Catalyst for enhancing high-temperature conversion and reducing N2O production

Abstract

The present invention relates to a catalyst for the treatment of exhaust gases from diesel combustion engines, comprising in particular a specific substrate and a coating arranged on the surface of the inner wall of said substrate, said coating comprising in particular a specific first non-zeolitic oxide material and a specific zeolitic material comprising Fe and Cu, said catalyst exhibiting a mass ratio of Fe, calculated as FeO, to Cu, calculated as CuO, FeO:CuO, of less than 0.1:1. Furthermore, the present invention relates to a specific method for producing said catalyst. Furthermore, the present invention relates to a system comprising said catalyst and its use.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a catalyst suitable for treating exhaust gas of a diesel combustion engine. Furthermore, the present invention relates to a catalyst that can be manufactured by the above method, and its use.

Background Art

[0002] Cu-containing zeolite-based materials, particularly zeolite-based materials having a framework structure type CHA, are currently used as selective catalytic reduction (LDD-SCR) catalysts for automotive light-duty diesel because they can remove NOx emissions from exhaust streams at very low temperatures. However, such catalysts typically exhibit relatively high N2O production at temperatures above 300 °C and poor NO x conversion at temperatures above 500 °C. Therefore, these Cu-containing zeolites, which achieve the best results at low temperatures, are typically poor in NOx conversion at high temperatures, especially when compared to Fe-beta zeolite. Efforts to solve the above defects by doping zeolite-based materials having a framework structure type CHA, particularly chabazite, with Fe usually result in catalysts that can often improve high-temperature conversion but cause a strong loss in low-temperature conversion.

[0003] In future regulations, particularly Euro 7 and 8 LDD regulations, N2O emission limits will be implemented, or N2O, a strong greenhouse gas, will be accounted for in terms of CO2 equivalence. Therefore, there is a need to provide a catalyst, particularly an SCR catalyst, that exhibits improved high-temperature conversion while showing greatly reduced N2O production.

[0004] WO2017 / 134581A1 relates to chabazite catalysts replaced with copper and iron. It is disclosed that such catalysts can be produced by contacting chabazite with copper and iron metal precursors. WO2020 / 063360A1 discloses a method for producing molecular sieve SCR catalysts in which molecular sieves can contain Fe and Cu. CN104607239A relates to a method for producing a copper-iron composite SCR catalyst. US2015 / 0290632A1 relates to iron and copper-containing chabazite zeolite catalysts for use in NOx reduction. WO2012 / 075400A1 discloses a catalyst composition comprising a zeolite material having a CHA framework structure and external catalyst metals selected from copper, iron and mixtures thereof, disposed on the zeolite material. WO2015 / 084817A1 relates to a composition comprising a synthetic zeolite having a CHA framework structure, which may contain iron and copper. WO2020 / 089275A1 relates to a selective catalytic reduction catalyst on a filter substrate. US2019 / 368399A1 relates to a particle filter having an SCR active coating. WO2014 / 062944A1 relates to a mixed metal 8-membered ring micropore molecular sieve catalyst composition, catalyst articles, systems and methods.

[0005] Considering the above, low temperature NO x Good low-temperature NO conversion, similar to known catalysts optimized for conversion. x It exhibits a transformation, but at the same time, it reduces N2O production, and / or improves high-temperature NO, especially at relatively high temperatures. x A catalyst that exhibits conversion is needed. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] WO2017 / 134581A1 [Patent Document 2] WO2020 / 063360A1 [Patent Document 3] CN104607239A [Patent Document 4] US2015 / 0290632A1 [Patent Document 5] WO2012 / 075400A1 [Patent Document 6] WO2015 / 084817A1 [Patent Document 7] WO2020 / 089275A1 [Patent Document 8] US2019 / 368399A1 [Patent Document 9] WO2014 / 062944A1 [Overview of the project] [Problems that the invention aims to solve]

[0007] Therefore, for the treatment of diesel engine exhaust gases, especially NO x Regarding the conversion and / or N2O generation, more specifically, NO at high temperatures x An object of the present invention is to provide an improved catalyst for conversion and / or N2O production at high temperatures, where high temperature, within the scope of the present invention, particularly includes temperatures above 350°C. [Means for solving the problem]

[0008] Therefore, surprisingly, catalysts for treating diesel exhaust gases are particularly effective in reducing NO x It has been found that one or more of the problems mentioned above can be solved with respect to improved performance in the conversion and / or N2O production. Surprisingly, it has been found that the present invention can provide an improved catalyst, which is characterized in particular as comprising certain zeolite materials including Fe and Cu. Surprisingly, the catalyst of the present invention enables improved catalytic activity. Furthermore, the catalyst of the present invention exhibits excellent behavior with respect to N2O production, particularly at relatively high temperatures, more specifically at temperatures above 350°C.

[0009] By doping a zeolite-based material having a framework structure type CHA with a small amount of Fe in addition to Cu doping, particularly Fe within the range of 0.1 to 0.3% by mass, the low-temperature NO x conversion of the zeolite-based material is not strongly affected, but the high-temperature NO x conversion is strongly improved and / or N2O generation is significantly reduced has been found.

[0010] Therefore, the present invention is a method for manufacturing a catalyst for treating exhaust gas of a diesel engine, (i) producing an aqueous mixture containing water, Fe, and a zeolite-based material having a framework structure type selected from the group consisting of CHA, AEI, RTH, LEV, DDR, KFI, ERI, AFX, mixtures of two or more thereof, and mixed types of two or more thereof, the framework structure of the zeolite-based material contains Si, Al, and O, and the aqueous mixture further contains a copper source, a first non-zeolite-based oxide-based material selected from the group consisting of alumina, silica, titania, zirconia, ceria, lanthana, praseodymium oxide, manganese oxide, and mixtures of one or more of Al, Si, Ti, Zr, La, Mn, Pr, and Ce, producing an aqueous mixture presenting a mass ratio of Fe2O3:CuO, calculated as Fe2O3, of Fe contained in the zeolite-based material to Cu contained in the copper source, calculated as CuO, of less than 0.1:1, (ii) disposing the aqueous mixture obtained in (i) on the surface of the inner wall of a substrate, which is a substrate and includes a plurality of flow paths 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 extending through the flow paths, over at least 55% of the substrate axial length, (iii) subjecting the substrate obtained in (ii) to a heat treatment in a gas atmosphere to obtain a catalyst, relates to a method.

[0011] The zeolite material according to method (i) preferably has a skeletal structure selected from the group consisting of CHA, AEI, RTH, mixtures of two or more of these, and mixed forms of two or more of these, more preferably selected from the group consisting of CHA and AEI, mixtures of these, and mixed forms thereof, and the zeolite material according to method (i) more preferably has a CHA skeletal structure.

[0012] In the aqueous mixture according to method (i), the mass ratio of Fe contained in the zeolite material according to (i), calculated as Fe2O3, to Cu contained in the copper source, calculated as CuO, Fe2O3:CuO, is preferably in the range of 0.010:1 to 0.095:1, more preferably in the range of 0.018:1 to 0.085:1, more preferably in the range of 0.030:1 to 0.075:1, and more preferably in the range of 0.040:1 to 0.067:1.

[0013] Preferably, 95 to 100% by mass, more preferably 98 to 100% by mass, and more preferably 99 to 100% by mass of the skeletal structure of the zeolite material according to method (i) consists of Si, Al, and O, 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 zeolite material according to (i) consists of Si, Al, O, Fe, and optionally H.

[0014] In the skeletal structure of the zeolite material according to method (i), the molar ratio of Si to Al, calculated as the molar ratio of SiO2:Al2O3, is preferably in the range of 1 to 50, more preferably in the range of 8 to 35, more preferably in the range of 13 to 23, more preferably in the range of 16 to 20, and more preferably in the range of 17 to 19.

[0015] The Cu content of the zeolite material calculated as CuO according to method (i) is preferably in the range of 0 to 0.001 mass% with respect to the sum of the mass of Si calculated as SiO2 and the mass of Al calculated as Al2O3 contained in the skeletal structure of the zeolite material according to method (i), and the zeolite material is more preferably essentially Cu-free, and more preferably Cu-free.

[0016] The zeolite-based material produced by method (i) is (a) Prepare a zeolite-based material having a skeletal structure type selected from the group consisting of CHA, AEI, RTH, LEV, DDR, KFI, ERI, AFX, two or more mixtures thereof, and two or more mixed types thereof, more preferably selected from the group consisting of CHA, AEI, RTH, two or more mixtures thereof, and two or more mixed types thereof, more preferably selected from the group consisting of CHA and AEI, mixtures thereof, and mixed types thereof, wherein the zeolite-based material more preferably has a CHA skeletal structure type. The zeolite material's skeletal structure contains Si, Al, and O. (b) Prepare a solution containing a dissolved iron salt, more preferably an aqueous solution containing a dissolved iron salt, more preferably manufacture (c) Impregnate the zeolite material prepared in (a) with the solution prepared in (b). It is preferable that it is obtained by a method including or obtained by a method including

[0017] The process further comprises producing a Fe-containing zeolite material according to (i), wherein the production method is (a) Prepare a zeolite-based material having a skeletal structure type selected from the group consisting of CHA, AEI, RTH, LEV, DDR, KFI, ERI, AFX, two or more mixtures thereof, and two or more mixed types thereof, more preferably selected from the group consisting of CHA, AEI, RTH, two or more mixtures thereof, and two or more mixed types thereof, more preferably selected from the group consisting of CHA and AEI, mixtures thereof, and mixed types thereof, wherein the zeolite-based material more preferably has a CHA skeletal structure type. The zeolite material's skeletal structure contains Si, Al, and O. (b) Prepare a solution containing a dissolved iron salt, more preferably an aqueous solution containing a dissolved iron salt, more preferably manufacture (c) Impregnate the zeolite material prepared in (a) with the solution prepared in (b). It is preferable that it includes.

[0018] If the zeolite material obtained by method (i) is obtained by a method comprising (a), (b), and (c), or if the method further comprises producing a Fe-containing zeolite material by (a), (b), and (c), it is preferable that 95 to 100% by mass, more preferably 98 to 100% by mass, and more preferably 99 to 100% by mass of the skeletal structure of the zeolite material by (a) consists of Si, Al, and O, and 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 by (a) consists of Si, Al, O, and H.

[0019] If the zeolite material obtained by method (i) is obtained by a method comprising (a), (b), and (c), or if the method further comprises producing a Fe-containing zeolite material by (a), (b), and (c), then in the framework structure of the zeolite material by method (a), the molar ratio of Si to Al, calculated as the molar ratio of SiO2:Al2O3, is more preferably in the range of 1 to 50, more preferably in the range of 8 to 35, more preferably in the range of 13 to 23, more preferably in the range of 16 to 20, and more preferably in the range of 17 to 19.

[0020] If the zeolite material obtained by method (i) is obtained by a method comprising (a), (b), and (c), or if the method further comprises producing a Fe-containing zeolite material by (a), (b), and (c), then the zeolite material by (a) is in H form or NH4 + It is preferable that it be in this form.

[0021] If the zeolite material obtained by method (i) is obtained by a method comprising (a), (b), and (c), or if the method further comprises producing a Fe-containing zeolite material by (a), (b), and (c), the zeolite material obtained by method (a) is preferably a calcined zeolite material, more preferably a zeolite material calcined in a gas atmosphere having a temperature in the range of 400 to 700°C, the gas atmosphere being more preferably one or more of oxygen, nitrogen, and air.

[0022] If the zeolite material according to process (i) is obtained by a method comprising (a), (b), and (c), or if the process further comprises producing a zeolite material containing Fe according to (a), (b), and (c), the zeolite material according to (a) preferably contains 0 to 0.1 mass% of one or more of Cu, Li, Na, and K, more preferably 0 to 0.01 mass%, and more preferably 0 to 0.001 mass%, of one or more of Cu, Li, Na, and K, and the zeolite material according to (a) preferably is essentially free of one or more of Cu, Li, Na, and K, and more preferably does not contain them.

[0023] If the zeolite material according to process (i) is obtained by a method comprising (a), (b), and (c), or if the process further comprises producing a Fe-containing zeolite material according to (a), (b), and (c), the zeolite material according to (a) is preferably a particle morphology characterized by a volume-based particle size distribution exhibiting a Dv90 value in the range of 1 to 15 micrometers, more preferably a particle morphology characterized by a volume-based particle size distribution exhibiting a Dv90 value in the range of 3 to 9 micrometers, and more preferably a particle morphology characterized by a Dv90 value in the range of 4 to 6 micrometers, wherein the Dv90 value is more preferably determined as described in Reference Example 2.

[0024] If the zeolite material according to process (i) is obtained by or has been obtained by a method comprising (a), (b), and (c), or if the process further comprises producing a Fe-containing zeolite material according to (a), (b), and (c), the zeolite material according to (a) is preferably in the form of particles characterized by a volume-based particle size distribution exhibiting a Dv50 value in the range of 0.5 to 10 micrometers, more preferably in the range of 1 to 5 micrometers, and more preferably in the range of 2 to 3 micrometers, the Dv50 value being more preferably determined as described in Reference Example 2.

[0025] If the zeolite material obtained by method (i) is obtained by a method comprising (a), (b), and (c), or if the method further comprises producing a Fe-containing zeolite material by (a), (b), and (c), then in the zeolite material by method (a), the average crystal size is preferably in the range of 0.1 to 5 micrometers, more preferably in the range of 0.2 to 2 micrometers, and more preferably in the range of 0.3 to 1 micrometer.

[0026] If the zeolite material obtained by method (i) is obtained by a method comprising (a), (b), and (c), or if the method further comprises producing a Fe-containing zeolite material by (a), (b), and (c), then the volume ratio V(s):V(z) of the volume V(s) of the solution provided in (b) to the pore volume V(z) of the zeolite material provided in (a) is preferably in the range of 0.5:1 to 1:1, more preferably in the range of 0.7:1 to 1:1, and more preferably in the range of 0.8:1 to 1:1, and the pore volume V(z) is preferably determined as described in Reference Example 1.

[0027] If the zeolite material according to (i) of process is obtained by a method comprising (a), (b), and (c), or if the process further comprises producing a zeolite material containing Fe according to (a), (b), and (c), the iron salt according to (b) is preferably an Fe(II) salt, an Fe(III) salt, or a mixture thereof, more preferably an Fe(III) salt, more preferably selected from the group consisting of Fe(III) nitrate, Fe(III) chloride, Fe(III) acetate, Fe(II) sulfate, and mixtures of two or more thereof, and more preferably the iron salt comprises Fe(III) nitrate, and more preferably an Fe(III) nitrate salt.

[0028] If the zeolite material obtained by method (i) is obtained by a method comprising (a), (b), and (c), or if the method further comprises producing an Fe-containing zeolite material by (a), (b), and (c), then it is preferable that 95 to 100% by mass of the solution by (b) consists of water and an iron salt, more preferably 98 to 100% by mass, and more preferably 99 to 100% by mass consists of water and an iron salt.

[0029] If the zeolite material obtained by method (i) is obtained by a method comprising (a), (b), and (c), or if the method further comprises producing an Fe-containing zeolite material by (a), (b), and (c), then the method is: (d)(c) is dried in a gas atmosphere, wherein the gas atmosphere is more preferably one or more of nitrogen, oxygen, and air, more preferably air. During drying, the gas atmosphere preferably has a temperature in the range of 50 to 140°C. It is preferable to further include providing.

[0030] A method comprising (a), (b), and (c), or a process comprising (a), (b), and (c), further comprising (d), is preferably used during drying by (d) to raise the temperature of the gas atmosphere from a temperature in the range of 50 to 70°C to a temperature in the range of 80 to 110°C, and more preferably to raise the temperature of the gas atmosphere from a temperature in the range of 80 to 110°C to a temperature in the range of 120 to 140°C.

[0031] Furthermore, if the zeolite material obtained by method (i) is obtained by a method comprising (a), (b), and (c), or if the method further comprises producing an Fe-containing zeolite material by (a), (b), and (c), then the method is: (e)(c), more preferably, the impregnated zeolite material obtained in (d) is subjected to calcination in a gas atmosphere, wherein the gas atmosphere includes one or more of nitrogen, oxygen, and air, more preferably air, and more preferably one or more of nitrogen, oxygen, and air, more preferably air. During firing, the gas atmosphere maintains a temperature within the range of 550-650°C, more preferably within the range of 570-610°C, more preferably within the range of 580-600°C. It is preferable to further include the following.

[0032] Furthermore, if the zeolite material obtained by method (i) is obtained by a method comprising (a), (b), and (c), or if the method further comprises producing a Fe-containing zeolite material by (a), (b), and (c), then after impregnation by (c), more preferably after drying by (d) as defined in Embodiment 20 or 21, and before (i), the zeolite material is not subjected to firing in a gas atmosphere containing air, more preferably air, preferably one or more of nitrogen, oxygen, and air, more preferably one or more of nitrogen, oxygen, and air, and more preferably not subjected to firing in a gas atmosphere, wherein the gas atmosphere is more preferably in the range of 580 to 600°C, more preferably in the range of 570 to 610°C, and more preferably in the range of 550 to 650°C.

[0033] The copper source according to method (i) is preferably a Cu(I) salt, a Cu(II) salt, or a mixture thereof, more preferably selected from the group consisting of copper acetate, copper nitrate, copper sulfate, copper formate, copper oxide, and mixtures of two or more thereof, more preferably selected from the group consisting of copper acetate, copper oxide, and mixtures thereof, more preferably the copper source contains copper oxide, preferably CuO, and more preferably consists of copper oxide, preferably CuO.

[0034] The aqueous mixture according to method (i) preferably contains a copper source calculated as CuO in an amount ranging from 0.025 to 7.5 mass%, more preferably in the range of 2 to 6.0 mass%, and more preferably in the range of 3.5 to 5.5 mass%, relative to the sum of the mass of Si calculated as SiO2 and the mass of Al calculated as Al2O3 contained in the skeletal structure of the zeolite material contained in the aqueous mixture according to method (i).

[0035] The first non-zeolite oxide material according to method (i) is preferably selected from the group consisting of a mixed oxide containing one or more of alumina, silica, titania, zirconia, Al, Si, Ti, and Zr, and mixtures of two or more thereof, more preferably selected from the group consisting of a mixed oxide containing one or more of alumina, silica, zirconia, Al, Si, and Zr, and mixtures of two or more thereof, and the first non-zeolite oxide material according to method (i) more preferably contains zirconia-alumina, and more preferably consists of zirconia-alumina.

[0036] The first non-zeolite oxide material according to method (i) is selected from the group consisting of a mixed oxide containing one or more of alumina, silica, titania, zirconia, Al, Si, Ti, and Zr, and mixtures of two or more thereof, more preferably selected from the group consisting of a mixed oxide containing one or more of alumina, silica, zirconia, Al, Si, and Zr, and mixtures of two or more thereof, more preferably selected from the group consisting of a mixed oxide containing one or more of alumina, zirconia, Al, and Zr, and mixtures of two or more thereof, and the ( If the first non-zeolite oxide material according to (i) more preferably contains zirconia-alumina and more preferably consists of zirconia-alumina, then, calculated as Al2O3, it is preferable that 30 to 100% by mass of the first non-zeolite oxide material according to (i) is aluminum, more preferably 60 to 85% by mass, and more preferably 75 to 82% by mass is aluminum, and preferably, calculated as ZrO2, 5 to 35% by mass, more preferably 15 to 25% by mass, and more preferably 18 to 22% by mass of the first non-zeolite oxide material according to (i) is zirconium.

[0037] The aqueous mixture according to method (i) preferably contains the first non-zeolite oxide material in an amount greater than 0% by mass to 20% by mass, more preferably in the range of 0.5 to 10.5% by mass, more preferably in the range of 2.0 to 5.5% by mass, and more preferably in the range of 3.5 to 5.2% by mass, relative to the sum of the mass of Si calculated as SiO2 and the mass of Al calculated as Al2O3 contained in the skeletal structure of the zeolite material contained in the aqueous mixture according to method (i).

[0038] The aqueous mixture according to method (i) preferably further comprises a source of a second non-zeolite oxide material different from the first non-zeolite oxide material, the second non-zeolite oxide material being selected from the group consisting of alumina, silica, titania, zirconia, ceria, lantana, praseodymium oxide, manganese oxide, mixed oxides containing one or more of Al, Si, Ti, Zr, La, Mn, Pr, and Ce, and mixtures of two or more thereof, more preferably alumina, silica, titania, zirconia, and ceria, mixed oxides containing one or more of Al, Si, Ti, Zr, and Ce, and mixtures of two or more thereof, more preferably silica, titania The second non-zeolite oxide material is selected from the group consisting of mixed oxides containing one or more of nia, zirconia, Si, Ti, and Zr, and mixtures of two or more of these, more preferably containing zirconia and more preferably consisting of zirconia, and the aqueous mixture according to (i) more preferably contains the second non-zeolite oxide material in an amount in the range of more than 0 mass% to 20 mass%, more preferably in the range of 0.5 to 10.5 mass%, more preferably in the range of 2.0 to 5.5 mass%, and more preferably in the range of 3.5 to 5.2 mass%, relative to the sum of the mass of Si calculated as SiO2 and the mass of Al calculated as Al2O3 contained in the skeletal structure of the zeolite material contained in the aqueous mixture according to (i).

[0039] The aqueous mixture according to method (i) further comprises a source of a second non-zeolite oxide material different from the first non-zeolite oxide material, wherein the second non-zeolite oxide material is more preferably selected from the group consisting of alumina, silica, titania, zirconia, ceria, lantana, praseodymium oxide, manganese oxide, Al, Si, Ti, Zr, La, Mn, Pr, and Ce, and mixtures of two or more thereof, more preferably selected from the group consisting of alumina, silica, titania, zirconia, and ceria, Al, Si, Ti, Zr, and Ce, and mixtures of two or more thereof, more preferably selected from the group consisting of alumina, silica, titania, zirconia, Si, Ti, and Zr, and mixtures of two or more thereof, and the second non-zeolite oxide material more preferably contains zirconia, more preferably consists of zirconia, ( i) is more preferably a second non-zeolite oxide material in an amount ranging from more than 0% to 20% by mass, more preferably 0.5 to 10.5% by mass, more preferably 2.0 to 5.5% by mass, and more preferably 3.5 to 5.2% by mass, relative to the sum of the mass of Si calculated as SiO2 and the mass of Al calculated as Al2O3 contained in the skeletal structure of the zeolite material contained in the aqueous mixture according to (i), the source of the second non-zeolite oxide material is preferably one or more of aluminum salts, silicon salts, zirconium salts, titanium salts, cerium salts, praseodymium salts, manganese salts and lanthanum salts, more preferably zirconium salts and aluminum salts, more preferably zirconium salts, more preferably one or more of zirconium acetate, zirconium hydroxide, zirconium chloride, zirconium nitrate and zirconium sulfate, and more preferably zirconium acetate.

[0040] Furthermore, the aqueous mixture according to method (i) further comprises a source of a second non-zeolite oxide material different from the first non-zeolite oxide material, wherein the second non-zeolite oxide material is more preferably selected from the group consisting of alumina, silica, titania, zirconia, ceria, lantana, praseodymium oxide, manganese oxide, Al, Si, Ti, Zr, La, Mn, Pr, and Ce, and mixtures of two or more thereof, more preferably selected from the group consisting of alumina, silica, titania, zirconia, and ceria, Al, Si, Ti, Zr, and Ce, and mixtures of two or more thereof, more preferably selected from the group consisting of alumina, silica, titania, zirconia, Al, Si, Ti, and Zr, and mixtures of two or more thereof, and the second non-zeolite oxide material more preferably contains zirconia, more preferably made from zirconia Furthermore, if the aqueous mixture according to (i) contains, more preferably, a second non-zeolite oxide material in an amount ranging from more than 0% to 20% by mass, more preferably 0.5 to 10.5% by mass, more preferably 2.0 to 5.5% by mass, and more preferably 3.5 to 5.2% by mass, relative to the sum of the mass of Si calculated as SiO2 and the mass of Al calculated as Al2O3 contained in the skeletal structure of the zeolite material contained in the aqueous mixture according to (i), then the second non-zeolite oxide material The oxalite oxide material is preferably made of zirconia, and the aqueous mixture according to (i) contains, with respect to the sum of the mass of Si calculated as SiO2 and the mass of Al calculated as Al2O3 contained in the skeletal structure of the zeolite material contained in the aqueous mixture according to (i), a second non-zeolite oxide material source calculated as ZrO2 in an amount within the range of 0.5 to 10 mass%, more preferably within the range of 2.5 to 5.5 mass%, and more preferably within the range of 4.8 to 5.2 mass%.

[0041] Method (i) is, (i.1) To produce a first aqueous mixture comprising water and a source of Cu, (i.2) More preferably, the first aqueous mixture is milled, more preferably, until the particles of the first aqueous mixture have a Dv90 in the range of 4.5 to 7.5 micrometers, more preferably in the range of 5.6 to 6.0 micrometers (where Dv90 is determined as described in Reference Example 2), (i.3) Optionally, add a second source of non-zeolite oxide material as defined in any one of Embodiments 29 to 31 to the first aqueous mixture obtained by (i.1), preferably (i.2). (i.4) To produce a second aqueous mixture comprising water and a zeolite material having a skeletal structure type selected from the group consisting of CHA, AEI, RTH, LEV, DDR, KFI, ERI, AFX, two or more mixtures thereof and two or more mixed forms thereof, more preferably selected from the group consisting of CHA, AEI, RTH, two or more mixtures thereof and two or more mixed forms thereof, more preferably selected from the group consisting of CHA and AEI, mixtures thereof and mixed forms thereof, wherein the zeolite material more preferably has a CHA skeletal structure type. To manufacture zeolite-based materials whose skeletal structure contains Si, Al, and O. The second aqueous mixture obtained in (i.5)(i.4) is mixed in (i.1), more preferably in (i.2) or (i.3), to obtain a third aqueous mixture. (i.6) More preferably, the third aqueous mixture is milled, more preferably, until the particles of the third aqueous mixture have a Dv90 in the range of 1.0 to 15 micrometers, preferably in the range of 3.0 to 7.0 micrometers, more preferably in the range of 4.8 to 5.6 micrometers, more preferably in the range of 5.0 to 5.4 micrometers, more preferably in the range of 5.1 to 5.3 micrometers (where Dv90 is determined as described in Reference Example 2). (i.7) To produce a fourth aqueous mixture comprising water and a first non-zeolite oxide material, (i.8)(i.7) is mixed with the third aqueous mixture obtained in (i.5) or (i.6). Includes, (i) preferably consists of (i.1) to (i.8).

[0042] If the method further comprises (i.1), preferably (i.2), optionally (i.3), (i.4), (i.5), preferably (i.6), (i.7), and (i.8), the third aqueous mixture obtained in (i.5) preferably has a pH in the range of 2.0 to 5.0, more preferably in the range of 2.4 to 4.5, and more preferably in the range of 3.4 to 4.2.

[0043] In Embodiment 33, the aqueous mixture obtained in method (i), more preferably in (i.8), preferably has a pH in the range of 2.0 to 6.0, more preferably in the range of 3.5 to 5.0, and more preferably in the range of 3.9 to 4.7.

[0044] The aqueous mixture obtained in method (i) is preferably distributed over 60-100% of the substrate's axial length on the surface of the inner wall of the substrate prepared in (ii), more preferably over 80-100%, and more preferably over 95-100%.

[0045] The aqueous mixture obtained in method (i) is preferably applied to the surface of the inner wall of the substrate by (ii), from the inlet end or outlet end of the substrate.

[0046] The substrate according to method (ii) is preferably a flow-through substrate or a wall-flow filter substrate, more preferably a flow-through substrate, the flow-through substrate being more preferably one or more of cordierite flow-through substrates and metal flow-through substrates, more preferably a cordierite flow-through substrate, the substrate preferably having a cylindrical shape, the diameter of the substrate being more preferably in the range of 25 to 380 mm, more preferably in the range of 45 to 280 mm, more preferably in the range of 55 to 200 mm, and the substrate having an axial length being more preferably in the range of 40 to 254 mm, more preferably in the range of 50 to 154 mm, more preferably in the range of 75 to 127 mm.

[0047] The number of flow channels per square inch of substrate according to method (ii) (6.4516 cm²) 2 The number of flow channels per unit is preferably in the range of 100 to 1200 cpsi, more preferably in the range of 200 to 900 cpsi, and more preferably in the range of 400 to 600 cpsi.

[0048] The gas atmosphere in method (iii) preferably has a temperature in the range of 60 to 150°C, more preferably in the range of 70 to 140°C, the heat treatment is carried out for a period of more preferably in the range of 0.1 to 2 hours, more preferably in the range of 0.4 to 0.6 hours, and the gas atmosphere more preferably contains one or more of oxygen, nitrogen and air, more preferably contains air, more preferably consists of one or more of oxygen, nitrogen and air, and more preferably consists of air.

[0049] The gas atmosphere in method (iii) preferably has a temperature in the range of 500 to 700°C, more preferably in the range of 570 to 610°C, the heat treatment is carried out for a period of more more in the range of 0.5 to 5 hours, more preferably in the range of 1.5 to 2.5 hours, and the gas atmosphere more preferably contains one or more of oxygen, nitrogen and air, more preferably contains air, more preferably consists of one or more of oxygen, nitrogen and air, and more preferably consists of air.

[0050] The heat treatment in method (iii) is (iii.1)(ii) is subjected to a first heat treatment in a gas atmosphere having a temperature in the range of 60 to 150°C, more preferably in the range of 70 to 140°C, wherein the first heat treatment is carried out for a period of more preferably in the range of 0.1 to 2 hours, more preferably in the range of 0.4 to 0.6 hours, and the gas atmosphere more preferably contains one or more of oxygen, nitrogen and air, more preferably contains air, more preferably consists of one or more of oxygen, nitrogen and air, and more preferably consists of air. (iii.2) The substrate obtained in (iii.1) is subjected to a second heat treatment in a gas atmosphere having a temperature in the range of 500 to 700°C, more preferably in the range of 570 to 610°C, wherein the second heat treatment is carried out for a period of more preferably in the range of 0.5 to 5 hours, more preferably in the range of 1.5 to 2.5 hours, and the gas atmosphere more preferably contains one or more of oxygen, nitrogen and air, more preferably contains air, more preferably consists of one or more of oxygen, nitrogen and air, and more preferably consists of air. It is preferable that it includes.

[0051] Furthermore, the present invention relates to a catalyst for treating exhaust gases of a diesel combustion engine, obtained or acquired by a method according to any one of the embodiments disclosed herein.

[0052] Furthermore, the present invention relates to a catalyst for treating exhaust gases of a diesel combustion engine, preferably a catalyst obtained by a method according to any one of the embodiments disclosed herein, wherein the catalyst is (A) A substrate, comprising a plurality of channels defined by an inlet end, an outlet end, a substrate axis length extending from the inlet end to the outlet end, and the inner wall of the substrate extending through the channels, (B) A coating provided on the inner wall surface of the substrate according to (A) over at least 55% of the substrate axial length, wherein the coating comprises a first non-zeolite oxide material and a zeolite material having a skeletal structure selected from the group consisting of Cu and Fe, CHA, AEI, RTH, LEV, DDR, KFI, ERI, AFX, two or more mixtures thereof, and two or more mixed types thereof, wherein the skeletal structure of the zeolite material comprises Si, Al, and O. The first non-zeolite oxide material is selected from the group consisting of alumina, silica, titania, zirconia, ceria, lantana, praseodymium oxide, manganese oxide, mixed oxides containing one or more of Al, Si, Ti, Zr, La, Mn, Pr, and Ce, and mixtures of two or more of these, and includes a coating. The coating by (B) exhibits a mass ratio of Fe calculated as Fe2O3 to Cu calculated as CuO, Fe2O3:CuO, which is less than 0.1:1. Regarding catalysts.

[0053] The zeolite material included in the coating with catalyst (B) preferably has a skeletal structure selected from the group consisting of CHA, AEI, RTH, mixtures of two or more of these, and mixed forms of two or more of these, more preferably selected from the group consisting of CHA and AEI, mixtures of these, and mixed forms thereof, and the zeolite material included in the coating with (B) preferably has a CHA skeletal structure.

[0054] The coating with catalyst (B) preferably exhibits a mass ratio of Fe calculated as Fe2O3 to Cu calculated as CuO, Fe2O3:CuO, in the range of 0.010:1 to 0.095:1, more preferably in the range of 0.018:1 to 0.085:1, more preferably in the range of 0.030:1 to 0.075:1, and more preferably in the range of 0.040:1 to 0.067:1.

[0055] The coating with catalyst (B) preferably exhibits a mass ratio of Fe calculated as Fe2O3 to Cu calculated as CuO, Fe2O3:CuO, in the range of 0.040:1 to 0.098:1, more preferably in the range of 0.060:1 to 0.097:1, and more preferably in the range of 0.070:1 to 0.096:1.

[0056] The copper contained in the coating with catalyst (B) is preferably included in one or more of the zeolite-based material and the first non-zeolite oxide-based material contained in the coating with (B).

[0057] Preferably, 75 to 100% by mass of the copper contained in the coating with catalyst (B) is contained in the zeolite-based material contained in the coating with (B), more preferably 78 to 100% by mass, and more preferably 80 to 100% by mass is contained in the zeolite-based material contained in the coating with (B).

[0058] The substrate for catalyst (A) is preferably a flow-through substrate or a wall-flow filter substrate, more preferably a flow-through substrate, and the flow-through substrate is more preferably one or more of cordierite flow-through substrates and metal flow-through substrates, more preferably a cordierite flow-through substrate.

[0059] The substrate of catalyst (A) is preferably cylindrical in shape, the diameter of the substrate is more preferably in the range of 25 to 380 mm, more preferably in the range of 45 to 280 mm, and more preferably in the range of 55 to 200 mm, and the substrate has an axial length more preferably in the range of 40 to 254 mm, more preferably in the range of 50 to 154 mm, and more preferably in the range of 75 to 127 mm.

[0060] (A) of the catalyst per square inch of the substrate (6.4516 cm²) 2 The number of flow channels per unit is preferably in the range of 100 to 1200 cpsi, more preferably in the range of 200 to 900 cpsi, and more preferably in the range of 400 to 600 cpsi.

[0061] Preferably, 95 to 100% by mass of the zeolite-based material skeleton structure contained in the coating with catalyst (B) consists of Si, Al, and O, more preferably 98 to 100% by mass, and more preferably 99 to 100% by mass consists of Si, Al, and O.

[0062] The zeolite material contained in the coating with catalyst (B) preferably exhibits a molar ratio of silicon dioxide to aluminum oxide (SiO2:Al2O3), calculated as SiO2 to Al2O3, in the range of 1 to 50, more preferably in the range of 8 to 35, more preferably in the range of 13 to 23, more preferably in the range of 16 to 20, and more preferably in the range of 17 to 19.

[0063] In the zeolite-based material included in the coating with catalyst (B), the average catalyst size is preferably in the range of 0.1 to 5.0 micrometers, more preferably in the range of 0.2 to 2.0 micrometers, and more preferably in the range of 0.3 to 1.0 micrometers.

[0064] The zeolite material included in the coating with catalyst (B) preferably contains Fe in an amount ranging from 0.05 to 2 mass%, more preferably in the range of 0.1 to 1 mass%, and more preferably in the range of 0.2 to 0.8 mass%, relative to the sum of the mass of Si calculated as SiO2 and the mass of Al calculated as Al2O3 contained in the skeletal structure of the zeolite material included in the coating with (B), with Fe calculated as Fe2O3.

[0065] The first non-zeolite oxide material included in the coating with catalyst (B) is preferably selected from the group consisting of a mixed oxide containing one or more of alumina, silica, titania, zirconia, Al, Si, Ti, and Zr, and mixtures of two or more of these, more preferably selected from the group consisting of a mixed oxide containing one or more of alumina, silica, zirconia, Al, Si, and Zr, and mixtures of two or more of these, and the first non-zeolite oxide material included in the coating with (B) more preferably contains zirconia-alumina, and more preferably consists of zirconia-alumina.

[0066] The first non-zeolite oxide material included in the coating with catalyst (B) contains zirconia-alumina, preferably consisting of zirconia-alumina, with 30-100% by mass, more preferably 60-85% by mass, and more preferably 75-82% by mass of the zirconia-alumina being alumina.

[0067] The first non-zeolite oxide material included in the coating with catalyst (B) preferably contains zirconia-alumina, more preferably zirconia-alumina, with 5 to 35% by mass, preferably 15 to 25% by mass, and more preferably 18 to 22% by mass of the zirconia-alumina being zirconia.

[0068] The catalyst preferably contains the first non-zeolite oxide material contained in the coating by (B) in an amount greater than 0% to 20% by mass, more preferably in the range of 0.5 to 10.5% by mass, more preferably in the range of 2.0 to 5.5% by mass, and more preferably in the range of 3.5 to 5.2% by mass, relative to the sum of the mass of Si calculated as SiO2 and the mass of Al calculated as Al2O3 contained in the skeletal structure of the zeolite material contained in the coating by (B).

[0069] The coating with catalyst (B) preferably further comprises a second non-zeolite oxide material different from the first non-zeolite oxide material, the second non-zeolite oxide material being selected from the group consisting of alumina, silica, titania, zirconia, ceria, lantana, praseodymium oxide, manganese oxide, mixed oxides containing one or more of Al, Si, Ti, Zr, La, Mn, Pr, and Ce, and mixtures of two or more thereof, more preferably selected from the group consisting of alumina, silica, titania, zirconia, and ceria, Al, Si, Ti, Zr, and Ce, and mixtures of two or more thereof, and more preferably Si The second non-zeolite oxide material is selected from the group consisting of lichen, titania, zirconia, mixed oxides containing one or more of Si, Ti, and Zr, and mixtures of two or more of these, more preferably containing zirconia and more preferably consisting of zirconia, and the catalyst contains the second non-zeolite material in an amount in the range of more than 0 mass% to 20 mass%, more preferably in the range of 0.5 to 10.5 mass%, more preferably in the range of 2.0 to 5.5 mass%, and more preferably in the range of 3.5 to 5.2 mass%, relative to the sum of the mass of Si calculated as SiO2 and the mass of Al calculated as Al2O3 contained in the skeletal structure of the zeolite material contained in the coating by (B).

[0070] If the coating with catalyst (B) further includes a second non-zeolite oxide material different from the first non-zeolite oxide material, it is preferable that the copper contained in the coating with (B) is included in one or more of the zeolite material contained in the coating with (B), the first non-zeolite oxide material contained in the coating with (B), and the second non-zeolite oxide material contained in the coating with (B).

[0071] The coating with catalyst (B) preferably comprises, as particles, one or more of a zeolite material, a first non-zeolite oxide material, and optionally a second non-zeolite oxide material as defined in Embodiment 60, wherein the particles are more preferably characterized by a volume-based particle size distribution exhibiting a Dv90 value in the range of 2 to 20 micrometers, more preferably in the range of 5 to 15 micrometers, and more preferably in the range of 8 to 12 micrometers, the Dv90 value being more preferably determined as described in Reference Example 2.

[0072] The coating with catalyst (B) preferably contains Cu in an amount of 3.0 to 7.5 mass%, more preferably in the range of 4.5 to 5.8 mass%, and more preferably in the range of 4.7 to 5.6 mass%, relative to the sum of the mass of Si calculated as SiO2 and the mass of Al calculated as Al2O3 contained in the zeolite material skeleton structure contained in the coating with (B).

[0073] The coating with catalyst (B) is preferably applied to the surface of the inner wall of the substrate by (A) over 60-100% of the substrate's axial length, more preferably over 80-100%, and more preferably over 95-100%.

[0074] The zeolite-based material contained in the coating by catalyst (B) is applied to the inner wall surface of the substrate by (A) at a concentration of 1.00 to 4.50 g / in 3It is preferable that the loading amount be within the range of 1.50 to 3.25 g / in. 3 Within this range, more preferably 1.65 to 3.10 g / in 3 It is arranged within a loading amount within the specified range.

[0075] The first non-zeolite oxide material contained in the coating with catalyst (B) is more preferably applied to the inner wall surface of the substrate with (A) at a concentration of 0.05 to 0.25 g / in 3 It is preferable that the loading amount be within the range of 0.08 to 0.20 g / in. 3 Within the range of 0.11 to 0.16 g / in, more preferably 0.11 to 0.16 g / in 3 It is arranged within a loading amount within the specified range.

[0076] Furthermore, if the coating by catalyst (B) further includes a second non-zeolite oxide material different from the first non-zeolite oxide material, the second non-zeolite oxide material contained in the coating by (B) will be present on the inner wall surface of the substrate by (A) at a concentration of 0.05~0.25 g / in 3 It is preferable that the loading amount be within the range of 0.08 to 0.20 g / in. 3 Within the range of 0.11 to 0.16 g / in, more preferably 0.11 to 0.16 g / in 3 It is arranged within a loading amount within the specified range.

[0077] The catalyst, calculated as Fe2O3, is present at a concentration of 0.001 to 0.030 g / in. 3 It is preferable to have an Fe loading amount within the range of 0.003 to 0.015 g / in. 3 Within this range, more preferably 0.004 to 0.010 g / in 3 The Fe loading amount is within the range of (B), and the Fe is more preferably contained in the zeolite-based material contained in the coating by (B).

[0078] The catalyst, calculated as CuO, is approximately 0.08-0.18 g / in. 3Preferably, the Cu loading amount is within the range of 0.10 to 0.16 g / in. 3 Within this range, more preferably 0.11 to 0.15 g / in 3 The Cu loading amount is within the range of (B), and the Cu is more preferably included, at least partially, in the zeolite-based material contained in the coating by (B).

[0079] The catalyst preferably has a loading amount of the first non-zeolite oxide material contained in the coating by (B) within the range of 1 to 10 mass%, more preferably within the range of 3 to 7 mass%, and more preferably within the range of 4 to 6 mass%, relative to the sum of the mass of Si calculated as SiO2 and the mass of Al calculated as Al2O3 contained in the skeletal structure of the zeolite material contained in the coating by (B).

[0080] Preferably, 95 to 100% by mass of the coating with catalyst (B) consists of a zeolite-based material, Fe, Cu, O, and a first non-zeolite oxide-based material contained in the coating with (B), more preferably 97 to 100% by mass, and more preferably 99 to 100% by mass consists of a zeolite-based material, Fe, Cu, O, and a first non-zeolite oxide-based material contained in the coating with (B).

[0081] The catalyst is coated with (B) in an amount of 1.0 to 5.0 g / in. 3 Preferably, it should be within the range of 1.75 to 3.75 g / in. 3 Within the range of 1.9 to 3.5 g / in, more preferably 1.9 to 3.5 g / in 3 It is possessed within the scope of.

[0082] Preferably, 95 to 100% by mass of the catalyst consists of a substrate by (A) and a coating by (B), more preferably 97 to 100% by mass, and more preferably 99 to 100% by mass consists of a substrate by (A) and a coating by (B).

[0083] Furthermore, the present invention relates to a system for treating exhaust gas of a diesel combustion engine, comprising a diesel oxidation catalyst, a catalytic soot filter, and a catalyst according to any one of embodiments (42) to (73), wherein the diesel oxidation catalyst is located upstream of the catalytic soot filter, and the catalytic soot filter is located upstream of the catalyst according to any one of embodiments (42) to (73).

[0084] The system preferably further includes a reducing agent injector, more preferably one or more of a hydrocarbon injector, a hydrocarbon in-cylinder post-injector, and a urea injector, wherein the reducing agent injector is more preferably arranged upstream of a catalytic soot filter, and more preferably downstream of a diesel oxidation catalyst.

[0085] Furthermore, the present invention relates to the use of any one of the catalysts or any one of the systems of any of the embodiments disclosed herein for the treatment of exhaust gases from a diesel combustion engine.

[0086] Furthermore, the present invention relates to a method for treating exhaust gases from a diesel combustion engine, comprising contacting the exhaust gases with a catalyst according to any one of the embodiments disclosed herein.

[0087] Furthermore, the present invention relates to a method for treating exhaust gases from a diesel combustion engine, the method comprising passing the exhaust gases through a system according to any one of the embodiments disclosed herein. [Brief explanation of the drawing]

[0088] [Figure 1]This graph shows the NOx conversion in the maximum NH3 slip at temperatures of 160°C, 500°C, and 600°C, as well as the NOx conversion in the 10 ppm NH3 slip at 180°C, for Example 1, Reference Example 3, and Comparative Example 1. The horizontal axis shows the temperature in °C, and the vertical axis shows the NOx conversion in %. [Figure 2] This graph shows the high-temperature N2O generation (referred to as N2O slip at ppm) at 160°C, 180°C, 500°C, and 600°C for Example 1, Reference Example 3, and Comparative Example 1. [Figure 3] These graphs show the NOx conversion at temperatures of 220°C, 575°C, and 630°C for Examples 3-7 and Comparative Example 2. The examples are listed on the horizontal axis, and the NOx conversion in percentage is shown on the vertical axis. [Figure 4] This graph shows the N2O emissions at temperatures of 220°C, 575°C, and 630°C for Examples 3-7 and Comparative Example 2. The examples are listed on the horizontal axis, and the N2O slip in ppm is shown on the vertical axis. [Figure 5] This graph shows the N2O emissions at temperatures of 200°C, 220°C, 580°C, and 630°C for Examples 9-12 and Comparative Example 2. The examples are listed on the horizontal axis, and the N2O slip in ppm is shown on the vertical axis. [Figure 6] These graphs show the NOx conversion during NH3 slippage for Examples 14-15 and Comparative Example 3. The horizontal axis shows temperature in °C, and the vertical axis shows NOx conversion in %. [Figure 7] These graphs show NOx conversion and NH3 slip for Examples 14-15 and Comparative Example 3. The horizontal axis shows time in seconds, and the vertical axis shows NOx conversion in percent and NH3 slip in ppm. [Figure 8] This graph shows the N2O slip during maximum NOx conversion for Examples 14-15 and Comparative Example 3. The horizontal axis shows temperature in °C, and the vertical axis shows N2O slip in ppm. [Figure 9]This graph shows the detailed procedure for the temperature rise test. The horizontal axis shows time in seconds, and the vertical axis shows the urea inlet volume in mg / second, the temperature in °C, and the NOx inlet volume in ppm. [Figure 10] This graph shows the NOx conversion for the catalysts of Example 15 and Comparative Example 3. The horizontal axis shows temperature in °C, the left vertical axis shows NOx conversion in %, and the right vertical axis shows NH3 slip in ppm. [Figure 11] This graph shows the N2O slip for the catalysts of Example 15 and Comparative Example 3. The horizontal axis shows temperature in °C, and the vertical axis shows N2O slip in ppm. [Figure 12] This graph shows the NOx conversion for the catalysts of Examples 15, 18 and Comparative Example 3 at a temperature of 210°C and a standardized stoichiometric ratio (NSR) of NH3 to NOx of 1.5, at a temperature of 260°C and a standardized stoichiometric ratio (NSR) of NH3 to NOx of 1.5, at a temperature of 600°C and a standardized stoichiometric ratio (NSR) of NH3 to NOx of 1, and at a temperature of 600°C and a standardized stoichiometric ratio (NSR) of NH3 to NOx of 3. The examples are listed on the horizontal axis, and the NOx conversion in percentage is shown on the vertical axis. [Figure 13] This graph shows the N2O slip for the catalysts of Examples 15, 18 and Comparative Example 3 at 210°C and a standardized stoichiometric ratio (NSR) of NH3 to NOx of 1.5, at 260°C and a standardized stoichiometric ratio (NSR) of NH3 to NOx of 1.5, at 600°C and a standardized stoichiometric ratio (NSR) of NH3 to NOx of 1, and at 600°C and a standardized stoichiometric ratio (NSR) of NH3 to NOx of 3. The examples are listed on the horizontal axis, and the N2O slip in ppm is shown on the vertical axis. [Modes for carrying out the invention]

[0089] The present invention will be further described by the following set of embodiments and combinations of embodiments derived from the indicated dependencies and backreferences. In particular, in each example where the scope of an embodiment is mentioned, it should be noted that in the context of terms such as, for example, “a more preferred embodiment (4) embodying any one of embodiments (1) to (3),” all embodiments within this scope are expressly disclosed to those skilled in the art, that is, those skilled in the art should understand the wording of this term to be synonymous with “a more preferred embodiment (4) embodying any one of embodiments (1), (2), and (3).” Furthermore, it should be made clear that the following set of embodiments does not constitute a set of claims that would determine the scope of protection, but rather represents suitably structured parts of the description that cover general and preferred aspects of the present invention.

[0090] According to Embodiment (1), the present invention is a method for producing a catalyst for treating exhaust gases of a diesel engine, (i) To produce an aqueous mixture containing water and Fe, and a zeolite material having a skeletal structure type selected from the group consisting of CHA, AEI, RTH, LEV, DDR, KFI, ERI, AFX, two or more mixtures thereof, and two or more mixed types thereof, wherein the skeletal structure of the zeolite material contains Si, Al, and O, and the aqueous mixture further comprises a source of Cu, a mixed oxide containing one or more of alumina, silica, titania, zirconia, ceria, lantana, praseodymium oxide, manganese oxide, Al, Si, Ti, Zr, La, Mn, Pr, and Ce, and a first non-zeolite oxide material selected from the group consisting of two or more mixtures thereof. To produce an aqueous mixture exhibiting a mass ratio of Fe (calculated as Fe2O3) in a zeolite material to Cu (calculated as CuO) in a copper source, where the aqueous mixture is less than 0.1:1, and the ratio is Fe2O3:CuO. (ii) Distribute the aqueous mixture obtained in (i) over a length of at least 55% of the substrate axis length on the surface of the inner wall of a substrate which is a substrate and includes a plurality of channels defined by an inlet end, an outlet end, a substrate axis length extending from the inlet end to the outlet end, and the inner wall of the substrate extending through the channels. The present invention relates to a method for obtaining a catalyst, which includes subjecting the substrate obtained in (iii)(ii) to heat treatment in a gas atmosphere.

[0091] A preferred embodiment (2) embodying embodiment (1) relates to a method wherein the zeolite material according to (i) has a skeletal structure selected from the group consisting of CHA, AEI, RTH, mixtures of two or more of these, and mixed forms of two or more of these, more preferably selected from the group consisting of CHA and AEI, mixtures of these, and mixed forms thereof, and the zeolite material according to (i) more preferably has a CHA skeletal structure.

[0092] A more preferred embodiment (3) embodying embodiment (1) or (2) relates to a method wherein, in the aqueous mixture according to (i), the mass ratio of Fe contained in the zeolite material according to (i), calculated as Fe2O3, to Cu contained in the copper source, calculated as CuO, Fe2O3:CuO, is in the range of 0.010:1 to 0.095:1, more preferably in the range of 0.018:1 to 0.085:1, more preferably in the range of 0.030:1 to 0.075:1, and more preferably in the range of 0.040:1 to 0.067:1.

[0093] A more preferred embodiment (4) that embodies any one of embodiments (1) to (3) relates to a method wherein 95 to 100% by mass, more preferably 98 to 100% by mass, and more preferably 99 to 100% by mass of the skeletal structure of the zeolite material according to (i) consists of Si, Al, and O, 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 zeolite material according to (i) consists of Si, Al, O, Fe, and optionally H.

[0094] A more preferred embodiment (5) that embodies any one of embodiments (1) to (4) relates to a method wherein, in the skeletal structure of the zeolite material according to (i), the molar ratio of Si to Al, calculated as the molar ratio of SiO2:Al2O3, is in the range of 1 to 50, more preferably in the range of 8 to 35, more preferably in the range of 13 to 23, more preferably in the range of 16 to 20, and more preferably in the range of 17 to 19.

[0095] A more preferred embodiment (6) that embodies any one of embodiments (1) to (5) is a method wherein the Cu content of the zeolite material according to (i), calculated as CuO, is in the range of 0 to 0.001 mass% with respect to the sum of the mass of Si, calculated as SiO2, and the mass of Al, calculated as Al2O3, contained in the skeletal structure of the zeolite material according to (i), wherein the zeolite material is more preferably essentially Cu-free, and more preferably Cu-free.

[0096] A more preferred embodiment (7) that embodies any one of embodiments (1) to (6) is the process wherein the zeolite material according to (i) is (a) Prepare a zeolite-based material having a skeletal structure type selected from the group consisting of CHA, AEI, RTH, LEV, DDR, KFI, ERI, AFX, two or more mixtures thereof, and two or more mixed types thereof, more preferably selected from the group consisting of CHA, AEI, RTH, two or more mixtures thereof, and two or more mixed types thereof, more preferably selected from the group consisting of CHA and AEI, mixtures thereof, and mixed types thereof, wherein the zeolite-based material more preferably has a CHA skeletal structure type. The zeolite material system has a framework structure containing Si, Al, and O. (b) Prepare a solution containing a dissolved iron salt, more preferably an aqueous solution containing a dissolved iron salt, more preferably manufacture (c) Impregnate the zeolite material prepared in (a) with the solution prepared in (b). This relates to a process that is obtained by or is obtained by a method that includes [a specific element].

[0097] A more preferred embodiment (8) that embodies any one of embodiments (1) to (6) is the process, which further comprises producing a Fe-containing zeolite material according to (i), (a) Prepare a zeolite-based material having a skeletal structure type selected from the group consisting of CHA, AEI, RTH, LEV, DDR, KFI, ERI, AFX, two or more mixtures thereof, and two or more mixed types thereof, more preferably selected from the group consisting of CHA, AEI, RTH, two or more mixtures thereof, and two or more mixed types thereof, more preferably selected from the group consisting of CHA and AEI, mixtures thereof, and mixed types thereof, wherein the zeolite-based material has a CHA skeletal structure type, The zeolite material's skeletal structure contains Si, Al, and O. (b) Prepare a solution containing a dissolved iron salt, more preferably an aqueous solution containing a dissolved iron salt, more preferably manufacture (c) Impregnate the zeolite material prepared in (a) with the solution prepared in (b). This includes methods (processes).

[0098] A more preferred embodiment (9) that embodies embodiment (7) or (8) relates to a method wherein 95 to 100% by mass, more preferably 98 to 100% by mass, and more preferably 99 to 100% by mass of the skeletal structure of the zeolite material according to (a) consists of Si, Al, and O, and 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 according to (a) consists of Si, Al, O, and H.

[0099] A more preferred embodiment (10) that embodies any one of embodiments (7) to (9) relates to a method wherein, in the skeletal structure of the zeolite material according to (a), the molar ratio of Si to Al, calculated as the molar ratio of SiO2:Al2O3, is more preferably in the range of 1 to 50, more preferably in the range of 8 to 35, more preferably in the range of 13 to 23, more preferably in the range of 16 to 20, and more preferably in the range of 17 to 19.

[0100] A more preferred embodiment (11) that embodies any one of embodiments (7) to (10) is a zeolite material according to (a) that is in H form or NH4 + This concerns the form and method.

[0101] A more preferred embodiment (12) that embodies any one of embodiments (7) to (11) is a method wherein the zeolite material according to (a) is a calcined zeolite material, more preferably a zeolite material calcined in a gas atmosphere having a temperature in the range of 400 to 700°C, and the gas atmosphere is more preferably one or more of oxygen, nitrogen and air.

[0102] A more preferred embodiment (13) that embodies any one of embodiments (7) to (12) relates to a method wherein the zeolite material according to (a) contains 0 to 0.1% by mass, more preferably 0 to 0.01% by mass, and more preferably 0 to 0.001% by mass, one or more of Cu, Li, Na, and K, and the zeolite material according to (a) is more preferably essentially free of, and more preferably does not contain, one or more of Cu, Li, Na, and K.

[0103] A more preferred embodiment (14) that embodies any one of embodiments (7) to (13) is a particle morphology characterized by a volume-based particle size distribution in which the zeolite material according to (a) exhibits a Dv90 value in the range of 1 to 15 micrometers, more preferably in the range of 3 to 9 micrometers, and more preferably in the range of 4 to 6 micrometers, wherein the Dv90 value is more preferably determined as described in Reference Example 2.

[0104] A more preferred embodiment (15) embodying any one of embodiments (7) to (14) is a particle morphology characterized by a volume-based particle size distribution in the range of 0.5 to 10 micrometers, more preferably in the range of 1 to 5 micrometers, and more preferably in the range of 2 to 3 micrometers, wherein the Dv50 value is more preferably determined as described in Reference Example 2.

[0105] A more preferred embodiment (16) that embodies any one of embodiments (7) to (15) relates to a method in which, in a zeolite-based material according to (a), the average catalyst size is in the range of 0.1 to 5 micrometers, more preferably in the range of 0.2 to 2 micrometers, and more preferably in the range of 0.3 to 1 micrometer.

[0106] A more preferred embodiment (17) embodying any one of embodiments (7) to (16) relates to a method in which the volume ratio V(s):V(z) of the volume V(s) of the solution provided in (b) to the pore volume V(z) of the zeolite material provided in (a) is in the range of 0.5:1 to 1:1, more preferably in the range of 0.7:1 to 1:1, more preferably in the range of 0.8:1 to 1:1, and the pore volume V(z) is more preferably determined as described in Reference Example 1.

[0107] A more preferred embodiment (18) embodying any one of embodiments (7) to (17) is a method wherein the iron salt according to (b) is an Fe(II) salt, an Fe(III) salt, or a mixture thereof, more preferably an Fe(III) salt, more preferably selected from the group consisting of Fe(III) nitrate, Fe(III) chloride, Fe(IIII) acetate, Fe(II) sulfate, and mixtures of two or more thereof, and more preferably the iron salt comprises Fe(III) nitrate, and more preferably consists of Fe(III) nitrate.

[0108] A more preferred embodiment (19) that embodies any one of embodiments (7) to (18) relates to a method wherein 95 to 100% by mass, more preferably 98 to 100% by mass, and more preferably 99 to 100% by mass of the solution according to (b) consists of water and an iron salt.

[0109] A more preferred embodiment (20) that embodies any one of embodiments (7) to (19) is: (d)(c) is subjected to drying in a gas atmosphere, wherein the gas atmosphere is more preferably one or more of nitrogen, oxygen, and air, more preferably air. During drying, the gas atmosphere preferably has a temperature in the range of 50 to 140°C. Regarding the method.

[0110] A more preferred embodiment (21) that embodies embodiment (20) relates to a method in which, during drying according to (d), the temperature of the gas atmosphere is increased from a temperature in the range of 50 to 70°C to a temperature in the range of 80 to 110°C, and more preferably from a temperature in the range of 80 to 110°C to a temperature in the range of 120 to 140°C.

[0111] A more preferred embodiment (22) that embodies any one of embodiments (7) to (21), more preferably (20) or (21), is: (e)(c) is more preferably subjected to calcination of the impregnated zeolite material obtained in (d) in a gas atmosphere, wherein the gas atmosphere includes one or more of nitrogen, oxygen, and air, more preferably air, more preferably one or more of nitrogen, oxygen, and air, more preferably air. During firing, the gas atmosphere has a temperature in the range of 550-650°C, more preferably in the range of 570-610°C, more preferably in the range of 580-600°C. Regarding the method.

[0112] A more preferred embodiment (23) that embodies any one of embodiments (7) to (21) is a method wherein, after impregnation by (c), more preferably after drying by (d) as defined in embodiment 20 or 21, and before (i), the zeolite material is not subjected to firing in a gas atmosphere containing air, more preferably air, preferably one or more of nitrogen, oxygen and air, more preferably one or more of nitrogen, oxygen and air, and more preferably not subjected to firing in a gas atmosphere, wherein the gas atmosphere has a temperature more preferably in the range of 580 to 600°C, more preferably in the range of 570 to 610°C, and more preferably in the range of 550 to 650°C.

[0113] A more preferred embodiment (24) embodying any one of embodiments (1) to (23) is a method wherein the copper source according to method (i) is a Cu(I) salt, a Cu(II) salt, or a mixture thereof, and the copper source according to (i) is more preferably selected from the group consisting of copper acetate, copper nitrate, copper sulfate, copper formate, copper oxide, and mixtures of two or more thereof, more preferably selected from the group consisting of copper acetate, copper oxide, and mixtures thereof, and more preferably the copper source comprises copper oxide, preferably CuO, and more preferably copper oxide, preferably CuO.

[0114] A more preferred embodiment (25) that embodies any one of embodiments (1) to (24) relates to a method wherein the aqueous mixture according to (i) contains a copper source calculated as CuO in an amount ranging from 0.025 to 7.5 mass%, more preferably from 2 to 6.0 mass%, and more preferably from 3.5 to 5.5 mass%, relative to the sum of the mass of Si calculated as SiO2 and the mass of Al calculated as Al2O3 contained in the skeletal structure of the zeolite material contained in the aqueous mixture according to (i), in an amount ranging from 0.025 to 7.5 mass%, more preferably from 2 to 6.0 mass%, and more preferably from 3.5 to 5.5 mass%.

[0115] A more preferred embodiment (26) embodying any one of embodiments (1) to (25) is a method wherein the first non-zeolite oxide material according to method (i) is selected from the group consisting of mixed oxides comprising one or more of alumina, silica, titania, zirconia, Al, Si, Ti, and Zr, and mixtures of two or more thereof, more preferably selected from the group consisting of mixed oxides comprising one or more of alumina, silica, zirconia, Al, Si, and Zr, and mixtures of two or more thereof, and the first non-zeolite oxide material according to method (i) more preferably comprises zirconia-alumina, and more preferably comprises zirconia-alumina.

[0116] A more preferred embodiment (27) that embodies embodiment (26) relates to a method in which, calculated as Al2O3, 30 to 100% by mass, preferably 60 to 85% by mass, more preferably 75 to 82% by mass of the first non-zeolite oxide material according to (i) is aluminum, and, calculated as ZrO2, 5 to 35% by mass, more preferably 15 to 25% by mass, more preferably 18 to 22% by mass of the first non-zeolite oxide material according to (i) is zirconium.

[0117] A more preferred embodiment (28) that embodies any one of embodiments (1) to (27) relates to a method wherein the aqueous mixture according to (i) contains the first non-zeolite oxide material in an amount in the range of more than 0% by mass to 20% by mass, more preferably 0.5 to 10.5% by mass, more preferably 2.0 to 5.5% by mass, and more preferably 3.5 to 5.2% by mass, relative to the sum of the mass of Si calculated as SiO2 and the mass of Al calculated as Al2O3 contained in the skeletal structure of the zeolite material contained in the aqueous mixture according to (i), in a range of more than 0% by mass to 20% by mass, more preferably 0.5 to 10.5% by mass, more preferably 2.0 to 5.5% by mass, and more preferably 3.5 to 5.2% by mass.

[0118] A more preferred embodiment (29) that embodies any one of embodiments (1) to (28) is wherein the aqueous mixture according to (i) further comprises a source of a second non-zeolite oxide material different from the first non-zeolite oxide material, the second non-zeolite oxide material being selected from the group consisting of alumina, silica, titania, zirconia, ceria, lantana, praseodymium oxide, manganese oxide, Al, Si, Ti, Zr, La, Mn, Pr, and Ce, and mixtures of two or more thereof, and more preferably selected from the group consisting of alumina, silica, titania, zirconia, and ceria, Al, Si, Ti, Zr, and Ce, and mixtures of two or more thereof. The present invention relates to a method wherein the second non-zeolite oxide material is selected from the group consisting of silica, titania, zirconia, mixed oxides containing one or more of Si, Ti, and Zr, and mixtures of two or more thereof, more preferably containing zirconia, and more preferably consisting of zirconia, and the aqueous mixture according to (i) preferably contains the second non-zeolite oxide material in an amount in the range of more than 0 mass% to 20 mass%, more preferably in the range of 0.5 to 10.5 mass%, more preferably in the range of 2.0 to 5.5 mass%, and more preferably in the range of 3.5 to 5.2 mass%, with respect to the sum of the mass of Si calculated as SiO2 and the mass of Al calculated as Al2O3 contained in the skeletal structure of the zeolite material contained in the aqueous mixture according to (i), in an amount in the range of more than 0 mass% to 20 mass%, more preferably in the range of 0.5 to 10.5 mass%, more preferably in the range of 2.0 to 5.5 mass%, and more preferably in the range of 3.5 to 5.2 mass%.

[0119] A more preferred embodiment (30) embodying embodiment (29) relates to a method in which the source of the second non-zeolite oxide material is one or more of aluminum salts, silicon salts, zirconium salts, titanium salts, cerium salts, praseodymium salts, manganese salts, and lanthanum salts, more preferably one or more of zirconium salts and aluminum salts, more preferably zirconium salts, more preferably one or more of zirconium acetate, zirconium hydroxide, zirconium chloride, zirconium nitrate, and zirconium sulfate, more preferably zirconium acetate.

[0120] A more preferred embodiment (30) embodying embodiment (29) or (30) is a method wherein the second non-zeolite oxide material is made of zirconia, and the aqueous mixture according to (i) contains, with respect to the sum of the mass of Si calculated as SiO2 and the mass of Al calculated as Al2O3 contained in the skeletal structure of the zeolite material contained in the aqueous mixture according to (i), the amount of the source of the second non-zeolite oxide material, calculated as ZrO2, in the range of 0.5 to 10 mass%, more preferably in the range of 2.5 to 5.5 mass%, and more preferably in the range of 4.8 to 5.2 mass%.

[0121] A more preferred embodiment (32) that embodies any one of embodiments (1) to (31) is that (i) (i.1) To produce a first aqueous mixture comprising water and a source of Cu, (i.2) Preferably, the first aqueous mixture is milled, more preferably, until the particles of the first aqueous mixture have a Dv90 in the range of 4.5 to 7.5 micrometers, more preferably in the range of 5.6 to 6.0 micrometers (where Dv90 is determined as described in Reference Example 2). (i.3) Optionally, add a second source of non-zeolite oxide material as defined in any one of Embodiments 29 to 31 to the first aqueous mixture obtained by (i.1), preferably (i.2). (i.4) To produce a second aqueous mixture comprising water and a zeolite material having a skeletal structure type selected from the group consisting of CHA, AEI, RTH, LEV, DDR, KFI, ERI, AFX, two or more mixtures thereof, and two or more mixed forms thereof, more preferably selected from the group consisting of CHA, AEI, RTH, two or more mixtures thereof, and two or more mixed forms thereof, more preferably selected from the group consisting of CHA and AEI, mixtures thereof, and mixed forms thereof, wherein the zeolite material has a CHA skeletal structure type, To manufacture zeolite-based materials whose skeletal structure contains Si, Al, and O. The second aqueous mixture obtained in (i.5)(i.4) is mixed in (i.1), more preferably in (i.2) or (i.3), to obtain a third aqueous mixture. (i.6) Preferably, the third aqueous mixture is milled, more preferably, the particles of the third aqueous mixture are milled until they have a Dv90 in the range of 1.0 to 15 micrometers, preferably in the range of 3.0 to 7.0 micrometers, more preferably in the range of 4.8 to 5.6 micrometers, more preferably in the range of 5.0 to 5.4 micrometers, more preferably in the range of 5.1 to 5.3 micrometers (where Dv90 is determined as described in Reference Example 2). (i.7) To produce a fourth aqueous mixture comprising water and a first non-zeolite oxide material, (i.8)(i.7) is mixed with the third aqueous mixture obtained in (i.5) or (i.6). Includes, (i) is arbitrary, consisting of (i.1) to (i.8), Regarding the method.

[0122] A more preferred embodiment (33) that embodies embodiment (32) relates to a method wherein the third aqueous mixture obtained in (i.5) has a pH in the range of 2.0 to 5.0, more preferably in the range of 2.4 to 4.5, and more preferably in the range of 3.4 to 4.2.

[0123] A more preferred embodiment (34) that embodies any one of embodiments (1) to (33) relates to a method wherein the aqueous mixture obtained in (i) according to embodiment 33, more preferably in (i.8), has a pH in the range of 2.0 to 6.0, more preferably in the range of 3.5 to 5.0, and more preferably in the range of 3.9 to 4.7.

[0124] A more preferred embodiment (35) that embodies any one of embodiments (1) to (34) is a method wherein the aqueous mixture obtained in (i) is distributed on the surface of the inner wall of the substrate according to (ii) over 60 to 100%, more preferably 80 to 100%, and more preferably 95 to 100% of the substrate's axial length.

[0125] A more preferred embodiment (36) that embodies any one of embodiments (1) to (35) relates to a method in which the aqueous mixture obtained in (i) is disposed on the surface of the inner wall of the substrate according to (ii) from the inlet end or outlet end of the substrate.

[0126] A more preferred embodiment (37) embodying any one of embodiments (1) to (36) is a method wherein the substrate according to (ii) is a flow-through substrate or a wall-flow filter substrate, more preferably a flow-through substrate, and the flow-through substrate is more preferably one or more of cordierite flow-through substrates and metal flow-through substrates, more preferably a cordierite flow-through substrate, the substrate preferably has a cylindrical shape, the diameter of the substrate is more preferably in the range of 25 to 380 mm, more preferably in the range of 45 to 280 mm, more preferably in the range of 55 to 200 mm, and the substrate has an axial length more preferably in the range of 40 to 254 mm, more preferably in the range of 50 to 154 mm, more preferably in the range of 75 to 127 mm.

[0127] A more preferred embodiment (38) that embodies any one of embodiments (1) to (37) is the number of flow channels per square inch of substrate according to (ii) (6.4516 cm 2 The present invention relates to a method wherein the number of flow channels per unit is in the range of 100 to 1200 cpsi, more preferably in the range of 200 to 900 cpsi, and more preferably in the range of 400 to 600 cpsi.

[0128] A more preferred embodiment (39) embodying any one of embodiments (1) to (38) relates to a method wherein the gas atmosphere in (iii) has a temperature in the range of 60 to 150°C, more preferably in the range of 70 to 140°C, the heat treatment is carried out for a period of more preferably in the range of 0.1 to 2 hours, more preferably in the range of 0.4 to 0.6 hours, and the gas atmosphere more preferably comprises one or more of oxygen, nitrogen and air, more preferably comprises air, more preferably consists of one or more of oxygen, nitrogen and air, and more preferably consists of air.

[0129] A more preferred embodiment (40) embodying any one of embodiments (1) to (38) relates to a method wherein the gas atmosphere in (iii) has a temperature in the range of 500 to 700°C, preferably in the range of 570 to 610°C, the heat treatment is carried out for a period of more preferably in the range of 0.5 to 5 hours, more preferably in the range of 1.5 to 2.5 hours, and the gas atmosphere more preferably comprises one or more of oxygen, nitrogen and air, more preferably comprises air, more preferably consists of one or more of oxygen, nitrogen and air, and more preferably consists of air.

[0130] A more preferred embodiment (41) that embodies any one of embodiments (1) to (38) is that the heat treatment in (iii) is (iii.1)(ii) is subjected to a first heat treatment in a gas atmosphere having a temperature in the range of 60 to 150°C, more preferably in the range of 70 to 140°C, wherein the first heat treatment is carried out for a period of more preferably in the range of 0.1 to 2 hours, more preferably in the range of 0.4 to 0.6 hours, and the gas atmosphere is more preferably composed of one or more of oxygen, nitrogen and air, more preferably composed of air, (iii.2) The substrate obtained in (iii.1) is subjected to a second heat treatment in a gas atmosphere having a temperature in the range of 500 to 700°C, more preferably in the range of 570 to 610°C, wherein the second heat treatment is carried out for a period of more preferably in the range of 0.5 to 5 hours, more preferably in the range of 1.5 to 2.5 hours, and the gas atmosphere is more preferably composed of one or more of oxygen, nitrogen and air, more preferably composed of air. This includes methods.

[0131] Embodiment (42) of the present invention relates to a catalyst for treating exhaust gases of a diesel combustion engine, obtained or acquired by a method according to any one of embodiments (1) to (41).

[0132] Embodiment (43) of the present invention is a catalyst for treating exhaust gas of a diesel combustion engine, preferably the catalyst of embodiment (42), wherein the catalyst is (A) A substrate, comprising a plurality of channels defined by an inlet end, an outlet end, a substrate axis length extending from the inlet end to the outlet end, and the inner wall of the substrate extending through the channels, (B) A coating provided on the inner wall surface of the substrate according to (A) over at least 55% of the substrate axial length, wherein the coating comprises a first non-zeolite oxide material and a zeolite material having a skeletal structure selected from the group consisting of Cu and Fe, CHA, AEI, RTH, LEV, DDR, KFI, ERI, AFX, two or more mixtures thereof, and two or more mixed types thereof, wherein the skeletal structure of the zeolite material comprises Si, Al, and O. The first non-zeolite oxide material is selected from the group consisting of alumina, silica, titania, zirconia, ceria, lantana, praseodymium oxide, manganese oxide, mixed oxides containing one or more of Al, Si, Ti, Zr, La, Mn, Pr, and Ce, and mixtures of two or more of these, and includes a coating. The present invention relates to a catalyst in which the coating by (B) exhibits a mass ratio of Fe calculated as Fe2O3 to Cu calculated as CuO, Fe2O3:CuO, which is less than 0.1:1.

[0133] A preferred embodiment (44) embodying embodiment (43) relates to the catalyst, wherein the zeolite material contained in the coating with (B) has a skeletal structure selected from the group consisting of CHA, AEI, RTH, mixtures of two or more of these, and mixed forms of two or more of these, more preferably selected from the group consisting of CHA and AEI, mixtures of these, and mixed forms thereof, and the zeolite material contained in the coating with (B) more preferably has a CHA skeletal structure.

[0134] A preferred embodiment (45) embodying embodiment (43) or (44) relates to the catalyst, wherein the coating by (B) exhibits a mass ratio of Fe calculated as Fe2O3 to Cu calculated as CuO, Fe2O3:CuO, in the range of 0.010:1 to 0.095:1, more preferably in the range of 0.018:1 to 0.085:1, more preferably in the range of 0.030:1 to 0.075:1, and more preferably in the range of 0.040:1 to 0.067:1.

[0135] A preferred embodiment (46) embodying embodiment (43) or (44) relates to the catalyst, wherein the coating by (B) exhibits a mass ratio of Fe calculated as Fe2O3 to Cu calculated as CuO, Fe2O3:CuO, in the range of 0.040:1 to 0.098:1, more preferably in the range of 0.060:1 to 0.097:1, and more preferably in the range of 0.070:1 to 0.096:1.

[0136] A more preferred embodiment (47) that embodies any one of embodiments (43) to (46) relates to the catalyst, wherein the copper contained in the coating with (B) is contained in one or more of the zeolite material contained in the coating with (B) and the first non-zeolite oxide material contained in the coating with (B).

[0137] A more preferred embodiment (48) that embodies any one of embodiments (43) to (47) relates to the catalyst, wherein 75 to 100% by mass, more preferably 78 to 100% by mass, and more preferably 80 to 100% by mass of the copper contained in the coating with (B) is contained in the zeolite material contained in the coating with (B).

[0138] A more preferred embodiment (49) that embodies any one of embodiments (43) to (45) relates to the catalyst, wherein the substrate according to (A) is a flow-through substrate or a wall-flow filter substrate, more preferably a flow-through substrate, and the flow-through substrate is more preferably one or more of cordierite flow-through substrates and metal flow-through substrates, more preferably a cordierite flow-through substrate.

[0139] A more preferred embodiment (50) that embodies any one of embodiments (43) to (49) relates to the catalyst, wherein the substrate according to (A) has a cylindrical shape, the diameter of the substrate is more preferably in the range of 25 to 380 mm, more preferably in the range of 45 to 280 mm, more preferably in the range of 55 to 200 mm, and the substrate has an axial length more preferably in the range of 40 to 254 mm, more preferably in the range of 50 to 154 mm, more preferably in the range of 75 to 127 mm.

[0140] A more preferred embodiment (51) that embodies any one of embodiments (43) to (50) is the catalyst, wherein the number of flow channels per square inch of substrate by (A) is (6.4516 cm 2 The present invention relates to a catalyst in which the (percent) is in the range of 100 to 1200 cpsi, more preferably in the range of 200 to 900 cpsi, and more preferably in the range of 400 to 600 cpsi.

[0141] A more preferred embodiment (52) that embodies any one of embodiments (43) to (51) relates to the catalyst wherein 95 to 100% by mass, more preferably 98 to 100% by mass, and more preferably 99 to 100% by mass, of the skeletal structure of the zeolite material contained in the coating with (B) consists of Si, Al, and O.

[0142] A more preferred embodiment (53) that embodies any one of embodiments (43) to (52) relates to the catalyst, wherein the zeolite material contained in the coating with (B) exhibits a molar ratio of silicon oxide to aluminum oxide, calculated as SiO2:Al2O3, in the range of 1 to 50, more preferably in the range of 8 to 35, more preferably in the range of 13 to 23, more preferably in the range of 16 to 20, and more preferably in the range of 17 to 19.

[0143] A more preferred embodiment (54) that embodies any one of embodiments (43) to (53) relates to the catalyst, wherein the zeolite material contained in the coating with (B) has an average catalyst size in the range of 0.1 to 5.0 micrometers, more preferably in the range of 0.2 to 2.0 micrometers, and more preferably in the range of 0.3 to 1.0 micrometers.

[0144] A more preferred embodiment (55) that embodies any one of embodiments (43) to (54) relates to the catalyst, wherein the zeolite material contained in the coating with (B) contains Fe in an amount calculated as Fe2O3, in the range of 0.05 to 2 mass%, more preferably in the range of 0.1 to 1 mass%, and more preferably in the range of 0.2 to 0.8 mass%, relative to the sum of the mass of Si calculated as SiO2 and the mass of Al calculated as Al2O3 contained in the skeletal structure of the zeolite material contained in the coating with (B).

[0145] A more preferred embodiment (56) that embodies any one of embodiments (43) to (55) relates to the catalyst, wherein the first non-zeolite oxide material contained in the coating of the catalyst with (B) is selected from the group consisting of a mixed oxide containing one or more of alumina, silica, titania, zirconia, Al, Si, Ti, and Zr, and two or more mixtures thereof, more preferably selected from the group consisting of a mixed oxide containing one or more of alumina, silica, zirconia, Al, Si, and Zr, and two or more mixtures thereof, and the first non-zeolite oxide material contained in the coating with (B) more preferably contains zirconia-alumina, more preferably consists of zirconia-alumina.

[0146] A more preferred embodiment (57) that embodies any one of embodiments (43) to (56) relates to the catalyst, wherein the first non-zeolite oxide material contained in the coating with (B) comprises zirconia-alumina, preferably zirconia-alumina, and 30 to 100% by mass, more preferably 60 to 85% by mass, and more preferably 75 to 82% by mass of the zirconia-alumina is alumina.

[0147] A more preferred embodiment (58) that embodies any one of embodiments (43) to (57) relates to the catalyst, wherein the first non-zeolite oxide material contained in the coating with (B) comprises zirconia-alumina, more preferably zirconia-alumina, and 5 to 35% by mass, preferably 15 to 25% by mass, and more preferably 18 to 22% by mass of the zirconia-alumina is zirconia.

[0148] A more preferred embodiment (59) that embodies any one of embodiments (43) to (58) relates to the catalyst, wherein the first non-zeolite oxide material contained in the coating with (B) is included in an amount in the range of more than 0% by mass to 20% by mass, more preferably in the range of 0.5 to 10.5% by mass, more preferably in the range of 2.0 to 5.5% by mass, and more preferably in the range of 3.5 to 5.2% by mass, with respect to the sum of the mass of Si calculated as SiO2 and the mass of Al calculated as Al2O3 contained in the skeletal structure of the zeolite material contained in the coating with (B), in an amount in the range of more than 0% by mass to 20% by mass, more preferably in the range of 0.5 to 10.5% by mass, more preferably in the range of 2.0 to 5.5% by mass, and more preferably in the range of 3.5 to 5.2% by mass.

[0149] A more preferred embodiment (60) that embodies any one of embodiments (43) to (59) is the catalyst, wherein the coating with (B) further comprises a second non-zeolite oxide material different from the first non-zeolite oxide material, the second non-zeolite oxide material being a mixed oxide containing one or more of alumina, silica, titania, zirconia, ceria, lantana, praseodymium oxide, manganese oxide, Al, Si, Ti, Zr, La, Mn, Pr, and Ce, and a mixture of two or more of these A second non-zeolite oxide material is selected from the group consisting of a mixture of oxides, more preferably a mixture of oxides containing one or more of alumina, silica, titania, zirconia, and ceria, Al, Si, Ti, Zr, and Ce, and mixtures thereof of two or more, more preferably a mixture of oxides containing one or more of silica, titania, zirconia, Si, Ti, and Zr, and mixtures thereof of two or more, and the second non-zeolite oxide material is more preferably comprising zirconia, and more preferably made of zirconia. The present invention relates to a catalyst wherein the catalyst more preferably contains a second non-zeolite material in an amount ranging from more than 0% to 20% by mass, more preferably 0.5 to 10.5% by mass, more preferably 2.0 to 5.5% by mass, and more preferably 3.5 to 5.2% by mass, relative to the sum of the mass of Si calculated as SiO2 and the mass of Al calculated as Al2O3 contained in the skeletal structure of the zeolite material contained in the coating by (B).

[0150] A more preferred embodiment (61) that embodies embodiment (60) relates to the catalyst, wherein the copper contained in the coating by (B) is contained in one or more of the zeolite material contained in the coating by (B), the first non-zeolite oxide material contained in the coating by (B), and the second non-zeolite oxide material contained in the coating by (B).

[0151] A more preferred embodiment (62) embodying any one of embodiments (43) to (61) relates to the catalyst, wherein the coating with (B) comprises, as particles, one or more of a zeolite material, a first non-zeolite oxide material, and a second non-zeolite oxide material as optionally defined in Embodiment 60, and the particles are characterized by a volume-based particle size distribution exhibiting a Dv90 value more preferably in the range of 2 to 20 micrometers, more preferably in the range of 5 to 15 micrometers, and more preferably in the range of 8 to 12 micrometers, the Dv90 value being more preferably determined as described in Reference Example 2.

[0152] A more preferred embodiment (63) that embodies any one of embodiments (43) to (62) relates to the catalyst, wherein the coating by (B) contains Cu in an amount calculated as CuO, in the range of 3.0 to 7.5 mass%, more preferably in the range of 4.5 to 5.8 mass%, and more preferably in the range of 4.7 to 5.6 mass%, relative to the sum of the mass of Si calculated as SiO2 and the mass of Al calculated as Al2O3 contained in the skeletal structure of the zeolite material contained in the coating by (B).

[0153] A more preferred embodiment (64) that embodies any one of embodiments (43) to (63) relates to the catalyst, wherein the coating by (B) is distributed on the surface of the inner wall of the substrate by (A) over 60 to 100%, more preferably over 80 to 100%, and more preferably over 95 to 100% of the substrate's axial length.

[0154] A more preferred embodiment (65) that embodies any one of embodiments (43) to (64) is the catalyst, wherein the zeolite material contained in the coating by (B) is present on the surface of the inner wall of the substrate by (A) at a concentration of 1.00 to 4.50 g / in 3 Within this range, more preferably 1.50 to 3.25 g / in 3 Within this range, more preferably 1.65 to 3.10 g / in 3 This relates to a catalyst, which is arranged in the loading amount.

[0155] A more preferred embodiment (66) that embodies any one of embodiments (43) to (65) is the catalyst, wherein the first non-zeolite oxide material contained in the coating by (B) is more preferably on the surface of the inner wall of the substrate by (A) at a concentration of 0.05 to 0.25 g / in 3 Within this range, more preferably 0.08 to 0.20 g / in 3 Within the range of 0.11 to 0.16 g / in, more preferably 0.11 to 0.16 g / in 3 This relates to a catalyst, which is arranged in a loading amount within a range.

[0156] A more preferred embodiment (67) that embodies any one of embodiments (60) to (66) is the catalyst, wherein the second non-zeolite oxide material contained in the coating by (B) is present on the surface of the inner wall of the substrate by (A) at a concentration of 0.05 to 0.25 g / in 3 Within this range, more preferably 0.08 to 0.20 g / in 3 Within the range of 0.11 to 0.16 g / in, more preferably 0.11 to 0.16 g / in 3 This relates to a catalyst, which is arranged in a loading amount within a range.

[0157] A more preferred embodiment (68) that embodies any one of embodiments (43) to (67) is the catalyst, calculated as Fe2O3, at a concentration of 0.001 to 0.030 g / in 3 Within this range, more preferably 0.003 to 0.015 g / in 3 Within this range, more preferably 0.004 to 0.010 g / in 3 The present invention relates to a catalyst having an Fe loading amount within the range, wherein the Fe is more preferably contained in a zeolite-based material contained in the coating by (B).

[0158] A more preferred embodiment (69) that embodies any one of embodiments (43) to (68) is the catalyst, calculated as CuO, at 0.08 to 0.18 g / in 3 Within the range of 0.10 to 0.16 g / in 3 More preferably 0.11~0.15 g / in 3 The present invention relates to a catalyst having a Cu loading amount within the range, wherein the Cu is more preferably contained in a zeolite-based material included in the coating by (B).

[0159] A more preferred embodiment (70) that embodies any one of embodiments (43) to (69) relates to the catalyst, wherein the amount of the first non-zeolite oxide material contained in the coating with (B) is in the range of 1 to 10 mass%, more preferably in the range of 3 to 7 mass%, and more preferably in the range of 4 to 6 mass%, relative to the sum of the mass of Si calculated as SiO2 and the mass of Al calculated as Al2O3 contained in the skeletal structure of the zeolite material contained in the coating with (B).

[0160] A more preferred embodiment (71) that embodies any one of embodiments (43) to (70) relates to the catalyst, wherein 95 to 100% by mass, more preferably 97 to 100% by mass, and more preferably 99 to 100% by mass of the coating by (B) consists of a zeolite-based material, Fe, Cu, O, and a first non-zeolite oxide-based material contained in the coating by (B).

[0161] A more preferred embodiment (72) that embodies any one of embodiments (43) to (71) is the catalyst, wherein the amount of coating by (B) is 1.0 to 5.0 g / in 3 Within this range, more preferably 1.75 to 3.75 g / in 3 Within the range of 1.9 to 3.5 g / in, more preferably 1.9 to 3.5 g / in 3 This relates to catalysts within the scope of [the specified range].

[0162] A more preferred embodiment (73) that embodies any one of embodiments (43) to (72) relates to the catalyst, wherein 95 to 100% by mass, more preferably 97 to 100% by mass, and more preferably 99 to 100% by mass of the catalyst comprises a catalyst consisting of a substrate according to (A) and a coating according to (B).

[0163] Furthermore, Embodiment (74) of the present invention relates to a system for treating exhaust gas of a diesel combustion engine, comprising a diesel oxidation catalyst, a catalytic soot filter, and a catalyst according to any one of Embodiments (42) to (73), wherein the diesel oxidation catalyst is located upstream of the catalytic soot filter, and the catalytic soot filter is located upstream of the catalyst according to any one of Embodiments (42) to (73).

[0164] A preferred embodiment (75) embodying embodiment (74) relates to the system further comprising one or more of a reducing agent injector, more preferably a hydrocarbon injector, a hydrocarbon in-cylinder post-injector, and a urea injector, wherein the reducing agent injector is more preferably arranged upstream of a catalytic soot filter, and the reducing agent injector is more preferably arranged downstream of a diesel oxidation catalyst.

[0165] Furthermore, embodiment (76) of the present invention relates to the use of any one catalyst from embodiments (42) to (73) or the system of embodiment (74) or (75) for the treatment of exhaust gases from a diesel combustion engine.

[0166] Furthermore, Embodiment (77) of the present invention relates to a method for treating exhaust gas from a diesel combustion engine, the method comprising contacting the exhaust gas with a catalyst according to any one of Embodiments (42) to (73).

[0167] Furthermore, embodiment (78) of the present invention relates to a method for treating exhaust gas from a diesel combustion engine, the method comprising passing the exhaust gas through a system according to embodiment (74) or (75).

[0168] According to the present invention, the pH value is preferably measured in accordance with the international standard ISO 34-8 (International Standard ISO 34-8: Quantities and Units - Part 8: Physical Chemistry and Molecular Physics, Annex C (Standard): pH. International Organization for Standardization, 1992). According to the present invention, it is even more preferable that the pH value specified in this application is determined in accordance with ISO 80000-9, Annex C, pH.

[0169] In the context of the present invention, the second non-zeolite oxide material functions particularly as a binder.

[0170] In the context of this invention, the term “interior wall surface” should be understood as the “raw,” “exposed,” or “blank” surface of the wall, that is, the surface of the wall in an untreated state consisting of the wall material (apart from any unavoidable impurities that may contaminate the surface).

[0171] In the context of the present invention, the term "consists of" with respect to the mass percentage of one or more components refers to the amount of the component in terms of mass percentage relative to 100 mass percent of the entity in question. For example, the phrase "0 to 0.001 mass percent of the first coating consists of X" indicates that 0 to 0.001 mass percent of the components making up 100 mass percent of the coating are X.

[0172] Furthermore, in the context of the present invention, the phrase "X is one or more of A, B, and C" should be understood to disclose that X is either A, B, or C, or A and B, or A and C, or B and C, or A and B and C, where each of A, B, and C represents a specific realization of the said characteristic. In this regard, it should be noted that the above abstract terms can be converted to concrete examples, for example, where X is a chemical element and A, B, and C are specific elements, such as Li, Na, and K, or where X is a temperature and A, B, and C are specific temperatures, such as 10°C, 20°C, and 30°C. In this regard, it should be noted that a person skilled in the art can further extend the above terms to a less specific realization of the aforementioned characteristics, for example, "X is one or more of A and B" to disclose that X is either A, or B, or A and B, or to a more specific realization of the aforementioned characteristics, for example, "X is one or more of A, B, C, and D" to disclose that X is either A, or B, or 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, or A and B and D, or B and C and D.

[0173] In the context of the present invention, the mass / loading amount of a non-zeolite oxide material is calculated as the mass / loading amount of each non-zeolite oxide material as an oxide, or as the sum of the mass / loading amounts of each non-zeolite oxide material as an oxide. For example, if the non-zeolite oxide material is silica, the mass of the non-zeolite oxide material is calculated as SiO2. As a further example, if the non-zeolite oxide material consists of a mixed oxide containing Ti and Al, the mass of the non-zeolite oxide material is calculated as the sum of TiO2 and Al2O3.

[0174] The present invention will be further explained by the following examples and reference examples. [Examples]

[0175] [Reference Example 1] Determination of pore volume Pore ​​volume was determined by mercury intrusion measurement using mercury porosimetry according to DIN 66133 and ISO 15901-1.

[0176] [Reference Example 2] Determination of volume-based particle size distribution The volume-based particle size distribution, particularly the Dv50 and Dv90 values, was determined by static light scattering using the Sympatec HELOS(3200) & QUIXEL instrument, with the optical density of the sample ranging from 6% to 10%.

[0177] [Comparative Example 1] Production of catalysts having a coating containing Cu-containing zeolite-based material Two different slurries, slurry (1) and slurry (2), were manufactured separately from each other.

[0178] For slurry (1), copper oxide powder with a Dv50 of 33 micrometers was added to the water as a copper source. The amount of copper oxide was calculated so that the total amount of copper in the coating after firing, calculated as CuO, was 5.5% by mass relative to the mass of the zeolite material having a skeletal structure type CHA. The resulting aqueous mixture was milled using a continuous milling apparatus, and the Dv90 value of the particles was approximately 5.8 micrometers. The resulting slurry had a solid content of 8% by mass relative to the total mass of the slurry. Zirconium acetate solution was added to the copper oxide-containing aqueous mixture forming the slurry as a source of oxide components. The amount of zirconium acetate was calculated so that the amount of zirconia in the coating, calculated as ZrO2, was 5% by mass relative to the mass of the zeolite material having a skeletal structure type CHA. Water and a zeolite material having a skeletal structure-type CHA (chabazite with a Dv50 of 2.2 micrometers, a Dv90 of 5.2 micrometers, an SiO2:Al2O3 molar ratio of 18, and an average crystal size of 0.4 micrometers) were added to a slurry to form an aqueous mixture having a solid content of approximately 40% by mass relative to the total mass of the aqueous mixture. The amount of Cu-containing zeolite material having a skeletal structure-type CHA was calculated so that the amount of Cu-containing zeolite material having a skeletal structure-type CHA loaded after calcination was 87% by mass of the amount of coating loaded in the catalyst after calcination. The obtained slurry was milled using a continuous milling apparatus, and the Dv90 value of the particles was smaller than 10 micrometers.

[0179] For slurry (2), an aqueous slurry was prepared having a solid content of 41.5% by mass relative to the total mass of the slurry, and containing water and alumina as a non-zeolite oxide material (consisting of 80% by mass of Al2O3 and 20% by mass of ZrO2). The amount of zirconia-containing alumina was calculated so that its amount after calcination was 5% by mass relative to the mass of the zeolite material having a skeletal structure type CHA after calcination.

[0180] Next, slurries (1) and (2) were combined to obtain the final slurry. The pH of the final slurry was determined to be 4.6. The solid content of the final slurry was approximately 40.3% by mass relative to the total mass of the final slurry.

[0181] A cylindrical cordierite flow-through substrate (with an axial length of 101.6 mm and a diameter of 58 mm) was coated with the final slurry from the inlet end to 100% of the substrate's axial length. To carry this out, the substrate was immersed in the final slurry, diluted to a solid content of 38 mass%, from the inlet end until the slurry reached the top of the substrate. Furthermore, the coated substrate was dried in air at 130°C for 30 minutes, and then calcined in air at 450°C for 2 hours.

[0182] The final coating load after firing is approximately 2g / in. 3 It is approximately 1.73 g / in 3 A zeolite-based material having a skeletal structure type CHA, 0.09 g / in 3 Zirconia-containing alumina, approximately 0.09 g / in 3 Zirconia and 0.095 g / in 3 It contained copper oxide.

[0183] [Example 1] Production of catalysts having a coating containing Fe and Cu-containing zeolite-based materials Zeolite materials with a skeletal CHA structure (chabazite with Dv50 of 2.2 micrometers, Dv90 of 5.2 micrometers, SiO2:Al2O3 molar ratio of 18, and an average crystal size of 0.4 micrometers) were impregnated in a solution of Fe(III) nitrate notahydrate (Fe(NO3)3·9H2O) and water. The amount of water was selected so that the solution filled 90% of the pore volume of the zeolite material, and the amount of Fe(III) nitrate notahydrate was selected so that the amount of iron oxide loaded in the zeolite material with a skeletal CHA structure after calcination was 0.2 mass%. Subsequently, the impregnated zeolite material was heated in air to 60°C and held at this temperature for 2 hours, then heated to 90°C and held at this temperature for 1 hour, then heated to 130°C and held at this temperature for 2 hours, and finally heated to 590°C and held at this temperature for 2 hours.

[0184] To produce the final slurry and coated substrate, the recipe according to Comparative Example 1 was followed, but the zeolite material having a skeletal structure CHA was replaced with a calcined Fe-impregnated zeolite material having a skeletal structure CHA. Furthermore, the copper oxide content in the zeolite material having a skeletal structure CHA was 4.8% by mass. The pH of slurry (1) containing the Fe-impregnated, copper oxide-containing zeolite material was determined to be 4.1 before milling. The pH of the final slurry was determined to be 4.4. The final wash coat load after calcination was 2.0 g / in. 3 That was the case.

[0185] [Reference Example 3] Production of catalysts having a coating containing Fe and Cu-containing zeolite-based materials Fe(III) nitrate notahydrate (Fe(NO3)3·9H2O) and Cu acetate monohydrate (CuAc2·H2O) were dissolved in water, and an additional 0.3% by mass of citric acid was added, calculated relative to the total mass of Cu acetate monohydrate. In the next step, the resulting solution was impregnated into a zeolite material having a skeletal structure type CHA (chabazite with Dv50 at 2.2 micrometers, Dv90 at 5.2 micrometers, an SiO2:Al2O3 molar ratio of 18, and an average crystal size of 0.4 micrometers). The amounts of Cu acetate monohydrate and Fe(III) nitrate notahydrate were selected so that the final copper oxide and iron oxide loads after calcination were 4.8% by mass and 0.2% by mass, respectively. The amount of water was selected so that the solution filled 90% of the pores of the zeolite material. Next, the obtained impregnated zeolite material was heated in air to 60°C and held at this temperature for 2 hours, then heated to 130°C and held at this temperature for 1 hour, and finally heated to 590°C and held at this temperature for 4 hours. To produce the final slurry and coated substrate, the recipe of Comparative Example 1 was followed without using copper oxide slurry. The pH of slurry (1) containing Fe-impregnated, copper oxide-containing zeolite material was determined to be 4 before milling. The pH of the final slurry was determined to be 4.4. The final wash coat load after calcination was 2.0 g / in. 3 That was the case.

[0186] [Example 2] Catalytic activity tests of the catalysts in Comparative Example 1, Example 1, and Reference Example 3 Catalytic activity tests were performed using cores with a diameter of 25.4 mm, drilled out from the fabricated coated substrate. The cores were further shortened to a length of 76.2 mm. The resulting samples were tested in a gas stream containing 150 ppm NO, 225 ppm NH3, 80 ppm C3H6 (C1 basis), 10% O2, 5% CO2, and 5% H2O. The gas space velocity per hour was set to 60,000 for measurements in the temperature range of 160–500°C and to 120,000 for measurements at 600°C. The results of the catalytic activity tests are shown in Figures 1 and 2.

[0187] As shown in Figure 1, NOx conversion is similar for the catalysts of Example 1 and Reference Example 3 across the entire temperature range compared to the catalyst of Comparative Example 1. At temperatures of 160°C and 180°C, Example 1 shows the highest NOx conversion. Furthermore, as shown in Figure 2, both the catalysts of Example 1 and Reference Example 3 show significantly reduced high-temperature N2O generation compared to Comparative Example 1.

[0188] [Comparative Example 2] Production of catalysts having a coating containing Cu-containing zeolite-based material Water was impregnated into a zeolite material having a skeletal structure of CHA (chabazite with Dv50 at 2.2 micrometers, Dv90 at 5.2 micrometers, an SiO2:Al2O3 molar ratio of 18, and an average crystal size of 0.4 micrometers) so that the volume of water filled 90% of the pores of the zeolite material having a skeletal structure of CHA. The resulting zeolite material was then calcined in air at 590°C. The recipe according to Comparative Example 1 was followed to produce the final slurry and coated substrate, but the zeolite material having a skeletal structure of CHA was replaced with the calcined zeolite material having a skeletal structure of CHA. Therefore, the copper oxide content in the zeolite material having a skeletal structure of CHA was 5.5% by mass. The final wash coat load after calcination was 2.0 g / in. 3 That was the case.

[0189] [Example 3] Production of catalysts having a coating containing Fe and Cu-containing zeolite-based materials Zeolite materials with a skeletal structure of CHA (chabazite with Dv50 at 2.2 micrometers, Dv90 at 5.2 micrometers, an SiO2:Al2O3 molar ratio of 18, and an average crystal size of 0.4 micrometers) were impregnated in a solution of Fe(III) nitrate notahydrate (Fe(NO3)3·9H2O) and water. The amount of water was selected so that the solution filled 90% of the pore volume of the zeolite material with a skeletal structure of CHA, and the amount of Fe(III) nitrate notahydrate was selected so that the amount of iron oxide loaded in the zeolite material after calcination was 0.3 mass%. To produce the final slurry and coated substrate, the recipe of Comparative Example 1 was followed, but the zeolite material with a skeletal structure of CHA was replaced with the Fe-impregnated zeolite material with a skeletal structure of CHA, and the copper oxide content in the zeolite material with a skeletal structure of CHA was 4.8 mass%. The final wash coat load after firing is 2.0 g / in. 3 That was the case.

[0190] [Examples 4-7] Production of catalysts having a coating containing Fe and Cu-containing zeolite-based materials Zeolite materials (chabazite with Dv50 at 2.2 micrometers, Dv90 at 5.2 micrometers, an SiO2:Al2O3 molar ratio of 18, and an average crystal size of 0.4 micrometers) were impregnated in a solution of Fe(III) nitrate notahydrate (Fe(NO3)3·9H2O) and water. The amount of water was selected so that the solution filled 90% of the pore volume of the zeolite material having a skeletal structure CHA. The amount of Fe(III) nitrate notahydrate (Fe(NO3)3·9H2O) was selected so that the amount of iron oxide loaded in the zeolite material having a skeletal structure CHA after calcination was as described for Examples 4-7 in Table 1 below. To produce the final slurry and coated substrate, the recipe according to Comparative Example 1 was followed, but the zeolite material having a skeletal structure CHA was replaced with the Fe-impregnated zeolite material having a skeletal structure CHA. The copper oxide content in the zeolite-based materials having a skeletal structure type CHA was as described in Table 1 below for Examples 4-7. The pH of the slurry (1) containing the Fe-impregnated, copper oxide-containing zeolite-based material was determined for each of Examples 4-7, and the respective values ​​are listed in Table 2. The pH of the final slurry was also determined for each of Examples 4-7. The final wash coat load after firing was 2.0 g / in for Examples 4-7. 3 That was the case.

[0191] [Table 1]

[0192] [Table 2]

[0193] [Example 8] Catalytic activity tests of the catalysts in Comparative Example 2 and Examples 3-7 The catalyst was tested with a Euro 6 engine. To do this, the coated catalyst was canned and hydrothermally aged at 800°C for 16 hours. The catalyst was then tested downstream of a DOC and CSF combination, with emission measurements taken at 220°C, 575°C, and 630°C. NOx inlet emissions included 470 ppm, 700 ppm, and 680 ppm, respectively, with a volumetric flow of 20 m³ for all temperatures. 3 Set to / time.

[0194] Figure 3 shows that low-temperature NOx conversion was similar for the catalyst of Example 3 compared to the catalyst of Comparative Example 2. The catalysts of Examples 4-5, manufactured with a copper oxide loading of 4.8 mass%, showed reduced NOx conversion, while the catalysts of Examples 6-7, having a copper oxide loading of 5.5 mass%, showed NOx conversion similar to that of Comparative Example 2. All catalysts of Examples 3-7 showed higher NOx conversion at higher temperatures.

[0195] Surprisingly, the catalyst of Example 3, which was produced without calcining the iron-impregnated zeolite material before further use, was found to exhibit improved catalytic performance compared to the catalyst of Example 5, which contained nearly the same concentrations of iron oxide and copper oxide. Furthermore, surprisingly, a higher copper oxide content of 5.5% by mass compared to 4.8% by mass was found to result in higher NOx conversion at low temperatures. High-temperature NOx conversion was improved by additional Fe impregnation in the catalysts of Examples 3-7.

[0196] Furthermore, the catalytic performance was evaluated in terms of N2O emissions generated by SCR. The results are shown in Figure 4. The catalysts of Examples 3-5, which contain 4.8 mass% CuO, showed significantly reduced N2O emissions at 575°C and 630°C compared to the catalyst of Comparative Example 2. 5.5 mass% copper oxide and 0.1 mass% FeO x Example 6, produced using [the specified method], similarly showed a significant reduction in N2O emissions. Furthermore, 5.5 mass% copper oxide and 0.3 mass% FeO [the specified method] were also used. x The catalyst of Example 7, which contained [the specified ingredient], showed better performance in terms of N2O emissions than the catalyst of Comparative Example 2.

[0197] [Examples 9-12] Production of catalysts having a coating containing Fe and Cu-containing zeolite-based materials Zeolite materials with a skeletal structure of CHA (chabazite with Dv50 at 2.2 micrometers, Dv90 at 5.2 micrometers, an SiO2:Al2O3 molar ratio of 18, and an average crystal size of 0.4 micrometers) were impregnated in a solution of Fe(III) nitrate notahydrate (Fe(NO3)3·9H2O) and water. The amount of water was selected so that the solution filled 90% of the pore volume of the zeolite material with a skeletal structure of CHA, and the amount of Fe(III) nitrate notahydrate was selected so that the amount of iron oxide loaded in the zeolite material with a skeletal structure of CHA after calcination was as given for Examples 9-12 in Table 3 below.

[0198] To produce the final slurry and coated substrate, the recipe of Comparative Example 1 was followed, but the zeolite material with skeletal structure CHA was replaced with an Fe-impregnated zeolite material with skeletal structure CHA. The copper oxide content in the zeolite material with skeletal structure CHA was as described in Table 4 for Examples 9-12. The final wash coat load after firing was 2.0 g / in. 3 That was the case.

[0199] [Table 3]

[0200] [Example 13] Catalytic activity tests of the catalysts in Examples 9-12 and Comparative Example 2 Examples 9-12 and Comparative Example 2 were tested using a Euro 6 engine. To do this, the coated catalysts were canned and hydrothermally aged at 800°C for 16 hours. The catalysts were then tested downstream of a DOC and CSF combination at temperatures of 200°C, 220°C, 575°C, and 630°C. NOx inlet emissions were 450 ppm, 480 ppm, 700 ppm, and 700 ppm, respectively, with a volumetric flow of 20 m³ for all temperatures. 3 Set to / time.

[0201] The results of the catalytic activity test are shown in Figure 5. It can be inferred that the low-temperature NOx conversion in Examples 9-12 is similar to that in Comparative Example 2. Furthermore, it can be observed that the high-temperature conversion was improved in Examples 9-12.

[0202] Furthermore, the catalytic performance was evaluated in terms of N2O emissions generated by SCR. The results are shown in Figure 5. It can be inferred that the amount of N2O generated by SCR was significantly reduced in the catalysts of Examples 9 to 12 compared to Comparative Example 2, especially at high temperatures.

[0203] Furthermore, it was observed that a relatively high copper content resulted in greater N2O emissions, while an increase in iron oxide content led to a reduction in N2O emissions.

[0204] [Comparative Example 3] Production of catalysts having a coating containing Cu-containing zeolite-based material For slurry (1), copper oxide powder (CuO powder with a Dv50 of 33 micrometers) was added to water. The amount of copper oxide was calculated so that the total amount of copper in the coating after firing, calculated as CuO, was 5.5% by mass relative to the mass of the zeolite material having a skeletal structure type CHA. The resulting aqueous mixture was milled using a continuous milling apparatus, and the Dv90 value of the particles was approximately 5.8 micrometers. The resulting slurry had a solid content of 30% by mass relative to the total mass of the slurry. Zirconium acetate solution was added to the copper oxide-containing aqueous mixture forming the slurry as a source of oxide components. The amount of zirconium acetate was calculated so that the amount of zirconia in the coating, calculated as ZrO2, was 5% by mass relative to the mass of the zeolite material having a skeletal structure type CHA. Water and a zeolite material having a skeletal structure-type CHA (chabazite with a Dv50 of 2.2 micrometers, a Dv90 of 5.2 micrometers, an SiO2:Al2O3 molar ratio of 18, and an average crystal size of 0.4 micrometers) were added to a slurry to form an aqueous mixture having a solid content of approximately 42.5 to 45% by mass relative to the total mass of the aqueous mixture. The amount of Cu-containing zeolite material having a skeletal structure-type CHA was calculated so that the amount of zeolite material having a skeletal structure-type CHA loaded after calcination was 87% of the amount of coating loaded in the catalyst after calcination. The obtained slurry was milled using a continuous milling apparatus, and the Dv90 value of the particles was smaller than approximately 7 micrometers.

[0205] For slurry (2), an aqueous slurry was separately prepared containing water and alumina as a non-zeolite oxide material (consisting of 80% by mass Al2O3 and 20% by mass ZrO2), with a solid content of approximately 42% by mass relative to the total mass of the slurry. The amount of zirconia-containing alumina was calculated so that its amount after calcination was 5% by mass relative to the mass of the Cu-containing zeolite material having a skeletal structure type CHA after calcination.

[0206] Subsequently, slurries (1) and (2) were combined, and the solid content of the resulting final slurry was about 42% by mass based on the total mass of the final slurry.

[0207] A cylindrical cordierite flow-through substrate (having a diameter of 143.8 mm and an axial length of 76.2 mm) was coated with the final slurry from the inlet end over 100% of the substrate axial length. To do this, the substrate was immersed in the final slurry diluted to a solid content of 38% by mass from the inlet end until the slurry reached the top of the substrate. Further, the coated substrate was dried in air at 130 °C for 30 minutes and then fired in air at 590 °C for 2 hours.

[0208] The final coating loading after firing was about 3.37 g / in 3 and contained a zeolite-based material having about 2.92 g / in 3 of framework structured CHA, 0.15 g / in 3 of zirconia-containing alumina, about 0.15 g / in 3 of zirconia and 0.16 g / in 3 of copper oxide.

[0209] [Example 14] Production of a catalyst having a coating containing an Fe- and Cu-containing zeolite-based material A zeolite-based material having framework structured CHA (chabazite having a Dv50 of 2.2 micrometers, a Dv90 of 5.2 micrometers, a SiO2:Al2O3 molar ratio of 18, and an average crystal size of 0.4 micrometers) was impregnated in a solution of iron(III) nitrate nonahydrate (Fe(NO3)3·9H2O) and water. The amount of water was selected such that the solution filled 90% of the pore volume of the zeolite-based material having framework structured CHA, and the amount of iron(III) nitrate nonahydrate was selected such that the loading of iron oxide in the zeolite-based material having framework structured CHA after firing was 0.2% by mass. Subsequently, the obtained impregnated zeolite-based material having framework structured CHA was dried and heated to a temperature of 590 °C in air and held at this temperature for 2 hours.

[0210] To produce the final slurry and the coated substrate, following the recipe according to Comparative Example 3, but replacing the zeolite-based material having a framework structure type CHA with an Fe-impregnated zeolite-based material having a framework structure type CHA, and the copper oxide content in the zeolite-based material having a framework structure type CHA was 4.8% by mass. The final washcoat loading amount after firing was 2.75 g / in 3 and it contained 2.39 g / in 3 of the zeolite-based material having a framework structure type CHA, 0.12 g / in 3 of zirconia-containing alumina, 0.11 g / in 3 of copper oxide, 0.12 g / in 3 of zirconia and 0.005 g / in 3 of FeO x

[0211] [Example 15] Production of a catalyst having a coating containing an Fe- and Cu-containing zeolite-based material A zeolite-based material having a framework structure type CHA (chabazite having a Dv50 of 2.2 micrometers, a Dv90 of 5.2 micrometers, a SiO2:Al2O3 molar ratio of 18, and an average crystal size of 0.4 micrometers) was impregnated with a solution of iron(III) nitrate nonahydrate (Fe(NO3)3·9H2O) and water. The amount of water was selected such that the solution filled 90% of the pore volume of the zeolite-based material having a framework structure type CHA, and the amount of iron(III) nitrate nonahydrate was selected such that the iron oxide loading amount in the zeolite-based material having a framework structure type CHA after firing was 0.3% by mass.

[0212] To produce the final slurry and the coated substrate, following the recipe according to Comparative Example 3, but replacing the zeolite-based material having a framework structure type CHA with an Fe-impregnated zeolite-based material having a framework structure type CHA, and the copper oxide content in the zeolite-based material having a framework structure type CHA was 4.8% by mass. The final washcoat loading amount after firing was 3.4 g / in 3 and it contained 2.95 g / in 3 ​A zeolite-based material having a skeletal structure type CHA, 0.15 g / in 3 Zirconia-containing alumina, 0.14 g / in 3 Copper oxide, 0.15 g / in 3 Zirconia and 0.009 g / in 3 FeO x It included.

[0213] [Example 16] Catalytic activity tests of the catalysts in Examples 14-15 and Comparative Example 3 In the first test set, Comparative Example 3 and Examples 14-15 were tested for catalytic performance in the reactants. Catalytic activity tests were performed using a core with a diameter of 25.4 mm, drilled out from a fabricated coated substrate. The core was further shortened to a length of 76.2 mm. The core was then hydrothermally aged at 800°C for 16 hours. The resulting samples were tested in a gas stream containing 325 ppm NO, 125 ppm NO2, and 750 ppm NH3. The gas space velocity was set to 100,000 / hour. The results of the catalytic activity tests are shown in Figures 6, 7, and 8.

[0214] Figure 6 shows that low-temperature NOx conversion was similar for the catalysts of Comparative Example 3 and Example 15, while the low-temperature conversion for the catalyst of Example 14 was only slightly reduced compared to these. Figure 7 shows that NH3 slip occurred early in Examples 14 and 15, but the increase in NOx conversion was steeper in Example 15 compared to Comparative Example 3. The NH3 slip shown is NH3 determined after SCR at a specific NH3 inlet feed. The N2O emissions shown in Figure 8 were reduced at temperatures below 300°C for the catalysts of Examples 14-15 compared to Comparative Example 3.

[0215] [Example 17] Catalytic activity tests of the catalysts in Examples 14-15 and Comparative Example 3 In the second test set, a catalytic activity test was performed on the full-size catalysts obtained from each of the examples. For this purpose, the catalyst included a cylindrical substrate having a diameter of 143.8 mm and an axial length of 76.2 mm. The catalyst was hydrothermally aged at 800 °C for 16 hours and then canned. In the temperature gradient test, the catalyst was tested with a Euro 6 engine. The test procedure is detailed in Figure 9. As can be seen from the graph shown in Figure 9, after filter regeneration, the catalyst was cooled to a temperature of about 220 °C and pre-filled with urea. A strong acceleration resulted in a temperature gradient.

[0216] The results of the test are shown in Figure 10. As can be seen from Figure 10, for the catalysts of Example 15 and Comparative Example 3, the NOx conversion at a temperature of 220 °C was over 90%. Furthermore, within the temperature range of 300 - 450 °C, for both catalysts, the NOx conversion was approximately 100%. At a temperature of 550 °C, the NOx conversion of the catalyst according to Example 15 was greatly enhanced compared to the NOx conversion of the catalyst of Comparative Example 3, and the NH3 slip occurred slightly earlier. As can be inferred from Figure 11, the N2O slip at temperatures above 450 °C was greatly reduced for the catalyst according to Example 15 compared to the catalyst of Comparative Example 3.

[0217] [Example 18] Manufacture of a catalyst having a coating containing an Fe- and Cu-containing zeolite-based material Following Example 15, slurries and coated substrates were produced taking into account the following. The copper oxide content in the zeolite-based material having a framework structure type CHA was 4.5 mass%, and the iron oxide loading was 0.3 mass%. The final washcoat loading after firing was 3.4 g / in 3 and consisted of 2.96 g / in 3 of a zeolite-based material having a framework structure type CHA, 0.15 g / in 3 of zirconia-containing alumina, 0.13 g / in 3 of copper oxide, 0.15 g / in 3 of zirconia and 0.009 g / in 3 of FeO x was included.

[0218] [Example 19] Catalytic activity tests of the catalysts in Examples 15, 18 and Comparative Example 3 For catalyst samples in Examples 15, 18 and Comparative Example 3, cylindrical cores with a diameter of 143.8 mm (5.66 inches) and an axial length of 76.2 mm (3 inches) were prepared. The samples were hydrothermally aged at 800°C for 16 hours. The samples were then tested on an engine bench. Urea was administered at 210°C and 260°C under multiple steady-state conditions. NOx conversion was measured at a 10 ppm NH3 slip, while the average NOx conversion at a constant slip was measured at 600°C. A volumetric flow of approximately 80 m³ was used. 3 The flow rate was set to / hour, and the NH3 / NOx molar ratio (standardized stoichiometric ratio (NSR)) was set to 1.5 at 210°C and 260°C. The NH3 / NOx molar ratio was calculated based on the assumption that one urea molecule decomposes into two NH3 molecules at temperatures above 200°C. At 600°C, the volume flow rate was set to 20 m³. 3 The time was set to / hours, and the NH3 / NOx molar ratio was set to 1 (gray bar) or 3 (white bar).

[0219] The test results are shown in Figures 12 and 13. As can be seen from Figure 12, low-temperature NOx conversion at 210°C and 260°C was similar for all three test catalysts. High-temperature NOx conversion was poorest in the case of the catalyst in Comparative Example 3. The best results in this regard were achieved in the case of the catalyst in Example 18.

[0220] As discussed above regarding the catalytic activity tests using the examples, N2O slip was significantly reduced in the catalyst of Example 15 compared to the catalyst of Comparative Example 3. The catalyst of Example 18 showed an even further improvement in reducing N2O slip.

[0221] References - US 2015 / 0290632 A1 - CN 104607239 A - WO 2020 / 063360 A1 - WO 2017 / 134581

Claims

1. A method for producing a catalyst for treating exhaust gases from a diesel engine, (i) To produce an aqueous mixture containing water and Fe, and a zeolite material having a skeletal structure type selected from the group consisting of CHA, AEI, RTH, LEV, DDR, KFI, ERI, AFX, two or more mixtures thereof, and two or more mixed types thereof, wherein the skeletal structure of the zeolite material contains Si, Al, and O, and the aqueous mixture further comprises a source of Cu, a mixed oxide containing one or more of alumina, silica, titania, zirconia, ceria, lantana, praseodymium oxide, manganese oxide, Al, Si, Ti, Zr, La, Mn, Pr, and Ce, and a first non-zeolite oxide material selected from the group consisting of two or more mixtures thereof, To produce an aqueous mixture exhibiting a mass ratio of Fe (calculated as Fe2O3) in a zeolite material to Cu (calculated as CuO) in a copper source, where the aqueous mixture is less than 0.1:1, and the ratio is Fe2O3:CuO. (ii) Distribute the aqueous mixture obtained in (i) over a length of at least 55% of the substrate axis length on the surface of the inner wall of a substrate which is a substrate and includes a plurality of channels defined by an inlet end, an outlet end, a substrate axis length extending from the inlet end to the outlet end, and the inner wall of the substrate extending through the channels. A method for obtaining a catalyst, comprising subjecting the substrate obtained in (iii) to heat treatment in a gas atmosphere.

2. The method according to claim 1, wherein in the skeletal structure of the zeolite material according to (i), the molar ratio of Si to Al, calculated as the molar ratio of SiO2:Al2O3, is in the range of 1 to 50.

3. The method according to claim 1 or 2, wherein the aqueous mixture according to (i) contains, with respect to the sum of the mass of Si calculated as SiO2 and the mass of Al calculated as Al2O3 contained in the skeletal structure of the zeolite material contained in the aqueous mixture according to (i), the copper source is calculated as CuO and is in an amount within the range of 0.025 to 7.5% by mass.

4. The method according to any one of claims 1 to 3, wherein the zeolite material according to (i) has a CHA skeletal structure.

5. The method according to any one of claims 1 to 4, wherein the copper source includes CuO.

6. The method according to any one of claims 1 to 5, wherein the zeolite material according to (i) has a CHA skeletal structure and the copper source includes CuO.

7. A catalyst for treating exhaust gases from a diesel combustion engine, (A) A substrate, comprising a plurality of channels defined by an inlet end, an outlet end, a substrate axis length extending from the inlet end to the outlet end, and the inner wall of the substrate extending through the channels, (B) A coating disposed on the surface of the inner wall of the substrate according to (A) over at least 55% of the substrate's axial length, wherein the coating comprises a first non-zeolite oxide material and a zeolite material having a skeletal structure type selected from the group consisting of Cu and Fe, CHA, AEI, RTH, LEV, DDR, KFI, ERI, AFX, two or more mixtures thereof, and two or more mixed types thereof, wherein the skeletal structure of the zeolite material comprises Si, Al, and O. The first non-zeolite oxide material is selected from the group consisting of alumina, silica, titania, zirconia, ceria, lantana, praseodymium oxide, manganese oxide, mixed oxides containing one or more of Al, Si, Ti, Zr, La, Mn, Pr, and Ce, and mixtures of two or more of these, and the coating. A catalyst in which the coating by (B) exhibits a mass ratio of Fe calculated as Fe2O3 to Cu calculated as CuO, Fe2O3:CuO, which is less than 0.1:

1.

8. The catalyst according to claim 7, wherein the zeolite-based material contained in the coating by (B) has a CHA skeletal structure.

9. The catalyst according to claim 7 or 8, wherein the zeolite material contained in the coating by (B) exhibits a molar ratio of silicon oxide to aluminum oxide SiO2:Al2O3 calculated as SiO2 to Al2O3 in the range of 1 to 50.

10. The catalyst according to any one of claims 7 to 9, wherein the copper contained in the coating by (B) is contained in one or more of the zeolite-based material and the first non-zeolite oxide-based material contained in the coating by (B).

11. The catalyst according to any one of claims 7 to 10, wherein the zeolite material contained in the coating according to (B) contains Fe in an amount calculated as Fe2O3, ranging from 0.05 to 2 mass%, relative to the sum of the mass of Si calculated as SiO2 and the mass of Al calculated as Al2O3 contained in the skeletal structure of the zeolite material contained in the coating according to (B).

12. The catalyst according to any one of claims 7 to 11, wherein the first non-zeolite oxide material contained in the coating according to (B) is contained in an amount ranging from more than 0% by mass to 20% by mass, relative to the sum of the mass of Si calculated as SiO2 and the mass of Al calculated as Al2O3 contained in the skeletal structure of the zeolite material contained in the coating according to (B).

13. The zeolite-based material contained in the coating by (B) is present on the inner wall surface of the substrate by (A) at a concentration of 1.00 to 4.50 g / (2.54 cm). ３ A catalyst according to any one of claims 7 to 12, which is arranged in a loading amount within the range.

14. Calculated as Fe2O3, 0.001 to 0.030 g / (2.54 cm) ３ A catalyst according to any one of claims 7 to 13, having an Fe loading amount within the range.

15. Calculated as CuO, the value is 0.08 to 0.18 g / (2.54 cm). ３ A catalyst according to any one of claims 7 to 14, having a Cu loading amount within the range.

16. 1.0~5.0g / (2.54cm) ３ The catalyst according to any one of claims 7 to 15, having a coating load amount by (B) within the range of .

17. A system for treating exhaust gases of a diesel combustion engine, comprising a diesel oxidation catalyst, a catalytic soot filter, and a catalyst according to any one of claims 7 to 16, wherein the diesel oxidation catalyst is located upstream of the catalytic soot filter, and the catalytic soot filter is located upstream of the catalyst according to any one of claims 7 to 16.

18. Use of a catalyst according to any one of claims 7 to 16 or a system according to claim 17 for treating exhaust gases from a diesel combustion engine.

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