and a PGM catalyst applied in the underlayer of either or both substrates extending from the outlet end of the substrate toward the inlet end and covering less than the entire length of the substrate. In some aspects, these catalyst compositions on the upstream and downstream portions of the second substrate may partially overlap. Figure 12 a shows a catalyst configuration having: a first upstream substrate having a Cu / Mn bimetallic substrate; followed by a second substrate having an Fe zeolite on the upstream portion of the second substrate and a Cu zeolite on the downstream portion of the second substrate, and a PGM catalyst applied in the underlayer extending from the outlet end of the second substrate toward the inlet end and covering less than the entire length of the substrate. As Figure 12As shown, the upstream catalyst composition and the downstream catalyst composition on the second substrate partially overlap - the Cu molecular sieve is applied from the downstream end of the substrate to cover less than 100% of the substrate length and the Fe molecular sieve is applied from the upstream end of the substrate to cover less than 100% of the substrate length. Figure 12 b shows a catalyst configuration having: a first upstream substrate having 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 of the substrate; and a PGM catalyst extending from the outlet end towards the inlet end of each of the upstream substrate and the downstream substrate and covering less than the entire length of the substrate and applied in the underlayer on each; and an additional catalyst located between the first substrate and the downstream substrate.

[0198] In some aspects, the catalyst configuration includes a layered structure having a Cu / Mn bimetallic molecular sieve in the top layer and an additional catalyst such as an SCR catalyst in the bottom layer. In some aspects, both the top layer and the bottom layer extend the entire length of the substrate. For example, Figure 13 shows a catalyst configuration having a Cu / Mn bimetallic molecular sieve extending the entire length of the substrate in the top layer and a Cu molecular sieve extending the entire length of the substrate in the bottom layer.

[0199] In some aspects, the catalyst configuration includes a layered structure having a top layer and a bottom layer, the top layer including a catalyst such as an SCR catalyst, the bottom layer including a Cu / Mn bimetallic molecular sieve in the upstream portion of the bottom layer and another catalyst such as an SCR catalyst in the downstream portion of the bottom layer. For example, Figure 14 shows a catalyst configuration having a top layer and a bottom layer, the top layer including an Fe molecular sieve, the bottom layer including a Cu / Mn bimetallic molecular sieve extending from the inlet end towards the outlet end of the substrate in the upstream portion and covering less than the entire length and also a Cu molecular sieve extending from the outlet end towards the inlet end of the substrate in the downstream portion of the bottom layer and covering less than the entire length of the substrate. As Figure 14 shown, the upstream catalyst composition and the downstream catalyst composition of the bottom layer may partially overlap.

[0200] In some aspects, the catalyst configuration may include a bottom layer and a top layer, the bottom layer having a catalyst such as an SCR catalyst, the top layer having a catalyst such as an SCR catalyst in the upstream portion of the top layer and a Cu / Mn bimetallic molecular sieve in the downstream portion of the top layer. For example, Figure 15 shows a catalyst configuration having a bottom layer and a top layer, the bottom layer including a Cu molecular sieve, the top layer including an Fe molecular sieve extending from the inlet end towards the outlet end of the substrate in the upstream portion and covering less than the entire length and also a Cu / Mn bimetallic molecular sieve extending from the outlet end towards the inlet end of the substrate in the downstream portion of the top layer and covering less than the entire length of the substrate. AsFigure 15 As shown, the upstream catalyst composition and the downstream catalyst composition at the top layer may partially overlap.

[0201] In some aspects, the catalyst structure includes a layered structure having a top layer and a bottom layer, the top layer including a Cu / Mn bimetallic molecular sieve, and the bottom layer including a catalyst such as an SCR catalyst in the upstream portion of the bottom layer and another catalyst such as an SCR catalyst in the downstream portion of the bottom layer. For example, Figure 16 A catalyst structure having a top layer and a bottom layer is shown, the top layer including a Cu / Mn bimetallic molecular sieve, and the bottom layer including an Fe molecular sieve extending from the inlet end to the outlet end of the substrate in the upstream portion and covering less than the entire length, and a Cu molecular sieve also extending from the outlet end to the inlet end of the substrate in the bottom layer and covering less than the entire length of the substrate. As Figure 16 As shown, the upstream catalyst composition and the downstream catalyst composition at the bottom layer may partially overlap.

[0202] In some aspects, the catalyst structure includes a layered structure having: a PGM catalyst applied in the bottom layer and extending from the outlet end to the inlet end of the substrate 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 in the top layer. For example, Figure 17 A catalyst structure is shown having: a PGM catalyst applied in the bottom layer and extending from the outlet end to the inlet end of the substrate 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 extending the entire length of the substrate and covering the Cu molecular sieve in the top layer.

[0203] In some aspects, the catalyst structure includes a layered structure having: a PGM catalyst applied in the bottom layer and extending from the outlet end to the inlet end of the substrate and covering less than the entire length of the substrate, a layer including a Cu / Mn bimetallic molecular sieve in the upstream portion of the layer and another catalyst such as an SCR catalyst in the downstream portion of the layer and covering the PGM catalyst, and a top layer including a catalyst such as an SCR catalyst. For example, Figure 18 A catalyst structure is shown having: a PGM catalyst applied in the bottom layer and extending from the outlet end to 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 extending from the inlet end to the outlet end of the substrate and covering less than the entire length in the upstream portion, and a Cu molecular sieve also extending from the outlet end to the inlet end of the substrate in the same layer, covering the PGM catalyst and covering less than the entire length of the substrate, and a top layer including an Fe molecular sieve. As Figure 18 As shown, the Cu / Mn bimetallic molecular sieve and the Cu molecular sieve catalyst may partially overlap.

[0204] In some aspects, the catalyst structure can include: a PGM catalyst applied in a bottom layer that extends from the outlet end of the substrate toward the inlet end and covers less than the entire length of the substrate, a next layer of a catalyst such as an SCR catalyst that extends the entire length of the substrate and covers the PGM catalyst, and a top layer having a catalyst such as an SCR catalyst in an upstream portion of the top layer and a Cu / Mn bimetallic zeolite in a downstream portion of the top layer. For example, Figure 19 A catalyst structure is shown having: a PGM catalyst applied in a bottom layer that extends from the outlet end of the substrate toward the inlet end and covers less than the entire length of the substrate, a next layer including a Cu zeolite that extends the entire length of the substrate and covers the PGM catalyst, and a top layer including an Fe zeolite that extends from the inlet end of the substrate toward the outlet end and covers less than the entire length in an upstream portion, and a Cu / Mn bimetallic zeolite that extends from the outlet end of the substrate toward the inlet end and covers less than the entire length of the substrate in a downstream portion of the substrate, also in the top layer. As Figure 19 shown, the upstream catalyst composition and the downstream catalyst composition of the top layer can partially overlap.

[0205] In some aspects, the catalyst structure includes a layered structure having: a PGM catalyst applied in a bottom layer that extends from the outlet end of the substrate toward the inlet end and covers less than the entire length of the substrate, a layer including a catalyst such as an SCR catalyst in an upstream portion of the layer and another catalyst such as an SCR catalyst in a downstream portion of the layer and covering the PGM catalyst, and a top layer including a Cu / Mn bimetallic zeolite. For example, Figure 20 A catalyst structure is shown having: a PGM catalyst applied in a bottom layer that extends from the outlet end of the substrate toward the inlet end and covers less than the entire length of the substrate, a next layer including an Fe zeolite that extends from the inlet end of the substrate toward the outlet end and covers less than the entire length in an upstream portion, and a Cu zeolite that also extends from the outlet end of the substrate toward the inlet end, covers the PGM catalyst, and covers less than the entire length of the substrate in the same layer, and a top layer including a Cu / Mn bimetallic zeolite that extends the entire length of the substrate. As Figure 20 shown, the Cu / Mn bimetallic zeolite and the Cu zeolite catalyst can partially overlap.

[0206] In some aspects, the catalyst structure includes a layered structure having: a Cu / Mn bimetallic zeolite that extends from the inlet end of the substrate toward the outlet end and covers less than the entire length of the substrate in the top layer, and an additional catalyst such as an SCR catalyst in the bottom layer. In some aspects, both the top layer and the bottom layer extend the entire length of the substrate. For example, Figure 21A catalyst structure is shown, which has: a Cu / Mn bimetallic molecular sieve extending from the inlet end to the outlet end of the substrate in the top layer and covering less than the entire length of the substrate, and a Cu molecular sieve extending the entire length of the substrate in the bottom layer.

[0207] In some aspects, the catalyst structure includes a layered structure having a top layer and a bottom layer. The top layer includes a catalyst such as an SCR catalyst that extends from the inlet end to the outlet end of the substrate and covers less than the entire length of the substrate. The bottom layer includes a Cu / Mn bimetallic molecular sieve in the upstream portion of the bottom layer and another catalyst such as an SCR catalyst in the downstream portion of the bottom layer. For example, Figure 22 A catalyst structure having a top layer and a bottom layer is shown. The top layer includes an Fe molecular sieve that extends from the inlet end to the outlet end of the substrate and covers less than the entire length of the substrate. The bottom layer includes a Cu / Mn bimetallic molecular sieve that extends from the inlet end to the outlet end of the substrate in the upstream portion and covers less than the entire length, and a Cu molecular sieve that also extends from the outlet end to the inlet end of the substrate in the bottom layer and covers less than the entire length of the substrate. As Figure 22 shown, the upstream catalyst composition and the downstream catalyst composition of the bottom layer may partially overlap.

[0208] In some aspects, the catalyst structure includes a layered structure having a top layer and a bottom layer. The top layer includes a Cu / Mn bimetallic molecular sieve that extends from the inlet end to the outlet end of the substrate and covers less than the entire length of the substrate. The bottom layer includes a catalyst such as an SCR catalyst in the upstream portion of the bottom layer and another catalyst such as an SCR catalyst in the downstream portion of the bottom layer. For example, Figure 23 A catalyst structure having a top layer and a bottom layer is shown. The top layer includes a Cu / Mn bimetallic molecular sieve that extends from the inlet end to the outlet end of the substrate and covers less than the entire length of the substrate. The bottom layer includes an Fe molecular sieve that extends from the inlet end to the outlet end of the substrate in the upstream portion and covers less than the entire length, and a Cu molecular sieve that also extends from the outlet end to the inlet end of the substrate in the bottom layer and covers less than the entire length of the substrate. As Figure 23 shown, the upstream catalyst composition and the downstream catalyst composition of the bottom layer may partially overlap.

[0209] In some aspects, the catalyst structure includes a layered structure having: a PGM catalyst that extends from the outlet end to the inlet end of the substrate in the bottom layer and covers less than the entire length of the substrate, a next layer having an additional catalyst such as an SCR catalyst that covers the entire length of the substrate and covers the PGM catalyst, and a Cu / Mn bimetallic molecular sieve that extends from the inlet end to the outlet end of the substrate in the top layer and covers less than the entire length of the substrate. For example, Figure 24A catalyst structure is shown having: a PGM catalyst applied in a bottom layer extending from an outlet end of a substrate toward an 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 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.

[0210] In some aspects, the catalyst structure includes a layered structure having: a PGM catalyst applied in a bottom layer extending from an outlet end of a substrate toward an inlet end and covering less than the entire length of the substrate, a layer including a Cu / Mn bimetallic molecular sieve in an upstream portion of the layer and another catalyst such as an SCR catalyst in a downstream portion of the layer and covering the PGM catalyst, and a top layer including a catalyst such as an SCR catalyst extending from the inlet end of the substrate toward the outlet end and covering less than the entire length of the substrate. For example, Figure 25 A catalyst structure is shown having: a PGM catalyst applied in a bottom layer extending from an outlet end of a substrate toward an inlet end and covering less than the entire length of the substrate, a lower layer including a Cu / Mn bimetallic molecular sieve extending from the inlet end of the substrate toward the outlet end and covering less than the entire length in an upstream portion, and also in the layer a Cu molecular sieve 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 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 Figure 25 shown, the Cu / Mn bimetallic molecular sieve and the Cu molecular sieve catalyst may partially overlap.

[0211] In some aspects, the catalyst structure includes a layered structure having: a PGM catalyst applied in a bottom layer extending from an outlet end of a substrate toward an inlet end and covering less than the entire length of the substrate, a layer including a catalyst such as an SCR catalyst in an upstream portion of the layer and another catalyst such as an SCR catalyst in a downstream portion of the layer and covering the PGM catalyst, and a top layer including a Cu / Mn bimetallic molecular sieve extending from the inlet end of the substrate toward the outlet end and covering less than the entire length of the substrate. For example. Figure 26 A catalyst structure is shown having: a PGM catalyst applied in a bottom layer extending from an outlet end of a substrate toward an inlet end and covering less than the entire length of the substrate, a lower 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 in an upstream portion, and also in the layer a Cu molecular sieve 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 including a Cu / Mn bimetallic molecular sieve extending from the inlet end of the substrate toward the outlet end and covering less than the entire length of the substrate. As Figure 26As shown, the Cu / Mn bimetallic zeolite and the Cu zeolite catalyst can partially overlap.

[0212] In some aspects, the catalyst structure includes a layered structure and a plurality of substrates having a first upstream substrate and a separate downstream substrate. The first upstream substrate has a Cu / Mn bimetallic zeolite in the top layer and an additional catalyst such as an SCR catalyst in the bottom layer, and the downstream substrate has an additional catalyst such as an SCR catalyst. In some aspects, the catalyst structure includes an additional catalyst between the first upstream substrate and the downstream substrate. For example, Figure 27 a shows a catalyst structure having a first upstream substrate and a downstream substrate. The first upstream substrate has a Cu / Mn bimetallic zeolite extending the entire length of the substrate in the top layer and a Cu zeolite extending the entire length of the substrate in the bottom layer, and the downstream substrate includes a Cu zeolite. Figure 27 b shows Figure 27 the catalyst structure of a, which further includes an additional catalyst between the first upstream substrate and the downstream substrate.

[0213] In some aspects, the catalyst structure includes a layered structure and a plurality of substrates having a first upstream substrate and a separate downstream substrate. The first upstream substrate has a top layer and a bottom layer. The top layer includes a catalyst such as an SCR catalyst, and the bottom layer includes a Cu / Mn bimetallic zeolite in the upstream portion of the bottom layer and another catalyst such as an SCR catalyst in the downstream portion of the bottom layer. The downstream substrate has an additional catalyst such as an SCR catalyst. In some aspects, the catalyst structure includes an additional catalyst between the first upstream substrate and the downstream substrate. For example, Figure 28 a shows a catalyst structure having a first upstream substrate and a downstream substrate. The first upstream substrate has a top layer and a bottom layer. The top layer includes an Fe zeolite, and the bottom layer includes a Cu / Mn bimetallic zeolite extending from the inlet end of the substrate towards the outlet end in the upstream portion and covering less than the entire length, and a Cu zeolite also extending from the outlet end of the substrate towards the inlet end in the bottom layer and covering less than the entire length of the substrate. The downstream substrate includes a Cu zeolite. As Figure 28 shown, the upstream catalyst composition and the downstream catalyst composition of the bottom layer can partially overlap. Figure 28 b shows Figure 28 the catalyst structure of a, which further includes an additional catalyst between the first upstream substrate and the downstream substrate.

[0214] In some aspects, a catalyst structure can include a first upstream substrate and a separate downstream substrate. The first upstream substrate has a bottom layer and a top layer. The bottom layer has a catalyst such as an SCR catalyst, and the top layer has a catalyst such as an SCR catalyst in the upstream portion of the top layer and a Cu / Mn bimetallic zeolite in the downstream portion of the top layer. The downstream substrate has an additional catalyst such as an SCR catalyst. In some aspects, the catalyst structure includes an additional catalyst between the first upstream substrate and the downstream substrate. For example, Figure 29 a shows a catalyst structure having a first upstream substrate and a downstream substrate. The first upstream substrate has a bottom layer and a top layer. The bottom layer includes a Cu zeolite, and the top layer includes an Fe zeolite that extends from the inlet end to the outlet end of the substrate in the upstream portion and covers less than the entire length, and a Cu / Mn bimetallic zeolite that also extends from the outlet end to the inlet end of the substrate in the downstream portion of the top layer and covers less than the entire length of the substrate. The downstream substrate includes a Cu zeolite. Figure 29 b shows Figure 29 the catalyst structure of a, which further includes an additional catalyst between the first upstream substrate and the downstream substrate

[0215] In some aspects, a catalyst structure includes a layered structure and a plurality of substrates having a first upstream substrate and a separate downstream substrate. The first upstream substrate has a top layer and a bottom layer. The top layer includes a Cu / Mn bimetallic zeolite, and the bottom layer includes a catalyst such as an SCR catalyst in the upstream portion of the bottom layer and another catalyst such as an SCR catalyst in the downstream portion of the bottom layer. The downstream substrate has an additional catalyst such as an SCR catalyst. In some aspects, the catalyst structure includes an additional catalyst between the first upstream substrate and the downstream substrate. For example, Figure 30 a shows a catalyst structure having a first upstream substrate and a downstream substrate. The first upstream substrate has a top layer and a bottom layer. The top layer includes a Cu / Mn bimetallic zeolite, and the bottom layer includes an Fe zeolite that extends from the inlet end to the outlet end of the substrate in the upstream portion and covers less than the entire length, and a Cu zeolite that also extends from the outlet end to the inlet end of the substrate in the bottom layer and covers less than the entire length of the substrate. The downstream substrate includes a Cu zeolite. Figure 30 b shows Figure 30 the catalyst structure of a, which further includes an additional catalyst between the first upstream substrate and the downstream substrate.

[0216] In some aspects, the catalyst structure includes a layered structure and a plurality of substrates having a first upstream substrate and a separate downstream substrate. The first upstream substrate has a Cu / Mn bimetallic zeolite in the top layer and an additional catalyst such as an SCR catalyst in the bottom layer. The downstream substrate has an additional catalyst such as an SCR catalyst and also has a PGM catalyst applied in the bottom layer that extends from the outlet end of one or both substrates toward the inlet end and extends less than the entire length of the substrate. In some aspects, the catalyst structure includes an additional catalyst between the first upstream substrate and the downstream substrate. For example, Figure 31 a shows a catalyst structure having a first upstream substrate and a downstream substrate. The first upstream substrate has a Cu / Mn bimetallic zeolite that extends the entire length of the substrate in the top layer and a Cu zeolite that extends the entire length of the substrate in the bottom layer. The downstream substrate includes a PGM catalyst applied in the bottom layer that extends from the outlet end of the substrate toward the inlet end and extends less than the entire length of the substrate and has a top layer including a Cu zeolite that covers the PGM catalyst and the entire length of the substrate. Figure 31 b shows a catalyst structure including a first upstream substrate and a downstream substrate. The first upstream substrate has a PGM catalyst applied in the bottom layer that extends from the outlet end of the substrate toward the inlet end and covers less than the entire length of the substrate, a Cu zeolite that extends the entire length of the substrate and covers the PGM catalyst, and a Cu / Mn bimetallic zeolite that extends the entire length of the substrate and covers the Cu zeolite in the top layer. The downstream substrate includes a PGM catalyst applied in the bottom layer that extends from the outlet end of the substrate toward the inlet end and extends less than the entire length of the substrate and has a top layer including a Cu zeolite that covers the PGM catalyst and the entire length of the substrate, and also includes an additional catalyst between the first upstream substrate and the downstream substrate.

[0217] In some aspects, the catalyst structure includes a layered structure and a plurality of substrates having a first upstream substrate and a separate downstream substrate. The first upstream substrate has a top layer and a bottom layer. The top layer includes a catalyst such as an SCR catalyst. The bottom layer includes a Cu / Mn bimetallic zeolite in the upstream portion of the bottom layer and another catalyst such as an SCR catalyst in the downstream portion of the bottom layer. The downstream substrate has an additional catalyst such as an SCR catalyst and also has a PGM catalyst applied in the bottom layer that extends from the outlet end of one or both substrates toward the inlet end and extends less than the entire length of the substrate. In some aspects, the catalyst structure includes an additional catalyst between the first upstream substrate and the downstream substrate. For example. Figure 32a shows a catalyst structure having a first upstream substrate and a downstream substrate. The first upstream substrate has a top layer and a bottom layer. The top layer includes an Fe zeolite, and the bottom layer includes a Cu / Mn bimetallic zeolite that extends from the inlet end of the substrate toward the outlet end in the upstream portion and covers less than the entire length, and a Cu zeolite that also extends from the outlet end of the substrate toward the inlet end in the bottom layer and covers less than the entire length of the substrate. The downstream substrate includes a PGM catalyst that is applied in the bottom layer and extends from the outlet end of the substrate toward the inlet end, with an extension less than the entire length of the substrate, and has a top layer that includes a Cu zeolite covering the entire length of the PGM catalyst and the substrate. Figure 32 b shows a first upstream substrate and a downstream substrate. The first upstream substrate includes a PGM catalyst that is applied in the bottom layer and extends from the outlet end of the substrate toward the inlet end, with an extension less than the entire length of the substrate, a lower layer that includes a Cu / Mn bimetallic zeolite that extends from the inlet end of the substrate toward the outlet end in the upstream portion and covers less than the entire length, and a Cu zeolite that also extends from the outlet end of the substrate toward the inlet end in this layer, covers the PGM catalyst, and has an extension less than the entire length of the substrate, and has a top layer that includes an Fe zeolite; the downstream substrate includes a PGM catalyst that is applied in the bottom layer and extends from the outlet end of the substrate toward the inlet end, with an extension less than the entire length of the substrate, and has a top layer that includes a Cu zeolite covering the entire length of the PGM catalyst and the substrate, and also includes an additional catalyst between the first upstream substrate and the downstream substrate.

[0218] In some aspects, the catalyst structure may include a first upstream substrate and a separate downstream substrate. The first upstream substrate has a bottom layer and a top layer. The bottom layer has a catalyst such as an SCR catalyst, and the top layer has a catalyst such as an SCR catalyst in the upstream portion of the top layer and a Cu / Mn bimetallic zeolite in the downstream portion of the top layer. The downstream substrate has an additional catalyst such as an SCR catalyst, and also has a PGM catalyst that is applied in the bottom layer and extends from the outlet end of one or both substrates toward the inlet end, with an extension less than the entire length of the substrate. In some aspects, the catalyst structure includes an additional catalyst between the first upstream substrate and the downstream substrate. For example, Figure 33 a shows a catalyst structure having a first upstream substrate and a downstream substrate. The first upstream substrate has a bottom layer and a top layer. The bottom layer includes a Cu zeolite, and the top layer includes an Fe zeolite that extends from the inlet end of the substrate toward the outlet end in the upstream portion and covers less than the entire length, and a Cu / Mn bimetallic zeolite that also extends from the outlet end of the substrate toward the inlet end in the downstream portion of the substrate in the top layer and covers less than the entire length of the substrate. The downstream substrate includes a PGM catalyst that is applied in the bottom layer and extends from the outlet end of the substrate toward the inlet end, with an extension less than the entire length of the substrate, and has a top layer that includes a Cu zeolite covering the entire length of the PGM catalyst and the substrate. Figure 33b shows a first upstream substrate and a downstream substrate. The first upstream substrate includes a PGM catalyst applied in the bottom layer that extends from the outlet end of the substrate towards the inlet end and covers less than the entire length of the substrate, a next layer of Cu molecular sieve that extends the entire length of the substrate and covers the PGM catalyst, and a top layer that includes an Fe molecular sieve extending from the inlet end of the substrate towards the outlet end in the upstream portion and covering less than the entire length, and also in the top layer, a Cu / Mn bimetallic molecular sieve extending from the outlet end of the substrate towards the inlet end in the downstream portion of the substrate and covering less than the entire length of the substrate; the downstream substrate includes a PGM catalyst applied in the bottom layer that extends from the outlet end of the substrate towards the inlet end and extends less than the entire length of the substrate and has a top layer that includes a Cu molecular sieve covering the PGM catalyst and the entire length of the substrate; and further includes an additional catalyst between the first upstream substrate and the downstream substrate.

[0219] In some aspects, the catalyst configuration includes a layered structure and a plurality of substrates having a first upstream substrate and a separate downstream substrate. The first upstream substrate has a top layer and a bottom layer. The top layer includes a Cu / Mn bimetallic molecular sieve. The bottom layer includes a catalyst such as an SCR catalyst in the upstream portion of the bottom layer and another catalyst such as an SCR catalyst in the downstream portion of the bottom layer. The downstream substrate has an additional catalyst such as an SCR catalyst and also has a PGM catalyst applied in the bottom layer that extends from the outlet end of one or both substrates towards the inlet end and extends less than the entire length of the substrate. In some aspects, the catalyst configuration includes an additional catalyst between the first upstream substrate and the downstream substrate. For example, Figure 34 a shows a catalyst configuration having a first upstream substrate and a downstream substrate. The first upstream substrate has a top layer and a bottom layer. The top layer includes a Cu / Mn bimetallic molecular sieve. The bottom layer includes an Fe molecular sieve extending from the inlet end of the substrate towards the outlet end in the upstream portion and covering less than the entire length and also a Cu molecular sieve extending from the outlet end of the substrate towards the inlet end in the bottom layer and covering less than the entire length of the substrate. The downstream substrate includes a PGM catalyst applied in the bottom layer that extends from the outlet end of the substrate towards the inlet end and extends less than the entire length of the substrate and has a top layer that includes a Cu molecular sieve covering the PGM catalyst and the entire length of the substrate. Figure 34b shows a catalyst structure having a first upstream substrate and a downstream substrate. The first upstream substrate has a PGM catalyst applied in the bottom layer that extends from the outlet end of the substrate toward the inlet end and covers less than the entire length of the substrate. The next layer in the upstream portion includes an Fe zeolite that extends from the inlet end of the substrate toward the outlet end and covers less than the entire length, and a Cu zeolite that also extends from the outlet end of the substrate toward the inlet end in this layer, covers the PGM catalyst, and covers less than the entire length of the substrate. The top layer includes a Cu / Mn bimetallic zeolite that extends the entire length of the substrate. The downstream substrate includes a PGM catalyst applied in the bottom layer that extends from the outlet end of the substrate toward the inlet end and extends less than the entire length of the substrate, and has a top layer that includes a Cu zeolite covering the PGM catalyst and the entire length of the substrate. It also includes an additional catalyst between the first upstream substrate and the downstream substrate.

[0220] In some aspects, the catalyst structure includes a layered structure and multiple substrates having a first upstream substrate and a separate downstream substrate. The first upstream substrate has a Cu / Mn bimetallic zeolite that extends from the inlet end of the substrate toward the outlet end in the top layer and covers less than the entire length of the substrate, and an additional catalyst such as an SCR catalyst in the bottom layer. The downstream substrate has an additional catalyst such as an SCR catalyst. In some aspects, the catalyst structure includes an additional catalyst between the first upstream substrate and the downstream substrate. For example, Figure 35 a shows a catalyst structure having a first upstream substrate and a downstream substrate. The first upstream substrate has a Cu / Mn bimetallic zeolite that extends from the inlet end of the substrate toward the outlet end in the top layer and covers less than the entire length of the substrate, and a Cu zeolite that extends the entire length of the substrate in the bottom layer. The downstream substrate includes a Cu zeolite. Figure 35 b shows Figure 35 the catalyst structure of a, which also includes an additional catalyst between the first upstream substrate and the downstream substrate.

[0221] In some aspects, the catalyst structure includes a layered structure and multiple substrates having a first upstream substrate and a separate downstream substrate. The first upstream substrate has a top layer and a bottom layer. The top layer includes a catalyst such as an SCR catalyst that extends from the inlet end of the substrate toward the outlet end and covers less than the entire length of the substrate. The bottom layer includes a Cu / Mn bimetallic zeolite in the upstream portion of the bottom layer and another catalyst such as an SCR catalyst in the downstream portion of the bottom layer. The downstream substrate has an additional catalyst such as an SCR catalyst. In some aspects, the catalyst structure includes an additional catalyst between the first upstream substrate and the downstream substrate. For example, Figure 36a shows a catalyst structure having a first upstream substrate and a downstream substrate. The first upstream substrate has a top layer and a bottom layer. The top layer includes an Fe molecular sieve that extends from the inlet end of the substrate toward the outlet end and covers less than the entire length of the substrate. The bottom layer includes a Cu / Mn bimetallic molecular sieve that extends from the inlet end of the substrate toward the outlet end in the upstream portion and covers less than the entire length, and a Cu molecular sieve that also extends from the outlet end of the substrate toward the inlet end in the bottom layer and covers less than the entire length of the substrate. The downstream substrate includes a Cu molecular sieve. As Figure 36 shown, the upstream catalyst composition and the downstream catalyst composition of the bottom layer may partially overlap. Figure 36 b shows Figure 36 the catalyst structure of a, which further includes an additional catalyst between the first upstream substrate and the downstream substrate.

[0222] In some aspects, the catalyst structure includes a layered structure and a plurality of substrates, having a first upstream substrate and a separate downstream substrate. The first upstream substrate has a top layer and a bottom layer. The top layer includes a Cu / Mn bimetallic molecular sieve that extends from the inlet end of the substrate toward the outlet end and covers less than the entire length of the substrate. The bottom layer includes a catalyst such as an SCR catalyst in the upstream portion of the bottom layer and another catalyst such as an SCR catalyst in the downstream portion of the bottom layer. The downstream substrate has an additional catalyst such as an SCR catalyst. In some aspects, the catalyst structure includes an additional catalyst between the first upstream substrate and the downstream substrate. For example, Figure 37 a shows a catalyst structure having a first upstream substrate and a downstream substrate. The first upstream substrate has a top layer and a bottom layer. The top layer includes a Cu / Mn bimetallic molecular sieve that extends from the inlet end of the substrate toward the outlet end and covers less than the entire length of the substrate. The bottom layer includes an Fe molecular sieve that extends from the inlet end of the substrate toward the outlet end in the upstream portion and covers less than the entire length, and a Cu molecular sieve that also extends from the outlet end of the substrate toward the inlet end in the bottom layer and covers less than the entire length of the substrate. The downstream substrate includes a Cu molecular sieve. Figure 37 b shows Figure 37 the catalyst structure of a, which further includes an additional catalyst between the first upstream substrate and the downstream substrate.

[0223] In some aspects, the catalyst structure includes a layered structure and a plurality of substrates having a first upstream substrate and a separate downstream substrate. The first upstream substrate has a Cu / Mn bimetallic molecular sieve extending from the inlet end of the substrate toward the outlet end in the top layer and covering less than the entire length of the substrate, and additional catalyst such as an SCR catalyst in the bottom layer. The downstream substrate has additional catalyst such as an SCR catalyst and also has a PGM catalyst applied in the bottom layer extending from the outlet end of one or both substrates toward the inlet end and covering less than the entire length of the substrate. In some aspects, the catalyst structure includes additional catalyst between the first upstream substrate and the downstream substrate. For example, Figure 38 a shows a catalyst structure having a first upstream substrate and a downstream substrate. The first upstream substrate has a Cu / Mn bimetallic molecular sieve extending from the inlet end of the substrate toward the outlet end in the top layer and covering less than the entire length of the substrate, and a Cu molecular sieve extending the entire length of the substrate in the bottom layer. The downstream substrate includes a PGM catalyst applied in the bottom layer extending from the outlet end of the substrate toward the inlet end and covering less than the entire length of the substrate, and has a top layer including a Cu molecular sieve covering the PGM catalyst and the entire length of the substrate. Figure 38 b shows a catalyst structure including a first upstream substrate and a downstream substrate. The first upstream substrate has a PGM catalyst applied in the 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 extending from the inlet end of the substrate toward the outlet end in the top layer and covering less than the entire length of the substrate. The downstream substrate includes a PGM catalyst applied in the bottom layer extending from the outlet end of the substrate toward the inlet end and covering less than the entire length of the substrate, and has a top layer including a Cu molecular sieve covering the PGM catalyst and the entire length of the substrate, and also includes additional catalyst between the first upstream substrate and the downstream substrate.

[0224] In some aspects, the catalyst structure includes a layered structure and a plurality of substrates having a first upstream substrate and a separate downstream substrate. The first upstream substrate has a top layer and a bottom layer. The top layer includes a catalyst such as an SCR catalyst extending from the inlet end of the substrate toward the outlet end and covering less than the entire length of the substrate. The bottom layer includes a Cu / Mn bimetallic molecular sieve in the upstream portion of the bottom layer and another catalyst such as an SCR catalyst in the downstream portion of the bottom layer. The downstream substrate has additional catalyst such as an SCR catalyst and also has a PGM catalyst applied in the bottom layer extending from the outlet end of one or both substrates toward the inlet end and covering less than the entire length of the substrate. In some aspects, the catalyst structure includes additional catalyst between the first upstream substrate and the downstream substrate. For example, Figure 39a shows a catalyst structure having a first upstream substrate and a downstream substrate. The first upstream substrate has a top layer and a bottom layer. The top layer includes an Fe molecular sieve that extends from the inlet end of the substrate toward the outlet end and covers less than the entire length of the substrate. The bottom layer includes a Cu / Mn bimetallic molecular sieve that extends from the inlet end of the substrate toward the outlet end in the upstream portion and covers less than the entire length, and a Cu molecular sieve that also extends from the outlet end of the substrate toward the inlet end in the bottom layer and covers less than the entire length of the substrate. The downstream substrate includes a PGM catalyst that is applied in the bottom layer and extends from the outlet end of the substrate toward the inlet end for less than the entire length of the substrate, and has a top layer that includes a Cu molecular sieve covering the entire length of the PGM catalyst and the substrate. Figure 39 b shows a first upstream substrate and a downstream substrate. The first upstream substrate includes a PGM catalyst that is applied in the bottom layer and extends from the outlet end of the substrate toward the inlet end for less than the entire length of the substrate, a lower layer that includes a Cu / Mn bimetallic molecular sieve that extends from the inlet end of the substrate toward the outlet end in the upstream portion and covers less than the entire length, and a Cu molecular sieve that also extends from the outlet end of the substrate toward the inlet end in this layer, covers the PGM catalyst, and covers less than the entire length of the substrate, and a top layer that includes an Fe molecular sieve that extends from the inlet end of the substrate toward the outlet end and covers less than the entire length of the substrate. The downstream substrate includes a PGM catalyst that is applied in the bottom layer and extends from the outlet end of the substrate toward the inlet end for less than the entire length of the substrate, and has a top layer that includes a Cu molecular sieve covering the entire length of the PGM catalyst and the substrate, and also includes an additional catalyst between the first upstream substrate and the downstream substrate.

[0225] In some aspects, the catalyst structure includes a layered structure and a plurality of substrates having a first upstream substrate and a separate downstream substrate. The first upstream substrate has a top layer and a bottom layer. The top layer includes a Cu / Mn bimetallic molecular sieve that extends from the inlet end of the substrate toward the outlet end and covers less than the entire length of the substrate. The bottom layer includes a catalyst such as an SCR catalyst in the upstream portion of the bottom layer and another catalyst such as an SCR catalyst in the downstream portion of the bottom layer. The downstream substrate has an additional catalyst such as an SCR catalyst, and also has a PGM catalyst that is applied in the bottom layer and extends from the outlet end of one or both substrates toward the inlet end for a length less than the entire length of the substrate. In some aspects, the catalyst structure includes an additional catalyst between the first upstream substrate and the downstream substrate. For example, Figure 40a shows a catalyst structure having a first upstream substrate and a downstream substrate. The first upstream substrate has a top layer and a bottom layer. The top layer includes a Cu / Mn bimetallic molecular sieve that extends from the inlet end of the substrate toward the outlet end and covers less than the entire length of the substrate. The bottom layer includes an Fe molecular sieve that extends from the inlet end of the substrate toward the outlet end in the upstream portion and covers less than the entire length, and a Cu molecular sieve that also extends from the outlet end of the substrate toward the inlet end in the bottom layer and covers less than the entire length of the substrate. The downstream substrate includes a PGM catalyst applied in the bottom layer that extends from the outlet end of the substrate toward the inlet end and extends less than the entire length of the substrate, and has a top layer including a Cu molecular sieve that covers the PGM catalyst and the entire length of the substrate. Figure 40 b shows a catalyst structure having a first upstream substrate and a downstream substrate. The first upstream substrate has a PGM catalyst applied in the bottom layer that extends from the outlet end of the substrate toward the inlet end and covers less than the entire length of the substrate, a lower layer including an Fe molecular sieve that extends from the inlet end of the substrate toward the outlet end in the upstream portion and covers less than the entire length, and a Cu molecular sieve that also extends from the outlet end of the substrate toward the inlet end in this layer, covers the PGM catalyst, and covers less than the entire length of the substrate, and a top layer including a Cu / Mn bimetallic molecular sieve that extends from the inlet end of the substrate toward the outlet end and covers less than the entire length of the substrate. The downstream substrate includes a PGM catalyst applied in the bottom layer that extends from the outlet end of the substrate toward the inlet end and extends less than the entire length of the substrate, and has a top layer including a Cu molecular sieve that covers the PGM catalyst and the entire length of the substrate, and also includes an additional catalyst between the first upstream substrate and the downstream substrate.

[0226] Beneficial Effects

[0227] It has surprisingly been found that the catalyst compositions of various aspects of the present invention comprising a molecular sieve having exchanged copper and exchanged manganese have distinct advantages for selective catalytic reduction processes. It has been found that such catalyst compositions facilitate the reaction of NH 3 with NOx to form nitrogen and water, i.e., selective catalytic reduction (SCR), while producing low N 2 O. Additionally, it has been found that such catalyst compositions enhance light-off and reduce N 2 O selectivity, and are stable to aging at 900 °C, while still maintaining good NO x conversion and N 2 O selectivity; aging includes, for example, exposure to 4.5% H 2Aged at O for 5 hours. For example, it has been found that under typical SCR conditions, the bimetallic Cu / Mn zeolite shows similar or improved activity and improved selectivity compared to monometallic Cu zeolite, monometallic Mn zeolite, and physically mixed Cu zeolite / Mn zeolite. It should be understood that such comparisons refer to zeolites containing the same or substantially the same total amount of transition metal. Such results can support the theory of balanced active sites in order to balance the elementary reaction steps to optimize performance.

[0228] In the following discussion, N 2 O selectivity is defined as the number of moles of N 2 O formed divided by the number of moles of NO x (NOx is defined as the number of moles of NO and NO 2 ), and the average N 2 O selectivity is defined as the average N 2 O selectivity in the test temperature range of 150 °C - 500 °C. The average N 2 O yield is defined as the amount of N 2 O produced on average in the test temperature range of 150 °C - 500 °C, and the total NO x conversion is defined as the average conversion of NO x % in the test temperature range of 150 °C - 500 °C.

[0229] Standard SCR

[0230] It has been found that when compared with monometallic zeolites such as Cu-exchanged zeolites under standard SCR conditions, the catalyst composition of the present invention produces significantly less N 2 O and similar or higher NO x conversion. Standard SCR conditions can include, for example, 500 ppm NH 3 , 500 ppm NO, 0 ppm NO 2 , 14% O 2 , 4.6% H 2 O, 5.0% CO 2 and the balance N 2 , with a space velocity of 90 Kh -1 .

[0231] In some aspects, the catalyst composition of the present invention produces about 33% less N 2 O and similar total NO x conversion under standard SCR conditions compared to Cu-exchanged zeolites. In some aspects, the catalyst composition of the present invention produces about 20% to about 45%, about 25% to about 40%, about 30% to about 35% less N 2 O under standard SCR conditions compared to Cu-exchanged zeolites.

[0232] In some aspects, the catalyst composition of the present invention produces about 65% less N 2 O under standard SCR conditions than a Mn-exchanged molecular sieve and converts about 45% more total NO x than a Mn-exchanged molecular sieve. In some aspects, 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 N 2 O under standard SCR conditions than a Mn-exchanged molecular sieve. In some aspects, the catalyst composition of the present invention converts about 30% to about 60%, about 35% to about 55%, or about 40% to about 50% more total NO x than a Mn-exchanged molecular sieve under standard SCR conditions.

[0233] In some aspects, the catalyst composition of the present invention produces about 4% less N 2 O under standard SCR conditions than a physical mixture of a Cu-exchanged molecular sieve and a Mn-exchanged molecular sieve and converts about 12% more total NO x than a Cu-exchanged molecular sieve. In some aspects, 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 N 2 O under standard SCR conditions than a physical mixture of a Cu-exchanged molecular sieve and a Mn-exchanged molecular sieve. In some aspects, the catalyst composition of the present invention converts about 1% to about 25%, about 5% to about 20%, or about 10% to about 15% more total NO x than a physical mixture of a Cu-exchanged molecular sieve and a Mn-exchanged molecular sieve under standard SCR conditions.

[0234] Fast SCR

[0235] It has been found that when compared to a monometallic molecular sieve such as a Cu-exchanged molecular sieve under fast SCR conditions, the catalyst composition of the present invention produces significantly less N 2 O and a similar or higher NO x conversion rate. Fast SCR conditions can include, for example, 500 ppm NH 3 , 250 ppm NO, 250 ppm NO 2 , 14% O 2 , 4.6% H 2 O, 5.0% CO 2 and the balance N 2 , with a space velocity of 90 Kh -1 . Different from Cu+Mn at "standard" conditions that provide better N 2 O performance but slightly lower NOx conversion rate, when NO 2When Cu + Mn provides better NOx conversion performance and better N 2 O performance - this may be more similar to real-world conditions. In some aspects, the catalyst composition of the present invention produces approximately 42% less N 2 O under fast SCR conditions than a Cu-exchanged molecular sieve and converts approximately 5% more total NO x than a Cu-exchanged molecular sieve. In some aspects, the catalyst composition of the present invention produces approximately 25% to approximately 60%, approximately 30% to approximately 50%, approximately 35% to approximately 45% less N 2 O under fast SCR conditions than a Cu-exchanged molecular sieve. In some aspects, the catalyst composition of the present invention converts approximately 1% to approximately 20%, approximately 1% to approximately 15%, or approximately 1% to approximately 10% more total NO x under fast SCR conditions than a Cu-exchanged molecular sieve.

[0236] Slow SCR

[0237] It has been found that when compared to a single-metal molecular sieve such as a Cu-exchanged molecular sieve under slow SCR conditions, the catalyst composition of the present invention produces significantly less N 2 O and similar or higher NO x conversion rates. Slow SCR conditions can include, for example, 500 ppm NH 3 , 175 ppm NO, 325 ppm NO 2 , 14% O 2 , 4.6% H 2 O, 5.0% CO 2 and the balance N 2 at a space velocity of 90 Kh -1 . In some aspects, the catalyst composition of the present invention produces approximately 33% less N 2 O and a similar total NO x conversion rate as a Cu-exchanged molecular sieve under slow SCR conditions. In some aspects, the catalyst composition of the present invention produces approximately 20% to approximately 45%, approximately 25% to approximately 40%, approximately 30% to approximately 35% less N 2 O under slow SCR conditions than a Cu-exchanged molecular sieve.

[0238] Aging

[0239] It has been found that the catalyst composition of the present invention can be stable for severe 900 °C aging while still maintaining good NO x conversion rate and N 2O selectivity. After hydrothermal aging at 900 °C under standard SCR conditions, it has been found that the catalyst compositions of the present invention produce significantly less N 2 O and similar NO x conversions. In some aspects, the catalyst compositions of the present invention produce about 48% less N 2 O and total NO similar to that of the Cu-exchanged molecular sieve after aging at 900 °C under standard SCR conditions x conversions. In some aspects, 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 N 2 O after aging at 900 °C under standard SCR conditions compared to the Cu-exchanged molecular sieve

[0240] Examples

[0241] Example 1 - Standard SCR

[0242] The molecular sieve was impregnated with metal using the required amounts of manganese(II) acetate and / or copper(II) acetate dissolved in demineralized water. The metal-impregnated samples were dried overnight at 80 °C and then calcined in air at 550 °C for 4 hours. Catalysts with the following formulations were prepared:

[0243] · AEI zeolite with 1.5 wt% exchanged Cu and 1.5 wt% exchanged Mn (1.5Cu-1.5Mn.AEI)

[0244] · AEI zeolite with 2 wt% exchanged Cu and 2 wt% exchanged Mn (2Cu-2Mn.AEI)

[0245] · AEI zeolite with 3 wt% exchanged Cu (3Cu.AEI)

[0246] Then, the granular samples of the powder catalyst were tested for NO x conversion and N 2 O production: 500 ppm NH 3 、500 ppm NO、0 ppm NO 2 、14% O 2 、4.6% H 2 O、5.0% CO 2 and the balance N 2 , with a space velocity of 90 K h -1 . The samples were heated from room temperature to 150 °C under the above gas mixture (except NH 3 ). At 150 °C, NH 3Added to the gas mixture, and the sample was maintained under these conditions for 30 minutes. Then the temperature was increased (ramped) from 150 °C to 500 °C at 5 °C min -1 The temperature was increased (ramped) from 150 °C to 500 °C.

[0247] The results are shown in Figure 41 and Figure 42 In standard SCR conditions, it has been found that both the Cu-Mn.AEI zeolite and the 3 wt% Cu-exchanged zeolite achieved similar total NO x conversions, 86% and 88% respectively. However, the Cu-Mn.AEI catalyst showed an average N 2 O selectivity of 0.7%, while the 3 wt% Cu-exchanged zeolite showed an average N 2 O selectivity of 1.1%. Therefore, relative to the typical Cu-exchanged zeolite, the catalyst of the present invention results in a significant reduction in N 2 O.

[0248] The catalyst was also aged in air at 900 °C in 4.5% water for 5 hours. The powdered catalyst sample was granulated and then heated only in air at 10 °C min- 1 to 250 °C. Then the sample was heated in air in 4.5% H 2 O at 10 °C min 1 to 900 °C. After holding at 900 °C for 5 hours, the sample was cooled in a steam / air mixture until the temperature < 250 °C. Then the sample was cooled from 250 °C to room temperature in only an air stream. Then the NO x conversion and N 2 O production of the granulated sample of the aged powder catalyst were tested under the following conditions: 500 ppm NH 3 , 500 ppm NO, 0 ppm NO 2 , 14% O 2 , 4.6% H 2 O, 5.0% CO 2 and the balance N 2 , with a space velocity of 90 K h -1 .

[0249] The results are shown in Figure 43 and Figure 44 In standard SCR conditions, it has been found that both 1.5Cu-1.5Mn.AEI and 3Cu.AEI achieved similar total NO x conversions, 82% and 83% respectively. However, Cu-Mn.AEI showed an average N 2 O selectivity of 0.8%, while the 3 wt% Cu-exchanged zeolite showed an average N 2O selectivity. These results indicate that the catalyst of the present invention is hydrothermally stable and maintains significant beneficial effects superior to those of monometallic molecular sieves after severe hydrothermal aging.

[0250] Example 2 - Fast SCR

[0251] The molecular sieve was impregnated with metal using the required amounts of manganese(II) acetate and / or copper(II) acetate dissolved in demineralized water. The metal-impregnated sample was dried overnight at 80 °C and then calcined in air at 550 °C for 4 hours. Catalysts with the following formulations were prepared:

[0252] · AEI zeolite with 1.5 wt% exchanged Cu and 1.5 wt% exchanged Mn, 1.5Cu-1.5Mn.AEI

[0253] · AEI zeolite with 3 wt% exchanged Cu, 3Cu.AEI

[0254] Granular samples of the powder catalyst were then tested for NO x conversion and N 2 O production: 500 ppm NH 3 、250 ppm NO、250 ppm NO 2 、14% O 2 、4.6% H 2 O、5.0% CO 2 and the balance N 2 at a space velocity of 90 K h -1 . The sample was heated from room temperature to 150 °C in the above gas mixture (except NH 3 ). At 150 °C, NH 3 was added to the gas mixture and the sample was held under these conditions for 30 minutes. The temperature was then increased (ramped) from 150 °C to 500 °C at 5 °C min -1 .

[0255] The results are shown in Figure 45 and Figure 46 . Under fast SCR conditions, it has been found that Cu-Mn.AEI exhibits an average N 2 O production of 8.4 ppm and a total NO x conversion of 82%, while the 3 wt% Cu-exchanged molecular sieve exhibits an average N 2 O production of 14.5 and a total NO x conversion of 77%. Thus, the bimetallic catalyst achieves a significantly lower average N 2 O production and a higher total NO x conversion than the monometallic Cu-exchanged molecular sieve.

[0256] Example 3 - Slow SCR

[0257] Impregnate the molecular sieve with the desired amounts of manganese(II) acetate and / or copper(II) acetate dissolved in demineralized water. Dry the metal-impregnated sample overnight at 80 °C and then calcine it in air at 550 °C for 4 hours. Prepare catalysts with the following formulations:

[0258] · AEI zeolite with 1.5 wt% exchanged Cu and 1.5 wt% exchanged Mn, 1.5Cu-1.5Mn.AEI

[0259] · AEI zeolite with 3 wt% exchanged Cu, 3Cu.AEI

[0260] Then test the granular samples of the powder catalyst for NO x conversion and N 2 O production: 500 ppm NH 3 、175 ppm NO、325 ppm NO 2 、14% O 2 、4.6% H 2 O、5.0% CO 2 and the balance N 2 at a space velocity of 90 K h -1 . Heat the sample from room temperature to 150 °C under the above gas mixture (except NH 3 ). At 150 °C, add NH 3 to the gas mixture and hold the sample under these conditions for 30 minutes. Then increase (ramp) the temperature from 150 °C to 500 °C at 5 °C min -1 .

[0261] The results are shown in Figure 47 and Figure 48 . Under slow SCR conditions, it has been found that Cu-Mn.AEI exhibits an average N 2 O production of 14.4 ppm and a total NO x conversion of 76%, while the 3 wt% Cu-exchanged molecular sieve exhibits an average N 2 O production of 21.4 and a total NO x conversion of 74%. Thus, relative to the single-metal Cu-exchanged molecular sieve, the bimetallic catalyst achieves a significantly lower average N 2 O production and a similar total NO x conversion.

[0262] Example 4 - Control Test

[0263] Impregnate the molecular sieve with the required amounts of manganese(II) acetate and / or copper(II) acetate dissolved in demineralized water. Dry the metal-impregnated sample overnight at 80 °C and then calcine it in air at 550 °C for 4 hours. Prepare catalysts with the following formulations:

[0264] · AEI zeolite with 1.5 wt% exchanged Cu and 1.5 wt% exchanged Mn, 1.5Cu-1.5Mn.AEI

[0265] · AEI zeolite with 1.5 wt% exchanged Mn, 1.5Mn.AEI

[0266] · AEI zeolite with 1.5 wt% exchanged Cu, 1.5Cu.AEI

[0267] · Physical mixture of AEI zeolite with 1.5 wt% exchanged Cu and AEI zeolite with 1.5 wt% exchanged Mn, Physical mixture

[0268] Then test the granular samples of the powder catalysts for NO x conversion and N 2 O production: 500 ppm NH 3 、500 ppm NO、0 ppm NO 2 、14% O 2 、4.6% H 2 O、5.0% CO 2 and the balance N 2 at a space velocity of 90 K h -1 . Heat the sample from room temperature to 150 °C under the above gas mixture (except NH 3 ). At 150 °C, add NH 3 to the gas mixture and hold the sample under these conditions for 30 minutes. Then increase (ramp) the temperature from 150 °C to 500 °C at 5 °C min -1 .

[0269] The results are shown in Figure 49 and Figure 50 In standard SCR conditions, it has been found that Cu-Mn.AEI achieves an average N 2 O selectivity of 0.7% and a total NO x conversion of 86%. The molecular sieve exchanged with 1.5 wt% Cu achieved an average N 2 O selectivity of 0.6%, but only achieved a total NO x conversion of 79%. Therefore, the bimetallic Cu-Mn molecular sieve exhibits significantly higher NO xConversion rate. And the Mn-exchanged zeolite shows an average N 2 O selectivity of 2.1% and a total NO x conversion rate of 41%. Therefore, the Cu / Mn-exchanged catalyst results in significantly enhanced selectivity and activity compared to the monometallic zeolite with the same Mn loading. In addition, a physical mixture of 1.5 wt% Cu-exchanged zeolite and 1.5 wt% Mn-exchanged zeolite shows an average N 2 O selectivity of 0.8% and a total NO x conversion rate of 74%, again demonstrating that the catalyst of the present invention exhibits significant selectivity and activity beneficial effects superior to those of the monometallic analogs. The results show that the NO x conversion rate is significantly increased when using the bimetallic Cu / Mn-exchanged zeolite compared to the individual and mixed monometallic zeolites.

[0270] Example 5 - Mn Loading

[0271] The zeolite was impregnated with metals using the required amounts of manganese(II) acetate and / or copper(II) acetate dissolved in demineralized water. The metal-impregnated samples were dried overnight at 80 °C and then calcined in air at 550 °C for 4 hours. Catalysts with the following formulations were prepared:

[0272] · AEI zeolite with 3 wt% exchanged Cu, 3Cu.AEI

[0273] · AEI zeolite with 1.5 wt% exchanged Cu, 1.5Cu.AEI

[0274] · AEI zeolite with 1.5 wt% exchanged Cu and 0.1 wt% exchanged Mn, 1.5Cu-0.1Mn.AEI

[0275] · AEI zeolite with 1.5 wt% exchanged Cu and 0.25 wt% exchanged Mn, 1.5Cu-0.25Mn.AEI

[0276] · AEI zeolite with 1.5 wt% exchanged Cu and 0.5 wt% exchanged Mn, 1.5Cu-0.5Mn.AEI

[0277] · AEI zeolite with 1.5 wt% exchanged Cu and 1.5 wt% exchanged Mn, 1.5Cu-1.5Mn.AEI

[0278] · AEI zeolite with 1.5 wt% exchanged Cu and 2.5 wt% exchanged Mn, 1.5Cu-2.5Mn.AEI

[0279] Then, the granular samples of the powder catalysts were tested for NO xConversion rate and N 2 O production: 500 ppm NH 3 、500 ppm NO、0 ppm NO 2 、14% O 2 、4.6% H 2 O、5.0% CO 2 and the balance of N 2 with a space velocity of 90 K h -1 . The sample was heated from room temperature to 150 °C under the above gas mixture (excluding NH 3 ). At 150 °C, NH 3 was added to the gas mixture, and the sample was maintained under these conditions for 30 minutes. Then the temperature was increased (ramped) from 150 °C to 500 °C at 5 °C min -1 .

[0280] The results are shown in Figure 51 and Figure 52 . Compared with the monometallic 1.5 wt% Cu molecular sieve, the addition of 0.1 wt% Mn (Cu:Mn = 15) led to a significantly increased light-off temperature. Further addition of Mn up to 1.5 wt% (Cu:Mn = 1) resulted in a further improvement in the light-off temperature without a significant increase in N 2 O selectivity. The results showed that at a constant Cu loading, the addition of Mn to the 1.5 wt% Cu catalyst significantly improved the NO x conversion rate of the Cu-SCR catalyst without significantly changing the N 2 O selectivity.

[0281] Then the NO x conversion rate and N 2 O production of the granular sample of the powder catalyst were tested under the following conditions: 500 ppm NH 3 、175 ppm NO、325 ppm NO 2 、14% O 2 、4.6% H 2 O、5.0% CO 2 and the balance of N 2 with a space velocity of 90 K h -1 . The sample was heated from room temperature to 150 °C under the above gas mixture (excluding NH 3 ). At 150 °C, NH 3 was added to the gas mixture, and the sample was maintained under these conditions for 30 minutes. Then the temperature was increased (ramped) from 150 °C to 500 °C at 5 °C min -1 .

[0282] The results are shown in Figure 53 and Figure 54In the case of a constant Cu loading of 1.5 wt%, compared with the monometallic 1.5 wt% Cu zeolite, the addition of 0.1 wt% Mn (Cu:Mn = 15) results in a decrease in NO 2 O production without significantly changing the light-off temperature. Further addition of 0.5 wt% Mn (Cu:Mn = 3), 1.0 wt% Mn (Cu:Mn = 1.5), and 1.5 wt% Mn (Cu:Mn = 1) causes the light-off temperature of NO x to gradually increase and decreases the NO 2 O production value. However, all aspects of Cu-Mn.AEI produce less NO 2 than the monometallic Cu.AEI analogues. Therefore, by varying the Cu-Mn ratio and the total metal content, the activity and selectivity of Cu-Mn can be tailored for specific applications.

[0283] Example 6 - Cu Loading

[0284] The zeolite was impregnated with metals using the required amounts of manganese(II) acetate and / or copper(II) acetate dissolved in demineralized water. The metal-impregnated samples were dried overnight at 80 °C and then calcined in air at 550 °C for 4 h. Catalysts with the following formulations were prepared:

[0285] · AEI zeolite with 3 wt% exchanged Cu, 3Cu.AEI

[0286] · AEI zeolite with 1.5 wt% exchanged Mn, 1.5Mn.AEI

[0287] · AEI zeolite with 1.5 wt% exchanged Mn and 0.5 wt% exchanged Cu, 0.5Cu-1.5Mn.AEI

[0288] · AEI zeolite with 1.5 wt% exchanged Mn and 1.0 wt% exchanged Cu, 1Cu-1.5Mn.AEI

[0289] · AEI zeolite with 1.5 wt% exchanged Mn and 1.5 wt% exchanged Cu, 1.5Cu-1.5Mn.AEI

[0290] · AEI zeolite with 1.5 wt% exchanged Mn and 2.0 wt% exchanged Cu, 1.5Cu-2Mn.AEI

[0291] · AEI zeolite with 1.5 wt% exchanged Mn and 2.5 wt% exchanged Cu, 1.5Cu-2.5Mn.AEI

[0292] · AEI zeolite with 1.5 wt% exchanged Mn and 3 wt% exchanged Cu, 3Cu-1.5Mn.AEI

[0293] Then, a granular sample of the powdered catalyst was tested for NO x conversion and N 2 O production under the following conditions: 500 ppm NH 3 , 500 ppm NO, 0 ppm NO 2 , 14% O 2 , 4.6% H 2 O, 5.0% CO 2 and the balance N 2 , with a space velocity of 90 K h -1 . The sample was heated from room temperature to 150 °C under the above gas mixture (except for NH 3 ). At 150 °C, NH 3 was added to the gas mixture, and the sample was held at these conditions for 30 minutes. Then the temperature was increased (ramped) from 150 °C to 500 °C at 5 °C min -1 .

[0294] The results are shown in Figure 55 and Figure 56 . At a constant Mn loading of 1.5 wt%, compared to the monometallic 1.5 wt% Mn catalyst, the addition of only 0.5 wt% Cu (Cu:Mn = 0.33) resulted in a significant improvement in NO x conversion and a significant decrease in N 2 O selectivity. When the Cu content was sequentially increased to 1 wt% (Cu:Mn = 0.67), 1.5 wt% (Cu:Mn = 1), and 3.0 wt% (Cu:Mn = 2), the NO x conversion increased sequentially, but at the cost of higher N 2 O selectivity. In addition, compared to the monometallic Cu or Mn zeolites, the 1Cu-1.5Mn.AEI and 1.5Cu-1.5Mn.AEI catalysts exhibited a significant decrease in N 2 O selectivity. However, if the ratio of Cu:Mn was increased too high, as demonstrated in the case of Cu:Mn, most of the N 2 O beneficial effects were lost. The results showed that at a constant Mn loading of 1.5 wt%, increasing the Cu content led to an increase in NO x conversion. However, as the Cu content increased above the Mn content, the selectivity for N 2 O increased.

[0295] Example 7 - Small-Pore Zeolite

[0296] Impregnate the molecular sieve with the required amounts of manganese(II) acetate and / or copper(II) acetate dissolved in demineralized water. Dry the metal-impregnated sample overnight at 80 °C and then calcine it in air at 550 °C for 4 hours. Prepare catalysts with the following formulations:

[0297] · AEI zeolite with 1.5 wt% exchanged Mn and 1.5 wt% exchanged Cu,

[0298] 1.5Cu-1.5Mn.AEI

[0299] · CHA zeolite with 1.5 wt% exchanged Mn and 1.5 wt% exchanged Cu,

[0300] 1.5Cu-1.5Mn.CHA

[0301] Standard SCR: Then test the granular samples of the powder catalyst for NO x conversion and N 2 O production: 500 ppm NH 3 、500 ppm NO、0 ppm NO 2 、14% O 2 、4.6% H 2 O、5.0% CO 2 and the balance N 2 at a space velocity of 90 Kh -1 . Heat the sample from room temperature to 150 °C under the above gas mixture (except NH 3 ). At 150 °C, add NH 3 to the gas mixture and hold the sample under these conditions for 30 minutes. Then increase (ramp) the temperature from 150 °C to 500 °C at 5 °C min -1 . The results are shown in Figure 57 and Figure 58 . The results show that the performance of Cu-Mn.CHA is similar to that of Cu-Mn.AEI, indicating that this strategy is feasible for small-pore zeolites.

[0302] Fast SCR: Then test the granular samples of the powder catalyst for NO x conversion and N 2 O production: 500 ppm NH 3 、250 ppm NO、250 ppm NO 2 、14% O 2 、4.6%H 2 O、5.0% CO 2 and the balance N 2 at a space velocity of 90 Kh -1. The sample was heated from room temperature to 150 °C under the above gas mixture (excluding NH 3 ). At 150 °C, NH 3 was added to the gas mixture, and the sample was held under these conditions for 30 minutes. Then the temperature was increased (ramped) from 150 °C to 500 °C at 5 °C min -1 . The results are shown in Figure 59 and Figure 60 . The results show that both Cu-Mn.CHA and Cu-Mn.AEI achieved a similar total NO x conversion of 82%. However, Cu-Mn.AEI produced less average N 2 O at 8.4 ppm than Cu-Mn.CHA (which produced an average of 11.8 ppm of N 2 O).

[0303] Slow SCR: Then the NO x conversion and N 2 O production of granular samples of the powder catalyst were tested under the following conditions: 500 ppm NH 3 , 175 ppm NO, 325 ppm NO 2 , 14% O 2 , 4.6% H 2 O, 5.0% CO 2 and the balance N 2 , with a space velocity of 90 Kh -1 . The sample was heated from room temperature to 150 °C under the above gas mixture (excluding NH 3 ). At 150 °C, NH 3 was added to the gas mixture, and the sample was held under these conditions for 30 minutes. Then the temperature was increased (ramped) from 150 °C to 500 °C at 5 °C min -1 . The results are shown in Figure 61 and Figure 62 . The results show that both Cu-Mn.CHA and Cu-Mn.AEI achieved a similar total NO x conversion of 76%. However, Cu-Mn.AEI produced less average N 2 O at 14.4 ppm than Cu-Mn.CHA (which produced an average of 17.1 ppm of N 2 O).

[0304] Example 8 - Medium / Large-Pore Zeolite

[0305] Impregnate the molecular sieve with the required amount of manganese(II) acetate and / or copper(II) acetate dissolved in demineralized water. Dry the metal-impregnated sample overnight at 80 °C and then calcine it in air at 550 °C for 4 hours. Prepare catalysts with the following formulations:

[0306] · BEA zeolite with 3 wt% exchanged Cu, 3Cu.BEA

[0307] · BEA zeolite with 1.5 wt% exchanged Mn and 1.5 wt% exchanged Cu, 1.5Cu-1.5Mn.BEA

[0308] · MFI zeolite with 3 wt% exchanged Cu, 3Cu.MFI

[0309] · MFI zeolite with 1.5 wt% exchanged Mn and 1.5 wt% exchanged Cu, 1.5Cu-1.5Mn.MFI

[0310] Then test the NO x conversion and N 2 O selectivity of the catalysts under the following conditions: 500 ppm NH 3 、500 ppm NO、0 ppm NO 2 、SV = 90K h -1 。 The results are shown in Figure 63 and Figure 64 。 Under standard SCR conditions, it has been found that both Cu-Mn.BEA and Cu.BEA achieve similar total NO x conversions, 82% and 85% respectively. However, Cu-Mn.BEA exhibits an average N 2 O selectivity of 0.8%, while Cu.BEA exhibits an average N 2 O selectivity of 5.9%. Therefore, relative to typical Cu-exchanged BEA, Cu-Mn.BEA results in a significant reduction in N 2 O. Under standard SCR conditions, it has also been found that Cu-Mn.MFI achieves a total NOx conversion of 72% and an average N 2 O selectivity of 1.5%. However, the single-metal Cu.MFI is able to achieve a higher NO x conversion of 79%, but exhibits a higher average N 2 O selectivity of 2.9%. Therefore, relative to typical Cu-exchanged BEA, Cu-Mn.BEA results in a significant reduction in N 2 O. The results show that, compared with Cu.BEA and Cu.MFI respectively, Cu-Mn.BEA and Cu-Mn.MFI experience N 2There is a significant decrease in O selectivity. Therefore, the strategy of using doubly Cu- and Mn-exchanged zeolites is also viable for both mesoporous and macroporous zeolites.

[0311] Example 9 - SAR Range

[0312] The zeolite was impregnated with metals using the required amounts of manganese(II) acetate and / or copper(II) acetate dissolved in demineralized water. The metal-impregnated samples were dried overnight at 80 °C and then calcined in air at 550 °C for 4 h. Catalysts with the following formulations were prepared:

[0313] ·CHA zeolite at SAR = 22, with 1.5 wt% exchanged Mn and 1.5 wt% exchanged Cu, SAR 22

[0314] ·CHA zeolite at SAR = 13, with 1.5 wt% exchanged Mn and 1.5 wt% exchanged Cu, SAR 13

[0315] Standard SCR: Granular samples of the powder catalyst were then tested for NO x conversion and N 2 O production: 500 ppm NH 3 、500 ppm NO、0 ppm NO 2 、14% O 2 、4.6% H 2 O、5.0% CO 2 and the balance N 2 , with a space velocity of 90 Kh -1 . The samples were heated from room temperature to 150 °C under the above gas mixture (except for NH 3 ). At 150 °C, NH 3 was added to the gas mixture, and the samples were held under these conditions for 30 min. The temperature was then increased (ramped) from 150 °C to 500 °C at 5 °C min -1 . The results are shown in Figure 65 and Figure 66 . The results showed that Cu-Mn.CHA at SAR 13 achieved a total NOx conversion of 92% and an average N 2 O selectivity of 0.5%, while Cu-Mn.CHA at SAR 22 achieved a total NO x conversion of 89% and an average N 2 O selectivity of 0.7%. These results indicate that the use of the Cu-Mn bimetallic zeolite strategy works for a range of SARs. Additionally, the lower SAR materials showed a decreased N 2 O selectivity.

[0316] Example 10 - Coated Monolith

[0317] Impregnate the molecular sieve with the required amount of manganese(II) acetate and / or copper(II) acetate dissolved in demineralized water. Dry the metal-impregnated sample overnight at 80 °C and then calcine it in air at 550 °C for 4 hours. Prepare catalysts with the following formulations:

[0318] · AEI zeolite with 3 wt% exchanged Cu, 3Cu.AEI

[0319] · AEI zeolite with 1.5 wt% exchanged Cu, 1.5Cu.AEI

[0320] · AEI zeolite with 1.5 wt% exchanged Mn and 1.5 wt% exchanged Cu,

[0321] 1.5Cu-1.5Mn.AEI

[0322] The Cu-zeolite and Mn-Cu-zeolite catalysts are prepared by known prior art ion exchange techniques involving copper acetate and manganese acetate solutions. The washcoat is prepared by mixing the exchanged Cu-zeolite or Mn-Cu-zeolite solution with an alumina binder and a hydroxyethyl cellulose rheology modifier. Apply the washcoat to the ceramic substrate and then pull the washcoat off the substrate using a vacuum. Dry the article and calcine it at about 500 °C for about 1 hour.

[0323] Standard SCR: Then test the NO x conversion and N 2 O production of the coated monolith under the following conditions: 550 ppm NH 3 、500 ppm NO、0 ppm NO 2 、10% O 2 、6.0% H 2 O、6.0% CO 2 and the balance N 2 , with a space velocity of 60 K h -1 . Heat the sample from room temperature to 150 °C under the above gas mixture (except NH 3 ). At 150 °C, add NH 3 to the gas mixture and hold the sample under these conditions until the concentrations of both NO x and NH 3 in the outlet gas reach steady state values. Then close the NO x flow and the NH 3 flow, then ramp the temperature up to 450 °C and hold for 10 minutes, and then cool to 200 °C. At 200 °C, open the NO x flow and the NH 3flow, and maintain the conditions until the concentrations of both NO and NH in the outlet gas reach steady-state values. Then repeat the whole process for additional temperatures of 250 °C, 350 °C, 450 °C, and 550 °C. x and NH 3 in the outlet gas reach steady-state values. Then repeat the whole process for additional temperatures of 250 °C, 350 °C, 450 °C, and 550 °C.

[0324] Table 1

[0325]

[0326] The results are shown in Table 1. Under standard SCR conditions, both Cu-Mn.AEI and 3 wt% Cu-exchanged zeolite have been found to achieve similar total NO conversion rates of 82% and 85%, respectively. However, Cu-Mn.AEI exhibits an average N2O production of 1.1 ppm, while the 3 wt% Cu-exchanged zeolite exhibits an average N2O production of 3.1 ppm. Therefore, the catalyst of the present invention results in a significant reduction in N2O relative to typical Cu-exchanged zeolites. Additionally, the 1.5 wt% Cu-exchanged AEI exhibits a similar average N2O production value of 1.2 ppm, but can only achieve a total NO conversion rate of 78%. Therefore, under standard SCR conditions, the full-formulation monolith coated with the Cu-Mn catalyst of the present invention exhibits significant advantages over the monolith containing only a single-metal catalyst. x conversion rates of 82% and 85%, respectively. However, Cu-Mn.AEI exhibits an average N 2 2O production of 1.1 ppm, while the 3 wt% Cu-exchanged zeolite exhibits an average N 2 2O production of 3.1 ppm. Therefore, the catalyst of the present invention results in a significant reduction in N 2 2O relative to typical Cu-exchanged zeolites. Additionally, the 1.5 wt% Cu-exchanged AEI exhibits an average N 2 2O production value of 1.2 ppm, but can only achieve a total NO x conversion rate of 78%. Therefore, under standard SCR conditions, the full-formulation monolith coated with the Cu-Mn catalyst of the present invention exhibits significant advantages over the monolith containing only a single-metal catalyst.

[0327] The coated monolith is also aged at 750 °C for 80 hours in 10% water in air. The sample is heated to 250 °C at a rate of 10 °C min 1 -1 only in air. Then the monolith is heated to 750 °C at a rate of 10 °C min 2 -1 in 10% H -1 2O in air. After maintaining at the temperature of 750 °C for 80 hours, the sample is cooled in a steam / air mixture until the temperature is <250 °C. Then the sample is cooled from 250 °C to room temperature in an air flow only. Then the NO conversion rate and N x 2O selectivity of the aged monolith are tested under the following conditions: 550 ppm NH 2 3, 500 ppm NO, 0 ppm NO 3 2, 10% O 2 2, 6.0% H 2 2O, 6.0% CO 2 2, and the balance N 2 2, with a space velocity of 60 K h 2 -1. -1 .

[0328] The results are shown in Table 1. After hydrothermal aging under standard SCR conditions, it has been found that Cu-Mn.AEI can achieve a total NO x conversion of 69% and maintain a low average N 2 O production of 2.6 ppm. The 3 wt% Cu-exchanged zeolite shows a total NO x conversion of 75%, however, it produces a large amount of N 2 O, with an average value of 7.8 ppm. In addition, the 1.5 wt% Cu-exchanged AEI also shows a higher average N 2 O production of 3.4 ppm and can only achieve a total NO x conversion of 50%. Therefore, compared to typical Cu-exchanged zeolites, the catalyst of the present invention results in a significant reduction in N 2 O.

[0329] Fast SCR: Then the NO x conversion and N 2 O production of the coated monolith were tested under the following conditions: 550 ppm NH 3 , 250 ppm NO, 250 ppm NO 2 , 10% O 2 , 6.0% H 2 O, 6.0% CO 2 and the balance N 2 , with a space velocity of 60 K h -1 . The sample was heated from room temperature to 150 °C under the above gas mixture (except NH 3 ). At 150 °C, NH 3 was added to the gas mixture, and the sample was maintained under these conditions until the concentrations of both NO x and NH 3 in the outlet gas reached steady-state values. Then the NO x flow and the NH 3 flow were turned off, then the temperature was ramped up to 450 °C and held for 10 minutes, after which it was cooled to 200 °C. At 200 °C, the NO x flow and the NH 3 flow were turned on, and the conditions were maintained until the concentrations of both NO x and NH 3 in the outlet gas reached steady-state values. Then the whole process was repeated for additional temperatures of 250 °C, 350 °C, 450 °C, and 550 °C.

[0330] The results are shown in Table 1. Under fast SCR conditions, it has been found that Cu-Mn.AEI can achieve a very high total NO x conversion of 88% and an average N 2O yield. However, the 3 wt% Cu-exchanged zeolite and the 1.5 wt% Cu-exchanged zeolite can only achieve total NOx conversion rates of 83% and 86% respectively, and average N 2 O yields of 8.9 ppm and 4.5 ppm respectively. Therefore, under fast SCR conditions, the full-formula monolith coated with the Cu-Mn catalyst of the present invention shows significant advantages over the monolith containing only the single-metal catalyst.

[0331] Slow SCR: Then, the NO of the coated monolith was tested under the following conditions x conversion rate and N 2 O yield: 550 ppm NH 3 、174 ppm NO、325 ppm NO 2 、10% O 2 、6.0% H 2 O、6.0% CO 2 and the balance N 2 , with a space velocity of 60 K h -1 . The sample was heated from room temperature to 150 °C under the above gas mixture (except NH 3 ). At 150 °C, NH 3 was added to the gas mixture, and the sample was maintained under these conditions until the concentrations of both NO x and NH 3 in the outlet gas reached steady-state values. Then the NO x flow and the NH 3 flow were turned off, then the temperature was ramped up to 450 °C and held for 10 minutes, and then cooled to 200 °C. At 200 °C, the NO x flow and the NH 3 flow were turned on, and the conditions were maintained until the concentrations of both NO x and NH 3 in the outlet gas reached steady-state values. Then the whole process was repeated for additional temperatures of 250 °C, 350 °C, 450 °C, and 550 °C.

[0332] The results are shown in Table 1. Under slow conditions, it has been found that Cu-Mn.AEI can achieve a very high total NO x conversion rate of 81% and an average N 2 O yield of 7.4 ppm. However, the 3 wt% Cu-exchanged zeolite and the 1.5 wt% Cu-exchanged zeolite can only achieve total NOx conversion rates of 75% and 72% respectively, and average N 2 O yields of 12.2 ppm and 7.5 ppm respectively. Therefore, under slow SCR conditions, the full-formula monolith coated with the Cu-Mn catalyst of the present invention shows significant advantages over the monolith containing only the single-metal catalyst.

Claims

1. A catalyst composition for treating exhaust gas, the catalyst composition comprising a molecular sieve, the molecular sieve comprising exchanged copper and exchanged manganese, wherein the molecular sieve comprises a small-pore aluminosilicate zeolite.

2. The catalyst composition according to claim 1, wherein the zeolite has a SAR of about 5 to about 200.

3. The catalyst composition according to claim 1, wherein the small-pore zeolite has a crystal framework type selected from AEI, CHA, and combinations thereof.

4. The catalyst composition according to claim 1, wherein the weight ratio of copper to manganese is about 0.1 to about 50.

5. The catalyst composition according to claim 1, wherein the copper and the manganese are present in a total amount of about 0.1 wt% to about 10 wt% based on the weight of the molecular sieve.

6. The catalyst composition according to claim 1, wherein the copper is present in an amount of about 0.05 wt% to about 7 wt% based on the weight of the molecular sieve.

7. The catalyst composition according to claim 1, wherein the manganese is present in an amount of about 0.05 wt% to about 7 wt% based on the weight of the molecular sieve.

8. The catalyst composition according to claim 1, wherein the molecular sieve has a ratio of copper and manganese to aluminum of <1.

9. The catalyst composition according to claim 1, wherein the catalyst composition is effective in promoting the reaction of NH 3 with NOx to form nitrogen and water.

10. A catalyst article comprising a substrate coated with the catalyst composition according to claim 1.

11. The catalyst article according to claim 10, further comprising one or more additional catalyst compositions.

12. The catalyst article according to claim 11, wherein the one or more additional catalyst compositions comprise a Cu-exchanged molecular sieve catalyst or an Fe-exchanged molecular sieve catalyst.

13. The catalyst article according to claim 11, wherein the molecular sieve comprising exchanged copper and exchanged manganese is present upstream of the one or more additional catalyst compositions.

14. The catalyst article according to claim 11, wherein the molecular sieve comprising exchanged copper and exchanged manganese is present in the top layer, and the one or more additional catalyst compositions are present in the bottom layer.

15. The catalyst article according to claim 10, further comprising a catalyst composition containing a platinum group metal.

16. A method for treating exhaust gas containing nitrogen oxides, comprising contacting the exhaust gas with a nitrogen-containing reducing agent in the presence of the catalyst composition according to claim 1.

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