Catalyst material containing FE-containing zeolite material for exhaust gas treatment

Abstract

The present invention relates to an iron-containing catalyst material for the selective catalytic reduction of NOx in exhaust gas from an internal combustion engine. The catalyst material comprises a zeolite material containing SiO2 and X2O3 in its skeletal structure, where X is a trivalent element such as aluminum, and the zeolite material has an FER-type skeletal structure, and the deconvolution of the zeolite material 29 The Si MAS NMR spectrum includes a specific first peak (P1) corresponding to the Q4(1Al) site, having a maximum value in the range of -103.5 to -108.5 ppm and a specific minimum integral for three other peaks in the range of -90.0 to -130.0 ppm. The catalyst material also contains Fe supported on a zeolite material. Furthermore, the present invention relates to a process for producing the catalyst material, an exhaust gas treatment system comprising the catalyst material according to the present invention and its use, and a process for treating the exhaust gas comprising the catalyst material.

Description

[Technical Field]

[0001] The present invention relates to a catalyst material for treating exhaust gas containing NOx, preferably for the selective catalytic reduction of NOx. Furthermore, the present invention relates to a process for preparing a catalyst material, a catalyst material obtained or obtainable by such process, an exhaust gas treatment system using the catalyst material of the present invention, a process for treating exhaust gas using the catalyst material of the present invention, and the use of the catalyst material according to the present invention for treating exhaust gas, preferably for the selective catalytic reduction of NOx. [Background technology]

[0002] This invention relates to the field of catalysts effective for selective catalytic reduction. The properties of a zeolite material having a skeletal structure with a maximum ring size of 10 or fewer T atoms that provides the best SCR performance when loaded with Fe are described. Furthermore, a process for preparing a catalytic material that allows for the incorporation of a relatively large amount of Fe into the zeolite material is described herein.

[0003] International Publication No. 2020 / 021054(A1) relates to a process for preparing zeolite materials having a skeletal FER. It discloses that the prepared zeolite material can be ion-exchanged with one or more ions from Cu, Pd, Rh, Pt, and Fe.

[0004] International Publication No. 2021 / 198339(A1) relates to catalysts for the selective catalytic reduction of nitrogen oxides, processes for preparing such catalysts, the use of such catalysts for the selective catalytic reduction of nitrogen oxides, and exhaust gas treatment systems comprising such catalysts. The catalyst may include a zeolite material having a skeletal structure selected from the group consisting of MFI, MWW, AEL, HEU, FER, AFO, mixtures of two or more thereof, and mixtures of two or more thereof, wherein the zeolite material can exchange ions with Fe.

[0005] International Publication No. 2015 / 128668(A1) relates to an SCR-active molecular sieve catalyst produced by combining a molecular sieve with at least one ionic iron species and at least one organic compound to form a mixture, and then calcining the mixture to remove at least one organic compound. This process is disclosed to improve the dispersion of iron within the molecular sieve compared to iron-containing molecular sieves that have not been treated with organic compounds. The prepared Fe-containing ferrielite zeolite was tested in the selective catalytic reduction of nitrogen oxides using NH3 or urea.

[0006] European Patent Application Publication No. 2857084(A1) relates to an apparatus for treating exhaust gas flowing in the exhaust line of an internal combustion engine, characterized by comprising a porous substrate coated and / or impregnated with a catalyst composition comprising a combination of H-form chabazite zeolite or impregnated copper and / or ferrielite zeolite that is in H form or impregnated with one or more of Cu and Fe.

[0007] German Patent Application Publication No. 102011012799(A1) relates to a catalyst comprising a carrier of a certain length and a catalytically active coating made from at least one material zone which may contain zeolite containing 1 to 10% by weight of copper, iron, and / or silver based on the total weight of the zeolite, wherein the zeolite may contain ferrierite (FER).

[0008] European Patent Application Publication No. 2409760(A1) relates to a gas treatment apparatus comprising such a composition containing ferrielite / iron-type zeolite. The disclosed substrate has an internal structure adapted for forming a particulate filter (1) and comprises a catalyst composition containing H-type ferrielite zeolite and iron (0.3-2% by mass) deposited on the substrate. The catalyst composition is configured to carry out chemical reactions such as the reduction of nitrogen oxides.

[0009] International Publication No. 2008 / 049557(A1) relates to a catalyst useful for the decomposition and / or reduction of nitrous oxide, wherein the catalyst may include an Fe-exchanged ferrielite-type zeolite.

[0010] U.S. Patent No. 5041272(A) relates to a method for removing nitrogen oxides from exhaust gas containing oxygen and moisture, comprising contacting the exhaust gas with a hydrogenated zeolite catalyst, or a hydrogenated zeolite catalyst impregnated with one or more types of metals selected from the group consisting of copper, zinc, vanadium, chromium, manganese, iron, cobalt, nickel, rhodium, palladium, platinum, and molybdenum, in the presence of an organic compound. The zeolite may be of the ferrielite type.

[0011] U.S. Patent Application Publication 2011 / 056187(A1) describes the selective catalytic reduction of nitrogen oxides (NOx) using ammonia or a compound decomposable to ammonia as a reducing agent on a molecular sieve-based SCR catalyst. x This relates to a process for treating diesel engine exhaust gas containing ) and hydrocarbons (HC).

[0012] P. Sarv et al., "Multinuclear MQMAS NMR Study of NH4 / Na-Ferrierites", J. Phys. Chem. B 1998, 102, 1372-1378, relates to (MQ)MAS NMR as a method for studying quadrupole nuclei, enabling the separation of chemical shift interactions from quadrupole interactions. NH4-ferrierites with peak distributions in the range of -90.0 to -120.0 ppm 29 Si MAS NMR spectra are provided as an example.

[0013] Therefore, an object of the present invention was to provide a catalyst material that exhibits improved performance in selective catalytic reduction (SCR), particularly in the selective catalytic reduction of NOx. In particular, an object of the present invention was to provide a catalyst material that exhibits improved performance in the selective catalytic reduction of NOx after aging. Furthermore, an object of the present invention was to provide a catalyst material that exhibits improved resistance to hydrocarbon poisoning. In addition, an object of the present invention was to provide a process for preparing a catalyst material that enables improved ion exchange of the zeolite material contained in the catalyst material, particularly with Fe. Moreover, an object of the present invention was to provide an exhaust gas treatment system comprising the catalyst material according to the present invention. An exemplary design for an exhaust gas treatment system according to the present invention is shown in Figure 14. [Modes for carrying out the invention]

[0014] Therefore, surprisingly, it has been found that catalyst materials exhibiting very good SCR performance, particularly after aging of the catalyst material, can be provided. The catalyst material of the present invention, characterized by containing an FER-type zeolite material, exhibits improved performance in selective catalytic reduction of NOx after aging, and improved resistance to hydrocarbon poisoning. Furthermore, surprisingly, it has been found that the use of one or more ammonium cations in the preparation of the catalyst material, particularly in combination with the adjustment of the pH of each aqueous reaction mixture, enables improved incorporation of Fe into the zeolite material contained in the catalyst material.

[0015] Therefore, the present invention relates to a catalyst material for the selective catalytic reduction of NOx, It contains a zeolite material that includes SiO2 and X2O3 in its skeletal structure. X is a trivalent element, The zeolite material has an FER-type skeletal structure, Deconvolution of zeolite materials 29The Si MAS NMR includes a first peak (P1) having a maximum value within the range of -103.5 to -108.5 ppm, the integration of the first peak is the area I1, and the integration of all peaks within the range of -90.0 to -130.0 ppm is the area I total and the ratio of the area I1 of the first peak to the area I total of all peaks is 0.20:1 or more, the catalyst material contains Fe, and Fe is supported on the zeolite material, the deconvoluted 29 Si MAS NMR is preferably determined according to Reference Example 1, and relates to the catalyst material.

[0016] the zeolite material 29 There are no specific restrictions according to the present invention regarding the state of receiving the Si MAS NMR experiment. However, 29 the values cited in this application for the Si MAS NMR spectrum have not undergone any post-synthesis treatment, and thus are preferably obtained from the zeolite material which is an as-crystallized untreated zeolite material. However, according to the present invention, 29 the values cited in this application for the Si MAS NMR spectrum are directly obtained from the as-crystallized zeolite material, and after its isolation, washing, and drying, the material has only undergone calcination, and preferably, the calcination is carried out according to any one of the specific preferred embodiments defined in this application, and more preferably, the calcination is carried out at 550 °C for a duration of 5 hours under air.

[0017] The ratio of the area I1 of the first peak to the area I total of all peaks within the range of -90.0 to -130.0 ppm is preferably 0.23:1 or more, more preferably more than 0.25:1.

[0018] The ratio of the area I1 of the first peak to the area I totalThe ratio is preferably in the range of 0.2:1 to 0.60:1, more preferably in the range of 0.23:1 to 0.50:1, and more preferably in the range of 0.30:1 to 0.50:1.

[0019] The first peak (P1) preferably has a maximum value within the range of -104.0 to -108.0 ppm, more preferably within the range of -104.5 to -107.5 ppm, and more preferably within the range of -105.0 to -107.0 ppm.

[0020] Deconvolution of zeolite materials 29 The Si MAS NMR spectrum includes a second peak (P2) with a maximum value in the range of -97.5 to -102.5 ppm, more preferably in the range of -99.0 to -101.0 ppm, and the integral of the second peak (P2) is more preferably the area I2, and the area I2 of the second peak versus the area I of all peaks in the range of -90.0 to -130.0 ppm total The ratio is preferably 0.05:1 or less, more preferably 0.04:1 or less, and more preferably 0.03:1 or less.

[0021] Deconvolution of zeolite materials 29 The Si MAS NMR spectrum includes a third peak (P3) with a maximum value in the range of -108.6 to -112.5 ppm, more preferably in the range of -110.0 to -112.0 ppm, and the integral of the third peak (P3) is more preferably area I3, and the area I3 of the third peak versus the area I of all peaks in the range of -90.0 to -130.0 ppm total The ratio is preferably 0.55:1 or less, more preferably 0.50:1 or less, and more preferably 0.45:1 or less.

[0022] Deconvolution of zeolite materials 29The Si MAS NMR spectrum includes a fourth peak (P4) with a maximum value in the range of -112.6 to -116.5 ppm, more preferably in the range of -113.0 to -115.0 ppm, wherein the integral of the fourth peak (P4) is more preferably area I4, and the area I4 of the fourth peak versus the area I of all peaks in the range of -90.0 to -130.0 ppm total The ratio is preferably 0.50:1 or less, more preferably 0.45:1 or less, and more preferably 0.40:1 or less.

[0023] Deconvolution of zeolite materials 29 The Si MAS NMR spectrum includes a fifth peak (P5) with a maximum value in the range of -93.0 to -97.0 ppm, more preferably in the range of -94.0 to -96.0 ppm, and the integral of the fifth peak (P5) is more preferably area I5, and the area I5 of the fifth peak versus the area I of all peaks in the range of -90.0 to -130.0 ppm total The ratio is preferably 0.05:1 or less, more preferably 0.3:1 or less, and more preferably 0.02:1 or less.

[0024] X is selected from the group consisting of Al, B, In, Ga, and mixtures of two or more of these, more preferably from the group consisting of Al, B, and mixtures thereof, and more preferably X is Al.

[0025] The zeolite material preferably has a molar ratio of SiO2 to X2O3 of 50 or less, more preferably 40 or less, more preferably 30 or less, more preferably in the range of 1 to 30, more preferably in the range of 5 to 25, and more preferably in the range of 10 to 20.

[0026] When X is Al, the zeolite material preferably has a molar ratio of SiO2 to Al2O3 of 50 or less, more preferably 40 or less, more preferably 30 or less, more preferably in the range of 1 to 30, more preferably in the range of 5 to 25, and more preferably in the range of 10 to 20.

[0027] Furthermore, independently of the above, according to the first alternative for the catalyst material, the catalyst material preferably has an atomic ratio of Al contained in the skeletal structure of the zeolite material calculated as an Fe pair element supported on a zeolite material calculated as an element in the range of 0.20:1 or more, preferably in the range of 0.20:1 to 0.50:1, more preferably in the range of 0.20:1 to 0.45:1, more preferably in the range of 0.20:1 to 0.40:1, and more preferably in the range of 0.20:1 to 0.35:1.

[0028] Furthermore, independently of the above, according to a second alternative for catalyst materials, it is preferable that the catalyst material contains Fe in an amount of 2.5% by weight or more, more preferably in the range of 2.5 to 10.0% by weight, more preferably in the range of 2.5 to 7.5% by weight, more preferably in the range of 4.0 to 6.5% by weight, more preferably in the range of 5.0 to 6.2% by weight, and more preferably in the range of 5.9 to 6.0% by weight, calculated as Fe2O3 supported on the zeolite material, which is calculated as the sum of the weights of SiO2 and X2O3 contained by the skeletal structure of the zeolite material.

[0029] Furthermore, the present invention relates to a process for producing a catalyst material, preferably according to any one of the specific preferred embodiments disclosed herein, (i) To provide an aqueous mixture comprising a zeolite material, one or more Fe sources, and one or more optionally substituted ammonium cations, (ii) The mixture obtained in (i) is subjected to ion exchange conditions, Zeolite material contains SiO2 and X2O3 in its skeletal structure. X is a trivalent element, The zeolite material has a maximum ring size of 10 or fewer T atoms. Deconvolution of zeolite materials 29The Si MAS NMR spectrum includes a first peak (P1) with a maximum value in the range of -103.5 to -108.5 ppm, and the integral of the first peak is area I1, and all peaks in the range of -90.0 to -130.0 ppm are area I total Therefore, the area of ​​the first peak I1 versus the area of ​​all peaks I total The ratio is 0.20:1 or greater, and Fe is supported on the zeolite material. Deconvolution of zeolite materials 29 The Si MAS NMR is preferably determined according to Reference Example 1, relating to the process.

[0030] In particular, the loading of Fe onto the zeolite material can be carried out via generally known processes, especially via ion exchange procedures, and the term "ion exchange" according to the present invention generally refers to non-skeletal ionic elements and / or molecules contained in the zeolite material. Generally, any conceivable ion exchange procedure using all possible ionic elements and / or molecules can be performed on the zeolite material, except for organic structure directing agents used in the synthesis of the zeolite material. Preferably, as the ionic element, preferably H + NH4 + At least one cationic and / or cationic element selected from the group consisting of , and Fe is employed. Furthermore, loading, in particular ion exchange, can be carried out via impregnation, preferably via an initial wetting technique. An initial wetting impregnation technique, also called capillary impregnation or dry impregnation, is commonly used for the synthesis of heterogeneous materials, i.e., catalysts. As a result, Fe can be loaded onto the zeolite material as a metal cluster and / or as a metal oxide.

[0031] Area of ​​the first peak I1 vs. Area of ​​all peaks in the range of -90.0 to -130.0 ppm I total The ratio is preferably 0.23:1 or greater, and more preferably greater than 0.25:1.

[0032] Area of ​​the first peak I1 vs. Area of ​​all peaks in the range of -90.0 to -130.0 ppm Itotal The ratio is preferably in the range of 0.2:1 to 0.60:1, more preferably in the range of 0.23:1 to 0.50:1, and more preferably in the range of 0.25:1 to 0.45:1.

[0033] The first peak (P1) preferably has a maximum value within the range of -104.0 to -108.0 ppm, more preferably within the range of -104.5 to -107.0 ppm, and more preferably within the range of -105.0 to -107.0 ppm.

[0034] Deconvolution of zeolite materials 29 The Si MAS NMR spectrum includes a second peak (P2) having a maximum value in the range of -97.5 to -102.5 ppm, more preferably in the range of -99.0 to -101.0 ppm, where the integral of the second peak (P2) is preferably the area I2, and the area I2 of the second peak versus the area I of all peaks in the range of -90.0 to -130.0 ppm total The ratio is preferably 0.05:1 or less, more preferably 0.04:1 or less, and more preferably 0.03:1 or less.

[0035] Deconvolution of zeolite materials 29 The Si MAS NMR spectrum includes a third peak (P3) with a maximum value in the range of -108.6 to -112.5 ppm, more preferably in the range of -110.0 to -112.0 ppm, and the integral of the third peak (P3) is more preferably area I3, and the area I3 of the third peak versus the area I of all peaks in the range of -90.0 to -130.0 ppm total The ratio is preferably 0.55:1 or less, more preferably 0.50:1 or less, and more preferably 0.45:1 or less.

[0036] Deconvolution of zeolite materials 29The Si MAS NMR spectrum includes a fourth peak (P4) with a maximum value in the range of -112.6 to -116.5 ppm, more preferably in the range of -113.0 to -115.0 ppm, wherein the integral of the fourth peak (P4) is more preferably area I4, and the area I4 of the fourth peak versus the area I of all peaks in the range of -90.0 to -130.0 ppm total The ratio is preferably 0.50:1 or less, more preferably 0.45:1 or less, and more preferably 0.40:1 or less.

[0037] Deconvolution of zeolite materials 29 The Si MAS NMR spectrum includes a fifth peak (P5) with a maximum value in the range of -93.0 to -97.0 ppm, more preferably in the range of -94.0 to -96.0 ppm, and the integral of the fifth peak (P5) is more preferably area I5, and the area I5 of the fifth peak versus the area I of all peaks in the range of -90.0 to -130.0 ppm total The ratio is preferably 0.05:1 or less, more preferably 0.3:1 or less, and more preferably 0.02:1 or less.

[0038] X is selected from the group consisting of Al, B, In, Ga, and mixtures of two or more of these, more preferably from the group consisting of Al, B, and mixtures thereof, and more preferably X is Al.

[0039] The zeolite material preferably has a molar ratio of SiO2 to X2O3 of 50 or less, more preferably 40 or less, more preferably 30 or less, more preferably in the range of 1 to 30, more preferably in the range of 5 to 25, and more preferably in the range of 10 to 20.

[0040] Ammonium cations substituted with one or more optional substitutions are NH4 + , ((C1~C 10 )alkyl)NH3 + , ((C1~C 10 )Alkyl)2NH2 + , ((C1~C 10 )Alkyl)3NH+ , ((C1~C 10 )Alkyl)4N + From the group consisting of , and two or more mixtures thereof, more preferably NH4 + , ((C1~C7)alkyl)NH3 + , ((C1~C7)alkyl)2NH2 + , ((C1~C7) alkyl)3NH + , ((C1~C7) alkyl) 4N + From the group consisting of , and two or more mixtures thereof, more preferably NH4 + , ((C1~C5)alkyl)NH3 + , ((C1~C5)alkyl)2NH2 + , ((C1~C5)alkyl)3NH + , ((C1~C5) alkyl) 4N + From the group consisting of , and two or more mixtures thereof, more preferably NH4 + , ((C1~C3)alkyl)NH3 + , ((C1~C3)alkyl)2NH2 + , ((C1~C3)alkyl)3NH + , ((C1~C3) alkyl) 4N + From the group consisting of , and two or more mixtures thereof, more preferably NH4 + , ((C2~C3)alkyl)NH3 + , ((C2~C3) alkyl)2NH2 + , ((C2~C3) alkyl)3NH + , ((C2~C3) alkyl) 4N + From the group consisting of , and two or more mixtures thereof, more preferably NH4 + (C2 alkyl)NH3 + (C2 alkyl)2NH2 + (C2 alkyl)3NH + (C2 alkyl) 4N + A selection from the group consisting of , and mixtures of two or more thereof, wherein the ammonium cation is substituted with one or more optional substitutions is more preferably NH4 + Preferably, it is one or more of the following: and tetraethylammonium.

[0041] One or more Fe sources are selected from the group consisting of Fe nitrate, Fe citrate, Fe ammonium citrate, Fe acetate, Fe sulfate, Fe ascorbate, and two or more mixtures thereof, more preferably from the group consisting of Fe(III) nitrate, Fe(III) citrate, Fe(III) ammonium citrate, Fe(III) acetate, Fe(III) sulfate, Fe(III) ascorbate, and two or more mixtures thereof, and it is preferable that one or more Fe sources are Fe(III) nitrate.

[0042] The mixture obtained in (i) preferably has a water-to-zeolite material weight ratio in the range of 4.0:1 to 10.0:1, more preferably in the range of 5.0:1 to 9.0:1, more preferably in the range of 6.0:1 to 8.0:1, and more preferably in the range of 6.5:1 to 7.5:1.

[0043] The pH of the mixture obtained in (i) is preferably in the range of 3.0 to 7.0, more preferably in the range of 3.5 to 6.5, more preferably in the range of 4.0 to 6.0, and more preferably in the range of 4.5 to 5.5.

[0044] The zeolite material contained in the mixture provided in (i) preferably has an AEI type, AFT type, AFX type, CHA type, FER type, or MFI type skeletal structure, more preferably a CHA type, FER type, or MFI type skeletal structure, more preferably a CHA type or FER type skeletal structure, and more preferably a FER type skeletal structure.

[0045] The ion exchange conditions preferably include heating the mixture obtained in (i) to a temperature in the range of 30 to 100°C, more preferably in the range of 35 to 80°C, more preferably in the range of 40 to 70°C, and more preferably in the range of 45 to 65°C.

[0046] The ion exchange conditions are preferably applied in (ii) for a duration of 0.1 to 48 hours, more preferably 0.5 to 25 hours, and more preferably 1 to 5 hours.

[0047] The ion exchange conditions preferably include stirring the mixture obtained in (i).

[0048] This process follows (ii), (s) Preferably further includes separating the catalyst material obtained in (ii) by filtration.

[0049] This process follows (ii), more preferably follows (s) as defined herein above. The catalyst material obtained in (w)(ii) is further washed with water, more preferably after (s), and the washing is carried out until the water has a conductivity of less than 200 μS.

[0050] This process follows (ii), more preferably after (s), more preferably after (w), (d) Preferably, the catalyst material obtained in (ii), (s), or (w) is further dried in a gas atmosphere having a temperature in the range of 70 to 135°C, more preferably in the range of 80 to 120°C, and more preferably in the range of 90 to 110°C.

[0051] This process follows (ii), more preferably after (s), more preferably after (w), more preferably after (d), (c) The catalyst material obtained in (ii), (s), (w), or (d) is further calcined in a gas atmosphere having a temperature in the range of 400 to 600°C, more preferably in the range of 420 to 500°C, more preferably in the range of 440 to 460°C, wherein the calcination is preferably carried out for a duration in the range of 0.5 to 24 hours, more preferably in the range of 1 to 5 hours.

[0052] If the process further includes (c), the gas atmosphere provided by (c) preferably includes one or more of nitrogen and oxygen, and more preferably includes air, and more preferably consists of air.

[0053] This process follows (ii), more preferably after (s), more preferably after (w), more preferably after (d), more preferably after (c), The method further comprises forming a mixture comprising a catalyst material obtained in (m)(ii), (s), (w), (d), or (c), and optionally a hydrated binder, the binder more preferably comprising one or more of Zr acetate, boehmite pseudo, alumina, silica-alumina, and mixtures of two or more thereof, the mixture preferably containing the binder calculated as an oxide in an amount in the range of 1 to 10% by weight, more preferably in the range of 4 to 6% by weight, based on the total weight of SiO2 and X2O3 contained in the skeletal structure of the zeolite material.

[0054] If this process further includes (m), then this process follows (m): It is preferable to further dry the mixture obtained by (md)(m) in a gas atmosphere having a temperature in the range of 500 to 650°C, more preferably in the range of 560 to 620°C, and more preferably in the range of 580 to 600°C.

[0055] Furthermore, if the process further includes (m), the process follows (m), more preferably after (md), The catalyst material obtained in (mc)(md) is further calcined in a gas atmosphere having a temperature in the range of 500 to 650°C, more preferably in the range of 560 to 620°C, and more preferably in the range of 580 to 600°C, wherein the calcination is preferably carried out for a duration in the range of 0.5 to 24 hours, and more preferably in the range of 1 to 5 hours.

[0056] If the process further includes (md) or (mc), then the gas atmosphere in one or more of (md) and (mc), more preferably one or more of nitrogen and oxygen, is preferably air, and more preferably consists of air.

[0057] Furthermore, if the process further includes (m), the process follows (m), more preferably after (md), more preferably after (mc), Preferably, the process further comprises grinding the mixture obtained by (mcr)(m), (md), or (mc), and this process is (msi) More preferably, the mixture obtained in (m), (md), (mc), or (mcr) is sieved into particles using a sieve having a mesh size in the range of 250 to 500 μm.

[0058] Furthermore, the present invention relates to catalyst materials obtained or obtainable by any one of the specific preferred embodiments disclosed herein.

[0059] Furthermore, the present invention relates to an exhaust gas treatment system comprising a component containing a catalyst material from any one of the specific preferred embodiments disclosed herein, an internal combustion engine, and an exhaust gas conduit in fluid communication with the internal combustion engine, wherein the component containing the catalyst material is located within the exhaust gas conduit.

[0060] The component containing the catalyst material preferably includes a substrate, and the catalyst material is preferably placed on the substrate.

[0061] The internal combustion engine is preferably a lean-burn engine or a lean gasoline direct injection (GDI) engine, more preferably a diesel engine, and more preferably a heavy-duty diesel engine.

[0062] The exhaust gas treatment system further comprises a diesel oxidation catalyst (DOC), and more preferably the diesel oxidation catalyst is located upstream of the components including the catalytic material.

[0063] The exhaust gas treatment system further comprises an optionally catalytic soot filter, which is preferably located upstream or downstream of the component containing the catalytic material.

[0064] The exhaust gas treatment system further comprises an ammonia oxidation catalyst (AMOX), and it is preferable that the ammonia oxidation catalyst (AMOX) is located upstream or downstream of the components containing the catalyst material.

[0065] Furthermore, independently of the above, according to the first alternative for the exhaust gas treatment system, it is preferable that the exhaust gas treatment system comprises, in a continuous order in the direction of the exhaust gas, an SCR component, an ammonia oxidation catalyst (AMOX), a diesel oxidation catalyst (DOC), a component containing a catalyst material, optionally a Cu-containing SCR component, and an ammonia oxidation catalyst (AMOX).

[0066] Furthermore, independently of the above, according to a second alternative for the exhaust gas treatment system, it is preferable that the exhaust gas treatment system comprises, in a continuous order in the direction of the exhaust gas, a component containing a catalytic material, an ammonia oxidation catalyst (AMOX), a diesel oxidation catalyst (DOC), optionally a Cu-containing SCR component, and an ammonia oxidation catalyst (AMOX).

[0067] Furthermore, independently of the above, according to a third alternative for the exhaust gas treatment system, it is preferable that the exhaust gas treatment system comprises, in a continuous order in the direction of the exhaust gas, a hydrocarbon injector, a diesel oxidation catalyst (DOC), a catalytic soot filter (CSF), a urea injector, components including catalytic material, and a composite selective catalytic reduction / ammonia oxidation catalyst.

[0068] Furthermore, independently of the above, according to a fourth alternative for the exhaust gas treatment system, it is preferable that the exhaust gas treatment system comprises, in a continuous order in the direction of the exhaust gas, a urea injector, a close-coupled selective catalytic reduction (cc-SCR), a hydrocarbon injector, a diesel oxidation catalyst (DOC), a catalytic soot filter (CSF), a urea injector, components including catalytic material, and a composite selective catalytic reduction / ammonia oxidation catalyst.

[0069] The exhaust gas treatment system further comprises a reducing agent injector, and the reducing agent injector is more preferably upstream of a component including a catalytic material. More preferably, the component is located between a diesel oxidation catalyst (DOC) and a component comprising the catalytic material defined herein for the first alternative for an exhaust gas treatment system, or between an internal combustion engine and a component comprising the catalytic material defined herein for the second alternative for an exhaust gas treatment system.

[0070] If the exhaust gas treatment system further includes a reducing agent injector, the reducing agent contains one or more of ammonia, hydrocarbons, and urea, and more preferably consists of these.

[0071] Furthermore, the present invention relates to a process for treating exhaust gas, preferably for the selective catalytic reduction of NOx contained in the exhaust gas, comprising contacting the exhaust gas flow with a catalytic material according to any one of the specific preferred embodiments disclosed herein.

[0072] Furthermore, the present invention relates to the use of a catalyst material or an exhaust gas treatment system according to any one of the specific preferred embodiments disclosed herein, for the treatment of exhaust gas containing NOx, preferably for selective catalytic reduction (SCR) of NOx contained in the exhaust gas.

[0073] The present invention is further illustrated by the following series of embodiments, as well as combinations of embodiments arising from dependencies and reverse references as shown. In particular, in each instance where the scope of an embodiment is referred to, for example, in the context of terms such as "the catalyst according to any one of Embodiments 1 to 4," all embodiments within this scope are intended to be expressly disclosed to those skilled in the art, i.e., the expression of this term will be understood by those skilled in the art to be synonymous with "the catalyst according to any one of Embodiments 1, 2, 3, and 4." Furthermore, it should be explicitly noted that the following series of embodiments represent a suitably structured portion of a description covering general preferred embodiments of the present invention, rather than a set of claims that determine the scope of protection. 1. A catalytic material for the selective catalytic reduction of NOx, It contains a zeolite material that includes SiO2 and X2O3 in its skeletal structure. X is a trivalent element, The zeolite material has an FER-type skeletal structure, Deconvolution of zeolite materials 29 The Si MAS NMR spectrum contains a first peak (P1) with a maximum value in the range of -103.5 to -108.5 ppm, and the integral of the first peak is area I1, and the integral of all peaks in the range of -90.0 to -130.0 ppm is area I total Therefore, the area of ​​the first peak I1 versus the area of ​​all peaks I total The ratio is 0.20:1 or greater, The catalyst material contains Fe, and the Fe is supported on a zeolite material. Deconvolution of zeolite materials 29 A catalyst material whose Si MAS NMR spectrum is preferably determined according to Reference Example 1. 2. Area of ​​the first peak I1 vs. Area of ​​all peaks in the range of -90.0 to -130.0 ppm I total The catalyst material according to Embodiment 1, wherein the ratio of is 0.23:1 or greater, preferably greater than 0.25:1. 3. Area of ​​the first peak I1 vs. Area of ​​all peaks in the range of -90.0 to -130.0 ppm I totalThe catalyst material according to Embodiment 1 or 2, wherein the ratio is in the range of 0.2:1 to 0.60:1, preferably in the range of 0.23:1 to 0.50:1, and more preferably in the range of 0.30:1 to 0.50:1. 4. The catalyst material according to any one of Embodiments 1 to 3, wherein the first peak (P1) has a maximum value in the range of -104.0 to -108.0 ppm, preferably in the range of -104.5 to -107.5 ppm, and more preferably in the range of -105.0 to -107.0 ppm. 5. Deconvolution of zeolite materials 29 The Si MAS NMR spectrum includes a second peak (P2) having a maximum value in the range of -97.5 to -102.5 ppm, preferably in the range of -99.0 to -101.0 ppm, and the integral of the second peak (P2) is preferably the area I2, and the area I2 of the second peak versus the area I of all peaks in the range of -90.0 to -130.0 ppm total The catalyst material according to any one of Embodiments 1 to 4, wherein the ratio is 0.05:1 or less, preferably 0.04:1 or less, and more preferably 0.03:1 or less. 6. Deconvolution of zeolite materials 29 The Si MAS NMR spectrum includes a third peak (P3) having a maximum value in the range of -108.6 to -112.5 ppm, preferably in the range of -110.0 to -112.0 ppm, and the integral of the third peak (P3) preferably equals area I3, and the area I3 of the third peak versus the area I of all peaks in the range of -90.0 to -130.0 ppm total The catalyst material according to any one of Embodiments 1 to 5, wherein the ratio is 0.55:1 or less, preferably 0.50:1 or less, and more preferably 0.45:1 or less. 7. Deconvolution of zeolite materials 29 The Si MAS NMR spectrum includes a fourth peak (P4) with a maximum value in the range of -112.6 to -116.5 ppm, preferably in the range of -113.0 to -115.0 ppm, and the integral of the fourth peak (P4) is preferably the area I4, and the area I4 of the fourth peak versus the area I of all peaks in the range of -90.0 to -130.0 ppm totalA catalyst material according to any one of Embodiments 1 to 6, wherein the ratio is 0.50:1 or less, preferably 0.45:1 or less, and more preferably 0.40:1 or less. 8. Deconvolution of zeolite materials 29 The Si MAS NMR spectrum includes a fifth peak (P5) with a maximum value in the range of -93.0 to -97.0 ppm, preferably in the range of -94.0 to -96.0 ppm, and the integral of the fifth peak (P5) is preferably the area I5, and the area I5 of the fifth peak versus the area I of all peaks in the range of -90.0 to -130.0 ppm total The catalyst material according to any one of Embodiments 1 to 7, wherein the ratio is 0.05:1 or less, preferably 0.3:1 or less, and more preferably 0.02:1 or less. 9. The catalyst material according to any one of Embodiments 1 to 8, wherein X is selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof, preferably selected from the group consisting of Al, B, and mixtures thereof, and X is more preferably Al. 10. The catalyst material according to any one of Embodiments 1 to 9, wherein the zeolite material has a molar ratio of SiO2 to X2O3 of 50 or less, preferably 40 or less, more preferably 30 or less, more preferably in the range of 1 to 30, more preferably in the range of 5 to 25, and more preferably in the range of 10 to 20. 11. A catalyst material according to any one of Embodiments 1 to 9, wherein X is Al, and the zeolite material has a molar ratio of SiO2 to Al2O3 of 50 or less, preferably 40 or less, more preferably 30 or less, more preferably in the range of 1 to 30, more preferably in the range of 5 to 25, and more preferably in the range of 10 to 20. 12.0.A catalyst material according to any one of Embodiments 1 to 11, having an atomic ratio of Al contained in the skeletal structure of a zeolite material calculated as an Fe pair element supported on a zeolite material calculated as an element in the range of 0.20:1 to 0.50:1, more preferably in the range of 0.20:1 to 0.45:1, more preferably in the range of 0.20:1 to 0.40:1, and more preferably in the range of 0.20:1 to 0.35:1. A catalyst material according to any one of Embodiments 1 to 11, comprising Fe calculated as Fe2O3 supported on a zeolite material, calculated as the sum of the weights of SiO2 and X2O3 contained by the skeletal structure of the zeolite material, in an amount of 13.2.5% by weight or more, more preferably in the range of 2.5 to 10.0% by weight, preferably in the range of 2.5 to 7.5% by weight, more preferably in the range of 4.0 to 6.5% by weight, more preferably in the range of 5.0 to 6.2% by weight, and more preferably in the range of 5.9 to 6.0% by weight, as the sum of the weights of SiO2 and X2O3 contained by the skeletal structure of the zeolite material. 14. A process for producing a catalyst material, preferably one of the embodiments 1 to 13, (i) To provide an aqueous mixture comprising a zeolite material, one or more Fe sources, and one or more optionally substituted ammonium cations, (ii) The mixture obtained in (i) is subjected to ion exchange conditions, Zeolite material contains SiO2 and X2O3 in its skeletal structure. X is a trivalent element The zeolite material has a maximum ring size of 10 or fewer T atoms. Deconvolution of zeolite materials 29 The Si MAS NMR spectrum includes a first peak (P1) with a maximum value in the range of -103.5 to -108.5 ppm, and the integral of the first peak is area I1, and all peaks in the range of -90.0 to -130.0 ppm are area I total Therefore, the area of ​​the first peak I1 versus the area of ​​all peaks I total The ratio is 0.20:1 or greater, and Fe is supported on the zeolite material. Deconvolution of zeolite materials 29 A process in which Si MAS NMR is preferably determined according to Reference Example 1. 15. Area of ​​the first peak I1 vs. Area of ​​all peaks in the range of -90.0 to -130.0 ppm I total The process according to Embodiment 14, wherein the ratio is 0.23:1 or greater, preferably greater than 0.25:1. 16. The ratio of the area I1 of the first peak to the area I of all peaks within the range of -90.0 to -130.0 ppm total is within the range of 0.2:1 to 0.60:1, preferably within the range of 0.23:1 to 0.50:1, more preferably within the range of 0.25:1 to 0.45:1, the process according to embodiment 14 or 15. 17. The first peak (P1) has a maximum value within the range of -104.0 to -108.0 ppm, preferably within the range of -104.5 to -107.0 ppm, more preferably within the range of -105.0 to -107.0 ppm, the process according to any one of embodiments 14 to 16. 18. The deconvoluted 29 Si MAS NMR of the zeolite material includes a second peak (P2) having a maximum value within the range of -97.5 to -102.5 ppm, preferably within the range of -99.0 to -101.0 ppm, the integration of the second peak (P2) preferably being area I2, and the ratio of the area I2 of the second peak to the area I of all peaks within the range of -90.0 to -130.0 ppm total is 0.05:1 or less, preferably 0.04:1 or less, more preferably 0.03:1 or less, the process according to any one of embodiments 14 to 17. 19. The deconvoluted 29 Si MAS NMR of the zeolite material includes a third peak (P3) having a maximum value within the range of -108.6 to -112.5 ppm, preferably within the range of -110.0 to -112.0 ppm, the integration of the third peak (P3) preferably being area I3, and the ratio of the area I3 of the third peak to the area I of all peaks within the range of -90.0 to -130.0 ppm total is 0.55:1 or less, preferably 0.50:1 or less, more preferably 0.45:1 or less, the process according to any one of embodiments 14 to 18. 20. The deconvoluted 29The Si MAS NMR includes a fourth peak (P4) having a maximum value within the range of -112.6 to -116.5 ppm, preferably within the range of -113.0 to -115.0 ppm. The integration of the fourth peak (P4) is preferably the area I4, and the ratio of the area I4 of the fourth peak to the area I of all peaks within the range of -90.0 to -130.0 ppm total is 0.50:1 or less, preferably 0.45:1 or less, more preferably 0.40:1 or less, the process according to any one of Embodiments 14 to 19. 21. The deconvolved 29 The Si MAS NMR includes a fifth peak (P5) having a maximum value within the range of -93.0 to -97.0 ppm, preferably within the range of -94.0 to -96.0 ppm. The integration of the fifth peak (P5) is preferably the area I5, and the ratio of the area I5 of the fifth peak to the area I of all peaks within the range of -90.0 to -130.0 ppm total is 0.05:1 or less, preferably 0.3:1 or less, more preferably 0.02:1 or less, the process according to any one of Embodiments 14 to 20. 22. X is selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof, preferably selected from the group consisting of Al, B, and mixtures thereof, and X is more preferably Al, the process according to any one of Embodiments 14 to 21. 23. The zeolite material has a molar ratio of SiO2 to X2O3 of 50 or less, preferably 40 or less, more preferably 30 or less, more preferably within the range of 1 to 30, more preferably within the range of 5 to 25, more preferably within the range of 10 to 20, the process according to any one of Embodiments 14 to 22. 24. One or more optionally substituted ammonium cations are NH4 + , ((C1 - C 10 ) alkyl)NH3 + , ((C1 - C 10 ) alkyl)2NH2 + , ((C1 - C 10 ) alkyl)3NH + , ((C1 - C 10 ) alkyl)4N+ From the group consisting of , and two or more mixtures thereof, preferably NH4 + , ((C1~C7)alkyl)NH3 + , ((C1~C7)alkyl)2NH2 + , ((C1~C7) alkyl)3NH + , ((C1~C7) alkyl) 4N + From the group consisting of , and two or more mixtures thereof, more preferably NH4 + , ((C1~C5)alkyl)NH3 + , ((C1~C5)alkyl)2NH2 + , ((C1~C5)alkyl)3NH + , ((C1~C5) alkyl) 4N + From the group consisting of , and two or more mixtures thereof, more preferably NH4 + , ((C1~C3)alkyl)NH3 + , ((C1~C3)alkyl)2NH2 + , ((C1~C3)alkyl)3NH + , ((C1~C3) alkyl) 4N + From the group consisting of , and two or more mixtures thereof, more preferably NH4 + , ((C2~C3)alkyl)NH3 + , ((C2~C3) alkyl)2NH2 + , ((C2~C3) alkyl)3NH + , ((C2~C3) alkyl) 4N + From the group consisting of , and two or more mixtures thereof, more preferably NH4 + (C2 alkyl)NH3 + (C2 alkyl)2NH2 + (C2 alkyl)3NH + (C2 alkyl) 4N + A selection from the group consisting of two or more mixtures thereof, wherein one or more optionally substituted ammonium cations are more preferably NH4 + The process according to any one of embodiments 14 to 23, wherein one or more of the following are present: and tetraethylammonium. 25. The process according to any one of Embodiments 14 to 24, wherein one or more Fe sources are selected from the group consisting of Fe nitrate, Fe citrate, Fe ammonium citrate, Fe acetate, Fe sulfate, Fe ascorbate, and two or more mixtures thereof, more preferably from the group consisting of Fe(III) nitrate, Fe(III) citrate, Fe(III) ammonium citrate, Fe(III) acetate, Fe(III) sulfate, Fe(III) ascorbate, and two or more mixtures thereof, and one or more Fe sources are more preferably Fe(III) nitrate. The process according to any one of Embodiments 14 to 25, wherein the mixture obtained in 26.(i) has a water-to-zeolite material weight ratio in the range of 4.0:1 to 10.0:1, preferably in the range of 5.0:1 to 9.0:1, more preferably in the range of 6.0:1 to 8.0:1, and more preferably in the range of 6.5:1 to 7.5:1. The process according to any one of Embodiments 14 to 26, preferably Embodiment 26, wherein the pH of the mixture obtained in 27.(i) is in the range of 3.0 to 7.0, preferably in the range of 3.5 to 6.5, more preferably in the range of 4.0 to 6.0, and more preferably in the range of 4.5 to 5.5. The process according to any one of Embodiments 14 to 27, wherein the zeolite material contained in the mixture provided in 28.(i) has an AEI type, AFT type, AFX type, CHA type, FER type, or MFI type skeletal structure, preferably a CHA type, FER type, or MFI type skeletal structure, more preferably a CHA type or FER type skeletal structure, and more preferably a FER type skeletal structure. 29. The process according to any one of Embodiments 14 to 28, wherein the ion exchange conditions include heating the mixture obtained in (i) to a temperature in the range of 30 to 100°C, preferably in the range of 35 to 80°C, more preferably in the range of 40 to 70°C, and more preferably in the range of 45 to 65°C. 30. The process according to any one of Embodiments 14 to 29, wherein the ion exchange conditions are applied in (ii) for a duration of 0.1 to 48 hours, preferably 0.5 to 25 hours, and more preferably 1 to 5 hours. 31. The process according to any one of Embodiments 14 to 30, wherein the ion exchange conditions include stirring the mixture obtained in (i). 32. After (ii), (s) The process according to any one of embodiments 14 to 31, further comprising separating the catalyst material obtained in (ii) preferably by filtration. 33. After (ii), preferably after (s) as defined in Embodiment 32, The process according to any one of Embodiments 14 to 32, further comprising washing the catalyst material obtained in (w)(ii) with water, preferably after (s), the washing being carried out until the water has a conductivity of less than 200 μS. 34. After (ii), preferably after (s), more preferably after (w), The process according to any one of Embodiments 14 to 33, further comprising drying the catalyst material obtained in (d)(ii), (s), or (w) in a gas atmosphere having a temperature in the range of 70 to 135°C, more preferably in the range of 80 to 120°C, and more preferably in the range of 90 to 110°C. 35. After (ii), preferably after (s), more preferably after (w), more preferably after (d), The process according to any one of Embodiments 14 to 34, further comprising calcining the catalyst material obtained in (c)(ii), (s), (w), or (d) in a gas atmosphere having a temperature in the range of 400 to 600°C, preferably in the range of 420 to 500°C, more preferably in the range of 440 to 460°C, wherein the calcination is carried out for a duration of more preferably in the range of 0.5 to 24 hours, preferably in the range of 1 to 5 hours. 36. The process according to Embodiment 34 or 35, wherein the gas atmosphere comprises one or more nitrogen and oxygen, and more preferably comprises air. 37. After (ii), preferably after (s), more preferably after (w), more preferably after (d), more preferably after (c), The process according to any one of Embodiments 14 to 36, further comprising forming a mixture comprising a catalyst material obtained in (m)(ii), (s), (w), (d), or (c), and optionally a hydrated binder, wherein the binder preferably comprises one or more of Zr acetate, boehmite pseudo, alumina, silica-alumina, and mixtures of two or more thereof, and the mixture comprises the binder calculated as an oxide in an amount in the range of 1 to 10% by weight, preferably in the range of 4 to 6% by weight, based on the total weight of SiO2 and X2O3 contained in the skeletal structure of the zeolite material. 38. After (m), The process according to Embodiment 37, further comprising drying the mixture obtained by (md)(m) in a gas atmosphere having a temperature in the range of 500 to 650°C, preferably in the range of 560 to 620°C, more preferably in the range of 580 to 600°C. 39. After (m), preferably after (md), The process according to Embodiment 37 or 38, further comprising calcining the catalyst material obtained by (mc)(m) in a gas atmosphere having a temperature in the range of 500 to 650°C, preferably in the range of 560 to 620°C, more preferably in the range of 580 to 600°C, wherein the calcination is carried out for a duration of more preferably in the range of 0.5 to 24 hours, preferably in the range of 1 to 5 hours. 40. The process according to Embodiment 38 or 39, wherein the gas atmosphere comprises one or more nitrogen and oxygen, and more preferably comprises air. 41. After (m), preferably after (md), more preferably after (mc), The process further includes grinding the mixture obtained by (mcr)(m), (md), or (mc), preferably, The process according to any one of Embodiments 37 to 40, further comprising sieving the mixture obtained in (m), (md), (mc), or (mcr) into particles using a sieve preferably having a mesh in the range of 250 to 500 μm. 42. A catalyst material obtained or obtainable by the process described in any one of Embodiments 14 to 41. 43. An exhaust gas treatment system comprising a component containing a catalyst material as described in any one of embodiments 1 to 13 and 42, an internal combustion engine, and an exhaust gas conduit in fluid communication with the internal combustion engine, wherein the component containing the catalyst material is located inside the exhaust gas conduit. 44. An exhaust gas treatment system according to Embodiment 43, wherein a component comprising a catalyst material as described in any one of Embodiments 1 to 13 and 42 includes a substrate, and the catalyst material is disposed on the substrate. 45. The exhaust gas treatment system according to embodiment 43 or 44, wherein the internal combustion engine is a lean-burn engine or a lean gasoline direct injection (GDI) engine, more preferably a diesel engine, and more preferably a heavy-duty diesel engine. 46. ​​An exhaust gas treatment system according to any one of embodiments 43 to 45, further comprising a diesel oxidation catalyst (DOC), wherein the diesel oxidation catalyst is preferably located upstream of a component comprising the catalyst material described in any one of embodiments 1 to 13 and 42. 47. An exhaust gas treatment system according to any one of embodiments 43 to 46, further comprising an optionally catalyzed soot filter, wherein the optionally catalyzed soot filter is located upstream or downstream of a component comprising a catalyst material according to any one of embodiments 1 to 13 and 42. 48. An exhaust gas treatment system according to any one of embodiments 43 to 47, further comprising an ammonia oxidation catalyst (AMOX), wherein the ammonia oxidation catalyst (AMOX) is located upstream or downstream of a component comprising a catalyst material according to any one of embodiments 1 to 13 and 42. 49. An exhaust gas treatment system according to any one of embodiments 43 to 45, comprising, in a continuous order in the direction of the exhaust gas, an SCR component, an ammonia oxidation catalyst (AMOX), a diesel oxidation catalyst (DOC), a component containing the catalyst material described in any one of embodiments 1 to 13 and 42, an optionally selected Cu-containing SCR component, and an ammonia oxidation catalyst (AMOX). 50. An exhaust gas treatment system according to any one of embodiments 43 to 45, comprising, in a continuous order in the direction of exhaust gas, a component containing a catalytic material according to any one of embodiments 1 to 13 and 42, an ammonia oxidation catalyst (AMOX), a diesel oxidation catalyst (DOC), optionally a Cu-containing SCR component, and an ammonia oxidation catalyst (AMOX). 51. An exhaust gas treatment system according to any one of embodiments 43 to 45, comprising, in a continuous order in the direction of the exhaust gas, a hydrocarbon injector, a diesel oxidation catalyst (DOC), a catalytic soot filter (CSF), a urea injector, a component comprising a catalytic material as described in any one of embodiments 1 to 13 and 42, and a composite selective catalytic reduction / ammonia oxidation catalyst. 52. An exhaust gas treatment system according to any one of embodiments 43 to 45, comprising, in a continuous order in the direction of the exhaust gas, a urea injector, a close-coupled selective catalytic reduction (cc-SCR), a hydrocarbon injector, a diesel oxidation catalyst (DOC), a catalytic soot filter (CSF), a urea injector, a component containing the catalytic material described in any one of embodiments 1 to 13 and 42, and a composite selective catalytic reduction / ammonia oxidation catalyst. 53. Further comprising a reducing agent injector, wherein the reducing agent injector is preferably upstream of a component containing the catalyst material described in any one of embodiments 1 to 13 and 42. An exhaust gas treatment system according to any one of embodiments 43 to 52, preferably located between a diesel oxidation catalyst (DOC) and a component comprising a catalytic material as defined in any one of embodiments 1 to 13 and 42 as defined in embodiment 49, or between an internal combustion engine and a component comprising a catalytic material as defined in any one of embodiments 1 to 13 and 42 as defined in embodiment 50. 54. The exhaust gas treatment system according to Embodiment 53, wherein the reducing agent comprises one or more of ammonia, hydrocarbons, and urea, more preferably consisting of these. 55. A process for the treatment of exhaust gas, preferably for the selective catalytic reduction of NOx contained in the exhaust gas, comprising contacting an exhaust gas flow with a catalytic material described in any one of embodiments 1 to 13 and 42. 56. For the treatment of exhaust gas containing NOx, preferably use of a catalyst material according to any one of embodiments 1 to 13 and 42 for selective catalytic reduction (SCR) of NOx contained in the exhaust gas, or an exhaust gas treatment system according to any one of embodiments 43 to 54.

[0074] The present invention is further illustrated by the following reference examples and comparative examples. [Examples]

[0075] Reference example 1: 29 Si MAS NMR 29 Si MAS NMR measurements were performed on a Varian Unity Inova 400 MHz spectrometer using a 7.5 mm rotor rotated at 3.5 kHz. Spectra were acquired using 128 scans with a 90-second recycle delay and 6.5 μs pi / 2 pulses. Prior to measurement, the samples were hydrated for at least 48 hours in a container with a saturated solution of ammonium chloride to maintain a relative humidity of >80%. Spectra were fitted and peaks deconvoluted using ACD Labs Spectrus software, employing a mixed Gaussian / Lorentz function and peak position variability of <100 Hz. Expected peak assignments are Q4(0Al) at -114 ppm and -111 ppm, Q4(1Al) at -106 ppm, and a potential overlap of Q3(0Al) and Q4(2Al) at -99 ppm.

[0076] Examples 1-8: Preparation of catalyst materials Four FER zeolite samples were obtained as powders from Zeolyst and Tosoh. These samples were loaded with Fe (atomic ratio Fe / Al = 0.25 or 0.40), aged, and then evaluated for SCR.

[0077] For impregnation, zeolite was loaded with a solution of nitric acid (Fe) using initial wet impregnation. The mixture was stored in an oven at 50°C for 20 hours. The obtained material was then dried and calcined at 450°C for 5 hours. A slurry was prepared from the obtained impregnated zeolite, and Zr acetate was added (5% by weight based on the zeolite). The resulting mixture was dried with stirring and then calcined at 550°C for 1 hour. The obtained material was pulverized and sieved (250-500 μm). A summary of the characteristics of the prepared catalyst material is given in Table 1 below.

[0078] [Table 1]

[0079] For the FER zeolite used in Examples 7 and 8, five peaks were observed in the range of -90.0 to -130.0 ppm. Details of these peaks are shown in Table 2 below. In particular, two individual peaks in the range of -93.0 to -101.0 ppm were observed. 29 Regarding Si MAS NMR, observations were made for the Q3(0Al) and Q4(2Al) sites according to the expected peak assignments detailed in Reference Example 1 above.

[0080] [Table 2]

[0081] Examples 9-12: Preparation of catalyst materials Four H-form FER zeolites (with silica-to-alumina ratios of 15.7, 17.5, 19.7, and 13.3 for Examples 9, 10, 11, and 12, respectively) were obtained from China Catalyst Holding Co., Ltd. These materials were loaded with Fe (5.9–6.0 wt% Fe2O3).

[0082] The FER zeolite materials of Examples 9-11 were subjected to ion exchange with Fe before the exchange. 29The H-forms of these zeolites were analyzed by Si MAS NMR. For this purpose, the FER zeolites were hydrated for 48 hours. The results are shown in Table 3 and Figures 1-3. For each FER zeolite, four peaks were observed in the range of -90.0 to -130.0 ppm.

[0083] Peaks within the range of -103.5 to -108.5 ppm can be attributed to the Q4(1Al) moiety in the FER zeolite. In relation to the results of the SCR test shown in Figure 6, it can be seen that catalyst materials containing FER zeolite with a relatively high content of the Q4(1Al) moiety exhibit relatively good SCR performance.

[0084] [Table 3]

[0085] For impregnation, zeolite was loaded with a nitric acid Fe solution using initial wet impregnation. The mixture was stored in an oven at 50°C for 20 hours. The obtained material was then dried and subsequently calcined at 450°C for 5 hours. A slurry was prepared from the obtained impregnated zeolite and Zr acetate was added (5 wt%) based on the zeolite. The resulting mixture was dried with stirring and then calcined at 550°C for 1 hour. The obtained material was crushed and sieved (250-500 μm). Each FER zeolite was loaded with 5.9-6.0 wt% Fe, calculated as Fe2O3, and based on the total weight of SiO2 and Al2O3 contained in the skeletal structure of the FER zeolite. 29 Regarding the determination of the Si MAS NMR spectrum, as described in Reference Example 1, peaks in the range of -103.5.0 to -108.5.0 ppm indicate the presence of the Q4(1Al) site. The present invention particularly includes zeolite materials having a specific Al distribution, and therefore particularly deconvoluted 29The patent claims are for a catalytic material that exhibits a first peak (P1) with a maximum value within the range in Si MAS NMR, while further having a specific integral ratio of the integral of all peaks in the range of -90.0 to -130.0 ppm relative to the first peak. In this regard, it should be noted that, as can be interpreted from the results shown in Tables 2 and 3, the peak integrals do not correlate with the silica-to-alumina ratio, so as to explain the specific Al distribution in the zeolite framework, which is independent of their respective silica-to-alumina ratios.

[0086] Example 13: Catalyst Test Prepared catalyst materials containing Fe-FER zeolite were tested for their SCR performance after being aged in a fresh state (as prepared) at 650°C for 50 hours in air containing 10% vapor, and after being aged at 820°C for 16 hours in air containing 10% vapor.

[0087] The following test conditions were applied. 80000h -1 A standard SCR feed having a gas hourly space velocity (GHSV) and containing 500 ppm NO, 500 ppm NH3, 5% H2O, 10% O2, and the remainder N2.

[0088] 80000h -1 A high-speed SCR feed having a gas space-time velocity (GHSV) and containing 250 ppm NO, 250 ppm NO2, 500 ppm NH3, 5% H2O, 10% O2, and the remainder N2. • First run for degreeing (standard SCR feed): T=200, 400, 575°C ·Standard SCR execution: T=175, 200, 225, 250, 350, 450, 550, 575℃ ·High-speed SCR execution: T=575, 550, 450, 350, 250, 225, 200, 175℃

[0089] The data obtained as a result of testing the aged catalyst materials according to Examples 1 to 8 are shown in Figures 4 and 5. As can be inferred from the results, the catalyst material according to the present invention showed very good SCR performance after aging at 650°C for 50 hours in air containing 10% vapor, and good performance after aging at 820°C for 16 hours in air containing 10% vapor.

[0090] The standard SCR performance of the catalyst materials from Examples 9-11 was measured after aging at 650°C / 50 hours and 820°C / 16 hours. The performance data shown in Figure 6 demonstrates that the catalyst material containing FER zeolite with an SAR of 15.7 exhibits the highest SCR activity compared to the remaining samples.

[0091] Example 14: Comparative catalyst test Two types of Fe-zeolites, namely Fe-CHA and Fe-BEA, are currently in common use. It is widely known that incorporating Fe into the pores of CHA zeolites is difficult. Activation by vapor or a reducing atmosphere is required to incorporate Fe into the pores of CHA zeolites, which significantly increases the cost of the final Fe-zeolite catalyst. BEA has the advantage of not requiring the activation step necessary to incorporate Fe and produce an active catalyst, however, it is known that BEA can be deactivated by hydrocarbons present in the gas feed. As a result, Fe-CHA is used in applications requiring hydrocarbon resistance instead of Fe-BEA. In contrast, FER zeolites offer the advantage of not requiring vapor activation and simultaneously exhibit hydrocarbon resistance. This is all the more surprising because FER zeolites belong to the group of medium-pore zeolites, particularly those containing pores with 10-membered rings, which are typically considered not to exhibit as much steric hindrance as observed in small-pore zeolites.

[0092] In addition, FER zeolite also exhibits resistance to humidity treatment.

[0093] Comparative catalyst tests were conducted, testing state-of-the-art Fe-BEA, state-of-the-art Fe-CHA, and catalyst materials from Examples 2 and 7 in a fresh state and after aging at 650°C for 50 hours in air containing 10% vapor.

[0094] The results of the catalyst test are shown in Figure 7. As can be inferred from the results, the catalyst material according to the present invention exhibits very good performance, especially at low temperatures. At high temperatures, the catalyst material, especially in a fresh state, exhibits very good performance.

[0095] Example 15: Preparation of a catalyst article containing Fe / FER (SAR=18, Fe2O3%=5.4%). A slurry was formed by mixing 89.9 parts by weight of FER in ammonia form, 5.1 parts by weight of iron nitrate calculated as Fe2O3, and 5.0 parts by weight of zirconium acetate calculated as ZrO2 in deionized water. The pH of the slurry was adjusted to 3.3 with TEAOH solution. The slurry was ground to a D90 particle size of 4 μm to 10 μm as measured by a Sympatec particle size analyzer. The slurry was coated onto a flow-through cordierite monolith substrate having a cell density of 600 cpsi and a wall thickness of 3 mils, followed by drying at 130°C and calcination at 590°C. The wash coat loading was 2.5 g / in. 3 That was the case.

[0096] Example 16: Preparation of a catalyst article containing Fe / FER (SAR=18, Fe2O3%=2.5%). A slurry was formed by mixing 92.6 parts by weight of FER in ammonia form, 2.4 parts by weight of iron nitrate calculated as Fe2O3, and 5.0 parts by weight of zirconium acetate calculated as ZrO2 in deionized water. The pH of the slurry was adjusted to 3.3 with a TEAOH solution. The slurry was ground to a D90 particle size of 4 μm to 10 μm as measured by a Sympatec particle size analyzer. The slurry was coated onto a flow-through cordierite monolith substrate having a cell density of 600 cpsi and a wall thickness of 3 mils, followed by drying at 130°C and calcination at 590°C. The wash coat loading was 2.5 g / in.3 That was the case.

[0097] Example 17: Preparation of a catalyst article containing Fe / FER (SAR=17, Fe2O3%=5.4%). A slurry was formed by mixing 89.9 parts by weight of FER in ammonia form, 5.1 parts by weight of iron nitrate calculated as Fe2O3, and 5.0 parts by weight of zirconium acetate calculated as ZrO2 in deionized water. The pH of the slurry was adjusted to 3.3 with NH4OH solution. The slurry was ground to a D90 particle size of 4 μm to 10 μm as measured by a Sympatec particle size analyzer. The slurry was coated onto a flow-through cordierite monolith substrate having a cell density of 600 cpsi and a wall thickness of 3 mils, followed by drying at 130°C and calcination at 590°C. The wash coat loading was 3.0 g / in. 3 That was the case.

[0098] Example 18: Preparation of a catalyst article containing Fe / FER (SAR=17, Fe2O3%=5.4%). A slurry was formed by mixing 89.9 parts by weight of FER in ammonia form, 5.1 parts by weight of iron nitrate calculated as Fe2O3, and 5.0 parts by weight of zirconium acetate calculated as ZrO2 in deionized water. The slurry was ground to a D90 particle size of 4 μm to 10 μm as measured by a Sympatec particle size analyzer. The slurry was coated onto a flow-through cordierite monolith substrate having a cell density of 600 cpsi and a wall thickness of 3 mils, followed by drying at 130°C and calcination at 590°C. The wash coat loading was 2.5 g / in. 3 That was the case.

[0099] Example 19: Preparation of a catalyst article containing Fe / FER (SAR=17, Fe2O3%=5.4%). A slurry was formed by mixing 89.9 parts by weight of FER in ammonia form, 5.1 parts by weight of iron(II) ascorbate solution calculated as Fe2O3, and 5.0 parts by weight of zirconium acetate calculated as ZrO2 in deionized water. The slurry was ground to a D90 particle size of 4 μm to 10 μm as measured by a Sympatec particle size analyzer. The slurry was coated onto a flow-through cordierite monolith substrate having a cell density of 600 cpsi and a wall thickness of 3 mils, followed by drying at 130°C and calcination at 590°C. The wash coat loading was 2.5 g / in. 3 That was the case.

[0100] Example 20: Preparation of a catalyst article containing Fe / FER (SAR=16, Fe2O3%=5.4%). A slurry was formed by mixing 89.9 parts by weight of hydrogen-based FER, 5.1 parts by weight of iron nitrate calculated as Fe2O3, and 5.0 parts by weight of zirconium acetate calculated as ZrO2 in deionized water. The pH of the slurry was adjusted to 3.3 with a TEAOH solution. The slurry was ground to a D90 particle size of 4 μm to 10 μm as measured by a Sympatec particle size analyzer. The slurry was coated onto a flow-through cordierite monolith substrate having a cell density of 600 cpsi and a wall thickness of 3 mils, followed by drying at 130°C and calcination at 590°C. The wash coat loading was 2.5 g / in. 3 That was the case.

[0101] Example 21: Preparation of a catalyst article containing Fe / FER (SAR=17, Fe2O3%=5.5%). 82 parts by weight of deionized water is combined with 12.8 parts by weight of ammonium form FER zeolite and 5.2 parts by weight of ferric nitrate solution (a 9.5% by weight aqueous solution calculated as Fe2O3). This solution is heated to 60°C with stirring, and then the pH is adjusted to 5.0–5.15 by using tetraethylammonium hydroxide (a 35% by weight aqueous solution) as a base. After pH adjustment, the solution is stirred at 60°C for 1 hour before stopping heating. The cooled solution is filtered and washed with deionized water until the conductivity of the filtrate is less than 200. The filter cake is then dried overnight at 90°C to obtain Fe / FER containing 5.5% Fe2O3.

[0102] A slurry was formed by mixing 95 parts by weight of Fe / FER containing 5.5% Fe2O3 and 5.0 parts by weight of zirconium acetate (calculated as ZrO2) in deionized water. The slurry was ground to a D90 particle size of 4 μm to 10 μm as measured by a Sympatec particle size analyzer. The slurry was coated onto a flow-through cordierite monolith substrate having a cell density of 600 cpsi and a wall thickness of 3 mils, followed by drying at 130°C and firing at 590°C. The wash coat loading was 2.5 g / in. 3 That was the case.

[0103] Example 22: Catalyst Test 60,000h -1 NOx conversion and N2O formation were tested using a fluid reactor under pseudo-steady-state conditions with a space velocity of 1000 ppmv NOx (NO2 / NOx ratio 0.5), 1050 ppmv NH3, 10 vol% O2, 7 vol% H2O, 8 vol% CO2, and the remainder N2. The SCR catalyst was aged in hot water at 650°C for 100 hours in 10% O2, 10% H2O, and the remainder N2, or degreeed at 550°C for 4 hours in 10% O2, 10% H2O, and the remainder N2. Examples 15-21 of the entire invention show improved NOx conversion compared to state-of-the-art Fe / CHA SCR, as shown in Figures 8-11.

[0104] Figure 12 shows that the SCR catalyst of the present invention maintains high NOx conversion at low temperatures such as 200°C over extended test times. In contrast, the low-temperature NOx conversion of state-of-the-art Fe / CHA decreases with increasing test time, likely due to the formation of NH4NO3, which partially blocks the active site.

[0105] The SCR catalyst of the present invention according to Example 17 was tested for its HC resistance after aging. The test conditions were as follows: 200 ppm NO, ammonia / NOx ratio of 1.05, 1000 ppm HC (C1 basis, 2:1 C3H6:C3H8), 10% O2, 7% H2O, 80 k / h SV, 300°C. The results are shown in Figure 13.

[0106] As can be inferred from the catalyst test results, the deconvolution of the zeolite material 29 The catalyst material according to the present invention is particularly characterized by exhibiting a first peak (P1) in Si MAS NMR with a maximum value in the range of -103.5 to -108.5 ppm, wherein the integral of the first peak is equal to the area I of all peaks. total The catalyst material, which has a specific area I1, achieves particularly favorable SCR activity after hydrothermal aging. [Brief explanation of the drawing]

[0107] [Figure 1] The deconvoluted 29Si MAS NMR spectrum of the zeolite material (SAR=19.7) used in the preparation of the catalyst material according to Example 11 is shown. The x-axis shift is described in ppm. [Figure 2] The deconvoluted 29Si MAS NMR spectrum of the zeolite material (SAR=15.7) used in the preparation of the catalyst material according to Example 9 is shown. The x-axis coordinate is described by a shift in ppm. [Figure 3]The deconvoluted 29Si MAS NMR spectrum of the zeolite material (SAR=17.5) used in the preparation of the catalyst material according to Example 10 is shown. The x-axis coordinate is described by a shift in ppm. [Figure 4] The results of catalyst testing of aged catalyst materials according to Examples 1-8 are shown. The horizontal axis represents temperature in °C, and the vertical axis represents NOx conversion in %. [Figure 5] The results of catalyst testing of aged catalyst materials according to Examples 1-8 are shown. The horizontal axis represents temperature in °C, and the vertical axis represents NOx conversion in %. [Figure 6] The standard SCR performance of the catalyst materials in Examples 9-12 after aging is shown. The horizontal axis represents temperature in °C, and the vertical axis represents NOx conversion in %. [Figure 7] The results of comparative catalyst tests of the catalyst materials in their fresh state, as well as the latest state Fe-BEA, the latest state Fe-CHA, and the catalyst materials according to Examples 2 and 7 after aging are shown. The horizontal axis represents temperature in °C, and the vertical axis represents NOx conversion in %. [Figure 8] The catalyst materials used in Examples 15, 17, 19-20, and the results of catalyst testing of state-of-the-art Fe-CHA are shown. The x-coordinate represents temperature in °C, and the y-coordinate represents NOx conversion in %. [Figure 9] The catalyst materials used in Examples 15, 17, 19-20, and the results of the most advanced Fe-CHA catalyst tests are shown. The horizontal axis represents temperature in °C, and the vertical axis represents N2O formation in ppm. [Figure 10] The catalyst materials used in Examples 18 and 21, and the results of catalyst testing of state-of-the-art Fe-CHA are shown. The x-coordinate represents temperature in °C, and the y-coordinate represents NOx conversion in %. [Figure 11] The catalyst materials used in Examples 18 and 21, and the results of the catalyst testing of state-of-the-art Fe-CHA are shown. The horizontal axis represents temperature in °C, and the vertical axis represents N2O formation in ppm. [Figure 12]The outlet NOx concentrations in catalyst tests at 200°C for the catalyst material and the cutting-edge Fe-CHA according to Example 15 are shown. The x-coordinate represents time in seconds, and the y-coordinate represents NOx concentration in ppm. [Figure 13] The results of the hydrocarbon resistance test of the catalyst material according to Example 17 after aging are shown. The horizontal axis represents time in seconds, and the vertical axis represents hydrocarbon concentration in ppm. [Figure 14] Two exemplary exhaust gas treatment systems are shown, both of which include, in a continuous order in the direction of the exhaust gas flow, a hydrocarbon injector, a diesel oxidation catalyst (DOC), a catalytic soot filter (CSF), a urea injector, a component comprising the catalytic material according to the present invention (SCR1), and a composite selective catalytic reduction / ammonia oxidation catalyst. The exemplary system in the lower part further includes a close-coupled selective catalytic reduction (cc-SCR) catalyst upstream of the hydrocarbon injector.

[0108] References: - International Publication No. 2020 / 021054(A1) - International Publication No. 2021 / 198339(A1) - International Publication No. 2015 / 128668(A1) - European Patent Application Publication No. 2857084(A1) -German Patent Application Publication No. 102011012799(A1) - European Patent Application Publication No. 2409760(A1) - International Publication No. 2008 / 049557(A1) - U.S. Patent No. 5041272(A) - U.S. Patent Application Publication No. 2011 / 056187(A1) -P. Sarv et al., "Multinuclear MQMAS NMR Study of NH4 / Na-Ferrierites", J. Phys. Chem. B 1998, 102, 1372-1378

Claims

1. A catalytic material for the selective catalytic reduction of NOx, In its skeletal structure is SiO ２ and X ２ O ３ Contains zeolite material including X is a trivalent element, The zeolite material has a FER-type skeletal structure, The deconvolution of the zeolite material ２９ The Si MAS NMR spectrum includes a first peak (P1) having a maximum value in the range of -103.5 to -108.5 ppm, and the integral of the first peak is over area I １ Therefore, the integral of all peaks in the range of -90.0 to -130.0 ppm is the area I ｔｏｔａｌ Therefore, the area I of the first peak １ The area I of all peaks ｔｏｔａｌ The ratio is 0.20:1 or greater, A catalyst material wherein the catalyst material contains Fe, and the Fe is supported on the zeolite material.

2. The deconvolved of the zeolite material ２９ The catalyst material according to claim 1, wherein the Si MAS NMR comprises a second peak (P2) having a maximum value within the range of -97.5 to -102.5 ppm.

3. The deconvolution of the zeolite material ２９ The catalyst material according to claim 1 or 2, wherein the Si MAS NMR includes a third peak (P3) having a maximum value in the range of -108.6 to -112.5 ppm.

4. The deconvolution of the zeolite material ２９ The catalyst material according to any one of claims 1 to 3, wherein the Si MAS NMR includes a fourth peak (P4) having a maximum value in the range of -112.6 to -116.5 ppm.

5. The deconvolution of the zeolite material ２９ The catalyst material according to any one of claims 1 to 4, wherein the Si MAS NMR includes a fifth peak (P5) having a maximum value in the range of -93.0 to -97.0 ppm.

6. The catalyst material according to any one of claims 1 to 5, wherein X is selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof.

7. The zeolite material has 50 or less SiO ２ vs X ２ O ３ A catalyst material according to any one of claims 1 to 6, having the molar ratio of .

8. A catalyst material according to any one of claims 1 to 7, having an atomic ratio of Al included in the skeletal structure of the zeolite material, calculated as an element in a ratio of 0.20:1 or greater, supported on the zeolite material.

9. 4.0 to 6.5% by weight of SiO contained in the skeletal structure of the zeolite material ２ and X ２ O ３ The Fe supported on the zeolite material is calculated as the total weight of the Fe ２ O ３ A catalyst material according to any one of claims 1 to 8, comprising Fe calculated as such.

10. A process for producing a catalyst material, preferably according to any one of claims 1 to 9, (i) To provide an aqueous mixture comprising a zeolite material, one or more Fe sources, and one or more optionally substituted ammonium cations, (ii) The mixture obtained in (i) is subjected to ion exchange conditions, The zeolite material has SiO in its skeletal structure. ２ and X ２ O ３ Includes, X is a trivalent element, The zeolite material has a maximum ring size of 10 or fewer T atoms, The deconvolution of the zeolite material ２９ The Si MAS NMR spectrum includes a first peak (P1) having a maximum value in the range of -103.5 to -108.5 ppm, and the integral of the first peak is over area I １ As a result, all peaks within the range of -90.0 to -130.0 ppm have an area of ​​I ｔｏｔａｌ Therefore, the area I of the first peak １ The area I of all peaks ｔｏｔａｌ A process in which the ratio of is 0.20:1 or greater, and Fe is supported on the zeolite material.

11. The ammonium cations that are optionally substituted with one or more of the above-mentioned NH ４ ＋ , ((C １ ~C １０ )alkyl)NH ３ ＋ , ((C １ ~C １０ )alkyl) ２ NH ２ ＋ , ((C １ ~C １０ )alkyl) ３ NH ＋ , ((C １ ~C １０ )alkyl) ４ N ＋ The process according to claim 10, selected from the group consisting of, and two or more mixtures thereof.

12. A catalyst material obtained or obtainable by the process described in claim 10 or 11.

13. An exhaust gas treatment system comprising a component containing a catalytic material according to any one of claims 1 to 9 and 12, an internal combustion engine, and an exhaust gas conduit in fluid communication with the internal combustion engine, wherein the component containing the catalytic material is located inside the exhaust gas conduit.

14. A process for treating exhaust gas, comprising contacting the exhaust gas flow with a catalyst material according to any one of claims 1 to 9 and 12.

15. Use of a catalyst material according to any one of claims 1 to 9 and 12 or an exhaust gas treatment system according to claim 14 for treating exhaust gas containing NOx.

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