Rare earth-containing zeolite material having AEI framework type and coated monolith substrate

Abstract

A rare earth element-containing zeolite material having an AEI-type framework structure, wherein the framework structure of the zeolite material comprises SiO2 and X2O3, where X is a trivalent element, and the zeolite material comprises one or more rare earth elements as counterions at ion exchange sites in the framework structure, and the zeolite material is obtainable and / or has been obtained by a method of hydrothermal treating the rare earth element-containing zeolite material at a temperature in the range of 400°C to 1,000°C. A coated monolith substrate comprising a rare earth element-containing zeolite material having an AEI-type framework structure, wherein the zeolite material is supported on the monolith substrate. A method for producing a coated monolith substrate comprising a rare earth element-containing zeolite material having an AEI-type framework structure.

Description

[Technical field]

[0001] The present invention relates to a rare earth element-containing zeolite material having an AEI type framework structure, and the zeolite material is obtained by subjecting the rare earth element-containing zeolite material to hydrothermal treatment at a temperature in the range of 400 to 1,000°C. Including The present invention further relates to a coated monolith substrate comprising a rare earth-containing zeolitic material having an AEI-type framework structure, wherein the zeolitic material is deposited on the monolith substrate. Support The present invention further relates to a method for producing a coated monolith substrate comprising a rare earth-containing zeolite material having an AEI-type framework structure. [Background technology]

[0002] NH3-SCR is the most effective technology for NOx reduction in exhaust aftertreatment of lean-burn engines. In this regard, Cu-SSZ-13 has been commercialized as an NH3-SCR catalyst due to its significant advantages of excellent catalytic performance and hydrothermal stability. However, with increasingly stringent regulations on engine emissions, it is highly desirable to further enhance the low-temperature NH3-SCR activity and hydrothermal stability of SCR catalysts, especially for vehicles under cold-start conditions.

[0003] Zhao, Z. et al., Appl. Catal. B: Environ. 2017, 217, 421-428, relates to the improvement of low temperature activity and hydrothermal stability of Cu-exchanged Al-rich SSZ-13 zeolite using sodium. Wang, J. et al., Ind. Eng. Chem. Res. 2016, 55, 1174-1182, relates to cerium-stabilized Cu-SSZ-13 and its use as catalyst in SCR. Iwasaki, M. et al., Chem. Commun. 2011, 47, 3966-3968, relates to the use of rare earth ions with diameters of 1.05-1.15 angstroms to improve the hydrothermal stability of Fe-beta zeolite and its use in SCR.

[0004] On the other hand, Shu, Y. et al., Top Catal 2015, 58, 334-342, relates to a method of using rare earth ions to improve the hydrothermal stability of Y-type zeolite used as an FCC catalyst.

[0005] Among SSZ-13 zeolites with similar Cu loading, Al-rich SSZ-13, i.e., SSZ-13 with a lower silica to alumina molar ratio, tends to show higher activity in SCR. Therefore, increasing the Al content in SSZ-13 zeolites is a promising way to enhance activity at low and high temperatures. However, the main challenge of Al-rich SSZ-13 zeolites is their low hydrothermal stability due to their high aluminum content, and the low-temperature activity is significantly reduced after deep hydrothermal aging. As a result, the relatively low hydrothermal stability of Al-rich Cu-SSZ-13 catalysts has hindered their practical application in NH3-SCR reactions.

[0006] In view of this, Zhao, Z. et al., Catal. Sci. Technol. 2019, 9, 241-251, propose rare earth ion-exchanged Cu-SSZ-13 zeolite from organic template-free synthesis, which shows improved hydrothermal stability in NH3-SCR.

[0007] However, there remains a need for improved catalytic materials, particularly for use in SCR, not only in terms of hydrothermal stability, but also in terms of catalytic activity and selectivity under the various reaction conditions encountered, and also in terms of the resistance of the catalytic materials to other negative factors, such as catalyst poisoning, and particularly sulfur poisoning of the catalyst. [Prior art documents] [Non-patent literature]

[0008] [Non-Patent Document 1] Zhao,Z.et al.,Appl.Catal.B:Environ.2017,217,421-428 [Non-Patent Document 2] Wang,J.et al.,Ind.Eng.Chem.Res.2016,55,1174-1182 [Non-Patent Document 3] Iwasaki,M.et al.,Chem.Commun.2011,47,3966-3968 [Non-Patent Document 4] Shu,Y.et al.,Top Catal 2015,58,334-342 [Non-Patent Document 5] Zhao,Z.et al.,Catal.Sci.Technol.2019,9,241-251 Summary of the Invention [Problem to be solved by the invention]

[0009] It is therefore an object of the present invention to provide an improved zeolitic material, in particular with regard to its hydrothermal stability and catalytic properties. x The object of the present invention is to provide an improved catalyst for use in selective catalytic reduction (SCR) of ethanol. Said object is achieved by the rare earth-containing zeolitic material having an AEI framework structure according to the invention, and the inventive process for its production, and its use as a catalyst, in particular in SCR. Thus, it has been surprisingly found that the inclusion of a rare earth element in a zeolitic material having an AEI framework structure prevents rapid collapse due to severe hydrothermal aging. Furthermore, it has been very surprisingly found that the inclusion of a rare earth element in a zeolitic material having an AEI framework structure significantly improves the resistance of the zeolitic material having an AEI framework structure, in particular the zeolitic catalyst having an AEI framework structure, to chemical poisoning by SO2, etc. [Means for solving the problem]

[0010] The present invention thus relates to a coated monolith substrate comprising a rare earth-containing zeolite material having an AEI-type framework structure, the framework structure of the zeolite material comprising SiO2 and X2O3, where X represents a trivalent element, the zeolite material contains one or more rare earth elements as counter ions at the ion exchange sites of the framework structure, and the zeolite material is coated on the monolith substrate. Support It has been done. [Brief description of the drawings]

[0011] [Figure 1] FIG. 1 shows the NO conversion as a function of temperature. [Diagram 2] FIG. 2 shows the NO conversion (a) and N2O yield (b). [Diagram 3] FIG. 3 shows the XRD pattern. [Figure 4] FIG. 4 shows the 27Al MAS NMR spectrum. [Diagram 5] FIG. 5 shows the NO conversion as a function of time at 250° C. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] No particular restrictions apply with regard to the physical or chemical properties of the monolith substrate. Thus, any monolith substrate may be used, as long as it is particularly suitable for being coated with a washcoat layer. The monolith substrate is preferably a wall-flow monolith substrate or a flow-through monolith substrate.

[0013] When the monolith substrate is a flow-through substrate, it is preferred that the flow-through monolith substrate is a honeycomb monolith substrate.

[0014] When the monolith substrate is a wall-flow substrate, the wall-flow monolith substrate is preferably a honeycomb monolith substrate having adjacent channels that are alternately plugged at the inlet and outlet ends thereof.

[0015] As mentioned above, no particular restrictions apply with respect to the physical or chemical properties of the monolith substrate. Thus, the monolith may be composed of any suitable material. The monolith substrate is preferably a ceramic and / or metal monolith substrate, preferably the monolith substrate comprises cordierite and / or silicon carbide, preferably cordierite, more preferably the monolith substrate consists of cordierite and / or silicon carbide, preferably cordierite.

[0016] The zeolite material is deposited on the monolith substrate by any convenient means. Support The zeolite material may be applied to the monolith substrate as, or as a component of, a washcoat layer. Support It is preferable that the above-mentioned

[0017] The present invention further relates to a rare earth element-containing zeolite material having an AEI-type framework structure, the framework structure of the zeolite material comprising SiO2 and X2O3, where X represents a trivalent element, the zeolite material contains one or more rare earth elements as counter ions at ion exchange sites of the framework structure, and the zeolite material is prepared by hydrothermally treating the rare earth element-containing zeolite material at a temperature in the range of 400 to 1,000°C. Including It is obtainable and / or obtained by the method.

[0018] The zeolite material is prepared by subjecting a rare earth element-containing zeolite material to hydrothermal treatment at a temperature in the range of 500 to 980°C, preferably in the range of 600 to 960°C, more preferably in the range of 700 to 940°C, more preferably in the range of 800 to 920°C, and more preferably in the range of 850 to 900°C. Including Preferably it is obtainable and / or obtained by a process.

[0019] No particular limitation is applied regarding the duration of the hydrothermal treatment. The rare earth element-containing zeolite material is hydrothermally treated for a period in the range of 0.5 to 72 hours, preferably in the range of 1 to 48 hours, more preferably in the range of 2 to 24 hours, more preferably in the range of 3 to 20 hours, more preferably in the range of 4 to 16 hours, more preferably in the range of 5 to 12 hours, and more preferably in the range of 6 to 8 hours. Including Preferably it is obtainable and / or obtained by a process.

[0020] The zeolite material is prepared by subjecting the rare earth element-containing zeolite material to hydrothermal treatment in an atmosphere containing 1 to 25% by volume of HO, preferably 3 to 20% by volume, more preferably 5 to 15% by volume, more preferably 7 to 13% by volume, and more preferably 9 to 11% by volume of HO. Including Preferably it is obtainable and / or obtained by a process.

[0021] The rare earth element-containing zeolite material is subjected to hydrothermal treatment in an atmosphere containing 1 to 25 volume % of HO. Including The zeolitic material may be obtained and / or has been obtained by the process comprising hydrothermally treating a rare earth-containing zeolitic material in an atmosphere containing air, preferably in air. Including Preferably it is obtainable and / or obtained by a process.

[0022] No particular restrictions apply with respect to the SiO2:X2O3 molar ratio of the coated monolith substrate zeolitic material or the rare earth-containing zeolitic material having an AEI-type framework structure disclosed herein. The SiO2:X2O3 molar ratio in the coated monolith substrate zeolitic material or the rare earth-containing zeolitic material having an AEI-type framework structure is preferably in the range of 6-200, preferably in the range of 8-100, more preferably in the range of 10-50, more preferably in the range of 13-30, more preferably in the range of 15-25, more preferably in the range of 17-23, and more preferably in the range of 19-21.

[0023] Furthermore, no special restrictions apply with respect to X in the coated monolith-based zeolitic material or rare earth-containing zeolitic material having an AEI framework structure disclosed herein. It is preferred that X in the coated monolith-based zeolitic material or rare earth-containing zeolitic material having an AEI framework structure is selected from the group consisting of Al, B, In, Ga, and combinations of two or more thereof. It is particularly preferred that X in the coated monolith-based zeolitic material or rare earth-containing zeolitic material having an AEI framework structure is Al.

[0024] It is preferred that the effective ionic radius of one or more rare earth elements contained as counter ions at the ion exchange sites of the framework structure of the zeolite material of the coated monolith substrate, or the rare earth-containing zeolite material having an AEI-type framework structure, is 1.3 angstroms or less, preferably 1.25 angstroms or less, more preferably 1.2 angstroms or less, more preferably 1.15 angstroms or less, more preferably 1.1 angstroms or less, more preferably 1.05 angstroms or less, more preferably 1.0 angstroms or less, more preferably 0.95 angstroms or less, more preferably 0.9 angstroms or less, and more preferably 0.88 angstroms or less.

[0025] The one or more rare earth elements of the zeolite material of the coated monolith substrate or the rare earth-containing zeolite material having an AEI-type framework structure are preferably selected from the group consisting of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, and Sc (including combinations of two or more thereof), preferably from the group consisting of Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, and Sc (including combinations of two or more thereof), more preferably from the group consisting of Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, and Sc (including combinations of two or more thereof), more preferably from the group consisting of Yb, Lu, Y, and Sc (including combinations of two or more thereof), more preferably the one or more rare earth elements are Y and / or Yb, preferably Y.

[0026] It is preferred that one or more rare earth elements contained as counter ions at the ion exchange sites of the zeolitic material of the coated monolith substrate, or the rare earth-containing zeolitic material having an AEI-type framework structure, are in the +2 and / or +3 oxidation state, preferably the +3 oxidation state.

[0027] The one or more rare earth elements of the zeolite material of the coated monolith substrate, or the rare earth-containing zeolite material having an AEI-type framework structure, are preferably contained in the zeolite material in an amount in the range of 0.1 to 7 mass%, preferably in the range of 0.3 to 5 mass%, more preferably in the range of 0.5 to 4.5 mass%, more preferably in the range of 0.7 to 4 mass%, more preferably in the range of 0.9 to 3.5 mass%, more preferably in the range of 1.1 to 3 mass%, more preferably in the range of 1.3 to 2.5 mass%, more preferably in the range of 1.5 to 2.2 mass%, and more preferably in the range of 1.6 to 2 mass%, based on 100 mass% of SiO2 contained in the zeolite material.

[0028] The molar ratio RE:X2O3 of one or more rare earth elements (RE), calculated as elements, to X2O3 contained in the zeolitic material of the coated monolith substrate, or the rare earth-containing zeolitic material having an AEI-type framework structure, is preferably in the range of 0.1 to 2, preferably in the range of 0.15 to 1.2, more preferably in the range of 0.18 to 0.8, more preferably in the range of 0.2 to 0.5, more preferably in the range of 0.22 to 0.35, more preferably in the range of 0.24 to 0.3, and more preferably in the range of 0.26 to 0.28.

[0029] The zeolite material of the coated monolith substrate, or the rare earth-containing zeolite material having an AEI-type framework structure, preferably further contains one or more transition metal elements M selected from the group consisting of Cr, Fe, Co, Ni, Cu, Zn, Pd and Pt (including combinations of two or more of these) as counter ions at the ion exchange sites of the framework structure, preferably the one or more transition metal elements are selected from the group consisting of Fe, Cu, Pd and Pt (including combinations of two or more of these), more preferably from the group consisting of Fe, Cu and Pd (including combinations of two or more of these), and more preferably the zeolite material further contains Fe and / or Cu, preferably Cu.

[0030] When the zeolite material of the coated monolith substrate or the rare earth-containing zeolite material having an AEI-type framework structure further contains one or more transition metal elements M selected from the group consisting of Cr, Fe, Co, Ni, Cu, Zn, Pd and Pt (including combinations of two or more of these) as counter ions at the ion exchange sites of the framework structure, it is preferred that the one or more transition metal elements M contained as counter ions at the ion exchange sites are in the +2 and / or +3 oxidation state, preferably in the +2 oxidation state.

[0031] Furthermore, when the zeolite material of the coated monolith substrate or the rare earth element-containing zeolite material having an AEI type framework structure further contains one or more transition metal elements M selected from the group consisting of Cr, Fe, Co, Ni, Cu, Zn, Pd and Pt (including combinations of two or more of these) as counter ions at the ion exchange sites of the framework structure, the one or more transition metal elements M are preferably contained in the zeolite material in an amount of 0.5 to 10 mass%, preferably 0.8 to 7 mass%, more preferably 1 to 5 mass%, more preferably 1.2 to 3.5 mass%, more preferably 1.5 to 3 mass%, more preferably 1.8 to 2.8 mass%, more preferably 2 to 2.6 mass%, and more preferably 2.2 to 2.4 mass%, based on 100 mass% of SiO2 contained in the zeolite material.

[0032] Furthermore, when the zeolite material of the coated monolith substrate or the rare earth element-containing zeolite material having an AEI type framework structure further contains one or more transition metal elements M selected from the group consisting of Cr, Fe, Co, Ni, Cu, Zn, Pd and Pt (including combinations of two or more of these) as counter ions at the ion exchange sites of the framework structure, the molar ratio M:X2O3 of the one or more rare earth elements M calculated as elements to X2O3 contained in the zeolite material is preferably in the range of 0.01 to 3, preferably in the range of 0.05 to 2, more preferably in the range of 0.1 to 1.5, more preferably in the range of 0.3 to 1, more preferably in the range of 0.4 to 0.8, more preferably in the range of 0.45 to 0.6, and more preferably in the range of 0.48 to 0.5.

[0033] The zeolitic material of the coated monolith substrate, or the rare earth-containing zeolitic material having an AEI-type framework structure, preferably comprises one or more zeolites selected from the group consisting of SSZ-39, SAPO-18 and SIZ-8 (including mixtures of two or more thereof), preferably the zeolitic material comprises SSZ-39, more preferably the zeolitic material is SSZ-39.

[0034] It is preferred that the framework of the zeolitic material of the coated monolith substrate, or the rare earth-containing zeolitic material having an AEI-type framework structure, is substantially free of phosphorus, and preferably the zeolitic material is substantially free of phosphorus and / or phosphorus-containing compounds.

[0035] The present invention further relates to a method for producing a coated monolith substrate comprising a rare earth-containing zeolitic material having an AEI-type framework structure, the framework structure of the zeolitic material comprising SiO2 and X2O3, where X represents a trivalent element, the method comprising: (1) providing a zeolitic material having an AEI-type framework structure, the framework structure comprising SiO2 and X2O3; (2) Optionally, the zeolitic material provided in step (1) is treated with H + and / or NH4 + , preferably NH4 + One or more ion exchangers using procedure A step of subjecting (3) subjecting the zeolitic material provided in step (1) or the zeolitic material obtained in step (2) to one or more ion exchange reactions with one or more rare earth elements. procedure A step of subjecting (4) optionally subjecting the zeolitic material obtained in step (3) to one or more ion exchange procedures with one or more transition metal elements M; and (5) Providing the zeolite material obtained by step (3) or (4) on a monolith substrate. process wherein the zeolite material is preferably provided on the monolith substrate as a washcoat layer or as a component of a washcoat layer. Includes.

[0036] The monolith substrate is preferably a wall-flow monolith substrate or a flow-through monolith substrate.

[0037] When the monolith substrate is a flow-through substrate, it is preferred that the flow-through monolith substrate is a honeycomb monolith substrate.

[0038] When the monolith substrate is a wall-flow substrate, the wall-flow monolith substrate is preferably a honeycomb monolith substrate having adjacent channels that are alternately plugged at the inlet and outlet ends.

[0039] Preferably, the monolith substrate is a ceramic and / or metal monolith substrate, more preferably the monolith substrate comprises cordierite and / or silicon carbide, preferably cordierite, more preferably the monolith substrate consists of cordierite and / or silicon carbide, preferably consists of cordierite.

[0040] No particular limitation is applied to the SiO2:X2O3 molar ratio of the zeolitic material provided in step (1). The SiO2:X2O3 molar ratio in the zeolitic material provided in step (1) is preferably in the range of 6-200, more preferably in the range of 8-100, more preferably in the range of 10-50, more preferably in the range of 13-30, more preferably in the range of 15-25, more preferably in the range of 17-23, and more preferably in the range of 19-21.

[0041] X is preferably selected from the group consisting of Al, B, In, Ga, and combinations of two or more of these. X is particularly preferably Al.

[0042] In step (3), the one or more rare earth elements are preferably selected from the group consisting of Y, La, Ce, Sm, and Yb (including combinations of two or more of these), more preferably from the group consisting of Y, La, Sm, and Yb (including combinations of two or more of these), more preferably the one or more rare earth elements are Y and / or Yb, preferably Y.

[0043] In step (3), it is preferred that the rare earth element or elements contained as counter ions at the ion exchange sites are in the +3 oxidation state.

[0044] Preferably, the zeolitic material having an AEI-type framework structure provided in step (1) comprises one or more zeolites selected from the group consisting of SSZ-39, SAPO-18 and SIZ-8 (including mixtures of two or more thereof), more preferably the zeolitic material comprises SSZ-39, more preferably the zeolitic material is SSZ-39.

[0045] It is preferred that the framework of the zeolitic material provided in step (1) is substantially free of phosphorus, more preferably the zeolitic material provided in step (1) is substantially free of phosphorus and / or phosphorus-containing compounds.

[0046] Preferably, the one or more transition metal elements M are selected from the group consisting of Cr, Fe, Co, Ni, Cu, Zn, Pd and Pt (including mixtures of two or more thereof), more preferably, the one or more transition metal elements M are selected from the group consisting of Fe, Cu, Pd and Pt (including mixtures of two or more thereof), more preferably, the one or more transition metal elements M are selected from the group consisting of Fe, Cu and Pd (including mixtures of two or more thereof), more preferably, the one or more transition metal elements M are Fe and / or Cu, preferably Cu.

[0047] The one or more transition metal elements M are preferably in the +2 oxidation state.

[0048] Furthermore, the present invention relates to a coated monolith substrate obtainable and / or obtained by the method of any one of the embodiments disclosed herein.

[0049] Furthermore, the present invention relates to an exhaust gas treatment system for treating exhaust gases from a combustion engine, preferably a diesel engine or a lean-burn gasoline engine, the exhaust gas treatment system comprising a coated monolith substrate or a rare earth-containing zeolite material according to any one of the embodiments disclosed herein.

[0050] Furthermore, the present invention relates to a method of using the coated monolith substrate or rare earth-containing zeolite material according to any one of the embodiments disclosed herein as a molecular sieve, as an adsorbent, for ion exchange, as a catalyst or precursor thereof, and / or as a catalyst support or precursor thereof, preferably as a catalyst or precursor thereof and / or as a catalyst support or precursor thereof, more preferably as a catalyst or precursor thereof, more preferably for the production of nitrogen oxides NO x for the storage and / or adsorption of CO2; for the oxidation of NH3, in particular for the oxidation of NH3 slip in diesel systems; for the decomposition of N2O; as an additive in fluid catalytic cracking (FCC) processes; and / or as a catalyst in organic conversion reactions, preferably the conversion of alcohols to olefins, and more preferably in methanol to olefins (MTO) catalysis; more preferably, for the decomposition of nitrogen oxides NO x and more preferably for selective catalytic reduction (SCR) of nitrogen oxides NO in exhaust gases from combustion engines, preferably diesel engines or lean-burn gasoline engines. x The present invention relates to a method for selective catalytic reduction (SCR) of a fuel cell.

[0051] The unit bar (abs) is 10 5 The unit Angstrom is 10 -10 Represents the length of m.

[0052] The present invention is further described by the following set of embodiments and combinations of embodiments obtained from the following dependent references and back references. In particular, in each case where a range of embodiments is mentioned, for example in the context of terms such as "the method according to any one of embodiments 1 to 4", it is noted that all embodiments in this range are clearly disclosed to those skilled in the art, that is, the expression of this term is understood by those skilled in the art as being equivalent to "the method according to any one of embodiments 1, 2, 3 and 4". Furthermore, it is expressly noted that the following set of embodiments is not a set of claims that determines the scope of protection, but represents a suitably constructed part of the description directed to the general and preferred aspects of the present invention.

[0053] 1. A coated monolith substrate comprising a rare earth-containing zeolite material having an AEI-type framework structure, the framework structure of the zeolite material comprising SiO2 and X2O3, where X represents a trivalent element, the zeolite material contains one or more rare earth elements as counter ions at ion exchange sites of the framework structure, and the zeolite material is coated on the monolith substrate. Support The coated monolith substrate is

[0054] 2. The coated monolith substrate of embodiment 1, wherein the monolith substrate is a wall-flow monolith substrate or a flow-through monolith substrate.

[0055] 3. The coated monolith substrate of embodiment 2, wherein the flow-through monolith substrate is a honeycomb monolith substrate.

[0056] 4. The coated monolith substrate of embodiment 2, wherein the wall-flow monolith substrate is a honeycomb monolith substrate having adjacent channels that are alternately plugged at the inlet and outlet ends thereof.

[0057] 5. The coated monolith substrate according to any one of the preceding claims, wherein the monolith substrate is a ceramic and / or metal monolith substrate, preferably the monolith substrate comprises cordierite and / or silicon carbide, preferably cordierite, more preferably the monolith substrate consists of cordierite and / or silicon carbide, preferably consists of cordierite.

[0058] 6. Zeolite material is applied as or as a component of a washcoat layer onto the monolith substrate. Support 6. The coated monolith substrate of any one of the preceding claims,

[0059] 7. A rare earth element-containing zeolite material having an AEI-type framework structure, the framework structure of the zeolite material comprising SiO2 and X2O3, where X represents a trivalent element, the zeolite material containing one or more rare earth elements as counter ions at ion exchange sites of the framework structure, and the zeolite material is prepared by subjecting the rare earth element-containing zeolite material to hydrothermal treatment at a temperature in the range of 400 to 1,000°C. Including A zeolitic material obtainable and / or obtained by the process.

[0060] 8. The zeolite material is prepared by subjecting a rare earth element-containing zeolite material to hydrothermal treatment at a temperature in the range of 500 to 980°C, preferably in the range of 600 to 960°C, more preferably in the range of 700 to 940°C, more preferably in the range of 800 to 920°C, and more preferably in the range of 850 to 900°C. Including 8. The zeolitic material according to embodiment 7, obtainable and / or obtained by the method.

[0061] 9. The rare earth element-containing zeolite material is hydrothermally treated for a period in the range of 0.5 to 72 hours, preferably in the range of 1 to 48 hours, more preferably in the range of 2 to 24 hours, more preferably in the range of 3 to 20 hours, more preferably in the range of 4 to 16 hours, more preferably in the range of 5 to 12 hours, and more preferably in the range of 6 to 8 hours. Including9. The zeolitic material according to embodiment 7 or 8, obtainable and / or obtained by the process.

[0062] 10. Hydrothermally treating a rare earth element-containing zeolite material in an atmosphere containing 1 to 25% by volume of HO, preferably 3 to 20% by volume, more preferably 5 to 15% by volume, more preferably 7 to 13% by volume, and more preferably 9 to 11% by volume of HO. Including 10. The zeolitic material according to any one of embodiments 7 to 9, obtainable and / or obtained by a process.

[0063] 11. Hydrothermally treating a rare earth element-containing zeolite material in an atmosphere containing air Including 11. The zeolitic material according to embodiment 10, obtainable and / or obtained by the process.

[0064] 12. The coated monolith substrate or zeolitic material according to any one of embodiments 1 to 11, wherein the SiO2:X2O3 molar ratio in the zeolitic material is in the range of 6 to 200, preferably in the range of 8 to 100, more preferably in the range of 10 to 50, more preferably in the range of 13 to 30, more preferably in the range of 15 to 25, more preferably in the range of 17 to 23, and more preferably in the range of 19 to 21.

[0065] 13. The coated monolith substrate or zeolitic material of any one of the preceding embodiments, wherein X is selected from the group consisting of Al, B, In, Ga, and combinations of two or more thereof, and X is preferably Al.

[0066] 14. The coated monolith substrate or zeolitic material of any one of the preceding embodiments, wherein the effective ionic radius of the one or more rare earth elements contained as counter ions in the ion exchange sites of the framework structure of the zeolitic material is 1.3 Angstroms or less, preferably 1.25 Angstroms or less, more preferably 1.2 Angstroms or less, more preferably 1.15 Angstroms or less, more preferably 1.1 Angstroms or less, more preferably 1.05 Angstroms or less, more preferably 1.0 Angstroms or less, more preferably 0.95 Angstroms or less, more preferably 0.9 Angstroms or less, and more preferably 0.88 Angstroms or less.

[0067] 15. The coated monolith substrate or zeolitic material according to any one of the preceding embodiments, wherein the one or more rare earth elements are selected from the group consisting of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y and Sc (including combinations of two or more thereof), preferably from the group consisting of Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y and Sc (including combinations of two or more thereof), more preferably from the group consisting of Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y and Sc (including combinations of two or more thereof), more preferably from the group consisting of Yb, Lu, Y and Sc (including combinations of two or more thereof), more preferably the one or more rare earth elements are Y and / or Yb, preferably Y.

[0068] 16. The coated monolith substrate or zeolitic material of any one of the preceding embodiments, wherein the rare earth element(s) contained as counterions at the ion exchange sites are in the +2 and / or +3 acid state, preferably in the +3 oxidation state.

[0069] 17. The coated monolith substrate or zeolite material according to any one of embodiments 1 to 16, wherein the one or more rare earth elements are contained in the zeolite material in an amount in the range of 0.1 to 7 mass%, preferably in the range of 0.3 to 5 mass%, more preferably in the range of 0.5 to 4.5 mass%, more preferably in the range of 0.7 to 4 mass%, more preferably in the range of 0.9 to 3.5 mass%, more preferably in the range of 1.1 to 3 mass%, more preferably in the range of 1.3 to 2.5 mass%, more preferably in the range of 1.5 to 2.2 mass%, and more preferably in the range of 1.6 to 2 mass%, based on 100 mass% of SiO2 contained in the zeolite material.

[0070] 18. The coated monolith substrate or zeolitic material according to any one of the preceding embodiments, wherein the molar ratio RE:X2O3 of one or more rare earth elements (RE), calculated as elements, to X2O3 contained in the zeolitic material is in the range of 0.1 to 2, preferably in the range of 0.15 to 1.2, more preferably in the range of 0.18 to 0.8, more preferably in the range of 0.2 to 0.5, more preferably in the range of 0.22 to 0.35, more preferably in the range of 0.24 to 0.3, and more preferably in the range of 0.26 to 0.28.

[0071] 19. The coated monolith substrate or zeolitic material according to any one of the preceding embodiments, wherein the zeolitic material further comprises one or more transition metal elements M selected from the group consisting of Cr, Fe, Co, Ni, Cu, Zn, Pd and Pt (including combinations of two or more thereof) as counter ions at the ion exchange sites of the framework structure, preferably the one or more transition metal elements are selected from the group consisting of Fe, Cu, Pd and Pt (including combinations of two or more thereof), more preferably from the group consisting of Fe, Cu and Pd (including combinations of two or more thereof), more preferably the zeolitic material further comprises Fe and / or Cu, preferably Cu.

[0072] 20. The coated monolith substrate or zeolitic material of embodiment 19, wherein one or more transition metal elements M contained as counterions at the ion exchange sites are in the +2 and / or +3 oxidation state, preferably in the +2 oxidation state.

[0073] 21. The coated monolith substrate or zeolite material according to embodiment 19 or 20, wherein the one or more transition metal elements M are contained in the zeolite material in an amount in the range of 0.5 to 10 mass%, preferably in the range of 0.8 to 7 mass%, more preferably in the range of 1 to 5 mass%, more preferably in the range of 1.2 to 3.5 mass%, more preferably in the range of 1.5 to 3 mass%, more preferably in the range of 1.8 to 2.8 mass%, more preferably in the range of 2 to 2.6 mass%, and more preferably in the range of 2.2 to 2.4 mass%, based on 100 mass% of SiO2 contained in the zeolite material.

[0074] 22. The coated monolith substrate or zeolitic material according to any one of embodiments 19 to 21, wherein the molar ratio M:X2O3 of the one or more rare earth elements M to X2O3 contained in the zeolitic material, calculated as element, is in the range of 0.01 to 3, preferably in the range of 0.05 to 2, more preferably in the range of 0.1 to 1.5, more preferably in the range of 0.3 to 1, more preferably in the range of 0.4 to 0.8, more preferably in the range of 0.45 to 0.6, and more preferably in the range of 0.48 to 0.5.

[0075] 23. The coated monolith substrate or zeolitic material according to any one of the preceding embodiments, wherein the zeolitic material having an AEI-type framework structure comprises one or more zeolites selected from the group consisting of SSZ-39, SAPO-18 and SIZ-8 (including mixtures of two or more thereof), preferably the zeolitic material comprises SSZ-39, more preferably the zeolitic material is SSZ-39.

[0076] 24. A coated monolith substrate or zeolitic material according to any one of the preceding embodiments, wherein the framework of the zeolitic material is substantially free of phosphorus, preferably the zeolitic material is substantially free of phosphorus and / or phosphorus-containing compounds.

[0077] 25. A method for producing a coated monolith substrate comprising a rare earth-containing zeolite material having an AEI-type framework structure, the framework structure of the zeolite material comprising SiO2 and X2O3, where X represents a trivalent element, comprising the steps of: (1) providing a zeolitic material having an AEI-type framework structure, the framework structure comprising SiO2 and X2O3; (2) Optionally, the zeolitic material provided in step (1) is treated with H + and / or NH4 + , preferably NH4 + One or more ion exchangers using procedure A step of subjecting (3) subjecting the zeolitic material provided in step (1) or the zeolitic material obtained in step (2) to one or more ion exchange reactions with one or more rare earth elements. procedure A step of subjecting (4) optionally subjecting the zeolitic material obtained in step (3) to one or more ion exchange procedures with one or more transition metal elements M; and (5) Providing the zeolite material obtained by step (3) or (4) on a monolith substrate. process wherein the zeolite material is preferably provided on the monolith substrate as a washcoat layer or as a component of a washcoat layer. A method comprising:

[0078] 26. The method of embodiment 25, wherein the monolith substrate is a wall-flow monolith substrate or a flow-through monolith substrate.

[0079] 27. The method of embodiment 26, wherein the flow-through monolith substrate is a honeycomb monolith substrate.

[0080] 28. The method of embodiment 26, wherein the wall-flow monolith substrate is a honeycomb monolith substrate having adjacent channels that are alternately plugged at the inlet and outlet ends.

[0081] 29. The method of any one of embodiments 25 to 28, wherein the monolith substrate is a ceramic and / or metal monolith substrate, preferably the monolith substrate comprises cordierite and / or silicon carbide, preferably cordierite, more preferably the monolith substrate consists of cordierite and / or silicon carbide, preferably consists of cordierite.

[0082] 30. The method according to any one of embodiments 25 to 29, wherein the SiO2:X2O3 molar ratio in the zeolitic material provided in step (1) is in the range of 6 to 200, preferably in the range of 8 to 100, more preferably in the range of 10 to 50, more preferably in the range of 13 to 30, more preferably in the range of 15 to 25, more preferably in the range of 17 to 23, and more preferably in the range of 19 to 21.

[0083] 31. The method of any one of embodiments 25 to 30, wherein X is selected from the group consisting of Al, B, In, Ga, and combinations of two or more thereof, and X is preferably Al.

[0084] 32. The method according to any one of embodiments 25 to 31, wherein in step (3), the one or more rare earth elements are selected from the group consisting of Y, La, Ce, Sm, and Yb (including combinations of two or more thereof), preferably from the group consisting of Y, La, Sm, and Yb (including combinations of two or more thereof), more preferably the one or more rare earth elements are Y and / or Yb, preferably Y.

[0085] 33. The method of any one of embodiments 25 to 32, wherein in step (3), the one or more rare earth elements contained as counterions at the ion exchange sites are in the +3 oxidation state.

[0086] 34. The method according to any one of embodiments 25 to 33, wherein the zeolitic material having an AEI-type framework structure provided in step (1) comprises one or more zeolites selected from the group consisting of SSZ-39, SAPO-18 and SIZ-8 (including mixtures of two or more thereof), preferably the zeolitic material comprises SSZ-39, more preferably the zeolitic material is SSZ-39.

[0087] 35. The method of any one of embodiments 25 to 34, wherein the framework of the zeolitic material provided in step (1) is substantially free of phosphorus, preferably the zeolitic material provided in step (1) is substantially free of phosphorus and / or phosphorus-containing compounds.

[0088] 36. The method according to any one of embodiments 25 to 35, wherein the one or more transition metal elements M are selected from the group consisting of Cr, Fe, Co, Ni, Cu, Zn, Pd and Pt (including mixtures of two or more thereof), preferably the one or more transition metal elements M are selected from the group consisting of Fe, Cu, Pd and Pt (including mixtures of two or more thereof), more preferably the one or more transition metal elements M are selected from the group consisting of Fe, Cu and Pd (including mixtures of two or more thereof), more preferably the one or more transition metal elements M are Fe and / or Cu, preferably Cu.

[0089] 37. The method of any one of embodiments 25 to 36, wherein one or more transition metal elements M are in the +2 oxidation state.

[0090] 38. A coated monolith substrate, obtainable and / or obtained by the method according to any one of embodiments 25 to 37.

[0091] 39. An exhaust treatment system for treating exhaust gas from a combustion engine, preferably a diesel engine or a lean-burn gasoline engine, comprising the coated monolith substrate or rare earth-containing zeolite material of any one of embodiments 1 to 24 and 38.

[0092] 40. A method of using the coated monolith substrate or rare earth-containing zeolite material according to any one of embodiments 1 to 24 and 38, as a molecular sieve, as an adsorbent, for ion exchange, as a catalyst or precursor thereof, and / or as a catalyst support or precursor thereof, preferably as a catalyst or precursor thereof and / or as a catalyst support or precursor thereof, more preferably as a catalyst or precursor thereof, more preferably as a catalyst or precursor thereof, and more preferably as a catalyst for the treatment of nitrogen oxides NO x for the storage and / or adsorption of CO; for the oxidation of NH, in particular for the oxidation of NH slip in diesel systems; for the decomposition of N; as an additive in fluid catalytic cracking (FCC) processes; and / or as a catalyst in organic conversion reactions, preferably the conversion of alcohols to olefins, and more preferably in methanol to olefins (MTO) catalysis; more preferably, for the decomposition of nitrogen oxides, NO x and more preferably for selective catalytic reduction (SCR) of nitrogen oxides NO in exhaust gases from a combustion engine, preferably a diesel engine or a lean-burn gasoline engine. x A method of use for selective catalytic reduction (SCR).

[0093] Description of the drawings Figure 1 shows the NO conversion as a function of temperature for the virgin and 800°C aged Cu-Y-AEI and Cu-CHA catalysts from Example 1 and Comparative Example 2, respectively, tested in Example 2. Reaction conditions: 500 ppm NO, 500 ppm NH3, 10% O2, 5% H2O, balance N2; GHSV=80,000 / h -1 .

[0094] FIG. 2 shows the NO conversion (a) and N2O yield (b) results for Cu-Y-AEI and Cu-CHA catalysts aged at 900° C. from Example 1 and Comparative Example 2, respectively, tested in Example 2. Reaction conditions: 500 ppm NO, 500 ppm NH3, 10% O2, 5% H2O, balance N2; GHSV=80,000 / h -1.

[0095] FIG. 3 shows the XRD patterns and results of aging with Example 2 from Example 1 and Comparative Example 2 for the virgin and 900° C. aged Cu-Y-AEI and Cu-CHA catalysts, respectively.

[0096] Figure 4 shows 27 14A-14C are Al MAS NMR spectra showing the results of aging with Example 2 from Example 1 and Comparative Example 2 for virgin and 900° C. aged Cu-Y-AEI and Cu-CHA catalysts, respectively.

[0097] 5 shows NO conversion as a function of time at 250° C. for Cu-AEI, Cu-Y-AEI, and Cu-CHA catalysts tested in the presence of SO2 in Example 2 from Comparative Example 1, Example 1, and Comparative Example 2, respectively. Reaction conditions: 500 ppm NO, 500 ppm NH3, 10% O2, 5% CO2, 5% H2O, 50 ppm SO2, GHSV=80,000 / h -1 . EXAMPLES

[0098] Catalyst Features Reference Example 1: Determination of the cation content in catalytic materials The cation contents in the catalysts were determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES, Optima2000DV, USA).

[0099] Reference Example 2: Determination of X-ray diffraction patterns of zeolite materials X-ray diffraction (XRD) analysis was performed on an X-ray diffractometer (Rigaku D-Max Rotaflex) using Cu Kα radiation (λ = 1.5418 Å) in the 2θ range of 2–50° and a scan rate of 5° / min. UV-Vis diffuse reflectance spectra were recorded on a JASCO V550 spectrometer in the range of 190–800 nm.

[0100] Reference Example 3: Zeolite material 27 Determination of Al MAS NMR spectrum All-solid-state NMR experiments were performed at 130.2 MHz on an Agilent DD2-500 MHz spectrometer using a 4 mm MAS NMR probe with a spin speed of 14 kHz. 27 Al MAS NMR spectra were acquired for 400 scans with a flip angle of π / 12 and a pulse delay of 1 s. 27 Al MAS NMR spectra were accumulated, and chemical shifts were referenced to a 1% Al(NO3)3 solution in water.

[0101] Reference Example 4: Preparation of Na-SSZ-39 a) Provision of N,N-diethyl-cis-2,6-dimethylpiperidinium hydroxide (DMPOH) Materials used: cis-2,6-Dimethylpiperidine (Sigma-Aldrich Reagent Co., Ltd.) 40g Iodoethane (99%, Aladdin Chemical Co., Ltd.) 222g Potassium bicarbonate (KHCO3, AR, 99.5%, Sinopharm Chemical Reagent Co., Ltd.) 71g Methanol (Sinopharm Chemical Reagent Co., Ltd.) 110g Diethyl ether (AR, 99.5%, Sinopharm Chemical Reagent Co., Ltd.) 1,000g Anion exchange resin (Amberlite IRN-78, OH type, Thermofisher) 300g N,N-Diethyl-cis-2,6-dimethylpiperidine iodide was synthesized by reacting cis-2,6-dimethylpiperidine, iodoethane and excess KHCO3 in the presence of methanol solvent, followed by refluxing at 70°C for 4 days. The KHCO3 was filtered, and then the solvent and excess iodoethane were removed by rotary evaporation. The product was washed with ether. The molecular structure was 1 H and 13The product was converted from the iodide form to the hydroxide form (represented as DMPOH) using an anion exchange resin.

[0102] b) Preparation of zeolitic materials with framework type AEI Materials used: Sodium aluminate (NaAlO2, AR, 99%, Sinopharm Chemical Reagent Co., Ltd.) 0.038g 4.4g deionized water DMPOH solution according to (a) above; 0.23M in water 10g Sodium hydroxide (NaOH, AR, 96%, Sinopharm Chemical Reagent Co., Ltd.) 0.55g Colloidal silica (40% by weight SiO2 in water, Sigma-Aldrich Reagent Co., Ltd.) 2.95 g AEI species (prepared according to Comparative Example 1 above) 0.02 g

[0103] NaAlO2 was dissolved in deionized water and then the DMPOH solution was added. After stirring for 2 hours at room temperature, NaOH was introduced, followed by the addition of colloidal silica and AEI seeds. This resulted in a synthesis mixture with the following molar composition: 1.0 SiO2:0.0083 Al2O3:0.35 Na2O:0.12 DMPOH:44 H2O:0.017 AEI Zeolite Seed

[0104] The ratio of SiO2:Al2O3 was 120:1. After stirring at room temperature for 10 min, the synthesis mixture was transferred into a Teflon-lined autoclave furnace and crystallized at 140°C for 3 days. After filtering, washing, drying, and calcining at 550°C for 4 h, the product was obtained and assigned as a zeolitic material (Si / Al=10) with framework type AEI by XRD analysis.

[0105] Example 1: Preparation of yttrium-containing zeolite material with copper-supported AEI framework structure Na-SSZ-39 with AEI structure obtained from Reference Example 4 was exchanged into NH4-form with 0.5M NH4NO3 aqueous solution at 80°C, then filtered, dried and calcined in air flow to obtain H-AEI. H-AEI was ion-exchanged with 0.002M Y(NO3)3 aqueous solution (pH=3.5) at 180°C for 12 hours. The zeolite slurry was then filtered, washed with deionized water and dried at 110°C. Cu was introduced by ion-exchanging Y-AEI with 0.016M Cu(CH3COO)2 aqueous solution at 50°C for 4 hours. The zeolite slurry was then filtered, washed with deionized water and dried at 110°C for 12 hours. The sample was then calcined in a muffle furnace at 550°C for 5 hours with a heating rate of 2°C / min.

[0106] The resulting catalyst was designated as 2.3Cu-1.8Y-AEI, indicating the contents of Cu and Y, respectively, determined by ICP.

[0107] Comparative Example 1: Preparation of a commercial zeolite material with copper-loaded AEI framework structure The AEI-structured Na-SSZ-39 from Reference Example 4 was exchanged into the NH4-form with 0.5M NH4NO3 aqueous solution at 80°C, followed by filtration, drying and calcination in air flow to obtain H-AEI. Cu was introduced by ion-exchanging H-AEI with 0.01M Cu(CH3COO)2 aqueous solution at 50°C for 4 hours. The zeolite slurry was then filtered, washed with deionized water and dried at 110°C for 12 hours. The sample was then calcined in a muffle furnace at 550°C for 5 hours with a heating rate of 2°C / min.

[0108] The resulting catalyst was designated as 3.0Cu-AEI, indicating the Cu content determined by ICP.

[0109] Comparative Example 2: Preparation of a commercial zeolite material with copper-loaded CHA framework structure For comparison, a conventional commercial Na-SSZ-13 zeolite (Si / Al=15, prepared according to the procedure described in Example 1 of WO2015 / 185625A) obtained from an organic template synthesis was successively ion-exchanged with ammonium and copper according to the procedure of Example 1, but without loading any rare earth elements before loading the copper, to obtain an SSZ-13 with 2.5 wt. % copper.

[0110] Example 2: NO x Catalyst testing in selective catalytic reduction of Prior to reaction testing, all catalyst powders were pelletized at 2 MPa, then crushed and sieved to obtain particles of 40-60 mesh.

[0111] For the tests, catalyst samples were tested in a fresh and aged state: for aging, each sample was hydrothermally aged at 800°C in 10% HO / air for 16 hours, or each sample was aged at 900°C in 10% HO / air for 7 hours.

[0112] NH3-SCR activity measurements were performed in a micro fixed-bed quartz reactor (inner diameter 6 mm) with an eight-channel gas delivery system to mix NO, NH3, C3H6, O2, SO2CO2, H2O, and N2 at the desired concentrations. Typically, the reaction gas mixture contained 500 ppm NO, 500 ppm NH3, 10% O2, 5% H2O, 50 ppm SO2 (as required) and balance N2. The total flow rate was 240 ml / min, which corresponds to a gas hourly space velocity (GHSV) of approximately 80,0000 h -1 The NO, NO2, and N2O contents were continuously monitored using a chemiluminescence spectrometer (ECO Physics, Switzerland) and an infrared absorption spectrometer (Sick Maihak, Germany). To avoid errors due to ammonia conversion in the analyzers, an ammonia trap containing phosphoric acid solution was installed upstream. All data were acquired when the SCR reaction reached steady state at each temperature.

[0113] Hydrothermal stability of Cu-AEI and Cu-Y-AEI The virgin Cu-AEI from Comparative Example 1 showed better SCR performance at low and high temperatures than the benchmark Cu-CHA from Comparative Example 2 (see Figure 1). The NO conversion of Cu-AEI was over 90% in the entire reaction temperature window. Although the addition of rare earth Y to Cu-AEI reduces the NO conversion at low and high temperatures, Cu-AEI still shows higher NO conversion than the benchmark Cu-CHA at high temperatures. After aging at 800°C, the aged Cu-AEI showed lower SCR activity at low temperatures. However, the aged 2.3Cu-1.8Y-AEI performed better than the benchmark Cu-CHA throughout.

[0114] It should be noted that based on the results shown in Figure 1, Cu-AEI is much better than Cu-CHA both before and after aging. Thus, in contrast to Cu-CHA, hydrothermal stabilization of Cu-AEI is not necessary at all when considering the conversion performance of NO in NH3-SCR.

[0115] However, after hydrothermal aging at 900°C, the NO conversion over Cu-AEI was significantly reduced compared to Cu-CHA, as can be seen in Figure 2. Comparing the X-ray diffraction patterns of Cu-CHA and Cu-AEI in the virgin state and after hydrothermal aging at 900°C, as can be seen in Figures 3 and 4, the aforementioned decrease in activity is due to the collapse of the framework structure of the material. This finding was highly unexpected given the high thermal stability of the material compared to Cu-CHA shown in Figure 1, even after extensive hydrothermal aging at 800°C.

[0116] However, it was found, quite surprisingly, that the inclusion of yttrium in the material according to Example 1 prevented the above-mentioned rapid collapse due to hydrothermal aging. Thus, as can be seen from the X-ray diffraction pattern in Figure 3, the Cu-Y-AEI material from Example 1 maintained its structure even after hydrothermal aging under the same conditions at 900°C. 27As can be seen from the Al MAS NMR spectrum, framework Al is maintained in Cu-Y-AEI, but framework Al is not maintained in Cu-AEI, even after severe hydrothermal aging at 900°C. Moreover, as can be seen from Figure 2, the material exhibits high NO conversion activity, which is obviously superior to Cu-CHA at high temperatures. Thus, unlike Cu-CHA, the catalytic activity of Cu-AEI does not undergo thermal decomposition even after hydrothermal aging at high temperatures such as 800°C, but it was unexpectedly found that the collapse of the framework structure at even higher temperatures such as 900°C can be effectively prevented by ion-exchanging yttrium into the zeolite material.

[0117] SO2 resistance of Cu-Y-AEI Figure 5 shows the effect of SO2 poisoning on Cu-AEI, Cu-Y-AEI, and Cu-CHA catalysts from Comparative Example 1, Example 1, and Comparative Example 2 tested in Example 2 in the presence of SO2, respectively. From Figure 5, it is clear that at 250°C in the presence of SO2, Cu-Y-AEI has the highest NO conversion among the tested catalysts, which is 76% after 22 hours of operation. The SO2 tolerance ability is 2.3Cu-1.8Y-AEI>Cu-AEI>2.5Cu-CHA (FR0287).

[0118] However, it was particularly surprising to discover at the beginning of the test procedure that the Cu-Y-AEI sample showed no inhibition over the course of more than an hour of testing, whereas all other samples showed no inhibition at all due to the addition of SO to the gas stream. s The net decrease in catalytic activity due to SO2 poisoning was already observed immediately after the start of the addition of SO2 (see boxed area in Figure 5). Thus, it was completely unexpectedly found that the effect of SO2 poisoning was substantially delayed by the use of Cu-Y-AEI in NH3-SCR.

[0119] Cited prior art: - Zhao,Z.et al.,Appl.Catal.B:Environ.2017,217,421-428 - Wang,J.et al.,Ind.Eng.Chem.Res.2016,55,1174-1182 - Iwasaki, M.et al., Chem.Commun.2011,47,3966-3968 - Shu,Y.et al.,Top Catal 2015,58,334-342 - Zhao,Z.et al.,Catal.Sci.Technol.2019,9,241-251

Claims

1. The present invention includes a rare earth element-containing zeolite material having an AEI type framework structure, the framework structure of which is SiO ２ and X ２ O ３ wherein X represents a trivalent element, the zeolitic material contains one or more rare earth elements as counter ions at ion exchange sites of a framework structure, and the zeolitic material is supported on the monolith substrate, the one or more rare earth elements are Y, and the Y is contained in the zeolite material in an amount ranging from 0.5 to 4.5 mass % based on 100 mass % of SiO 2 contained in the zeolite material; Coated monolith substrate.

2. 10. The coated monolith substrate of claim 1, wherein the monolith substrate is a wall-flow monolith substrate or a flow-through monolith substrate.

3. 3. The coated monolith substrate of claim 1 or 2, wherein the zeolite material is supported on the monolith substrate as or as a component of a washcoat layer.

4. A rare earth element-containing zeolite material having an AEI type framework structure, the framework structure of the zeolite material being SiO ２ and X ２ O ３ wherein X represents a trivalent element, the zeolitic material contains one or more rare earth elements as counter ions at ion exchange sites of the framework structure, and the zeolitic material is obtainable and / or has been obtained by a process comprising hydrothermally treating the rare earth element-containing zeolitic material at a temperature in the range of 400 to 1,000° C. for a period in the range of 0.5 to 72 hours, the one or more rare earth elements are Y, and the Y is contained in the zeolite material in an amount ranging from 0.5 to 4.5 mass % based on 100 mass % of SiO 2 contained in the zeolite material; Rare earth element-containing zeolite materials.

5. The zeolite material is 1 to 25 volume percent H ２ 5. The zeolitic material of claim 4, obtainable and / or obtained by a process comprising hydrothermally treating the rare earth-containing zeolitic material in an O-containing atmosphere.

6. SiO in the zeolite material ２ :X ２ O ３ 6. The coated monolith substrate or zeolite material according to any one of claims 1 to 5, wherein the molar ratio is in the range of 6 to 200.

7. 7. The coated monolith substrate or zeolitic material of claim 1, wherein X is selected from the group consisting of Al, B, In, Ga, and combinations of two or more thereof.

8. A method for producing a coated monolith substrate comprising the rare earth-containing zeolite material having an AEI-type framework structure according to any one of claims 1 to 3 and 6 to 7, comprising the steps of: (1) It has an AEI type skeletal structure, and the skeletal structure is SiO ２ and X ２ O ３ providing a zeolite material comprising: (2) Optionally, the zeolitic material provided in step (1) is subjected to H ＋ and / or NH ４ + subjecting the resulting mixture to one or more ion exchange procedures; (3) subjecting the zeolitic material provided in step (1) or obtained in step (2) to one or more ion exchange procedures with one or more rare earth elements; (4) optionally subjecting the zeolitic material obtained in step (3) to one or more ion exchange procedures with one or more transition metal elements M; and (5) providing the zeolite material obtained by step (3) or (4) on a monolith substrate. and In step (3), the one or more rare earth elements are Y. method.

9. SiO in the zeolite material provided in step (1) ２ :X ２ O ３ The process of claim 8, wherein the molar ratio is in the range of 6 to 200.

10. 10. The method of claim 8 or 9, wherein X is selected from the group consisting of Al, B, In, Ga, and combinations of two or more thereof.

11. 8. An exhaust gas treatment system for treating exhaust gases from a combustion engine, comprising a coated monolith substrate or a rare earth-containing zeolite material according to any one of claims 1 to 7.

12. 8. Use of the coated monolith substrate or rare earth-containing zeolitic material according to any one of claims 1 to 7 as a molecular sieve, as an adsorbent, for ion exchange, as a catalyst or precursor thereof, and / or as a catalyst support or precursor thereof.

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