Catalyst for selective catalytic reduction of exhaust gases

Abstract

This invention provides a catalyst for selective catalytic reduction for treating exhaust gases from internal combustion engines. [Solution] A selective catalytic reduction catalyst comprising: (i) a substrate having an inlet end, an outlet end, a substrate axial length extending from the inlet end to the outlet end, and a plurality of passages defined by the inner wall of the substrate and extending within the substrate; and (ii) a coating disposed on the substrate, comprising a first non-zeolite oxidizing material containing aluminum, an eight-membered ring-pore zeolite material containing one or more of copper and iron, and a second non-zeolite oxidizing material containing cerium and one or more of zirconium, aluminum, silicon, lanthanum, niobium, iron, manganese, titanium, tungsten, copper, molybdenum, neodymium, cobalt, chromium, tin, and praseodymium, wherein at least 65% by mass of the coating is made of an eight-membered ring-pore zeolite material containing one or more of copper and iron.

Description

[Technical Field]

[0001] The present invention relates to a selective catalytic reduction catalyst for treating exhaust gas from an internal combustion engine, a method for preparing a selective catalytic reduction catalyst for treating exhaust gas from an internal combustion engine, the use of the catalyst, and a system containing the catalyst. [Background technology]

[0002] US2011 / 0142737A1 discloses a catalyst for selective catalytic reduction of nitrogen oxides in a diesel engine, the catalyst comprising a zeolite or zeolite-like compound and cerium oxide or a cerium-zirconium mixed oxide. DE102011012799A1 discloses a catalyst for removing nitrogen oxides from the exhaust gas of a diesel engine, the catalyst comprising a support and a catalytically active coating comprising one or more material zones. Finally, US2013 / 0156668A1 also discloses a catalyst for removing nitrogen oxides from the exhaust gas of a diesel engine, this last catalyst comprising a support and a catalytically active coating comprising one or more material zones, the coating comprising a zeolite or zeolite-like compound and at least one compound such as barium oxide, barium hydroxide, barium carbonate, strontium oxide, strontium hydroxide, strontium carbonate. However, improved NO while maintaining or reducing back pressure X There is still a need to provide selective catalytic reduction catalysts that exhibit conversion. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] US2011 / 0142737A1 [Patent Document 2] DE102011012799A1 [Patent Document 3] US2013 / 0156668A1 [Overview of the project] [Problems that the invention aims to solve]

[0004] Therefore, the object of the present invention is to improve NO while maintaining or reducing back pressure. X The objective is to provide a selective catalytic reduction catalyst for treating exhaust gases from internal combustion engines that exhibit conversion. Surprisingly, the selective catalytic reduction catalyst for treating exhaust gases from internal combustion engines according to the present invention maintains or reduces back pressure while producing NO X We found that we could improve the transition. [Means for solving the problem]

[0005] Therefore, the present invention relates to a selective catalytic reduction catalyst for treating exhaust gas from an internal combustion engine, wherein the catalyst is (i) A substrate having an inlet end, an outlet end, a substrate axial length extending from the inlet end to the outlet end, and a plurality of passages defined by the inner wall of the substrate and extending within the substrate, (ii) A coating disposed on a substrate (i), the coating comprising a first non-zeolite oxide material containing aluminum, and a second non-zeolite oxide material containing cerium and one or more of zirconium, aluminum, silicon, lanthanum, niobium, iron, manganese, titanium, tungsten, copper, molybdenum, neodymium, cobalt, chromium, tin, and praseodymium, and further comprising an eight-membered ring-pore zeolite material containing one or more of copper and iron, wherein at least 65% by mass of the coating consists of the eight-membered ring-pore zeolite material containing one or more of copper and iron. This relates to catalysts for selective catalytic reduction, including [specific component].

[0006] The first non-zeolite oxide preferably contains alumina, and more preferably 98 to 100% by mass, even more preferably 99 to 100% by mass, and more preferably 99.5 to 100% by mass of the first non-zeolite material consists of alumina.

[0007] The first non-zeolite material is 120-300m 2in the range of / g, more preferably in the range of 150 to 250 m 2 / g, even more preferably in the range of 170 to 220 m 2 It preferably has a BET specific surface area in the range of / g, and the BET specific surface area is determined according to the definition in Reference Example 1.

[0008] It is alternatively preferable that the first non-zeolite-based oxidation material further contains one or more of zirconium, silicon, and titanium, more preferably one or more of zirconium and silicon, and even more preferably silicon. According to the alternative, it is more preferable that the first non-zeolite-based material contains aluminum and silicon. 98 to 100% by mass, more preferably 99 to 100% by mass, and even more preferably 99.5 to 100% by mass of the first non-zeolite-based oxidation material consists of aluminum, silicon, and oxygen. More preferably, 90 to 99% by mass, more preferably 92 to 96% by mass of the first non-zeolite-based oxidation material consists of aluminum calculated as Al2O3. More preferably, 1 to 10% by mass, more preferably 4 to 8% by mass of the first non-zeolite-based oxidation material consists of silicon calculated as SiO2.

[0009] According to the alternative, the first non-zeolite-based material has a BET specific surface area in the range of 50 to 180 m 2 / g, more preferably in the range of 70 to 160 m 2 / g, even more preferably in the range of 80 to 110 m 2 / g, and the BET specific surface area is determined according to the definition in Reference Example 1.

[0010] In the context of the present invention, the first non-zeolite-based oxidation material in coating (ii) is preferably composed in an amount in the range of 2 to 28% by mass, more preferably in the range of 5 to 25% by mass, more preferably in the range of 6 to 18% by mass, more preferably in the range of 7 to 17% by mass, more preferably in the range of 8 to 15% by mass, and more preferably in the range of 9 to 13% by mass, based on the mass of the 8-membered ring pore zeolite-based material.

[0011] The second non-zeolite oxide material included in coating (ii) preferably includes a mixed oxide of cerium and one or more of zirconium, aluminum, silicon, lanthanum, niobium, iron, manganese, titanium, tungsten, copper, molybdenum, neodymium, cobalt, chromium, tin, and praseodymium, or a mixture of cerium oxide and one or more oxides of zirconium, aluminum, silicon, lanthanum, niobium, iron, manganese, titanium, tungsten, copper, molybdenum, neodymium, cobalt, chromium, tin, and praseodymium.

[0012] If the second non-zeolite oxide material included in coating (ii) contains a mixed oxide, it is preferable that the material contains a mixed oxide of cerium and one or more of zirconium, aluminum, silicon, lanthanum, niobium, iron, manganese, titanium, tungsten, copper, molybdenum, neodymium, cobalt, chromium, tin, and praseodymium, more preferably a mixed oxide of cerium and one or more of zirconium, aluminum, and silicon. If the second non-zeolite oxide material included in coating (ii) contains a mixed oxide, it is even more preferable that the material contains a mixed oxide of cerium and zirconium.

[0013] A mixed oxide of cerium and zirconium is a crystalline phase Ce a Zr 1-a It is preferable to have O2 (wherein a is in the range of 0.1 to 0.9, more preferably in the range of 0.2 to 0.8, and even more preferably in the range of 0.25 to 0.75).

[0014] If the second non-zeolite oxide material included in coating (ii) contains mixed oxides, it is preferable that the material further contains one or more oxides of lanthanum, niobium, iron, manganese, titanium, tungsten, copper, molybdenum, neodymium, cobalt, chromium, tin, and praseodymium, more preferably one or more oxides of lanthanum and niobium, even more preferably lanthanum oxide, and even more preferably niobium oxide.

[0015] It is preferable that one or more oxides from among lanthanum, niobium, iron, manganese, titanium, tungsten, copper, molybdenum, neodymium, cobalt, chromium, tin, and praseodymium are supported on the mixed oxide. In the mixed oxide of cerium and zirconium, it is more preferable that lanthanum is supported.

[0016] It is preferable that one or more oxides of lanthanum, niobium, iron, manganese, titanium, tungsten, copper, molybdenum, neodymium, cobalt, chromium, tin, and praseodymium are included in the second non-zeolite oxide material contained in coating (ii) in an amount ranging from 2 to 25% by mass, more preferably from 3 to 20% by mass, and even more preferably from 4 to 16% by mass, based on the mass of the mixed oxide.

[0017] The second non-zeolite oxide material comprises (more preferably consists of) one or more oxides of lanthanum and niobium, more preferably an oxide of lanthanum or niobium, and one or more mixed oxides of cerium and zirconium, aluminum and silicon, more preferably a mixed oxide of cerium and zirconium, and the oxide of lanthanum or niobium is more preferably supported on the mixed oxide of cerium and zirconium.

[0018] Preferably 98 to 100% by mass, more preferably 99 to 100% by mass, and even more preferably 99.5 to 100% by mass of the second non-zeolite oxide material consists of a mixed oxide of cerium and one or more of zirconium, aluminum, silicon, lanthanum, niobium, iron, manganese, titanium, tungsten, copper, molybdenum, neodymium, cobalt, chromium, tin, and praseodymium, more preferably the oxides defined above.

[0019] The first non-zeolite oxide material contains alumina, more preferably 98-100% by mass, more preferably 99-100% by mass, and even more preferably 99.5-100% by mass of the first non-zeolite oxide material is alumina, and the second non-zeolite oxide material contains a mixed oxide of cerium and one or more of zirconium, aluminum and silicon, more preferably a mixed oxide of cerium and zirconium.

[0020] The first non-zeolite oxide material contains alumina, more preferably 98-100% by mass, more preferably 99-100% by mass, and even more preferably 99.5-100% by mass of the first non-zeolite oxide material is alumina, and the second non-zeolite oxide material contains a mixed oxide of cerium and zirconium, and more preferably contains an oxide of lanthanum.

[0021] Alternatively, it is more preferable that the first non-zeolite oxide material contains aluminum and silicon, and the second non-zeolite oxide material contains a mixed oxide of cerium and zirconium, aluminum and silicon, or more preferably a mixed oxide of cerium and zirconium.

[0022] According to the above alternative, it is more preferable that the first non-zeolite oxide material comprises aluminum and silicon, the second non-zeolite oxide material comprises a mixed oxide of cerium and zirconium, and further comprises lanthanum oxide.

[0023] In the present invention, if the second non-zeolite oxidizing material contained in coating (ii) does not contain mixed oxides, it is preferable that the material is a mixture of cerium oxide and one or more of zirconium oxide, aluminum oxide, silicon oxide, lanthanum oxide, niobium oxide, iron oxide, manganese oxide, titanium oxide, tungsten oxide, copper oxide, molybdenum oxide, neodymium oxide, cobalt oxide, chromium oxide, tin oxide, and praseodymium oxide; more preferably, a mixture of cerium oxide and one or more of zirconium oxide, aluminum oxide, silicon oxide, lanthanum oxide, and niobium oxide; and even more preferably, a mixture of cerium oxide and one or more of aluminum oxide, lanthanum oxide, and niobium oxide.

[0024] It is more preferable that the second non-zeolite oxidizing material included in coating (ii) includes a mixture of cerium oxide, aluminum oxide, and lanthanum oxide.

[0025] Preferably 98-100% by mass, more preferably 99-100% by mass, and even more preferably 99.5-100% by mass of the second non-zeolite oxide material contained in coating (ii) consists of a mixture of cerium oxide, aluminum oxide, and lanthanum oxide, and more preferably 2-20% by mass, and even more preferably 5-15% by mass of the second non-zeolite material consists of lanthanum calculated as La2O3.

[0026] The first non-zeolite oxide material contains alumina, more preferably 98-100% by mass, more preferably 99-100% by mass, and even more preferably 99.5-100% by mass of the first non-zeolite oxide material is alumina, and the second non-zeolite oxide material contained in coating (ii) more preferably contains a mixture of cerium oxide, aluminum oxide and lanthanum oxide.

[0027] Alternatively, if the second non-zeolite oxide material included in coating (ii) does not contain mixed oxides, it is more preferable that the material contains a mixed oxide of cerium oxide, aluminum oxide, and niobium oxide. Preferably 98-100% by mass, more preferably 99-100% by mass, and even more preferably 99.5-100% by mass of the second non-zeolite oxide material contained in coating (ii) consists of a mixture of cerium oxide, aluminum oxide, and niobium oxide, and more preferably 2-20% by mass, and even more preferably 5-15% by mass of the second non-zeolite material consists of niobium calculated as Nb2O5.

[0028] The first non-zeolite oxide material contains alumina, more preferably 98 to 100% by mass, more preferably 99 to 100% by mass, and more preferably 99.5 to 100% by mass of the first non-zeolite oxide material is alumina, and the second non-zeolite oxide material contained in coating (ii) more preferably contains a mixture of cerium oxide, aluminum oxide and niobium oxide.

[0029] In the context of the present invention, the second non-zeolite oxidizing material is 50-700 m as determined by the method described in Reference Example 1. 2 Range of / g, more preferably 60-600m 2 Range of / g, more preferably 70-580m 2 It is preferable to have a BET specific surface area within the range of / g.

[0030] The second non-zeolite oxidizing material is preferably included in coating (ii) in an amount ranging from 15 to 35% by mass, more preferably from 16 to 30% by mass, and even more preferably from 17 to 25% by mass, based on the mass of the 8-membered ring-pore zeolite material. More preferably, the second non-zeolite oxidizing material is included in coating (ii) in an amount ranging from 18 to 23% by mass, based on the mass of the 8-membered ring-pore zeolite material.

[0031] The ratio (defined as (w1):(w2)) of the mass of the first non-zeolite oxidizing material (w1) to the mass of the second non-zeolite oxidizing material (w2) is preferably in the range of 0.2:1 to 0.7:1, more preferably in the range of 0.3:1 to 0.6:1, even more preferably in the range of 0.4:1 to 0.55:1, and even more preferably in the range of 0.45:1 to 0.55:1.

[0032] The eight-membered ring-pore zeolite material included in coating (ii) preferably has a skeleton type selected from the group consisting of CHA, AEI, RTH, LEV, DDR, KFI, ERI, AFX, LTA, and two or more mixed types thereof, more preferably a skeleton type selected from the group consisting of CHA, AEI, RTH, and two or more mixed types thereof, and more preferably a skeleton type selected from the group consisting of CHA and AEI. It is even more preferable that the eight-membered ring-pore zeolite material included in coating (ii) has a skeleton type CHA.

[0033] The zeolite-based material included in coating (ii) preferably contains copper, and the amount of copper in the zeolite-based material (calculated as CuO) is more preferably in the range of 0.1 to 10 mass%, more preferably in the range of 1.5 to 5.5 mass%, more preferably in the range of 2.5 to 5.0 mass%, more preferably in the range of 3.0 to 4.75 mass%, and more preferably in the range of 3.25 to 4.5 mass%, based on the mass of the zeolite-based material.

[0034] The amount of iron contained in the zeolite material (calculated as Fe2O3) is preferably in the range of 0 to 0.01 mass%, more preferably in the range of 0 to 0.001 mass%, and more preferably in the range of 0 to 0.0001 mass%, based on the mass of the zeolite material. In other words, the zeolite material is preferably substantially iron-free, and more preferably iron-free.

[0035] Preferably, 95 to 100% by mass, more preferably 98 to 100% by mass, more preferably 99 to 100% by mass, and more preferably 99.5 to 100% by mass of the zeolite material's skeletal structure consists of Si, Al, O, and optionally H, and in the skeletal structure, the molar ratio of Si to Al (calculated as molar SiO2:Al2O3) is more preferably in the range of 2:1 to 50:1, more preferably in the range of 5:1 to 45:1, more preferably in the range of 10:1 to 40:1, more preferably in the range of 13:1 to 30:1, more preferably in the range of 14:1 to 27:1, and more preferably in the range of 15:1 to 26:1.

[0036] The molar ratio of Si to Al (calculated as moles of SiO2:Al2O3) is more preferably in the range of 15:1 to 20:1, and more preferably in the range of 16:1 to 19:1. Alternatively, the molar ratio of Si to Al (calculated as moles of SiO2:Al2O3) is more preferably in the range of 22:1 to 26:1.

[0037] Furthermore, it is preferable that the zeolite-based material contained in coating (ii) contains iron, and the amount of iron contained in the zeolite-based material (calculated as Fe2O3) is more preferably in the range of 0.1 to 10.0 mass%, more preferably 0.5 to 7.0 mass%, even more preferably 1.0 to 5.5 mass%, and even more preferably 2.0 to 5.5 mass%, based on the mass of the zeolite-based material. It is more preferable that 95-100% by mass, more preferably 98-100% by mass, even more preferably 99-100% by mass, and even more preferably 99.5-100% by mass of the zeolite material's skeletal structure consists of Si, Al, O, and optionally H, and that the molar ratio of Si to Al (calculated as moles of SiO2:Al2O3) in the skeletal structure is more preferably in the range of 2:1-50:1, more preferably in the range of 5:1-45:1, more preferably in the range of 10:1-40:1, more preferably in the range of 13:1-30:1, more preferably in the range of 14:1-27:1, and even more preferably in the range of 15:1-26:1. The molar ratio of Si to Al (calculated as moles of SiO2:Al2O3) is more preferably in the range of 15:1-20:1, and even more preferably in the range of 16:1-19:1. Alternatively, it is more preferable that the molar ratio of Si to Al (calculated as molar SiO2:Al2O3) is in the range of 22:1 to 26:1.

[0038] With respect to the 8-membered ring-pore zeolite material (preferably having a skeletal CHA) included in coating (ii), it is preferable that it contains crystals having an average crystal size in the range of 0.05 to 5 μm, more preferably 0.06 to 2 μm, more preferably 0.07 to 1 μm, even more preferably 0.1 to 0.8 μm, and more preferably 0.2 to 0.6 μm, the average crystal size is determined in the same manner as in Reference Example 8.

[0039] The 8-membered ring-pore zeolite material (more preferably having a skeletal CHA) included in coating (ii) is 50-900 m as determined by the method described in Reference Example 1. 2 Range of / g, more preferably 150~700m 2 / g, more preferably 250-650m 2It is preferable to have a BET specific surface area in the range of / g.

[0040] Preferably, 65-80% by mass, more preferably 70-78% by mass, and even more preferably 72-76% by mass of the coating (ii) consists of an 8-membered ring-pore zeolite material containing one or more copper and iron.

[0041] The 8-membered ring pore zeolite material has a concentration of 0.5-5 g / in. 3 The range is, more preferably 0.75 to 4 g / in. 3 In the range of 1-3 g / in 3 It is more preferable that the coating (ii) contains a loading within the range of .

[0042] It is more preferable that coating (ii) further comprises an oxidizing binder. The oxidizing binder comprises a mixed oxide containing one or more of zirconia, alumina, titania, and silica, and two or more of Zr, Al, Ti, and Si; more preferably, it comprises one or more of silica, alumina, and zirconia; more preferably, it comprises one or more of alumina and zirconia; and more preferably, it comprises zirconia.

[0043] The oxidizing binder (more preferably zirconia) is preferably included in the coating (ii) in an amount ranging from 0.1 to 8% by mass, more preferably 1 to 7% by mass, more preferably 2 to 6.5% by mass, more preferably 3 to 6% by mass, and more preferably 4 to 5.5% by mass, based on the mass of the 8-membered ring-pore zeolite material.

[0044] The loading amount of coating (ii) is 1-5 g / in 3 The range is, more preferably 1.5 to 3 g / in 3 The range, more preferably 1.75 to 2.5 g / in 3 It is preferable that it be within the range of [specify range].

[0045] The coating (ii) preferably extends over x% of the axial length of the substrate (where x is in the range of 80 to 100, more preferably 90 to 100, more preferably 95 to 100, and more preferably 98 to 100), or more preferably extends from the inlet end to the outlet end of the substrate.

[0046] Preferably 98 to 100% by mass, more preferably 99 to 100% by mass, and even more preferably 99.5 to 100% by mass of coating (ii) consists of an 8-membered ring-pore zeolite material comprising a first non-zeolite oxide material containing aluminum, a second non-zeolite oxide material containing cerium and one or more of zirconium, aluminum, silicon, lanthanum, niobium, iron, manganese, titanium, tungsten, copper, molybdenum, neodymium, cobalt, chromium, tin, and praseodymium, and one or more of copper and iron, more preferably an oxidizing binder as defined above.

[0047] Preferably, 0 to 0.001% by mass, more preferably 0 to 0.0001% by mass, and more preferably 0 to 0.00001% by mass of coating (ii) consists of platinum, more preferably platinum, palladium, and rhodium, and more preferably any platinum group metal. In other words, preferably coating (ii) is substantially platinum-free, more preferably platinum-free, more preferably platinum-free, more preferably platinum, palladium, and rhodium-free, and more preferably platinum group metal-free.

[0048] It is preferable that 0 to 0.01% by mass, more preferably 0 to 0.001% by mass, and even more preferably 0 to 0.0001% by mass of coating (ii) consists of vanadium. In other words, it is preferable that coating (ii) is substantially vanadium-free, more preferably vanadium-free.

[0049] The coating (ii) is preferably placed on the surface of the inner wall of the substrate, and its surface defines the boundary between the inner wall and the passage and / or the inside of the inner wall of the substrate.

[0050] The substrate is preferably a wall flow filter substrate or a flow-through substrate, more preferably a wall flow filter substrate, and the plurality of passages preferably include an inlet passage having an open inlet end and a closed outlet end, and an outlet passage having a closed inlet end and an open outlet end.

[0051] The wall flow filter substrate is a porous wall flow filter substrate, and more preferably it is one or more of a cordierite wall flow filter substrate, a silicon carbide wall flow filter substrate, or an aluminum titanate wall flow filter substrate, even more preferably one or more of a silicon carbide wall flow filter substrate and an aluminum titanate wall flow filter substrate, and even more preferably a silicon carbide wall flow filter substrate. The coating (ii) is disposed within the inner wall of the porous wall flow filter and on the surface of the inner wall of the substrate, and it is more preferable that at least 95% by mass, more preferably at least 98% by mass, of the coating (ii) is present within the inner wall of the substrate. The amount of coating within and / or on the inner wall of the substrate is measured by an electron microscope such as a TEM.

[0052] The catalyst of the present invention preferably consists of a substrate (i) and a coating (ii).

[0053] The present invention further relates to a method for preparing a selective catalytic reduction catalyst for treating exhaust gas from an internal combustion engine (preferably, a selective catalytic reduction catalyst according to the present invention), That method is (a) Prepare a mixture comprising water, a first non-zeolite oxide material containing aluminum, a second non-zeolite oxide material containing one or more of cerium, zirconium, aluminum, silicon, lanthanum, niobium, iron, manganese, titanium, tungsten, copper, molybdenum, neodymium, cobalt, chromium, tin, and praseodymium, and an eight-membered ring pore zeolite material containing one or more of copper and iron. (b) The mixture obtained in (a) is placed on a substrate that includes a plurality of passages defined by an inlet end, an outlet end, a substrate axial length extending from the inlet end to the outlet end, and the inner wall of the substrate, thereby obtaining a mixture-processed substrate. (c)(b) The mixture-treated substrate obtained by firing is fired to obtain a substrate having a coating placed thereon, wherein at least 65% by mass of the coating consists of an 8-membered ring-pore zeolite material containing one or more of copper and iron. Includes.

[0054] (a) preferably includes (more preferably consists of) the following (a.1) to (a.6): (a.1) Prepare a first aqueous mixture containing an 8-membered ring-pore zeolite material and one or more of copper salts and iron salts (more preferably copper salts), or Prepare a first aqueous mixture containing an 8-membered ring pore zeolite material containing copper and one or more (more preferably copper salts) of copper salts and iron salts. The obtained first aqueous mixture is calcined in a gas atmosphere having a temperature preferably in the range of 300 to 700°C, the gas atmosphere being more preferably air, to obtain an 8-membered ring porous zeolite material containing one or more of copper and iron (more preferably copper). (a.2) Prepare a second aqueous mixture comprising water and a first non-zeolite oxidizing material containing aluminum. (a.1) The 8-membered ring-pore zeolite material containing one or more of copper and iron obtained by (a.1) is impregnated with a second aqueous mixture. The first non-zeolite oxide material containing aluminum is obtained by firing in a gas atmosphere having a temperature in the range of 300 to 700°C, wherein the gas atmosphere is more preferably air, and using an 8-membered ring-pore zeolite material containing one or more of copper and iron (more preferably copper). (a.3) Prepare a third aqueous mixture comprising water, a first non-zeolite oxidizing material containing aluminum together with an 8-membered ring-pore zeolite material containing one or more of copper and iron obtained in (a.2), and more preferably a precursor of an oxidizing binder. (a.4) More preferably, the third aqueous mixture obtained by (a.3) is ground to a Dv90 of 1 to 10 μm, more preferably 2 to 7 μm, and even more preferably 3 to 5 μm (where Dv90 is determined as described in Reference Example 3). (a.5) Prepare a fourth aqueous mixture comprising water, a second non-zeolite oxidizing material, and more preferably an acid (more preferably an organic acid). Mix the third aqueous mixture obtained by (a.6)(a.3)(more preferably (a.4)) with the fourth aqueous mixture obtained by (a.5).

[0055] The firing in (a.1) is preferably carried out in a gas atmosphere having a temperature in the range of 400 to 600°C, more preferably in the range of 450 to 550°C.

[0056] The firing of (a.1) is preferably carried out in a gas atmosphere for a duration of 0.5 to 4 hours, more preferably 1 to 3 hours.

[0057] The gas atmosphere preferably contains oxygen, and more preferably air.

[0058] The firing in (a.2) is preferably carried out in a gas atmosphere having a temperature in the range of 400 to 600°C, more preferably in the range of 450 to 550°C. The firing in (a.2) is preferably carried out in a gas atmosphere for a duration of 0.5 to 4 hours, more preferably 1 to 3 hours.

[0059] The gas atmosphere preferably contains oxygen, and more preferably air.

[0060] The precursor of the oxidizing binder contained in the third aqueous mixture is preferably one or more of aluminum salts, silicon salts, zirconium salts, and titanium salts, more preferably one or more of zirconium salts and aluminum salts, more preferably zirconium salt, and more preferably zirconium acetate.

[0061] The third aqueous mixture prepared by (a.3) preferably further contains an acid, more preferably an organic acid, the organic acid being more preferably one or more of tartaric acid, acetic acid, citric acid, nitric acid, hydrochloric acid, and sulfuric acid, and the organic acid being more preferably acetic acid.

[0062] The organic acid contained in the fourth aqueous mixture prepared by (a.5) is preferably one or more of tartaric acid, acetic acid, citric acid, nitric acid, hydrochloric acid, and sulfuric acid.

[0063] Alternatively, regarding (a), (a.1') Prepare a first aqueous mixture containing copper and an 8-membered ring pore zeolite material containing one or more of copper oxide and iron oxide (more preferably copper oxide). (a.2') Prepare a second aqueous mixture comprising water, a first non-zeolite oxidizing material containing aluminum, and more preferably an acid (more preferably an organic acid). A third aqueous mixture is obtained by mixing the first aqueous mixture obtained by (a.3')(a.1') with the second aqueous mixture obtained by (a.2'), (a.4') Prepare a fourth aqueous mixture comprising water, a second non-zeolite oxidizing material, and more preferably an acid (more preferably an organic acid). Mixing the third aqueous mixture obtained by (a.5')(a.3') with the fourth aqueous mixture obtained by (a.4'). It is preferable to include (more preferably consist of)

[0064] (a.1') (a.1'.1) Prepare a mixture containing water and one or more of copper oxide and iron oxide (more preferably copper oxide, more preferably CuO). (a.1'.2) More preferably, the mixture prepared according to (a.1'.1) is ground until the particles of the mixture have a Dv90 in the range of 3 to 20 μm, more preferably in the range of 6 to 10 μm (where Dv90 was determined as described in Reference Example 3). (a.1'.3) More preferably, an oxidizing binder precursor (which is more preferably as defined above) is added to the mixture obtained by (a.1'.1) (more preferably, (a.1'.2)), (a.1'.4) Prepare a mixture containing water and an 8-membered ring pore zeolite material containing copper. Mixing the mixture prepared by (a.1'.5)(a.1'.4) with the mixture prepared by (a.1'.1), more preferably (a.1'.2), more preferably (a.1'.3). It is preferable to include (more preferably consist of)

[0065] It is preferable that the organic acid contained in the second aqueous mixture prepared by (a.2') is one or more of tartaric acid, acetic acid, citric acid, nitric acid, hydrochloric acid, and sulfuric acid.

[0066] The organic acid contained in the second aqueous mixture prepared by (a.4') is preferably one or more of tartaric acid, acetic acid, citric acid, nitric acid, hydrochloric acid, and sulfuric acid.

[0067] In the context of the present invention, it is preferable that the first non-zeolite oxidizing material is one defined above together with the catalyst of the present invention.

[0068] The second non-zeolite oxidizing material is preferably as defined above, together with the catalyst of the present invention.

[0069] The 8-membered ring-pore zeolite material is preferably as defined above, together with the catalyst of the present invention.

[0070] Placing the mixture obtained by (a) onto the substrate by (b) is preferably done by immersing the substrate in the mixture obtained by (a).

[0071] The substrate is preferably as defined above, together with the catalyst according to the present invention.

[0072] According to (b), it is preferable that the mixture prepared according to (a) is placed on the substrate over an area of ​​x% of the substrate axial length (where x is in the range of 80 to 100, more preferably 90 to 100, more preferably 95 to 100, and more preferably 98 to 100).

[0073] It is preferable that the mixture prepared by (a) is placed on the substrate from the inlet end to the outlet end.

[0074] (b) preferably further includes, after placing the mixture obtained in (a) onto a substrate, drying the substrate treated with the mixture in a gas atmosphere having a temperature in the range of 50 to 300°C, more preferably in the range of 60 to 190°C (the gas atmosphere is more preferably air). Drying is preferably carried out for a duration ranging from 0.1 to 240 minutes, more preferably from 0.15 to 120 minutes.

[0075] Preferably, (b) further includes (b.1) and (b.2): (b.1)(a) is placed on a substrate which includes a first portion of the mixture obtained in (a) and which includes a plurality of passages extending within the substrate, defined by an inlet end, an outlet end, a substrate axial length extending from the inlet end to the outlet end, and the inner wall of the substrate (this arrangement is more preferably in the direction from the inlet end to the outlet end of the substrate), and the substrate which includes the first portion of the mixture placed on the substrate is dried. (b.2)(i) is placed on the substrate obtained in (b.2) which includes the first portion of the mixture placed on the substrate (more preferably in the direction from the inlet end to the outlet end of the substrate), and more preferably the substrate including the first and second portions of the mixture placed on the substrate is dried.

[0076] The firing according to (c) is preferably carried out in a gas atmosphere having a temperature in the range of 300 to 800°C, more preferably in the range of 350 to 700°C, and the gas atmosphere is more preferably air.

[0077] The firing according to (c) is preferably carried out in a gas atmosphere for a duration of 10 to 240 minutes, more preferably 20 to 160 minutes, and the gas atmosphere is more preferably air.

[0078] The method according to the present invention preferably comprises (a), (b), (c), and (d).

[0079] The present invention further relates to a selective catalytic reduction catalyst (preferably, the selective catalytic reduction catalyst according to the present invention and the selective catalytic reduction catalyst defined above) that can be obtained or obtained by the method according to the present invention.

[0080] The present invention further relates to the use of a selective catalytic reduction catalyst according to the present invention for the selective catalytic reduction of nitrogen oxides.

[0081] The present invention further relates to a method for selective catalytic reduction of nitrogen oxides, the method comprising: (1) The exhaust gas flow is preferably supplied from an internal combustion engine (more preferably a diesel engine), (2) Passing the exhaust gas flow provided in (1) through the selective catalytic reduction catalyst according to the present invention.

[0082] The present invention further relates to an exhaust gas treatment system for treating exhaust gas flow discharged from an internal combustion engine (preferably a diesel engine), wherein the exhaust gas treatment system has an upstream end for introducing the exhaust gas flow into the exhaust gas treatment system. The aforementioned exhaust gas treatment system is The first selective catalytic reduction catalyst according to the present invention as defined above, Diesel oxidation catalyst, second selective catalytic reduction catalyst, ammonia oxidation catalyst, NO X A diesel oxidation catalyst including a storage function, and one or more of the following: Includes. [Brief explanation of the drawing]

[0083] [Figure 1] The NOx conversion measured for the catalysts of Examples 1-3, Comparative Example 1, and Reference Example 5 at 200°C (20 ppm NH3 slip - space velocity 40 k / h) is shown. [Figure 2] The back pressure measured for the catalysts of Examples 1-3, Comparative Example 1, and Reference Example 5 at 293K (flow rate 27 m3 / h) is shown. [Figure 3] The NOx conversion measured for the catalysts of Example 5, Example 6, and Comparative Example 2 at 200°C (20 ppm NH3 slip - space velocities of 40 k / h and 80 k / h) is shown. [Figure 4] The NOx conversion measured for the catalysts of Example 5, Example 6, and Comparative Example 2 at 600°C (20 ppm NH3 slip - space velocities of 40 k / h and 80 k / h) is shown. [Figure 5] The NOx conversion of the catalysts in Reference Examples 6.1 to 6.3 is shown, measured at 575°C (20 ppm NH3 slip - 94 k / h space velocity). [Figure 6] The back pressure measured for the catalysts in Reference Examples 6.1 to 6.3 at 293K (flow rate 65 m3 / h) is shown. [Figure 7] The XRD analysis results for Examples 1-3 are shown. [Figure 8] The XRD analysis results for Example 5 are shown. [Modes for carrying out the invention]

[0084] The present invention is further described by the following series of embodiments and combinations of embodiments as shown arising from dependencies and backreferences. In particular, it should be noted that in each example in which the scope of an embodiment is referred to (for example, in the context of terms such as “any one catalyst of Embodiments 1 to 4”), all embodiments within that scope are expressly disclosed to those skilled in the art, i.e., the wording of this term should be understood by those skilled in the art as synonymous with “any one catalyst of Embodiments 1, 2, 3, and 4”. Furthermore, it should be clearly noted that the following series of embodiments represent a description of suitably configured parts directed to a general and preferred viewpoint of the present invention, rather than a series of claims that determine the scope of protection.

[0085] 1. A selective catalytic reduction catalyst for treating exhaust gas from an internal combustion engine, wherein the catalyst is: (i) A substrate having an inlet end, an outlet end, a substrate axial length extending from the inlet end to the outlet end, and a plurality of passages defined by the inner wall of the substrate and extending within the substrate, (ii) A coating disposed on a substrate (i), comprising a first non-zeolite oxide material containing aluminum, a second non-zeolite oxide material containing one or more of cerium and zirconium, aluminum, silicon, lanthanum, niobium, iron, manganese, titanium, tungsten, copper, molybdenum, neodymium, cobalt, chromium, tin, and praseodymium, wherein the coating further comprises an eight-membered ring-pore zeolite material containing one or more of copper and iron, and at least 65% by mass of the coating consists of the eight-membered ring-pore zeolite material containing one or more of copper and iron. A catalyst for selective catalytic reduction, including the following:

[0086] 2. The first non-zeolite oxide material contains alumina, and preferably 98-100% by mass, more preferably 99-100% by mass, and more preferably 99.5-100% by mass of the first non-zeolite material consists of alumina. The first non-zeolite material is more preferably 120-300 m 2 Range of / g, more preferably 150-250m 2 Range of / g, more preferably 170-220m 2 The catalyst according to Embodiment 1, having a BET specific surface area in the range of / g, wherein the BET specific surface area is preferably determined as defined in Reference Example 1.

[0087] 3. The catalyst according to Embodiment 1, wherein the first non-zeolite oxidizing material comprises one or more of zirconium, silicon, and titanium, preferably one or more of zirconium and silicon, more preferably silicon, and the first non-zeolite material more preferably comprises aluminum and silicon.

[0088] 4. 98 to 100% by mass, preferably 99 to 100% by mass, and more preferably 99.5 to 100% by mass of the first non-zeolite oxide material consist of aluminum, silicon, and oxygen. Preferably, 90-99% by mass, more preferably 92-96% by mass (calculated as Al2O3), of the first non-zeolite oxide material is aluminum, and preferably 1-10% by mass, more preferably 4-8% by mass (calculated as SiO2), of the first non-zeolite oxide material is silicon. The first non-zeolite material is more preferably 50-180m 2 Range of / g, more preferably 70-160m 2 The range is / g, more preferably 80-110m 2 The catalyst according to Embodiment 3, having a BET specific surface area in the range of / g, wherein this BET specific surface area is preferably determined as defined in Reference Example 1.

[0089] 5. The catalyst according to any one of Embodiments 1 to 4, wherein the first non-zeolite oxidizing material is included in the coating (ii) in an amount ranging from 2 to 28% by mass, preferably 5 to 25% by mass, more preferably 6 to 18% by mass, more preferably 7 to 17% by mass, more preferably 8 to 15% by mass, and more preferably 9 to 13% by mass, based on the mass of the 8-membered ring-pore zeolite material.

[0090] 6. The catalyst according to any one of Embodiments 1 to 5, wherein the second non-zeolite oxide material contained in coating (ii) comprises a mixed oxide of cerium and one or more of zirconium, aluminum, silicon, lanthanum, niobium, iron, manganese, titanium, tungsten, copper, molybdenum, neodymium, cobalt, chromium, tin, and praseodymium, or a mixture of cerium oxide and one or more oxides of zirconium, aluminum, silicon, lanthanum, niobium, iron, manganese, titanium, tungsten, copper, molybdenum, neodymium, cobalt, chromium, tin, and praseodymium.

[0091] 7. The catalyst according to Embodiment 6, wherein the second non-zeolite oxide material included in coating (ii) comprises a mixed oxide of cerium and one or more of zirconium, aluminum, silicon, lanthanum, niobium, iron, manganese, titanium, tungsten, copper, molybdenum, neodymium, cobalt, chromium, tin, and praseodymium, preferably a mixed oxide of cerium and one or more of zirconium, aluminum, and silicon, more preferably a mixed oxide of cerium and zirconium.

[0092] 8. A mixed oxide of cerium and zirconium forms a crystalline phase Ce a Zr 1-a The catalyst according to Embodiment 7, comprising O2 (wherein a is in the range of 0.1 to 0.9, preferably in the range of 0.2 to 0.8, and more preferably in the range of 0.25 to 0.75).

[0093] 9. The second non-zeolite oxide material included in coating (ii) further comprises one or more oxides of lanthanum, niobium, iron, manganese, titanium, tungsten, copper, molybdenum, neodymium, cobalt, chromium, tin, and praseodymium, preferably one or more oxides of lanthanum and niobium, more preferably an oxide of lanthanum or even more preferably an oxide of niobium. The catalyst according to Embodiment 7 or 8, wherein one or more oxides from lanthanum, niobium, iron, manganese, titanium, tungsten, copper, molybdenum, neodymium, cobalt, chromium, tin, and praseodymium are preferably supported on a mixed oxide.

[0094] 10. The catalyst according to Embodiment 9, wherein one or more oxides from lanthanum, niobium, iron, manganese, titanium, tungsten, copper, molybdenum, neodymium, cobalt, chromium, tin, and praseodymium are included in the second non-zeolite oxidizing material contained in coating (ii) in an amount of 2 to 25% by mass, preferably 3 to 20% by mass, and more preferably 4 to 16% by mass, based on the mass of the mixed oxide.

[0095] 11. The second non-zeolite oxide material comprises one or more oxides of lanthanum and niobium, preferably an oxide of lanthanum or niobium, and a mixed oxide of one or more of cerium, zirconium, aluminum, and silicon, more preferably a mixed oxide of cerium and zirconium. The catalyst according to Embodiment 9 or 10, wherein the lanthanum or niobium oxide is preferably supported on a mixed oxide of cerium and zirconium.

[0096] 12. The catalyst according to any one of Embodiments 7 to 11, wherein 98 to 100% by mass, preferably 99 to 100% by mass, and more preferably 99.5 to 100% by mass of the second non-zeolite oxide material is a mixed oxide of cerium and one or more of zirconium, aluminum, silicon, lanthanum, niobium, iron, manganese, titanium, tungsten, copper, molybdenum, neodymium, cobalt, chromium, tin, and praseodymium, and preferably consists of an oxide as defined in Embodiment 9 or 10.

[0097] 13. The catalyst according to Embodiment 6, wherein the second non-zeolite oxidizing material contained in coating (ii) comprises a mixture of cerium oxide and one or more of zirconium oxide, aluminum oxide, silicon oxide, lanthanum oxide, niobium oxide, iron oxide, manganese oxide, titanium oxide, tungsten oxide, copper oxide, molybdenum oxide, neodymium oxide, cobalt oxide, chromium oxide, tin oxide, and praseodymium oxide; preferably a mixture of cerium oxide and one or more of zirconium oxide, aluminum oxide, silicon oxide, lanthanum oxide, and niobium oxide; more preferably a mixture of cerium oxide and one or more of aluminum oxide, lanthanum oxide, and niobium oxide; more preferably a mixture of cerium oxide, aluminum oxide, and lanthanum oxide; or more preferably a mixture of cerium oxide, aluminum oxide, and niobium oxide.

[0098] 14. The catalyst according to Embodiment 13, wherein 98 to 100% by mass, preferably 99 to 100% by mass, more preferably 99.5 to 100% by mass of the second non-zeolite oxidizing material contained in coating (ii) consists of a mixture of cerium oxide, aluminum oxide, and lanthanum oxide, and preferably 2 to 20% by mass, more preferably 5 to 15% by mass (calculated as La2O3) of the second non-zeolite oxidizing material consists of lanthanum.

[0099] 15. The catalyst according to Embodiment 13, wherein 98 to 100% by mass, preferably 99 to 100% by mass, more preferably 99.5 to 100% by mass of the second non-zeolite oxidizing material contained in coating (ii) consists of a mixture of cerium oxide, aluminum oxide, and niobium oxide, and preferably 2 to 20% by mass, more preferably 5 to 15% by mass (calculated as Nb2O5) of the second non-zeolite material consists of niobium.

[0100] 16. The second non-zeolite material was determined by the method described in Reference Example 1, with a length of 50-700 m 2 A range of / g, preferably 60-600m 2 Range of / g, more preferably 70-580m 2 A catalyst according to any one of Embodiments 1 to 15, having a BET specific surface area in the range of / g.

[0101] 17. The catalyst according to any one of Embodiments 1 to 16, wherein the second non-zeolite oxidizing material is included in the coating (ii) in an amount ranging from 15 to 35% by mass, preferably from 16 to 30% by mass, and more preferably from 17 to 25% by mass, based on the mass of the 8-membered ring-pore zeolite material.

[0102] 18. The catalyst according to Embodiment 17, wherein a second non-zeolite oxidizing material is included in the coating (ii) in an amount ranging from 18 to 23% by mass, based on the mass of the 8-membered ring-pore zeolite material.

[0103] 19. The catalyst according to any one of Embodiments 1 to 18, wherein the ratio (defined as (w1):(w2)) of the mass of a first non-zeolite oxidizing material (w1) to the mass of a second non-zeolite oxidizing material (w2) is in the range of 0.2:1 to 0.7:1, preferably in the range of 0.3:1 to 0.6:1, more preferably in the range of 0.4:1 to 0.55:1, and even more preferably in the range of 0.45:1 to 0.55:1.

[0104] 20. The catalyst according to any one of Embodiments 1 to 19, wherein the eight-membered ring-pore zeolite material contained in coating (ii) has a skeletal type selected from the group consisting of CHA, AEI, RTH, LEV, DDR, KFI, ERI, AFX, LTA, two or more mixtures thereof, and two or more mixed types thereof, preferably a skeletal type selected from the group consisting of CHA, AEI, RTH, two or more mixtures thereof, and two or more mixed types thereof, more preferably a skeletal type selected from the group consisting of CHA and AEI, and more preferably the eight-membered ring-pore zeolite material contained in coating (ii) has a skeletal type CHA.

[0105] 21. The catalyst according to any one of Embodiments 1 to 20, wherein the zeolite material contained in coating (ii) contains copper, and the amount of copper in the zeolite material, calculated as CuO, is preferably in the range of 0.1 to 10 mass%, more preferably in the range of 1.5 to 5.5 mass%, more preferably in the range of 2.5 to 5.0 mass%, more preferably in the range of 3.0 to 4.75 mass%, and more preferably in the range of 3.25 to 4.5 mass% based on the mass of the zeolite material.

[0106] 22. The catalyst according to Embodiment 22, wherein the amount of iron contained in the zeolite material, calculated as Fe2O3, is in the range of 0 to 0.01% by mass, preferably 0 to 0.001% by mass, and more preferably 0 to 0.0001% by mass, based on the mass of the zeolite material.

[0107] 23. The catalyst according to any one of Embodiments 1 to 22, wherein 95 to 100% by mass, preferably 98 to 100% by mass, more preferably 99 to 100% by mass, and even more preferably 99.5 to 100% by mass of the zeolite material's skeletal structure consists of Si, Al, O, and optionally H, and in the skeletal structure, the molar ratio of Si to Al (calculated as molar SiO2:Al2O3) is preferably in the range of 2:1 to 50:1, more preferably in the range of 5:1 to 45:1, more preferably in the range of 10:1 to 40:1, more preferably in the range of 13:1 to 30:1, more preferably in the range of 14:1 to 27:1, more preferably in the range of 15:1 to 26:1, more preferably in the range of 15:1 to 20:1, or more preferably in the range of 22:1 to 26:1.

[0108] 24. The zeolite material contained in coating (ii) contains iron, and the amount of iron contained in the zeolite material (calculated as Fe2O3) is preferably in the range of 0.1 to 10.0 mass%, more preferably in the range of 0.5 to 7.0 mass%, more preferably in the range of 1.0 to 5.5 mass%, and more preferably in the range of 2.0 to 5.5 mass%, based on the mass of the zeolite material, and preferably 95 to 100 mass%, more preferably 98 to 100 mass%, more preferably 99 to 100 mass%, and more preferably 99.5 to 100 mass% of the skeletal structure of the zeolite material consists of Si, Al, O, and optionally H, and the molar ratio of Si to Al in the skeletal structure (calculated as molar SiO2:Al2O3) is preferably in the range of 2:1 to 50:1, more preferably in the range of 5:1 to 45:1, and more preferably in the range of 10:1 to 40: A catalyst according to any one of Embodiments 1 to 20, wherein the ratio is in the range of 1, more preferably in the range of 13:1 to 30:1, even more preferably in the range of 14:1 to 27:1, more preferably in the range of 15:1 to 26:1, even more preferably in the range of 15:1 to 20:1, or more preferably in the range of 22:1 to 26:1.

[0109] 25. The catalyst according to any one of Embodiments 1 to 24, wherein the coating (ii) contains an 8-membered ring-pore zeolite material, preferably having a skeletal CHA, and comprises crystals having an average crystal size in the range of 0.05 to 5 μm, preferably 0.06 to 2 μm, more preferably 0.07 to 1 μm, even more preferably 0.1 to 0.8 μm, and more preferably 0.2 to 0.6 μm, the average crystal size being preferably determined as in Reference Example 8.

[0110] 26. The 8-membered ring-pore zeolite material included in coating (ii), preferably having a skeletal CHA, has a BET specific surface area of ​​50 to 900 m² as determined by the method described in Reference Example 1. 2 Range of / g, preferably 150-700m 2 Range of / g, more preferably 250~650m 2 A catalyst according to any one of Embodiments 1 to 25, in the range of / g.

[0111] 27. The catalyst according to any one of Embodiments 1 to 26, wherein 65 to 80% by mass of coating (ii), preferably 70 to 78% by mass, and more preferably 72 to 76% by mass, consists of an 8-membered ring-pore zeolite material containing one or more copper and iron.

[0112] 28. 8-membered ring-pore zeolite material, 0.5~5 g / in 3 The range is preferably 0.75 to 4 g / in. 3 In the range of 1-3 g / in, more preferably 1-3 g / in 3 A catalyst according to any one of Embodiments 1 to 27, included in coating (ii) in a supported amount within the range of [specify range].

[0113] 29. The catalyst according to Embodiments 1 to 28, wherein the coating (ii) further comprises an oxidizing binder, the oxidizing binder preferably comprising one or more of zirconia, alumina, titania, and silica, and two or more of Zr, Al, Ti, and Si, more preferably comprising one or more of silica, alumina, and zirconia, more preferably comprising one or more of alumina and zirconia, and more preferably comprising zirconia.

[0114] 30. The catalyst according to Embodiment 29, wherein an oxidizing binder (preferably zirconia) is included in the coating (ii) in an amount ranging from 0.1 to 8% by mass, preferably 1 to 7% by mass, more preferably 2 to 6.5% by mass, more preferably 3 to 6% by mass, and more preferably 4 to 5.5% by mass, based on the mass of the 8-membered ring-pore zeolite material.

[0115] 31. The loading amount of coating (ii) is 1-5 g / in. 3 The range is preferably 1.5 to 3 g / in. 3 The range, more preferably 1.75 to 2.5 g / in 3 A catalyst according to any one of Embodiments 1 to 30, which falls within the range of [the specified range].

[0116] 32. The catalyst according to any one of Embodiments 1 to 31, wherein the coating (ii) extends over x% of the axial length of the substrate (where x is in the range of 80 to 100, preferably 90 to 100, more preferably 95 to 100, and more preferably 98 to 100), preferably from the inlet end to the outlet end of the substrate.

[0117] 33. A catalyst according to any one of Embodiments 1 to 32, wherein 98 to 100% by mass, preferably 99 to 100% by mass, more preferably 99.5 to 100% by mass of coating (ii) comprises a second non-zeolite oxidizing material comprising a first non-zeolite oxidizing material containing aluminum, a second non-zeolite oxidizing material comprising one or more of cerium and zirconium, aluminum, silicon, lanthanum, niobium, iron, manganese, titanium, tungsten, copper, molybdenum, neodymium, cobalt, chromium, tin, and praseodymium, and an 8-membered ring pore zeolite material comprising one or more of copper and iron, preferably an oxidizing binder according to Embodiment 29 or 30.

[0118] 34. The catalyst according to any one of embodiments 1 to 33, wherein the coating (ii) is disposed on the surface of the inner wall of the substrate, and this surface defines the boundary between the inner wall and the passage and / or the inside of the inner wall of the substrate.

[0119] 35. The catalyst according to any one of Embodiments 1 to 34, wherein the substrate is a wall-flow filter substrate or a flow-through substrate, preferably a wall-flow filter substrate, and the plurality of passages preferably include an inlet passage having an open inlet end and a closed outlet end, and an outlet passage having a closed inlet end and an open outlet end.

[0120] 36. The wall flow filter substrate is a porous wall flow filter substrate. The wall flow filter substrate is preferably one or more of a cordierite wall flow filter substrate, a silicon carbide wall flow filter substrate, and an aluminum titanate wall flow filter substrate, more preferably one or more of a silicon carbide wall flow filter substrate and an aluminum titanate wall flow filter substrate, and more preferably a silicon carbide wall flow filter substrate, and the coating (ii) is preferably the catalyst according to Embodiment 35, which is disposed within the inner wall of the porous wall flow filter.

[0121] 37. A catalyst according to any one of Embodiments 1 to 36, comprising a substrate (i) and a coating (ii).

[0122] 38. A method for preparing a selective catalytic reduction catalyst for treating exhaust gas from an internal combustion engine (preferably the selective catalytic reduction catalyst described in any one of Embodiments 1 to 37), (a) Prepare a mixture comprising water, a first non-zeolite oxide material containing aluminum, a second non-zeolite oxide material containing one or more of cerium, zirconium, aluminum, silicon, lanthanum, niobium, iron, manganese, titanium, tungsten, copper, molybdenum, neodymium, cobalt, chromium, tin, and praseodymium, and an eight-membered ring pore zeolite material containing one or more of copper and iron. (b) The mixture obtained in (a) is placed on a substrate having an inlet end, an outlet end, a substrate axial length extending from the inlet end to the outlet end, and a plurality of passages extending within the substrate defined by the inner wall of the substrate, in order to obtain a substrate treated with the mixture. (c)(b) The mixture-treated substrate obtained by (c)(b) is fired to obtain a substrate having a coating placed on the substrate, wherein at least 65% by mass of the coating consists of an 8-membered ring-pore zeolite material containing one or more of copper and iron. A preparation method including the following.

[0123] 39. (a) is, (a.1) Prepare a first aqueous mixture containing an 8-membered ring-pore zeolite material and one or more (preferably copper salts) of copper salts and iron salts; or Prepare a first aqueous mixture containing an 8-membered ring pore zeolite material containing copper and one or more of copper salts and iron salts (preferably copper salts). The obtained first aqueous mixture is calcined in a gas atmosphere (preferably air) having a temperature in the range of 300 to 700°C to obtain an 8-membered ring porous zeolite material containing one or more of copper and iron (preferably copper). (a.2) Prepare a second aqueous mixture comprising water and a first non-zeolite oxidizing material containing aluminum. The 8-membered ring-pore zeolite material containing one or more of copper and iron obtained by (a.1) is impregnated with the second aqueous mixture. Preferably, the materials are fired in a gas atmosphere (preferably air) having a temperature in the range of 300 to 700°C to obtain a first non-zeolite oxide material containing aluminum together with an 8-membered ring porous zeolite material containing one or more of copper and iron (preferably copper). (a.3) Prepare a third aqueous mixture comprising water, a first non-zeolite oxidizing material containing aluminum together with an 8-membered ring-pore zeolite material containing one or more of copper and iron obtained in (a.2), and preferably a precursor of an oxidizing binder. (a.4) Preferably, the third aqueous mixture obtained by (a.3) is ground, more preferably, until the particles of the mixture have a Dv90 (preferably measured as described in Reference Example 3) in the range of 1 to 10 μm, more preferably in the range of 2 to 7 μm, and more preferably in the range of 3 to 5 μm. (a.5) Prepare a fourth aqueous mixture comprising water, a second non-zeolite oxidizing material, and preferably an acid (more preferably an organic acid). (a.6)(a.3) preferably mix the third aqueous mixture obtained by (a.4) with the fourth aqueous mixture obtained by (a.5). The method according to Embodiment 38, which includes (preferably consists of)

[0124] 40. The method according to Embodiment 39, wherein the firing in (a.1) is carried out in a gas atmosphere having a temperature in the range of 400 to 600°C, preferably in the range of 450 to 550°C, and the firing is carried out for a duration of preferably 0.5 to 4 hours, more preferably in the range of 1 to 3 hours.

[0125] 41. The method of Embodiment 39 or 40, wherein the firing in (a.2) is carried out in a gas atmosphere having a temperature in the range of 400 to 600°C, preferably in the range of 450 to 550°C, and the firing is carried out for a duration of preferably 0.5 to 4 hours, more preferably in the range of 1 to 3 hours.

[0126] 42. The method according to any one of Embodiments 39 to 41, wherein the precursor of the oxidizing binder contained in the third aqueous mixture is one or more of aluminum salts, silicon salts, zirconium salts, and titanium salts, preferably one or more of zirconium salts and aluminum salts, more preferably zirconium salt, and even more preferably zirconium acetate.

[0127] 43. The method according to any one of Embodiments 39 to 42, wherein the third aqueous mixture prepared by (a.3) further comprises an acid (preferably an organic acid), the organic acid being more preferably one or more of tartaric acid, acetic acid, citric acid, nitric acid, hydrochloric acid, and sulfuric acid, and the organic acid being more preferably acetic acid.

[0128] 44. The method according to any one of Embodiments 39 to 43, wherein the organic acid contained in the fourth aqueous mixture prepared by (a.5) is one or more of tartaric acid, acetic acid, citric acid, nitric acid, hydrochloric acid, and sulfuric acid.

[0129] 45. (a) is, (a.1') Prepare a first aqueous mixture containing an 8-membered ring pore zeolite material containing copper and one or more of copper oxide and iron oxide (preferably copper oxide). (a.2') Prepare a second aqueous mixture comprising water, a first non-zeolite oxidizing material containing aluminum, and preferably an acid (more preferably an organic acid). A third aqueous mixture is obtained by mixing the first aqueous mixture obtained by (a.3')(a.1') with the second aqueous mixture obtained by (a.2'), (a.4') Prepare a fourth aqueous mixture comprising water, a second non-zeolite oxidizing material, and preferably an acid (more preferably an organic acid). Mix the third aqueous mixture obtained by (a.5')(a.3') with the fourth aqueous mixture obtained by (a.4'). The method according to Embodiment 38, which includes (preferably consists of)

[0130] 46. ​​(a.1') is, (a.1'.1) Prepare a mixture containing water and one or more of copper oxide and iron oxide (preferably copper oxide, more preferably CuO). (a.1'.2) Preferably, the mixture prepared according to (a.1'.1) is preferably ground until the particles of the mixture have a Dv90 (preferably measured as described in Reference Example 3) in the range of 3 to 20 μm, more preferably in the range of 6 to 10 μm. (a.1'.3) Preferably, an oxidizing binder precursor is added to the mixture obtained by (a.1'.1) (preferably (a.1'.2)), where the oxidizing binder precursor is preferably as defined in Embodiment 39. (a.1'.4) Prepare a mixture containing water and an 8-membered ring pore zeolite material containing copper. Mix the mixture prepared by (a.1'.5)(a.1'.4) with the mixture prepared by (a.1'.1) (preferably (a.1'.2), preferably (a.1'.3)). The method according to Embodiment 45, which includes (preferably consists of)

[0131] 47. The method according to Embodiment 45 or 46, wherein the organic acid contained in the second aqueous mixture prepared by (a.2') is one or more of tartaric acid, acetic acid, citric acid, nitric acid, hydrochloric acid, and sulfuric acid.

[0132] 48. The method according to any one of Embodiments 45 to 47, wherein the organic acid contained in the second aqueous mixture prepared by (a.4') is one or more of tartaric acid, acetic acid, citric acid, nitric acid, hydrochloric acid, and sulfuric acid.

[0133] 49. The method according to any one of Embodiments 38 to 48, wherein the first non-zeolite oxidizing material is as defined in any one of Embodiments 2 to 5.

[0134] 50. The method according to any one of Embodiments 38 to 49, wherein the second non-zeolite oxidizing material is as defined in any one of Embodiments 6 to 18.

[0135] 51. The method according to any one of embodiments 38 to 50, wherein the mixture obtained by (a) is placed on a substrate by (b) by immersing the substrate in the mixture obtained by (a).

[0136] 52. The method according to any one of embodiments 38 to 51, wherein in (b), the mixture prepared in (a) is disposed on the substrate over an area of ​​x% of the axial length of the substrate (where x is in the range of 80 to 100, preferably 90 to 100, more preferably 95 to 100, and even more preferably 98 to 100).

[0137] 53. The method according to any one of embodiments 38 to 52, wherein the mixture prepared by (a) is placed on the substrate from the inlet end to the outlet end of the substrate.

[0138] 54. The method according to any one of Embodiments 38 to 53, wherein (b) further comprises placing the mixture obtained in (a) onto a substrate, and then drying the mixture-treated substrate in a gas atmosphere (preferably air) having a temperature preferably in the range of 50 to 300°C, more preferably in the range of 60 to 190°C.

[0139] 55. The method according to Embodiment 54, wherein drying is performed for a duration in the range of 0.1 to 240 minutes, preferably in the range of 0.15 to 120 minutes.

[0140] 56. (b) is, (b.1) Distribute a first portion of the mixture obtained in (a) onto a substrate having an inlet end, an outlet end, a substrate axial length extending from the inlet end to the outlet end, and a plurality of passages extending within the substrate defined by the inner wall of the substrate, preferably from the inlet end to the outlet end of the substrate; and dry the substrate containing the first portion of the mixture distributed on the substrate. (b.2)(i) is placed on the substrate obtained in (b.2) which includes the first portion of the mixture placed on the substrate, preferably from the inlet end to the outlet end of the substrate; preferably the substrate containing the first and second portions of the mixture placed on the substrate is dried. The method according to any one of embodiments 38 to 55, further comprising the above.

[0141] 57. The method according to any one of embodiments 38 to 56, wherein the firing according to (c) is carried out in a gas atmosphere having a temperature in the range of 300 to 800°C, preferably in the range of 350 to 700°C (preferably the gas atmosphere is air).

[0142] 58. The method according to any one of embodiments 38 to 57, wherein the firing according to (c) is carried out in a gas atmosphere (preferably the gas atmosphere is air) for a duration of 10 to 240 minutes, preferably 20 to 160 minutes.

[0143] 59. The method according to any one of embodiments 38 to 58, comprising (a), (b), (c), and (d).

[0144] 60. A selective catalytic reduction catalyst obtained or obtainable by the method described in any one of Embodiments 38 to 59 (preferably the selective catalytic reduction catalyst described in any one of Embodiments 1 to 37).

[0145] 61. Use of a selective catalytic reduction catalyst according to any one of embodiments 1 to 37 and 60 for the selective catalytic reduction of nitrogen oxides.

[0146] 62. A selective catalytic reduction method for nitrogen oxides, wherein the method is (1) Preferably, an exhaust gas flow is provided from an internal combustion engine (more preferably a diesel engine), (2) Pass the exhaust gas flow provided in (1) through the selective catalytic reduction catalyst described in any one of embodiments 1 to 37 and 60. Methods that include...

[0147] 63. An exhaust gas treatment system for treating an exhaust gas flow discharged from an internal combustion engine (preferably a diesel engine), wherein the exhaust gas treatment system has an upstream end for introducing the exhaust gas flow into the exhaust gas treatment system. The exhaust gas treatment system comprises a first selective catalytic reduction catalyst described in any one of embodiments 1 to 37 and 60, a diesel oxidation catalyst, a second selective catalytic reduction catalyst, an ammonia oxidation catalyst, and NO X An exhaust gas treatment system comprising one or more of the following: a diesel oxidation catalyst with a storage function, and a particulate filter.

[0148] In this invention, "based on the mass of the zeolite material" means the mass of the zeolite material alone (i.e., the mass without copper).

[0149] Furthermore, in the context of the present invention, the term “inner wall surface” shall be understood as the “bare” or “exposed” or “nothing” surface of the wall, that is, the untreated surface of the wall consisting of the wall material, except for any unavoidable impurities that may contaminate the surface.

[0150] Furthermore, in the context of the present invention, the term "internal combustion engine" preferably refers to a diesel engine.

[0151] Furthermore, in the context of the present invention, the term "X is one or more of A, B, and C" (where X is a given feature and each of A, B, and C represents a specific aspect of that feature) is understood to disclose that X is either A, or B, or C, or A and B, or A and C, or B and C, or A and B and C. In this regard, those skilled in the art will understand that the above abstract terms can be translated into specific examples, for example, that X is a chemical element and A, B, and C are specific elements such as Li, Na, and K, or that X is a temperature and A, B, and C are specific temperatures such as 10°C, 20°C, and 30°C. In this regard, those skilled in the art will understand that the above terms can be extended to specific embodiments with fewer of the aforementioned features, for example, "X is one or more of A and B" (disclosing that X is either A, B, or A and B), or to specific embodiments with more of the aforementioned features, for example, "X is one or more of A, B, C, and D" (disclosing that X is either A, B, C, or D, or A and B, or A and C, or A and D, or B and C, or B and D, or C and D, or A and B and C and D).

[0152] Furthermore, in the context of the present invention, the expression "coating placed on the substrate" preferably means that the coating is placed on the surface of the inner wall of the substrate, and that this surface defines the boundary between the inner wall and the passage and / or the inside of the inner wall of the substrate.

[0153] Furthermore, in the context of the present invention, the term "consisting of" with respect to the mass percentage of one or more components indicates the amount of that component in mass percentage relative to 100 mass percent of the entity in question. For example, the expression "0 to 0.0001 mass percent of the coating consists of platinum" indicates that 0 to 0.0001 mass percent of the 100 mass percent of components that make up the coating is platinum. [Examples]

[0154] The present invention will be further explained by the following reference examples, comparative examples, and examples.

[0155] Reference Example 1: Measurement of BET specific surface area The BET specific surface area was measured using liquid nitrogen according to DIN66131 or DIN-ISO9277.

[0156] Reference Example 2: Measurement of mean porosity and mean pore diameter of porous wall-flow substrates The average porosity of porous wall-flow substrates was measured by mercury intrusion using mercury porosimetry, in accordance with DIN66133 and ISO15901-1.

[0157] Reference Example 3: Measurement of Particle Size Distribution Based on Volume The particle size distribution was determined by static light scattering using a Sympatec HELOS(3200)&QUIXEL instrument, within the range of optical density of the sample from 6% to 10%.

[0158] Reference Example 4: Cu-chabacite prepared according to a standard liquid-phase ion exchange (LPIE) method. The zeolite-based materials having a Cu-containing skeletal structure CHA, used in some examples herein, were essentially prepared as disclosed in US 8,293,199 B2. See, in particular, Example 2 of US 8,293,199 B2 (column 15, pages 26-52).

[0159] Comparative Example 1: Method for preparing a selective catalytic reduction catalyst made of a copper-containing zeolite material not according to the present invention Slurry 1: CuO powder with a Dv50 of 33 μm was added to water. The amount of CuO was calculated so that the total amount of copper (calculated as CuO) contained in the coating after firing was 4.15% by mass based on the mass of chabazite. The resulting mixture was ground using a continuous grinding apparatus so that the particle Dv50 value was approximately 2 μm and the particle Dv90 value was approximately 5 μm. The resulting slurry had a solid content of 8% by mass based on the mass of the slurry. Acetic acid and an aqueous solution of zirconium acetate were added to the CuO-containing mixture forming the slurry. The amount of acetic acid was calculated so that it amounted to 1.7% by mass of chabazite, and the amount of zirconium acetate was calculated so that the amount of zirconia in the coating (calculated as ZrO2) was 5% by mass based on the mass of chabazite. Separately, chabazite (Dv50 of 2.2 μm, SiO2:Al2O3 of 18, average crystal size of 0.4 μm (SEM analysis)) was added to water to form a mixture with a solid content of 36% by mass, based on the mass of the mixture. This Cu-chabazite mixture was mixed into a copper-containing slurry. At this time, the amount of Cu-chabazite was calculated to be 84% of the amount of coating supported on the catalyst after calcination. The obtained slurry was pulverized using a continuous grinding apparatus until the particle Dv90 value was approximately 4.5 μm.

[0160] Slurry 2: Separately, based on the mass of the slurry, it has a solid content of 12% by mass, and consists of water and alumina (Al2O3 95% by mass, SiO2 5% by mass, BET specific surface area approximately 180 m²). 2 An aqueous slurry containing alumina ( / g, Dv90 approximately 5μm) was prepared. The amount of alumina + silica was calculated so that the amount of alumina + silica after calcination would be 10% by mass based on the mass of chabazite.

[0161] Subsequently, when slurries 1 and 2 were combined, the solid content of the final slurry was approximately 31% by mass, based on the total mass of the final slurry.

[0162] A porous, uncoated wall-flow filter substrate, silicon carbide (average porosity 60.5%, average pore size 20 μm, 350 CPSI, wall thickness 0.33 mm (13 mil), diameter: 1.5 inches (38.1 mm) × length: 6 inches (152.4 mm)) was coated twice with the final slurry from the inlet end to the outlet end, covering 100% of the substrate's axial length. To achieve this, the substrate was immersed in the final slurry from the inlet end until the slurry reached the top of the substrate. Furthermore, a pressure pulse was applied to the inlet end to uniformly disperse the slurry within the substrate. The coated substrate was then dried at 130°C for 30 minutes and fired at 450°C for 2 hours. This was repeated once. The final coating load after firing was approximately 1.68 g / in, based on the mass of the CHA zeolite material. 3 CHA zeolite-based material, 0.17 g / in 3 Alumina + Silica, approximately 0.084 g / in 3 Approximately 2 g / in (calculated as CuO) along with zirconia and 4.15 mass% Cu. 3 That's what happened.

[0163] Reference Example 5: Method for preparing a selective catalytic reduction catalyst containing a copper-containing zeolite material not according to the present invention.

[0164] In the first step, a zeolite material having a skeletal CHA structure (Dv50 of 5 μm, SiO2:Al2O3 of 18, average crystal size of approximately 0.4 μm (SEM analysis), and pore volume of 1 m / g) was added to an aqueous copper acetate solution (Cu content of 3.51 mass%, calculated as CuO). The aqueous copper acetate solution was provided in an amount sufficient to fill the pores of the CHA zeolite material by induce wetness impregnation, such that the Cu content, calculated as CuO, was approximately 4.15 mass%. After impregnation, the Cu-containing zeolite material was calcined in air at 500°C for 2 hours.

[0165] In the second step, alumina sol (solid content 22-25% by mass, Dv50 of alumina sol approximately 90 nm) was dispersed in water and impregnated into the calcined Cu-zeolite material so that the mass percentage of alumina after calcination was 10% by mass based on the mass of the zeolite material. After impregnation, the Cu-zeolite material + alumina was calcined in air at 500°C for 2 hours. Subsequently, the calcined Cu-zeolite + alumina was dispersed in water and an aqueous zirconium acetate solution to form a slurry. The amount of zirconium acetate was calculated so that the amount of zirconia in the coating, calculated as ZrO2, was 5% by mass based on the mass of the zeolite material. Finally, acetic acid (1.7% by weight based on the mass of the zeolite material) was added to the slurry. The obtained slurry was pulverized using a continuous grinding apparatus so that the particle size Dv90 value was approximately 4 μm, and the solid content of the obtained slurry was adjusted to 31% by mass based on the mass of the slurry.

[0166] The obtained slurry was processed according to the method described in Comparative Example 1 above, using a porous, uncoated wall flow filter substrate, silicon carbide, (average porosity 60.5%, average pore size 20 μm, 350 CPSI, wall thickness 0.33 mm (13 mil), diameter: 1.5 inches (38.1 mm) × The length was 6 inches (152.4 mm) and coated twice. The final coating load after firing was approximately 1.73 g / in, based on the mass of the CHA zeolite material. 3 CHA zeolite-based material, 0.173 g / in 3 Alumina + Silica, approximately 0.0865 g / in 3 Approximately 2.1 g / in (calculated as CuO) along with zirconia and 4.15 mass% Cu. 3 That's what happened.

[0167] Example 1: Method for preparing a selective catalytic reduction catalyst comprising a copper-containing zeolite material, a first oxidizing material, and a second oxidizing material according to the present invention. To prepare the catalyst of Example 1, steps 1 and 2 of Reference Example 5 were repeated. As a result, the Dv90 value of the particles in the obtained Cu zeolite calcined body + alumina slurry was approximately 4 μm, and the solid content of the obtained slurry was adjusted to 31% by mass, similar to Reference Example 5.

[0168] Separately, the cerium-zirconium mixed oxide (Ce content (calculated as CeO2) is approximately 70% by mass based on the total mass of the mixed oxide, Zr content (calculated as ZrO2) is approximately 30% by mass based on the total mass of the mixed oxide, and the BET specific surface area is 222 m² 2 La (19.2 μm) was added to a lanthanum nitrate solution (calculated as 13% by mass of lanthanum, La2O3) in an amount sufficient to fill the pores of the mixed oxide (intensive wetness impregnation), so that the La content (calculated as La2O3) was 10% by mass based on the mass of the mixed oxide. After impregnation, the La+Ce-Zr mixed oxide was calcined in air at 590°C for 2 hours. The calcined La-doped Ce-Zr oxide was dispersed in water.

[0169] Subsequently, the calcined Cu-zeolite material + alumina (Dv90 approximately 4 μm) obtained in the second step of Reference Example 5 was added to the La+Ce-Zr oxide slurry so that the amount of Ce-Zr oxide was 20% by mass based on the mass of the zeolite material. The solid content of the resulting slurry was adjusted to 31% by mass based on the mass of the slurry.

[0170] The obtained slurry was processed according to the method described in Comparative Example 1 above, using a porous, uncoated wall flow filter substrate, silicon carbide, (average porosity 60.5%, average pore size 20 μm, 350 CPSI, wall thickness 0.33 mm (13 mil), diameter: 1.5 inches (38.1 mm) × The length was 6 inches (152.4 mm) and it was coated twice. The final coating load after firing was approximately 1.48 g / in, based on the mass of the CHA zeolite material. 3 CHA zeolite-based material, 0.148 g / in 3 Alumina, 0.32 g / in 3La-doped Ce-Zr oxide, approximately 0.074 g / in 3 Approximately 2.1 g / in (calculated as Cu) with zirconia and 4.15 mass% Cu. 3 That was the case.

[0171] Example 2: Preparation of a selective catalytic reduction catalyst comprising a copper-containing zeolite material, a first oxidizing material, and a second oxidizing material according to the present invention. The catalyst in Example 2 is a cerium-zirconium mixed oxide (based on the total mass of the mixed oxide, with a Ce content of approximately 58% by mass (calculated as CeO2), a Zr content of approximately 42% by mass (calculated as ZrO2), and 116m 2 The catalyst for Example 2 was prepared using the method of the catalyst for Example 1, except that the BET specific surface area (Dv50) of / g was replaced with 13.5 microns.

[0172] Example 3: Preparation of a selective catalytic reduction catalyst comprising a copper-containing zeolite material, a first oxidizing material, and a second oxidizing material according to the present invention. The Ce-Zr mixed oxide used in Example 1 was replaced with a cerium-zirconium mixed oxide (based on the total mass of the mixed oxide, with a Ce content of approximately 30% by mass (calculated as CeO2), a Zr content of approximately 70% by mass (calculated as ZrO2), and 85m 2 The catalyst for Example 3 was prepared using the method of the catalyst for Example 1, except that the BET specific surface area ( / g) and Dv50 (10 μm) were replaced.

[0173] A summary table is shown below. [Table 1] a: ISIE, In-situ ion exchange of zeolite-based materials (no pre-exchange). *: Based on the mass of zeolite-based material SAR: Molar ratio of silica / alumina

[0174] analysis For the La-Ce-Zr oxides of Examples 1-3, XRD was performed after impregnation with La and calcination. No CeOX or LaOx phases were observed; only the Ce-Zr mixed oxide phase was present (see Figure 7). Therefore, the obtained oxide was a mixed oxide of cerium and zirconium with a La oxide (La2O3) layer on top.

[0175] Example 4: Testing of catalysts from Comparative Example 1, Reference Example 5, and Examples 1-3 - NO X Regarding conversion and back pressure 4.1 NO X conversion The catalyst was hydrothermally aged in an 800°C oven for 16 hours (20% O2, 10% H2O in %N2). NO of the aged catalyst with a 20 ppm ammonia slip. X The conversion was measured in a reactor equipped with two FTIR (Fourier Transform Infrared Spectrometer) units capable of measuring with a 1.5-inch core. The measurements were performed at 200°C and a space velocity of 40 k / h (500 ppm NO, NH3 / NO). X (=1.5, 5% CO2, 5% H2O, 80 ppm C3H6). The results are shown in Figure 1.

[0176] As is clear from Figure 1, the catalysts from Examples 1-3 showed improved NO2 at 200°C compared to the catalyst of Comparative Example 1 and the catalyst of Reference Example 5. X This makes it possible to obtain conversion. X The addition of NO X This shows that it leads to improved conversion rates.

[0177] 4.2 Back pressure The catalyst was aged in an 800°C oven for 16 hours (20% O2, 10% H2O in %N2), and then aged at room temperature for 27 m 3 Cold flow back pressure data for / h was recorded and is shown in Figure 2. It can be seen that the back pressure obtained using the catalysts according to the present invention (Examples 1-3) is significantly reduced compared to the back pressure obtained using the catalyst of Comparative Example 1 and the catalyst of Reference Example 5. Thus, Ce-ZrO X Formulas containing not only reduce back pressure but also NO XThis can also lead to improved conversion rates.

[0178] Comparative Example 2: Method for preparing a selective catalytic reduction catalyst containing a copper-containing zeolite material not according to the present invention Slurry 1: CuO powder with a Dv50 of 33 μm was added to water. The amount of CuO was calculated so that the total amount of copper (calculated as CuO) contained in the coating after firing was 3.5% by mass, based on the mass of chabasite. The resulting mixture was ground using a continuous grinding apparatus so that the particle Dv50 value was approximately 2 μm and the particle Dv90 value was approximately 5 μm. The resulting slurry had a solid content of 8% by mass, based on the mass of the slurry. Acetic acid and an aqueous solution of zirconium acetate were added to the CuO-containing mixture forming the slurry. The amount of acetic acid was calculated so that it was 1.7% by mass of chabasite, and the amount of zirconium acetate was calculated so that the amount of zirconia in the coating (calculated as ZrO2), based on the mass of the zeolite material, was 5% by mass. Separately, as described in Reference Example 4, a Cu-CHA (Dv50 of 1.5 μm, SiO2:Al2O3 of 25, average crystal size of less than 0.5 μm, approximately 555 m) with a Cu content of 1.25 mass% (calculated as CuO) based on the mass of the zeolite material prepared. 2 The BET specific surface area (BET) per g was added to water to form a mixture having a solid content of 37% by mass, based on the mass of the mixture. The Cu-CHA mixture was mixed into a copper-containing slurry. The amount of Cu-CHA was calculated so that the amount of zeolite material supported after calcination was approximately 86% of the amount of coating supported on the catalyst after calcination. The resulting slurry was pulverized using a continuous grinding apparatus so that the particle Dv90 value was approximately 5 μm.

[0179] Slurry 2: Separately, an aqueous slurry containing 30% solids by mass and water and La-zirconia (mass percent is based on the mass of the slurry) (68m 2A slurry was prepared with a BET specific surface area of ​​1 / g, containing 10% by mass of La2O3 and 90% by mass of ZrO2, and having a Dv90 of approximately 16 μm. The amount of La-zirconia was calculated so that the amount of La-zirconia after calcination would be 10% by mass based on the mass of chabasite. The obtained slurry was pulverized using a continuous grinding apparatus until the particle Dv90 value was approximately 5.5 μm.

[0180] Subsequently, slurries 1 and 2 were combined, and the solid content of the resulting final slurry was adjusted to approximately 30% by mass, based on the total mass of the final slurry.

[0181] A porous, uncoated wall-flow filter substrate, silicon carbide (average porosity 60.5%, average pore size 20 μm, 350 CPSI, wall thickness 0.28 mm (11 mil), diameter: 1.5 inches (38.1 mm) × length: 6 inches (152.4 mm)) was coated twice with the final slurry over 100% of its axial length, from the inlet end to the outlet end. To achieve this, the substrate was immersed in the final slurry until the slurry reached the top surface of the substrate from the inlet end. Furthermore, a pressure pulse was applied to the inlet end to uniformly disperse the slurry within the substrate. The coated substrate was then dried at 130°C for 30 minutes and fired at 450°C for 2 hours. This was repeated once. The final coating load after firing was approximately 1.5 g / in, based on the mass of the CHA zeolite material. 3 CHA zeolite-based material, 0.15 g / in 3 La-zirconia, approximately 0.08 g / in 3 Along with zirconia and 3.5 mass% Cu (calculated as CuO), approximately 1.8 g / in 3 That was the case.

[0182] Example 5: Method for preparing selective catalytic reduction comprising a copper-containing zeolite material, a first oxidizing material, and a second oxidizing material according to the present invention. In the first step, a Cu-containing zeolite material having a skeletal CHA with a Cu content (calculated as CuO) of approximately 1.25 mass%, based on the mass of the zeolite material prepared by the method described in Reference Example 4 (Dv50, SiO2:Al2O3=25, average crystal size less than 0.5 μm (SEM analysis), approximately 555 m) is prepared. 2 The BET specific surface area per g was added to an aqueous copper acetate solution (calculated as 3.51 mass% Cu, CuO). The aqueous copper acetate solution was supplied in an amount sufficient to fill the pores of the CHA zeolite material by induce wetness impregnation, resulting in a Cu content of approximately 3.5 mass% (calculated as CuO). After impregnation, the Cu-containing zeolite material was calcined in air at 500°C for 2 hours.

[0183] In the second step, alumina sol (solid content 22-25% by mass, Dv50 at approximately 90 nm) was dispersed in water and impregnated into the calcined Cu-zeolite material so that the mass percentage of alumina was 10% by mass based on the mass of the calcined zeolite material. After impregnation, the Cu-zeolite material + alumina was calcined in air at 500°C for 2 hours. Separately, acetic acid (1.7% by mass based on the mass of the zeolite material) and zirconium acetate solution were dispersed in water. The amount of zirconium acetate was calculated so that the amount of zirconia in the coating (calculated as ZrO2) was 5% by mass based on the mass of the zeolite material. Subsequently, the calcined Cu-zeolite + alumina was added to the acetic acid + zirconium acetate solution to form a slurry. The obtained slurry was pulverized using a continuous grinding apparatus so that the particle size Dv90 value was approximately 4 μm, and the solid content of the obtained slurry was adjusted to 34% by mass based on the mass of the slurry.

[0184] Separately, the cerium-aluminum oxide (Ce content (calculated as CeO2) is approximately 50% by mass based on the total mass of Ce-Al oxides, and the Al content (calculated as Al2O3) is approximately 50% by mass based on the total mass of Ce-Al oxides, which is 155m 2The Nb content (calculated as Nb2O5) was adjusted to 10% by mass based on the mass of the Ce-Al oxide. This was achieved by impregnating ammonium niobate (V) hydrate dispersed in enough water to fill the pores of the Ce-Al oxide (intensive wetness impregnation). After impregnation, the Nb+Ce-Al oxide was calcined in air at 590°C for 2 hours. The calcined Nb-doped Ce-Al oxide was dispersed in water, and the solid content of the slurry was adjusted to 38% by mass based on the mass of the slurry.

[0185] Subsequently, a Cu-zeolite material + alumina slurry was added to the Nb-doped Ce-Al oxide slurry so that the amount of Ce-Al oxide was 20% by mass based on the mass of the zeolite material. The solid content of the resulting slurry was adjusted to 31% by mass based on the mass of the slurry.

[0186] The obtained slurry was coated twice onto a porous, uncoated wall-flow filter substrate, silicon carbide (average porosity of 60.5%, average pore size of 20 μm, 350 CPSI, wall thickness of 0.28 mm (11 mil), diameter: 1.5 inches (38.1 mm) × length: 6 inches (15.24 mm)) according to the method described in Comparative Example 2. The final coating load after firing was approximately 1.48 g / in, based on the mass of the CHA zeolite material. 3 CHA zeolite-based material, 0.15 g / in 3 Alumina, 0.33 g / in 3 Nb-doped Ce-Al oxide, approximately 0.075 g / in 3 Approximately 2.1 g / in (calculated as CuO) along with zirconia and 3.5 mass% Cu. 3 That was the case.

[0187] Example 6: Method for preparing selective catalytic reduction comprising a copper-containing zeolite material, a first oxidizing material, and a second oxidizing material according to the present invention. Slurry 1: The slurry was prepared using the same method as slurry 1 in Comparative Example 2.

[0188] Slurry 2: The slurry used in Comparative Example 1 was replaced with alumina (95% by mass Al2O3, 5% by mass SiO2, approximately 180 m 2 The slurry was prepared using the same method as Slurry 2 in Comparative Example 1, except that the solid content of the aqueous slurry was set to 35% by mass using a Dv90 with a BET specific surface area of ​​approximately 18 μm per g.

[0189] Separately, a cerium-zirconium mixed oxide (with a Ce content of approximately 50% by mass (calculated as CeO2) and a Zr content of approximately 50% by mass (calculated as ZrO2) based on the total mass of the mixed oxide, and a pore volume of approximately 0.37 mL / g) was added to a lanthanum nitrate solution (13.4% lanthanum content (calculated as La2O3)) in an amount sufficient to fill the pores of the mixed oxide (intensive wetness impregnation), resulting in a La content of 10% by mass (calculated as La2O3) based on the mass of the mixed oxide. After impregnation, the La+Ce-Zr mixed oxide was calcined in air at 590°C for 2 hours. The calcined La-doped Ce-Zr oxide was dispersed in water, and the solid content of the slurry was adjusted to 38% by mass based on the mass of the slurry.

[0190] Subsequently, a Cu zeolite-based material + alumina slurry was added to the La-doped Ce-Zr oxide slurry so that the amount of Ce-Zr oxide was 20% by mass based on the mass of the zeolite-based material (the amount of La-doped Ce-Zr was 22% by mass based on the mass of the zeolite-based material). The solid content of the resulting slurry was adjusted to 31% by mass based on the mass of the slurry.

[0191] The resulting slurry was coated twice onto a porous uncoated wall flow filter substrate, silicon carbide, (average porosity of 60.5%, average pore diameter of 20 μm, 350 CPSI, wall thickness of 0.28 mm (11 mils), diameter: 1.5 inches (38.1 mm) × length: 6 inches (15.24 mm)) according to the method described in Comparative Example 2 above. The final coating loading after firing was (about 1.48 g / in based on the mass of the CHA zeolite-based material) 3 of the CHA zeolite-based material, 0.15 g / in 3 of alumina, 0.33 g / in 3 of Ce-Zr oxide doped with La, about 0.075 g / in 3 of zirconia, and (together with 3.5% by mass of Cu (calculated as CuO)) about 2.1 g / in 3 was.

[0192] The table summarized below is shown.

Table 2

[0193] Analysis Nb after firing 10 Ce 0.5 Al 0.5 XRD characterization of the oxides was performed (see Example 5 - Figure 8). No mixed oxide phase was observed, and both the Al2O3 phase and the CeO2 phase were observed. Thus, the resulting oxide is a mixed oxide of Al and Ce. Since Nb does not form a crystalline phase or is present in an amount below the detection limit, the oxide of Nb was not detected.

[0194] Example 7: Testing of the catalysts of Comparative Example 1, Reference Example 5, and Examples 1 to 3 - NO X Conversion NO X Conversion The catalyst was hydrothermally aged in an oven at 800 °C for 16 hours (20% O2, 10% H2O, 70% N2). NO of the aged catalyst at an ammonia slip of 20 ppm was measured in a reactor equipped with two Fourier transform infrared spectrometers capable of measuring a 1.5-inch core X Conversion was measured. The measurements were carried out at 200 °C and 600 °C, space velocities of 40 k / h and 80 k / h (500 ppm of NO, NH3 / NO X = 1.5, 5% of CO2, 5% of H2O, 80 ppm of C3H6). The results are shown in Fig. 3

[0195] As is clear from Figs. 3 and 4, the catalysts of Examples 5 and 6 can achieve improved NO X conversion at high temperature (600 °C) at 40 k / h and 80 k / h, while showing the same NO X conversion as the catalyst of Comparative Example 2 at low temperature (200 °C). Thus, it can be seen that the addition of the second oxidizing substance can improve NO X conversion

[0196] Reference Example 6: Effect of different first oxidizing materials The slurry and the catalyst were prepared similarly to the slurry of Example 6, but did not contain the second oxidizing material, and the content of the first oxidizing material was 20% by mass instead of 10% by mass. The outline is shown in Table 3 below. The coating was carried out in the same manner as in Example 5, but it was a wall-flow filter core without a porous coating, silicon carbide, (average porosity 63%, average pore diameter 20 μm, 300 CPSI and wall thickness of 0.304 mm (12 mils), diameter: 58 mm × length: 140.5 mm)

[0197]

Table 3

[0198] NO X Conversion The catalyst was hydrothermally aged (20% O2, 10% H2O, 70% N2) in an oven at 800 °C for 16 hours. At a temperature of 575 °C, a space velocity of 94 k / h, a NO[[ID=?]] X concentration of 90 ppm, and a HC concentration of 20 ppm (concentration based on the content of carbon atoms), using a 2L Euro6 engine, the NO conversion at an ammonia slip of 20 ppm of the aged catalyst was measured. The results are shown in Figure 5. X The results are shown in Figure 5.

[0199] The high-temperature NO conversion shown in Figure 6 X is considered to be approximately the same for the three designs (Reference Examples 6.1 to 6.3). That is, it can be seen that the designs containing silica alumina, La-zirconia, and alumina sol as the first oxide material result in approximately the same high TNO X conversion.

[0200] Back pressure The catalyst was aged in an oven at 800 °C for 16 hours (20% O2, 10% H2O, 70% N2). Figure 6 shows the data of the cold flow back pressure measured at a flow rate of 65 m 3 / h at room temperature. A decrease in back pressure was observed in the design containing alumina sol, and a slight advantage in back pressure was observed in the design containing La-zirconia.

[0201] Reference Example 7: Effect of different oxidants It should be noted that there seems to be an unclear or incorrect tag "? X " in the original text. I have translated it as best as possible while maintaining the integrity of the content.Reference Example 7.1 was prepared by preparing a slurry with a silica / alumina (SAR) content of 25, a Cu content (calculated as CuO) of 3.75% by mass based on the mass of chabasite, and a solid content of 30% by mass based on the mass of the slurry. The slurry was pulverized at 300 rpm for 5 minutes. The slurry was dried under stirring, calcined at 550°C for 1 hour (heating rate 5K / min), pulverized, and sieved through a 250-500 μm sieve.

[0202] A. General compounding and molding procedures 1. Take the Cu-zeolite. 2. Form into a slurry (with a solid content of approximately 30% by mass). 3. Grind (5 minutes, 300 rpm). 4. Mix a certain amount of slurry with the oxidizing agent powder from B (if necessary) or other oxidizing agent powder. 5. Dry while stirring. 6. Bake at 550°C for 1 hour (heating rate 5K / min). 7. Crush it. 8. Sieve through a 250-500 μm sieve.

[0203] B. Impregnation Procedure 1. Remove the carrier material. 2. Impregnate with a metal precursor solution. 3. Mix and ensure uniform dispersion. 4. Dry. 5. Bake at 550°C for 1 hour (heating rate 5K / min). 6. Grind it in a mortar and pestle.

[0204] Reference Example 7.2: The chabasite used in Reference Example 7.1 was diluted with α-Al2O3 so that the total amount of chabasite was the same as in Reference Example 7.1 (see Table 4). The amount of α-Al2O3 was 20% by mass based on the mass of chabasite.

[0205] Reference Example 7.3: Add silica alumina (95% by mass alumina, 5% by mass silica, 5 μm Dv90, 180 m) to the chabazite slurry of Reference Example 1.2 The amount of silica-alumina was added based on the mass of chabazite, using the BET specific surface area per g as the reference (see Table 4).

[0206] Reference examples 7.4 to 7.14 were prepared according to the general procedure (A+B) described above. The composition of each sample is summarized in Tables 4 and 5 below.

[0207] [Table 4] *: Cu-CHA, Cu content of 3.75 mass% (calculated as CuO) (Dv90 of 4.5 μm, 555 m 2 (BET specific surface area per gram) **Based on the mass of the zeolite**

[0208] [Table 5] *: Cu-CHA, Cu content of 3.75 mass% (calculated as CuO) (Dv90 of 4.5 μm, 555 m 2 (BET specific surface area per gram) **Based on the mass of the zeolite** Ce 0.73 Zr 0.20 La 0.02 Nd 0.05 O x :60m 2 BET specific surface area / g Zr 0.9 La 0.1 : 8μm Dv90, 67.5m 2 BET specific surface area / g Ce 0.5 Al 0.5 O x : 35μm Dv90, 155m 2 BET specific surface area per gram, pore volume of 0.95 ml / g

[0209] From the table above, 10-15 mass% LaO X Ce-Zr oxide doped with, or 10% by mass of NbO X or 10% by mass of LaO XWhen using doped Ce-Al oxide, NO is compared to the reference example. X It can be seen that the conversion rate can be improved.

[0210] Reference Example 8: Measurement of the average crystal diameter of zeolite-based materials The average crystal size of zeolite materials was determined by analyzing zeolite material powders using TEM (transmission electron microscopy). The size of individual crystals was determined by averaging the crystal sizes of 20 to 30 individual crystals from at least two TEM images taken at magnifications ranging from 5,000 to 12,000.

Claims

1. A selective catalytic reduction catalyst for treating exhaust gases from an internal combustion engine, (i) A substrate having an inlet end, an outlet end, a substrate axial length extending from the inlet end to the outlet end, and a plurality of passages defined by the inner wall of the substrate and extending within the substrate, (ii) A coating disposed on the substrate (i), wherein the coating comprises a first non-zeolite oxide material containing aluminum, a second non-zeolite oxide material containing one or more of cerium and zirconium, aluminum, silicon, lanthanum, niobium, iron, manganese, titanium, tungsten, copper, molybdenum, neodymium, cobalt, chromium, tin, and praseodymium, and the coating further comprises an eight-membered ring-pore zeolite material containing one or more of copper and iron, and at least 65% by mass of the coating consists of the eight-membered ring-pore zeolite material containing one or more of copper and iron. A catalyst for selective catalytic reduction, including the following:

2. The first non-zeolite oxide material contains alumina, and preferably 98 to 100% by mass, more preferably 99 to 100% by mass, and more preferably 99.5 to 100% by mass of the first non-zeolite material is alumina, and the first non-zeolite material is more preferably 120 to 300 m ２ range of / g, more preferably 150 to 250 m ２ The range is / g, more preferably 170 to 220m ２ The catalyst according to claim 1, having a BET specific surface area in the range of / g.

3. The catalyst according to claim 1, wherein the first non-zeolite oxidizing material comprises one or more of zirconium, silicon, and titanium, preferably one or more of zirconium and silicon, more preferably silicon, and the first non-zeolite material more preferably comprises aluminum and silicon.

4. The catalyst according to any one of claims 1 to 3, wherein the first non-zeolite oxidizing material is included in the coating (ii) in an amount ranging from 2 to 28% by mass, preferably 5 to 25% by mass, more preferably 6 to 18% by mass, more preferably 7 to 17% by mass, more preferably 8 to 15% by mass, and more preferably 9 to 13% by mass, based on the mass of the eight-membered ring-pore zeolite material.

5. The catalyst according to any one of claims 1 to 4, wherein the second non-zeolite oxide material contained in the coating (ii) comprises a mixed oxide of cerium and one or more of zirconium, aluminum, silicon, lanthanum, niobium, iron, manganese, titanium, tungsten, copper, molybdenum, neodymium, cobalt, chromium, tin, and praseodymium, or a mixture of cerium oxide and one or more oxides of zirconium, aluminum, silicon, lanthanum, niobium, iron, manganese, titanium, tungsten, copper, molybdenum, neodymium, cobalt, chromium, tin, and praseodymium.

6. The catalyst according to claim 5, wherein the second non-zeolite oxide material contained in the coating (ii) comprises a mixed oxide of cerium and one or more of zirconium, aluminum, silicon, lanthanum, niobium, iron, manganese, titanium, tungsten, copper, molybdenum, neodymium, cobalt, chromium, tin, and praseodymium, preferably a mixed oxide of cerium and one or more of zirconium, aluminum, and silicon, more preferably a mixed oxide of cerium and zirconium.

7. A mixed oxide of cerium and zirconium forms the crystalline phase Ce ａ Zr １－ａ O ２ The catalyst according to claim 6, wherein a is in the range of 0.1 to 0.9, preferably in the range of 0.2 to 0.8, and more preferably in the range of 0.25 to 0.

75.

8. The catalyst according to claim 5, wherein the second non-zeolite oxidizing substance contained in the coating (ii) comprises a mixture of cerium oxide and one or more of zirconium oxide, aluminum oxide, silicon oxide, lanthanum oxide, niobium oxide, iron oxide, manganese oxide, titanium oxide, tungsten oxide, copper oxide, molybdenum oxide, neodymium oxide, cobalt oxide, chromium oxide, tin oxide, and praseodymium oxide, preferably a mixture of cerium oxide and one or more of zirconium oxide, aluminum oxide, silicon oxide, lanthanum oxide, and niobium oxide, more preferably a mixture of cerium oxide and one or more of aluminum oxide, lanthanum oxide, and niobium oxide, more preferably a mixture of cerium oxide, aluminum oxide, and lanthanum oxide, or more preferably a mixture of cerium oxide, aluminum oxide, and niobium oxide.

9. The catalyst according to any one of claims 1 to 8, wherein the ratio (defined as (w1):(w2)) of the mass of the first non-zeolite oxidizing material (w1) to the mass of the second non-zeolite oxidizing material (w2) is in the range of 0.2:1 to 0.7:1, preferably in the range of 0.3:1 to 0.6:1, more preferably in the range of 0.4:1 to 0.55:1, and more preferably in the range of 0.45:1 to 0.55:

1.

10. The catalyst according to any one of claims 1 to 9, wherein the eight-membered ring-pore zeolite material contained in the coating (ii) has a skeletal structure selected from the group consisting of CHA, AEI, RTH, LEV, DDR, KFI, ERI, AFX, LTA, two or more mixtures thereof, and two or more mixed forms thereof, preferably a skeletal structure selected from the group consisting of CHA, AEI, RTH, two or more mixtures thereof, and two or more mixed forms thereof, more preferably a skeletal structure selected from the group consisting of CHA and AEI, and more preferably the eight-membered ring-pore zeolite material contained in the coating (ii) has a skeletal CHA.

11. The catalyst according to any one of claims 1 to 10, wherein the eight-membered ring-pore zeolite material contained in the coating (ii), preferably the eight-membered ring-pore zeolite material having a skeletal CHA, includes crystals having an average grain size in the range of 0.05 to 5 μm, preferably 0.06 to 2 μm, more preferably 0.07 to 1 μm, more preferably 0.1 to 0.8 μm, and more preferably 0.2 to 0.6 μm.

12. The catalyst according to any one of claims 1 to 11, wherein the substrate is a wall flow filter substrate or a flow-through substrate, preferably a wall flow filter substrate, and the plurality of passages preferably include an inlet passage having an open inlet end and a closed outlet end, and an outlet passage having a closed inlet end and an open outlet end.

13. A selective catalytic reduction catalyst for treating exhaust gas from an internal combustion engine, preferably a method for preparing a selective catalytic reduction catalyst according to any one of claims 1 to 12, (a) Prepare a mixture comprising water, a first non-zeolite oxide material containing aluminum, a second non-zeolite oxide material containing one or more of cerium, zirconium, aluminum, silicon, lanthanum, niobium, iron, manganese, titanium, tungsten, copper, molybdenum, neodymium, cobalt, chromium, tin, and praseodymium, and an eight-membered ring pore zeolite material containing one or more of copper and iron. (b) Placing the mixture obtained in (a) onto a substrate to obtain a substrate treated with the mixture, wherein the substrate includes a plurality of passages extending within the substrate, defined by an inlet end, an outlet end, a length in the axial direction of the substrate extending from the inlet end to the outlet end, and the inner wall of the substrate. (c) The substrate treated with the mixture obtained by (b) is fired to obtain a substrate having a coating placed on the substrate, wherein at least 65% by mass of the coating consists of an 8-membered ring-pore zeolite material containing one or more of copper and iron. A preparation method including the following.

14. (b) is, (b.1) The first portion of the mixture obtained in (a) is placed on a substrate which includes an inlet end, an outlet end, a substrate axial length extending from the inlet end to the outlet end and a plurality of passages extending within the substrate which are defined by the inner wall of the substrate, wherein the placement is preferably from the inlet end to the outlet end of the substrate, and the substrate including the first portion of the mixture placed on the substrate is dried. (b.2) The second portion of the mixture obtained in (i) is placed on the substrate which includes the first portion of the mixture placed on the substrate obtained in (b.2), preferably from the inlet end to the outlet end of the substrate, and preferably the substrate which includes the first and second portions of the mixture placed on the substrate is dried. The method according to claim 13, further comprising:

15. An exhaust gas treatment system for treating an exhaust gas flow discharged from an internal combustion engine, preferably a diesel engine, wherein the exhaust gas treatment system has an upstream end for introducing the exhaust gas flow into the exhaust gas treatment system, and the exhaust gas treatment system comprises a first selective catalytic reduction catalyst according to any one of claims 1 to 12, a diesel oxidation catalyst, a second selective catalytic reduction catalyst, an ammonia oxidation catalyst, and NO Ｘ An exhaust gas treatment system comprising one or more of the following: a diesel oxidation catalyst with a storage function, and a particulate filter.

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