Method for producing AEI type zeolite materials having defined morphology

Abstract

The present invention relates to a zeolitic material having an AEI type framework structure comprising SiO2, Al2O3 and B2O3, wherein the molar ratio of Al:B of the zeolitic material is comprised within the range of 3 to 500, and the zeolitic material exhibits a molar ratio of Si:(Al+B) of the zeolitic material comprised within the range of 2 to 11. The present invention also relates to a process for the preparation of the zeolitic material according to the invention, a process for the treatment of NOx by selective catalytic reduction and a device for the treatment of a gas stream containing NOx, as well as the use of the zeolitic material according to the invention.

Description

[Technical field]

[0001] The present invention relates to a zeolite material having an AEI-type framework structure containing SiO2, Al2O3 and B2O3, as well as a method for preparing the zeolite material according to the present invention, a method for selective catalytic reduction of NO x Processing method and NO x The present invention relates to a method for treating a gas stream containing the zeolitic material, as well as to the use of the zeolitic material according to the invention. [Background technology]

[0002] Small pore zeolite materials, such as those of the AEI framework type, have been used in industrial applications to treat combustion exhaust gases, e.g., to reduce nitrogen oxides (NO x It is known that synthetic AEI zeolitic materials are potentially useful as catalysts or catalytic components for the conversion of zeolitic cations such as phosphate, phosphate-phosphate esters ...

[0003] However, zeolitic materials are known to be very versatile, particularly in catalytic applications.

[0004] Considering the decreasing amount of oil reserves constituting the feedstock for the production of short-chain hydrocarbons and their derivatives, alternative processes for the production of such base chemicals are becoming increasingly important. In such alternative methods for the production of short-chain hydrocarbons and their derivatives, often highly specific catalysts are used to convert other feedstocks and / or chemicals into hydrocarbons and their derivatives, in particular short-chain olefins. The particular challenges involved in such processes depend not only on the optimal selection of reaction parameters, but also, more importantly, on the use of specific catalysts that allow a highly efficient and selective conversion into the desired hydrocarbons or their derivatives, in particular olefinic fractions. In this regard, the methods in which methanol is used as starting material are of particular importance, whose catalytic conversion usually results in a mixture of hydrocarbons and their derivatives, in particular olefins, paraffins, and aromatics.

[0005] A particular challenge in such catalytic conversions therefore lies in the optimization and fine-tuning of the catalysts used (in particular the zeolite pore structure, the type and strength of the acid) as well as the process architecture and parameters, so that high selectivity to the least possible products can be achieved. For this reason, such processes are often named after the products for which particularly high selectivity can be achieved in the process. Thus, the processes that have been developed over the past decades for the conversion of oxygenates to olefins, and in particular for the conversion of methanol to olefins, which have become increasingly important in view of the dwindling oil reserves, are called methanol-to-olefins processes (MTO-processes for methanol to olefins).

[0006] Among the catalytic materials found for use in such conversions, zeolitic materials have proven to be highly efficient, in particular zeolitic materials of the pentasil type, more particularly zeolitic materials having MFI and MEL framework structures, in particular zeolitic materials including such zeolites exhibiting MFI-MEL intergrowth framework structures. On the other hand, US Patent No. 5,958,370, which relates to the preparation of SSZ-39 having AEI framework structure, also describes their use in the catalytic conversion of methanol to olefins. That is, US Patent No. 5,958,370 relates to SSZ-39 and its preparation using cyclic or polycyclic quaternary ammonium cations as templating agents.

[0007] Moliner, M. et al. in Chem. Commun. 2012, 48, pages 8264-8266, on the other hand, relate to Cu-SSZ-39 and its use for selective catalytic reduction (SCR) of nitrogen oxides NOx, where SSZ-39 is prepared using N,N-dimethyl-3,5-dimethylpiperidinium cation as organic template. Maruo, T. et al. in Chem. Lett. 2014, 43, pages 302-304 relate to the synthesis of AEI zeolite by hydrothermal transformation of FAU zeolite in the presence of tetraethylphosphonium cation. Martin, N. et al. in Chem. Commun. 2015, 51, 11030-11033 relate to the synthesis of Cu-SSZ-39 and its use as catalyst in SCR of nitrogen oxides NOx. Regarding the synthesis methods of SSZ-39 zeolite in the above-mentioned documents, these methods include the use of N,N-dimethyl-3,5-dimethylpiperidinium cation and the use of tetraethylphosphonium cation.Dusselier, M. et al. in ACS Catal. 2015, 5, 10, 6078-6085, on the other hand, describes the catalysis of methanol to olefins using hydrothermally treated SSZ-39.

[0008] US Patent Application Publication No. 2015 / 0118150A1 describes a method for synthesizing zeolites comprising the use of N,N-dimethyl-3,5-dimethylpiperidinium cation and a method for synthesizing zeolites comprising the use of N,N-dimethyl-2,6-dimethylpiperidinium cation, respectively. International Patent Application Publication No. 2016 / 149234A1 and Ransom, R. et al. in Ind. Eng. Chem. Res. 2017, 56, 4350-4356 each relate to the synthesis of SSZ-39 by a zeolite conversion method of faujasite using N,N-dimethyl-3,5-dimethylpiperidinium cation as an organic template. Meanwhile, WO 2018 / 113566 A1 relates to the synthesis of zeolites by solvent-free zeolite conversion, and describes the synthesis of SSZ-39 from the zeolite conversion of zeolite Y using N,N-dimethyl-2,6-dimethylpiperidinium cation.

[0009] JP 2018-087105 A relates to a boron-containing zeolite material exhibiting an AEI-type framework structure, which is prepared using tetraethylphosphonium as a template agent.

[0010] Despite the various methods known to those skilled in the art for the synthesis of small pore zeolites, there remains a need for methods that result in new and improved small pore zeolitic materials. In particular, there remains a need for synthesis methods that allow for the tailoring of the physical and chemical properties of small pore zeolitic materials, with a view to providing materials with new properties that provide improved results in known applications, and further enabling their use in new applications. Summary of the Invention

[0011] The object of the present invention was therefore to provide an improved synthesis method for the preparation of small pore zeolite materials with novel physical and chemical properties, in particular with regard to their catalytic properties. It was therefore surprisingly found that AEI zeolite materials exhibiting novel and unexpected properties can be obtained by using a reaction mixture containing a relatively small amount of boron and tetraalkylammonium cations as template agents. In particular, it was found quite unexpectedly that the inclusion of a relatively small amount of boron in the reaction mixture in combination with tetraalkylammonium cations as template agents surprisingly increases the size of the primary crystallites. As a result, the AEI zeolite materials of the present invention exhibit a substantially lower surface area to volume ratio, which leads to different physical and chemical properties of the resulting materials, in particular with regard to their catalytic properties. Furthermore, it was found quite unexpectedly that the measure of the surprising technical effect of the present invention is substantially proportional to the amount of boron used, but that the physical and chemical properties of the resulting materials can be effectively fine-tuned with high precision without affecting the overall ratio of tetravalent element Y to trivalent element X in the framework structure. In particular, it has surprisingly been found that the technical effect of the present invention can be achieved with relatively low amounts of boron, such that the amount of catalytically active Al sites in the framework structure of the resulting material remains high.

[0012] The present invention therefore relates to a zeolitic material having an AEI type framework structure comprising SiO2, Al2O3 and B2O3, wherein the zeolitic material, preferably the framework structure of the zeolitic material, has an Al:B molar ratio comprised within the range of 3-500, and the zeolitic material exhibits a Si:(Al+B) molar ratio comprised within the range of 2-11.

[0013] The zeolitic material, preferably the framework structure of the zeolitic material, has an Al:B molar ratio in the range of 5-200, preferably 8-100, more preferably 10-50, more preferably 11-35, more preferably 12-25, more preferably 13-20, more preferably 15-16.

[0014] The zeolitic material, preferably the framework structure of the zeolitic material, has a molar ratio of Si:B of 30 or more, preferably in the range of 40-2000, preferably 50-1200, more preferably 60-800, more preferably 70-500, more preferably 100-300, more preferably 150-250, more preferably 180-220.

[0015] The zeolitic material, preferably the framework structure of the zeolitic material, has a Si:Al molar ratio in the range of 2-500, preferably 3-200, more preferably 4-100, more preferably 5-50, more preferably 6-25, more preferably 7-20, more preferably 8-15, more preferably 9-12, more preferably 10-11.

[0016] The zeolitic material, preferably the framework structure of the zeolitic material, has a Si:(Al+B) molar ratio in the range of 4-10.5, preferably 5-10, more preferably 5.5-9.5, more preferably 6-9, more preferably 6.5-8.5, more preferably 7-8.

[0017] The average particle size of the primary crystals of the zeolite material is within the range of 0.5 to 4.0 μm, preferably 0.6 to 3.0 μm, more preferably 0.8 to 2.5 μm, more preferably 1.0 to 2.0 μm, more preferably 1.2 to 1.8 μm, and more preferably 1.4 to 1.6 μm, and the average particle size of the primary crystals of the zeolite material is preferably obtained according to the method of Reference Example 4.

[0018] The primary crystals of the zeolite material have an average aspect ratio of more than 1.2, preferably within the range of 1.3 to 6.0, more preferably 1.4 to 5.0, more preferably 1.5 to 4.5, more preferably 2.0 to 4.0, more preferably 2.5 to 3.5, and the average aspect ratio of the primary crystals of the zeolite material is preferably obtained according to the method of Reference Example 4.

[0019] It is preferable that 95% by weight or more, preferably 95 to 100% by weight, more preferably 97 to 100% by weight, and more preferably 99 to 100% by weight of the skeleton of the zeolite material is composed of Si, Al, B, O, and H, calculated based on the total weight of the skeleton of the zeolite material.

[0020] The zeolite material further contains, at the ion exchange sites of the framework structure, one or more metals selected from the group consisting of alkali metals and alkaline earth metals, preferably one or more metals selected from the group consisting of Li, Na, K, Rb, Cs, Mg, and Ca, more preferably one or more metals selected from the group consisting of Li, Na, and K. It is more preferable that the zeolite material further contains K and / or Na, preferably Na, at the ion exchange sites of the framework structure.

[0021] When the zeolite material further contains one or more metals selected from the group consisting of alkali metals and alkaline earth metals at the ion exchange sites of the framework structure, the zeolite material preferably further contains Mg, Ca, or Mg and Ca at the ion exchange sites of the framework structure.

[0022] The zeolite material is selected from the group consisting of Sr, Zr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Sc, and mixtures of two or more thereof, preferably selected from the group consisting of Sr, Zr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more thereof, more preferably selected from the group consisting of Sr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ag, and mixtures of two or more thereof. , more preferably selected from the group consisting of Cr, Mo, Fe, Ni, Cu, Zn, Ag and mixtures of two or more thereof, more preferably selected from the group consisting of Mo, Fe, Ni, Cu, Zn, Ag and mixtures of two or more thereof, more preferably the one or more cations M comprise Cu and / or Fe, preferably comprise Cu, even more preferably the one or more cations M consist of Cu and / or Fe, preferably consist of Cu, and the one or more metal cations M are preferably present on ion-exchange sites in the framework structure of the zeolitic material.

[0023] When the zeolitic material contains one or more metal cations M, the zeolitic material preferably contains the one or more metal cations M in an amount in the range of 0.01 to 5 wt %, preferably in the range of 0.05 to 4 wt %, more preferably in the range of 0.1 to 3 wt %, more preferably in the range of 0.2 to 2.5 wt %, more preferably in the range of 0.4 to 2 wt %, more preferably in the range of 0.6 to 1.5 wt %, more preferably in the range of 0.8 to 1.2 wt %, based on 100 wt % Si (silicon) in the zeolitic material calculated as SiO2.

[0024] When the zeolitic material contains one or more metal cations M, it is further preferred that 95% or more by weight, preferably from 95 to 100% by weight, more preferably from 97 to 100% by weight, more preferably from 99 to 100% by weight, of the zeolitic material, calculated based on the total weight of the zeolitic material, consists of Si, Al, B, O, H, and one or more metal cations M.

[0025] It is preferred that the zeolitic material having an AEI-type framework structure is 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.

[0026] The zeolite material preferably contains phosphorus (P) of 5 wt % or less, preferably 3 wt % or less, more preferably 1 wt % or less, more preferably 0.5 wt % or less, more preferably 0.1 wt % or less, more preferably 0.05 wt % or less, more preferably 0.01 wt % or less, more preferably 0.005 wt % or less, more preferably 0.001 wt % or less, more preferably 0.0005 wt % or less, and more preferably 0.0001 wt % or less, calculated as an element with SiO2 contained in the zeolite material as 100 wt %.

[0027] The present invention also relates to a method for the preparation of a zeolitic material having an AEI type framework structure comprising SiO2, Al2O3 and B2O3, preferably a zeolitic material according to any one of the particular and preferred embodiments of the present invention, the method comprising the steps of: (1) preparing a mixture comprising one or more organic templates as structure directing agents, one or more SiO sources, one or more BO sources, one or more AlO sources, optionally seed crystals, and a solvent system; (2) heating the mixture obtained in (1) to crystallize a zeolitic material from the mixture, the zeolitic material comprising SiO, BO, and AlO in its framework structure; The one or more organic templates are each selected from the group consisting of one or more tetraalkylammonium cations R 1 R2 R 3 R 4 N + R 1 , R 2 , R 3 each independently represents alkyl; R 4 represents alkyl or aryl.

[0028] The molar ratio of silicon to boron, i.e., the Si:B molar ratio, in the mixture prepared according to (1), each calculated as an element, is preferably in the range of 1 to 80, preferably 2 to 50, more preferably 3 to 35, more preferably 4 to 25, more preferably 6 to 20, more preferably 8 to 18, more preferably 10 to 15.

[0029] The molar ratio of silicon to aluminum, i.e., the Si:Al molar ratio, in the mixture prepared according to (1), each calculated as an element, is preferably within the range of 1 to 300, preferably 3 to 200, more preferably 5 to 120, more preferably 10 to 80, more preferably 15 to 50, more preferably 20 to 35, more preferably 25 to 30.

[0030] It is preferred that the molar ratio of SiO2, i.e., the molar ratio of the one or more organic templates of the one or more SiO2 sources to the one or more organic templates in the mixture prepared in (1), is within the range of 1-50, preferably 2-35, more preferably 3-25, more preferably 4-18, more preferably 5-12, more preferably 6-9, and more preferably 6.5-7.

[0031] R 1 , R 2 , R 3 , and R 4 each independently represents an alkyl group; R 3 and R 4 preferably form a common alkyl chain.

[0032] R 1 , R 2 , R3 , and R 4 are each independently an alkyl group; R 3 and R 4 form a common alkyl chain, R 1 and R 2 are each independently an optionally branched (C1-C6) alkyl, preferably a (C1-C5) alkyl, more preferably a (C1-C4) alkyl, more preferably a (C1-C3) alkyl, more preferably R 1 and R 2 Preferably, independently of each other, represent methyl or ethyl, more preferably methyl.

[0033] R 1 , R 2 , R 3 , and R 4 are each independently an alkyl group; R 3 and R 4 form a common alkyl chain, R 3 and R 4 represents a common (C4-C8) alkyl chain, more preferably a common (C4-C7) alkyl chain, more preferably a common (C4-C6) alkyl chain, and more preferably, the common alkyl chain represents a C4 or C5 alkyl chain, more preferably a C5 alkyl chain.

[0034] Additionally, and independently of the above, one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N +The compound to be contained is selected from the group consisting of N,N-di(C1-C4)alkyl-3,5-di(C1-C4)alkylpyrrolidinium compounds, N,N-di(C1-C4)alkyl-3,5-di(C1-C4)alkylpiperidinium compounds, N,N-di(C1-C4)alkyl-3,5-di(C1-C4)alkylhexahydroazepinium compounds, N,N-di(C1-C4)alkyl-2,6-di(C1-C4)alkylpyrrolidinium compounds, N,N-di(C1-C4)alkyl-2,6-di(C1-C4)alkylpiperidinium compounds, N,N-di(C1-C4)alkyl-2,6-di(C1-C4)alkylhexahydroazepinium compounds, and mixtures of two or more thereof, Preferably, from the group consisting of N,N-di(C1-C3)alkyl-3,5-di(C1-C3)alkylpyrrolidinium compounds, N,N-di(C1-C3)alkyl-3,5-di(C1-C3)alkylpiperidinium compounds, N,N-di(C1-C3)alkyl-3,5-di(C1-C3)alkylhexahydroazepinium compounds, N,N-di(C1-C3)alkyl-2,6-di(C1-C3)alkylpyrrolidinium compounds, N,N-di(C1-C3)alkyl-2,6-di(C1-C3)alkylpiperidinium compounds, N,N-di(C1-C3)alkyl-2,6-di(C1-C3)alkylhexahydroazepinium compounds, and mixtures of two or more thereof, More preferably, from the group consisting of N,N-di(C1-C2)alkyl-3,5-di(C1-C2)alkylpyrrolidinium compounds, N,N-di(C1-C2)alkyl-3,5-di(C1-C2)alkylpiperidinium compounds, N,N-di(C1-C2)alkyl-3,5-di(C1-C2)alkylhexahydroazepinium compounds, N,N-di(C1-C2)alkyl-2,6-di(C1-C2)alkylpyrrolidinium compounds, N,N-di(C1-C2)alkyl-2,6-di(C1-C2)alkylpiperidinium compounds, N,N-di(C1-C2)alkyl-2,6-di(C1-C2)alkylhexahydroazepinium compounds, and mixtures of two or more thereof, More preferably, the compound contains one or more ammonium compounds selected from the group consisting of N,N-di(C1-C2)alkyl-3,5-di(C1-C2)alkylpiperidinium compounds, N,N-di(C1-C2)alkyl-2,6-di(C1-C2)alkylpiperidinium compounds, and mixtures of two or more thereof, and more preferably contains one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + The containing compound preferably comprises one or more N,N-dimethyl-3,5-dimethylpiperidinium and / or N,N-diethyl-2,6-dimethylpiperidinium compounds, preferably one or more N,N-dimethyl-3,5-dimethylpiperidinium compounds.

[0035] Further, the N,N-dialkyl-2,6-dialkylpyrrolidinium compounds, N,N-dialkyl-2,6-dialkylpiperidinium compounds, and / or N,N-dialkyl-2,6-dialkylhexahydroazepinium compounds may exhibit a cis configuration, a trans configuration, or may contain a mixture of cis and trans isomers; Preferably, the N,N-dialkyl-2,6-dialkylpyrrolidinium compounds, the N,N-dialkyl-2,6-dialkylpiperidinium compounds and / or the N,N-dialkyl-2,6-dialkylhexahydroazepinium compounds exhibit a cis configuration, More preferably, said one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + The containing compound comprises one or more ammonium compounds selected from the group consisting of N,N-di(C1-C2)alkyl-cis-2,6-di(C1-C2)alkylpiperidinium compounds and mixtures of two or more thereof, and more preferably one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N +Preferably, the containing compound comprises one or more N,N-diethyl-cis-2,6-dimethylpiperidinium compounds.

[0036] It is preferred that the one or more organic templates are provided as a salt, preferably one or more salts selected from the group consisting of halides, sulfates, nitrates, phosphates, acetates, and mixtures of two or more thereof, more preferably bromides, chlorides, hydroxides, sulfates, and mixtures of two or more thereof, more preferably the one or more organic templates are provided as hydroxides and / or bromides, more preferably hydroxides.

[0037] It is preferred that the mixture prepared in (1) contains seed crystals, and the amount of the seed crystals contained in the mixture prepared in (1) is within the range of 0.1 to 15 wt%, preferably 0.5 to 11 wt%, more preferably 0.8 to 8 wt%, more preferably 1.2 to 5 wt%, more preferably 1.5 to 3 wt%, and more preferably 1.8 to 2.5 wt%, based on 100 wt% of Si in the mixture calculated as SiO2.

[0038] It is preferred that the mixture prepared in (1) comprises seed crystals, the seed crystals comprising one or more zeolitic materials having an AEI-type framework structure.

[0039] The mixture prepared in (1) preferably contains a hydroxide salt.

[0040] OH in the mixture prepared in (1) - The molar ratio of :Si is preferably within the range of 0.05 to 5, preferably 0.1 to 3, more preferably 0.2 to 1, more preferably 0.3 to 0.8, more preferably 0.45 to 0.65, more preferably 0.5 to 0.6, more preferably 0.52 to 0.56.

[0041] It is preferred that the mixture prepared in (1) contains one or more metals selected from the group consisting of alkali metals and alkaline earth metals, preferably one or more metals selected from the group consisting of Li, Na, K, Rb, Cs, Mg, and Ca, more preferably one or more metals selected from the group consisting of Li, Na, and K, and more preferably the mixture prepared in (1) contains K and / or Na, preferably Na.

[0042] When the mixture prepared in (1) contains one or more metals selected from the group consisting of alkali metals and alkaline earth metals, it is preferable that the mixture prepared in (1) contains Mg, Ca, or Mg and Ca.

[0043] When the mixture prepared in (1) contains one or more metals selected from the group consisting of alkali metals and alkaline earth metals, the molar ratio of the one or more metals selected from the group consisting of alkali metals and alkaline earth metals to the one or more organic templates in the mixture prepared in (1) is further preferably within the range of 0.01 or less to 50, preferably 0.05 or less to 25, more preferably 0.1 or less to 15, more preferably 0.5 or less to 10, more preferably 1 to 7, more preferably 2 to 5, more preferably 3 to 4, and more preferably 3.4 to 3.6.

[0044] The heating in (2) is preferably carried out for a duration within the range of 0.25 to 12 days, preferably 0.5 to 8 days, more preferably 1 to 6 days, more preferably 1.5 to 4.5 days, more preferably 2 to 4 days, and more preferably 2.5 to 3.5 days.

[0045] The heating in (2) is preferably carried out at a temperature within the range of 80 to 220°C, preferably 100 to 200°C, more preferably 120 to 180°C, more preferably 130 to 170°C, more preferably 140 to 160°C, and more preferably 145 to 155°C.

[0046] The heating in (2) is preferably carried out under autogenous pressure, preferably under solvothermal conditions, more preferably under hydrothermal conditions, and preferably the heating in (2) is carried out in a pressure vessel, preferably in an autoclave.

[0047] The zeolitic material crystallized in (2) preferably has an AEI-type framework structure.

[0048] A method for preparing a zeolite material having an AEI-type framework structure containing SiO2, Al2O3, and B2O3, comprising the steps of: (3) It is preferred that the method further comprises subjecting the zeolitic material obtained in (2) to ion exchange with one or more metal cations M.

[0049] If the method includes (3), then (3) is The zeolite material obtained in (3a)(2) was + and / or NH4 + , preferably NH4 + and subjecting the resulting mixture to one or more ion exchange steps according to (3b) subjecting the zeolitic material obtained in (3a) to one or more ion-exchange procedures with one or more metal cations M, It is preferred that (3a) and / or (3b) are repeated independently of each other, preferably 1 to 3 times, more preferably 1 or 2 times, more preferably 1 time.

[0050] It is further preferred that in (3), the zeolitic material obtained in (2) is directly subjected to ion-exchange with one or more metal cations M, and that no ion-exchange is carried out prior to the ion-exchange step of the zeolitic material obtained in (2) with one or more metal cations M.

[0051] In (3), the one or more metal cations M are selected from the group consisting of Sr, Zr, Cr, Mg, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Sc, and mixtures of two or more thereof, preferably selected from the group consisting of Sr, Zr, Cr, Mg, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more thereof, more preferably Sr, Cr, Mg, Mo, Fe , Co, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, more preferably selected from the group consisting of Cr, Mg, Mo, Fe, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, more preferably selected from the group consisting of Mg, Mo, Fe, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, more preferably the one or more cations M comprise Cu and / or Fe, preferably comprise Cu, even more preferably the one or more cations M consist of Cu and / or Fe, preferably consist of Cu.

[0052] Still further, in (3), the one or more metal cations M are provided as a salt, preferably one or more salts selected from the group consisting of halides, sulfates, nitrates, phosphates, acetates, and mixtures of two or more thereof, more preferably sulfates, nitrates, acetates, and mixtures of two or more thereof, and more preferably the one or more metal cations M used to prepare the mixture according to (1) are provided as nitrates and / or acetates, more preferably acetates.

[0053] The method further comprises the steps of: after (2) and before (3), (i) optionally isolating the zeolitic material obtained in (2), preferably by filtration; and / or, preferably, and (ii) optionally washing the zeolitic material obtained in (2) or (i), preferably with distilled water; and / or, preferably, and (iii) optionally drying the zeolitic material obtained in (2), (i), or (ii); and / or, preferably, and (iv) optionally calcining the zeolitic material obtained in (2), (i), (ii), or (iii).

[0054] The calcination in (iv) is preferably carried out for a duration in the range of 0.5 to 15 hours, preferably 1 to 10 hours, more preferably 1.5 to 8 hours, more preferably 2 to 6 hours, more preferably 2.5 to 5.5 hours, more preferably 3 to 5 hours, more preferably 3.5 to 4.5 hours.

[0055] Furthermore, and independently of the above conditions, the calcination in (iv) is preferably carried out at a temperature in the range of 300 to 900°C, preferably 350 to 800°C, more preferably 400 to 750°C, more preferably 450 to 700°C, more preferably 500 to 650°C, more preferably 560 to 600°C.

[0056] The one or more SiO sources 2 are selected from the group consisting of silicon-containing zeolites having a FAU, FER, GIS, MOR, LTA, TON, MTT, BEA, and / or MFI framework structure, silica, silicates, silicic acid, and combinations of two or more thereof, preferably selected from the group consisting of silicon-containing zeolites having a FAU, GIS, BEA, and / or MFI framework structure, silica, alkali metal silicates, silicic acid, and combinations of two or more thereof, more preferably selected from the group consisting of silicon-containing zeolites having a FAU, BEA, and / or MFI framework structure, fumed silica, It is preferably selected from the group consisting of colloidal silica, reactive amorphous solid silica, silica gel, pyrogenic silica, lithium silicate, sodium silicate, potassium silicate, silicic acid, and a combination of two or more thereof, more preferably selected from the group consisting of a silicon-containing zeolite having an FAU framework structure, colloidal silica, fumed silica, silica gel, pyrogenic silica, and a combination of two or more thereof, and more preferably the one or more SiO sources 2 include a silicon-containing zeolite having an FAU framework structure, colloidal silica, and / or fumed silica.

[0057] In this regard, the zeolite having an FAU-type framework structure is selected from the group consisting of ZSM-3, faujasite, [Al-Ge-O]-FAU, CSZ-1, ECR-30, zeolite X, zeolite Y, LZ-210, SAPO-37, ZSM-20, Na-X, US-Y, Na-Y, [Ga-Ge-O]-FAU, Li-LSX, [Ga-Al-Si-O]-FAU, and [Ga-Si-O]-FAU (including mixtures of two or more thereof); Preferably, it is selected from the group consisting of ZSM-3, faujasite, CSZ-1, ECR-30, zeolite X, zeolite Y, LZ-210, ZSM-20, Na-X, US-Y, Na-Y, and Li-LSX (including mixtures of two or more thereof), more preferably from the group consisting of faujasite, zeolite X, zeolite Y, Na-X, US-Y, and Na-Y (including mixtures of two or more thereof), more preferably from the group consisting of faujasite, zeolite X, and zeolite Y (including mixtures of two or more thereof); More preferably, the zeolite having an FAU-type framework structure comprises zeolite X and / or zeolite Y, preferably zeolite Y; more preferably, the zeolite having an FAU-type framework structure is zeolite X and / or zeolite Y, preferably zeolite Y.

[0058] In addition, and independently of the above conditions, zeolites having a BEA-type framework structure include zeolite beta, tsarnikite, [B-Si-O]- * BEA, CIT-6, [Ga-Si-O]- * BEA, beta polymorph B, SSZ-26, SSZ-33, beta polymorph A, [Ti-Si-O]- * From the group consisting of BEA, and pure silica beta (including mixtures of two or more thereof), Preferably, it is selected from the group consisting of zeolite beta, CIT-6, beta polymorph B, SSZ-26, SSZ-33, beta polymorph A, and pure silica beta (including mixtures of two or more thereof); More preferably, the zeolite having a BEA-type framework structure comprises zeolite beta, preferably zeolite beta obtained from synthesis without the use of organic templates; More preferably, the zeolite having a BEA-type framework structure is zeolite beta, preferably zeolite beta obtained from an organic template-mediated synthesis or from a synthesis without using an organic template, more preferably zeolite beta obtained from an organic template-free synthesis.

[0059] Further, and independently of the above conditions, the zeolite having an MFI type framework structure may be selected from the group consisting of silicalite, ZSM-5, [Fe-Si-O]-MFI, [Ga-Si-O]-MFI, [As-Si-O]-MFI, AMS-1B, AZ-1, Bor-C, Encilite, Boralite C, FZ-1, LZ-105, Mucinite, NU-4, NU-5, TS-1, TSZ, TSZ-III, TZ-01, USC-4, USI-108, ZBH, ZKQ-1B, ZMQ-TB, MnS-1, and FeS-1 (including mixtures of two or more thereof), Preferably, it is selected from the group consisting of silicalite, ZSM-5, AMS-1B, AZ-1, Encilite, FZ-1, LZ-105, Mucinite, NU-4, NU-5, TS-1, TSZ, TSZ-III, TZ-01, USC-4, USI-108, ZBH, ZKQ-1B, and ZMQ-TB (including mixtures of two or more thereof); More preferably, the zeolite having an MFI type framework structure comprises silicalite and / or ZSM-5, preferably ZSM-5; More preferably, the zeolite having an MFI type framework structure is the zeolite silicalite and / or ZSM-5, preferably ZSM-5.

[0060] It is preferred that the one or more B2O3 sources are selected from the group consisting of boric acid, borates, borate esters, and mixtures of two or more thereof, preferably from the group consisting of boric acid, borates, triethyl borate, trimethyl borate, boron esters, and mixtures of two or more thereof, more preferably the one or more B2O3 sources comprise boric acid and / or borates, preferably boric acid, more preferably the one or more B2O3 sources consist of boric acid and / or borates, preferably boric acid.

[0061] The one or more AlO sources 3 comprise one or more compounds selected from the group consisting of aluminum-containing zeolites having a FAU framework structure and aluminum salts. Preferably, the one or more AlO sources 3 comprise an aluminum-containing zeolite having a FAU framework structure or aluminum nitrate. More preferably, the one or more AlO sources 3 consist of an aluminum-containing zeolite having a FAU framework structure or aluminum nitrate.

[0062] The one or more SiO2 sources and the one or more Al2O3 sources include a silicon- and aluminum-containing zeolite having a FAU framework structure, and preferably, the one or more SiO2 sources and the one or more Al2O3 sources consist of a silicon- and aluminum-containing zeolite having a FAU framework structure.

[0063] It is preferred that the solvent system is selected from the group consisting of optionally branched chain (C1-C4) alcohols, distilled water, and mixtures thereof, preferably from the group consisting of optionally branched chain (C1-C3) alcohols, distilled water, and mixtures thereof, more preferably from the group consisting of methanol, ethanol, distilled water, and mixtures thereof, more preferably the solvent system comprises distilled water, more preferably the solvent system consists of distilled water.

[0064] It is preferred that the mixture prepared in (1) and crystallized in (2) contains 5% by weight or less, preferably 3% by weight or less, more preferably 1% by weight or less, more preferably 0.5% by weight or less, more preferably 0.1% by weight or less, more preferably 0.05% by weight or less, more preferably 0.01% by weight or less, more preferably 0.005% by weight or less, more preferably 0.001% by weight or less, more preferably 0.0005% by weight or less, and more preferably 0.0001% by weight or less, calculated as an element, with the mixture prepared in (1) being 100% by weight.

[0065] The mixture prepared in (1) comprises seed crystals, the seed crystals comprising one or more zeolitic materials having in their framework structure a zeolitic material comprising SiO, B0, and Al0 obtained according to the method according to any one of embodiments 15 to 59, preferably the one or more zeolitic materials of the seed crystals are obtainable and / or obtained according to the method according to any one of embodiments 15 to 59.

[0066] The present invention also relates to a zeolitic material having an AEI-type framework structure, preferably according to any one of the particular preferred embodiments of the present invention, which is obtainable and / or obtainable by the process of any one of the particular preferred embodiments of the present invention.

[0067] The present invention also relates to a method for producing NO by selective catalytic reduction. x A method for treating (A) providing a gas stream containing one or more nitrogen oxides; (B) contacting the gas stream provided in step (A) with a zeolitic material according to any one of the specific preferred embodiments of the present invention.

[0068] Preferably, the gas stream provided in (A) further comprises one or more reducing agents, which preferably comprise ammonia and / or urea.

[0069] The gas stream provided in (A) comprises one or more waste gases, preferably one or more waste gases from one or more industrial processes, more preferably the waste gas stream comprises one or more waste gas streams obtained in a process for combusting nitrogen-containing substances comprising a process for producing adipic acid, nitric acid, hydroxylamine derivatives, caprolactam, glyoxal, methyl-glyoxal, glyoxylic acid or a mixture of waste gas streams from two or more of the above mentioned processes, even more preferably the waste gas stream comprises one or more waste gas streams obtained in a process for producing adipic acid and / or nitric acid.

[0070] The gas stream provided in (A) preferably comprises one or more waste gases from an internal combustion engine, preferably a diesel engine or a lean-burn gasoline engine.

[0071] The contact of the gas stream in (B) with the zeolitic material is preferably carried out at a temperature comprised within the range of 250-550°C, preferably 300-500°C, more preferably 325-450°C, more preferably 350-425°C, more preferably 380-420°C, even more preferably 390-410°C.

[0072] The present invention also provides a method for producing a x The present invention relates to an apparatus for the treatment of a gas stream containing a zeolitic material according to any one of the particular preferred embodiments of the present invention, comprising a catalyst bed provided in fluid contact with the gas stream to be treated, the catalyst bed comprising a zeolitic material according to any one of the particular preferred embodiments of the present invention.

[0073] In this regard, it is preferred that the catalyst bed is a fixed bed catalyst or a fluidized bed catalyst, preferably a fixed bed catalyst.

[0074] Additionally, the apparatus preferably further comprises one or more devices disposed upstream of the catalyst bed for injecting one or more reducing agents into the gas stream, the reducing agents preferably comprising ammonia and / or urea.

[0075] The present invention also relates to the use of a zeolitic material according to any one of the particular and preferred embodiments of the present invention as a molecular sieve, as an adsorbent, for ion exchange, as a catalyst or a precursor thereof and / or as a catalyst support or a precursor thereof, preferably as a catalyst or a precursor thereof and / or as a catalyst support or a precursor thereof, more preferably as a catalyst or a precursor thereof, more preferably for the production of nitrogen oxides NO xas catalysts for selective catalytic reduction (SCR) of nitrous oxides, for storage and / or adsorption of CO2, for oxidation of NH3, in particular for oxidation of NH3 slip in diesel systems, for the decomposition of N2O; as additives in fluid catalytic cracking (FCC) processes; and / or as catalysts in organic conversion reactions, preferably in the conversion of alcohols to olefins, more preferably in the catalysis of methanol to olefins (MTO), more preferably in the decomposition of nitrogen oxides NO x More preferably, for selective catalytic reduction (SCR) of nitrogen oxides NO in exhaust gases from a combustion engine, preferably from a diesel engine or from a lean-burn gasoline engine. x for selective catalytic reduction (SCR).

[0076] The present invention is further described by the following set of embodiments and combinations of embodiments resulting from dependencies and reverse references as indicated. In particular, in each case where a range of embodiments is mentioned, for example in the context of a term such as "any one of the methods of embodiments 1-4", it is to be noted that all embodiments within this range are meant to be explicitly disclosed to those skilled in the art, i.e., the expression of this term is understood by those skilled in the art to be synonymous with "any one of the methods of embodiments 1, 2, 3, and 4". Furthermore, it is to be clearly noted that the following set of embodiments represents a properly structured part of the description directed to the general and preferred aspects of the present invention, rather than a set of claims defining the scope of protection. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0077] 1. A zeolitic material having an AEI type framework structure comprising SiO2, Al2O3 and B2O3, wherein the zeolitic material, preferably the framework structure of the zeolitic material, has an Al:B molar ratio comprised within the range of 3-500, and the zeolitic material, preferably the framework structure of the zeolitic material, has a Si:(Al+B) molar ratio comprised within the range of 2-11.

[0078] 2. The zeolitic material according to embodiment 1, wherein the Al:B molar ratio of the zeolitic material, preferably the framework structure of the zeolitic material, is in the range of 5-200, preferably 8-100, more preferably 10-50, more preferably 11-35, more preferably 12-25, more preferably 13-20, more preferably 15-16.

[0079] 3. The zeolitic material, preferably the zeolitic material according to embodiment 1 or 2, wherein the Si:B molar ratio of the framework structure of the zeolitic material is 30 or more, preferably in the range of 40 to 2000, preferably 50 to 1200, more preferably 60 to 800, more preferably 70 to 500, more preferably 100 to 300, more preferably 150 to 250, more preferably 180 to 220.

[0080] 4. The zeolitic material according to any one of embodiments 1 to 3, wherein the Si:Al molar ratio of the zeolitic material, preferably the framework structure of the zeolitic material, is in the range of 2 to 500, preferably 3 to 200, more preferably 4 to 100, more preferably 5 to 50, more preferably 6 to 25, more preferably 7 to 20, more preferably 8 to 15, more preferably 9 to 12, more preferably 10 to 11.

[0081] 5. The zeolitic material according to any one of embodiments 1 to 4, wherein the Si:(Al+B) molar ratio of the zeolitic material, preferably the framework structure of the zeolitic material, is in the range of 4 to 10.5, preferably 5 to 10, more preferably 5.5 to 9.5, more preferably 6 to 9, more preferably 6.5 to 8.5, more preferably 7 to 8.

[0082] 6. The zeolite material according to any one of embodiments 1 to 5, wherein the average particle size of the primary crystals of the zeolite material is within the range of 0.5 to 4.0 μm, preferably 0.6 to 3.0 μm, more preferably 0.8 to 2.5 μm, more preferably 1.0 to 2.0 μm, more preferably 1.2 to 1.8 μm, more preferably 1.4 to 1.6 μm, and the average particle size of the primary crystals of the zeolite material is preferably obtained according to the method of Reference Example 4.

[0083] 7. The zeolite material according to any one of embodiments 1 to 6, wherein the primary crystals of the zeolite material have an average aspect ratio of more than 1.2, preferably an average aspect ratio in the range of 1.3 to 6.0, more preferably 1.4 to 5.0, more preferably 1.5 to 4.5, more preferably 2.0 to 4.0, more preferably 2.5 to 3.5, and the average aspect ratio of the primary crystals of the zeolite material is preferably obtained according to the method of Reference Example 4.

[0084] 8. The zeolite material according to any one of embodiments 1 to 7, wherein 95% by weight or more, preferably 95 to 100% by weight, more preferably 97 to 100% by weight, more preferably 99 to 100% by weight of the skeleton of the zeolite material is composed of Si, Al, B, O, and H, calculated based on the total weight of the skeleton of the zeolite material.

[0085] 9. The zeolite material according to any one of embodiments 1 to 8, further comprising, at the ion exchange sites of the framework structure, one or more metals selected from the group consisting of alkali metals and alkaline earth metals, preferably one or more metals selected from the group consisting of Li, Na, K, Rb, Cs, Mg, and Ca, more preferably one or more metals selected from the group consisting of Li, Na, and K, and further comprising, at the ion exchange sites of the framework structure, K and / or Na, preferably Na.

[0086] 10. The zeolitic material of embodiment 9, wherein the zeolitic material further contains Mg, Ca, or Mg and Ca in the ion-exchange sites of the framework structure.

[0087] 11. The zeolite material is selected from the group consisting of Sr, Zr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Sc, and mixtures of two or more thereof, preferably from the group consisting of Sr, Zr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more thereof, more preferably from the group consisting of Sr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, more preferably Cr, 11. The zeolitic material according to any one of embodiments 1 to 10, preferably comprising one or more metal cations M selected from the group consisting of Mo, Fe, Ni, Cu, Zn, Ag and mixtures of two or more thereof, more preferably from the group consisting of Mo, Fe, Ni, Cu, Zn, Ag and mixtures of two or more thereof, more preferably the one or more cations M comprises Cu and / or Fe, preferably comprises Cu, even more preferably the one or more cations M consists of Cu and / or Fe, preferably consists of Cu, and the one or more metal cations M are preferably present at ion-exchange sites of the framework structure of the zeolitic material.

[0088] 12. The zeolitic material according to embodiment 11, wherein when the zeolitic material contains one or more metal cations M, the zeolitic material contains the one or more metal cations M in an amount in the range of 0.01 to 5 wt%, preferably in the range of 0.05 to 4 wt%, more preferably in the range of 0.1 to 3 wt%, more preferably in the range of 0.2 to 2.5 wt%, more preferably in the range of 0.4 to 2 wt%, more preferably in the range of 0.6 to 1.5 wt%, more preferably in the range of 0.8 to 1.2 wt%, based on 100 wt% Si (silicon) in the zeolitic material calculated as SiO2.

[0089] 13. The zeolitic material according to embodiment 11 or 12, wherein if the zeolitic material comprises one or more metal cations M, at least 95% by weight, preferably from 95 to 100% by weight, more preferably from 97 to 100% by weight, more preferably from 99 to 100% by weight, of the zeolitic material, calculated on the total weight of the zeolitic material, consists of Si, Al, B, O, H, and one or more metal cations M.

[0090] 14. The zeolitic material according to any one of embodiments 1 to 13, wherein the zeolitic material having an AEI-type framework structure is 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.

[0091] 15. The zeolite material according to any one of embodiments 1 to 14, wherein the zeolite material contains phosphorus (P) in an amount of 5% by weight or less, preferably 3% by weight or less, more preferably 1% by weight or less, more preferably 0.5% by weight or less, more preferably 0.1% by weight or less, more preferably 0.05% by weight or less, more preferably 0.01% by weight or less, more preferably 0.005% by weight or less, more preferably 0.001% by weight or less, more preferably 0.0005% by weight or less, and more preferably 0.0001% by weight or less, calculated as an element with respect to SiO2 contained in the zeolite material being 100% by weight.

[0092] 16. A method for preparing a zeolitic material having an AEI-type framework structure comprising SiO2, Al2O3, and B2O3, preferably according to any one of embodiments 1 to 15, comprising: (1) preparing a mixture comprising one or more organic templates as structure directing agents, one or more SiO sources, one or more BO sources, one or more AlO sources, optionally seed crystals, and a solvent system; (2) heating the mixture obtained in (1) to crystallize a zeolitic material from the mixture, the zeolitic material comprising SiO, BO, and AlO in its framework structure; The one or more organic templates are each selected from the group consisting of one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + Containing compound (in the formula, R 1 , R 2 , R 3 each independently represents an alkyl group; R 4 represents alkyl or aryl.

[0093] 17. The method according to embodiment 16, wherein the molar ratio of silicon to boron, i.e., the molar ratio Si:B, in the mixture prepared according to (1), each calculated as an element, is in the range of 1 to 80, preferably 2 to 50, more preferably 3 to 35, more preferably 4 to 25, more preferably 6 to 20, more preferably 8 to 18, more preferably 10 to 15.

[0094] 18. The method according to embodiment 16 or 17, wherein the molar ratio of silicon to aluminum, i.e., the molar ratio Si:Al, in the mixture prepared according to (1), each calculated as an element, is in the range of 1 to 300, preferably 3 to 200, more preferably 5 to 120, more preferably 10 to 80, more preferably 15 to 50, more preferably 20 to 35, more preferably 25 to 30.

[0095] 19. The method according to any one of embodiments 16 to 18, wherein the molar ratio of SiO2, i.e., the molar ratio of the organic templates of the one or more SiO2 sources to the one or more organic templates in the mixture prepared in (1), is in the range of 1 to 50, preferably 2 to 35, more preferably 3 to 25, more preferably 4 to 18, more preferably 5 to 12, more preferably 6 to 9, more preferably 6.5 to 7.

[0096] 20.R 1 , R 2 , R 3 and R 4 are each independently an alkyl group; R 3 and R 420. The method of any one of embodiments 16 to 19, wherein:

[0097] 21.R 1 and R 2 are each independently an optionally branched (C1-C6) alkyl, preferably a (C1-C5) alkyl, more preferably a (C1-C4) alkyl, more preferably a (C1-C3) alkyl, more preferably R 1 and R 2 21. The method according to embodiment 20, wherein each independently represents methyl or ethyl, more preferably methyl.

[0098] 22.R 3 and R 4 form a common (C4-C8) alkyl chain, more preferably a common (C4-C7) alkyl chain, more preferably a common (C4-C6) alkyl chain, more preferably the common alkyl chain is a C4 or C5 alkyl chain, more preferably a C5 alkyl chain.

[0099] 23. One or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + The containing compound includes one or more ammonium compounds selected from the group consisting of N,N-di(C1-C4)alkyl-3,5-di(C1-C4)alkylpyrrolidinium compounds, N,N-di(C1-C4)alkyl-3,5-di(C1-C4)alkylpiperidinium compounds, N,N-di(C1-C4)alkyl-3,5-di(C1-C4)alkylhexahydroazepinium compounds, N,N-di(C1-C4)alkyl-2,6-di(C1-C4)alkylpyrrolidinium compounds, N,N-di(C1-C4)alkyl-2,6-di(C1-C4)alkylpiperidinium compounds, N,N-di(C1-C4)alkyl-2,6-di(C1-C4)alkylhexahydroazepinium compounds, and mixtures of two or more thereof; Preferably, from the group consisting of N,N-di(C1-C3)alkyl-3,5-di(C1-C3)alkylpyrrolidinium compounds, N,N-di(C1-C3)alkyl-3,5-di(C1-C3)alkylpiperidinium compounds, N,N-di(C1-C3)alkyl-3,5-di(C1-C3)alkylhexahydroazepinium compounds, N,N-di(C1-C3)alkyl-2,6-di(C1-C3)alkylpyrrolidinium compounds, N,N-di(C1-C3)alkyl-2,6-di(C1-C3)alkylpiperidinium compounds, N,N-di(C1-C3)alkyl-2,6-di(C1-C3)alkylhexahydroazepinium compounds, and mixtures of two or more thereof, More preferably, from the group consisting of N,N-di(C1-C2)alkyl-3,5-di(C1-C2)alkylpyrrolidinium compounds, N,N-di(C1-C2)alkyl-3,5-di(C1-C2)alkylpiperidinium compounds, N,N-di(C1-C2)alkyl-3,5-di(C1-C2)alkylhexahydroazepinium compounds, N,N-di(C1-C2)alkyl-2,6-di(C1-C2)alkylpyrrolidinium compounds, N,N-di(C1-C2)alkyl-2,6-di(C1-C2)alkylpiperidinium compounds, N,N-di(C1-C2)alkyl-2,6-di(C1-C2)alkylhexahydroazepinium compounds, and mixtures of two or more thereof, More preferably, the compound contains one or more ammonium compounds selected from the group consisting of N,N-di(C1-C2)alkyl-3,5-di(C1-C2)alkylpiperidinium compounds, N,N-di(C1-C2)alkyl-2,6-di(C1-C2)alkylpiperidinium compounds, and mixtures of two or more thereof, and more preferably contains one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N +The method of any one of embodiments 20 to 22, wherein the containing compound comprises one or more N,N-dimethyl-3,5-dimethylpiperidinium and / or N,N-diethyl-2,6-dimethylpiperidinium compounds, preferably one or more N,N-dimethyl-3,5-dimethylpiperidinium compounds.

[0100] 24. The N,N-dialkyl-2,6-dialkylpyrrolidinium compounds, N,N-dialkyl-2,6-dialkylpiperidinium compounds, and / or N,N-dialkyl-2,6-dialkylhexahydroazepinium compounds exhibit a cis configuration, a trans configuration, or contain a mixture of cis and trans isomers; Preferably, the N,N-dialkyl-2,6-dialkylpyrrolidinium compounds, the N,N-dialkyl-2,6-dialkylpiperidinium compounds and / or the N,N-dialkyl-2,6-dialkylhexahydroazepinium compounds exhibit a cis configuration, More preferably, said one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + The containing compound comprises one or more ammonium compounds selected from the group consisting of N,N-di(C1-C2)alkyl-cis-2,6-di(C1-C2)alkylpiperidinium compounds and mixtures of two or more thereof, and more preferably one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + 24. The method of embodiment 23, wherein the containing compound comprises one or more N,N-diethyl-cis-2,6-dimethylpiperidinium compounds.

[0101] 25. The method according to any one of embodiments 16 to 24, wherein the one or more organic templates are provided as a salt, preferably one or more salts selected from the group consisting of halides, sulfates, nitrates, phosphates, acetates, and mixtures of two or more thereof, more preferably bromides, chlorides, hydroxides, sulfates, and mixtures of two or more thereof, more preferably the one or more organic templates are provided as hydroxides and / or bromides, more preferably hydroxides.

[0102] 26. The method according to any one of embodiments 16 to 25, wherein the mixture prepared in (1) contains seed crystals, and the amount of seed crystals contained in the mixture prepared in (1) is within the range of 0.1 to 15 wt%, preferably 0.5 to 11 wt%, more preferably 0.8 to 8 wt%, more preferably 1.2 to 5 wt%, more preferably 1.5 to 3 wt%, and more preferably 1.8 to 2.5 wt%, based on 100 wt% Si (silicon) in the mixture calculated as SiO2.

[0103] 27. The method of any one of embodiments 16 to 26, wherein the mixture prepared in (1) comprises seed crystals, the seed crystals comprising one or more zeolitic materials having an AEI-type framework structure.

[0104] 28. The method of any one of embodiments 16 to 27, wherein the mixture prepared in (1) comprises a hydroxide salt.

[0105] 29.OH in the mixture prepared in (1) - The method according to any one of embodiments 16 to 28, wherein the molar ratio of Si to Mn is in the range of 0.05 to 5, preferably 0.1 to 3, more preferably 0.2 to 1, more preferably 0.3 to 0.8, more preferably 0.45 to 0.65, more preferably 0.5 to 0.6, more preferably 0.52 to 0.56.

[0106] 30. The method according to any one of embodiments 16 to 29, wherein the mixture prepared in (1) comprises one or more metals selected from the group consisting of alkali metals and alkaline earth metals, preferably one or more metals selected from the group consisting of Li, Na, K, Rb, Cs, Mg, and Ca, more preferably one or more metals selected from the group consisting of Li, Na, and K, more preferably the mixture prepared in (1) comprises K and / or Na, preferably Na.

[0107] 31. The method of any one of embodiments 30, wherein the mixture prepared in (1) comprises Mg, Ca, or Mg and Ca.

[0108] 32. The method according to embodiment 30 or 31, wherein the molar ratio of the one or more metals selected from the group consisting of alkali metals and alkaline earth metals to the one or more organic templates in the mixture prepared in (1) is within the range of 0.01 or less to 50, preferably 0.05 or less to 25, more preferably 0.1 or less to 15, more preferably 0.5 or less to 10, more preferably 1 to 7, more preferably 2 to 5, more preferably 3 to 4, and more preferably 3.4 to 3.6.

[0109] 33. The method according to any one of embodiments 16 to 32, wherein the heating in (2) is carried out for a duration in the range of 0.25 to 12 days, preferably 0.5 to 8 days, more preferably 1 to 6 days, more preferably 1.5 to 4.5 days, more preferably 2 to 4 days, more preferably 2.5 to 3.5 days.

[0110] 34. The method according to any one of embodiments 16 to 33, wherein the heating in (2) is carried out at a temperature in the range of 80 to 220°C, preferably 100 to 200°C, more preferably 120 to 180°C, more preferably 130 to 170°C, more preferably 140 to 160°C, more preferably 145 to 155°C.

[0111] 35. The method according to any one of embodiments 16 to 34, wherein the heating in (2) is carried out under autogenous pressure, preferably under solvothermal conditions, more preferably under hydrothermal conditions, and preferably, the heating in (2) is carried out in a pressure vessel, preferably in an autoclave.

[0112] 36. The method of any one of embodiments 16 to 35, wherein the zeolitic material crystallized in (2) has an AEI-type framework structure.

[0113] 37. The method according to any one of embodiments 16 to 36, further comprising (3) subjecting the zeolitic material obtained in (2) to ion exchange with one or more metal cations M.

[0114] 38.(3) The zeolite material obtained in (3a)(2) was + and / or NH4 + , preferably NH4 + and subjecting the resulting mixture to one or more ion exchange steps according to (3b) subjecting the zeolitic material obtained in (3a) to one or more ion-exchange procedures with one or more metal cations M, The method according to embodiment 37, wherein (3a) and / or (3b) are repeated independently of each other, preferably 1 to 3 times, more preferably 1 or 2 times, more preferably 1 time.

[0115] 39. The method according to embodiment 37 or 38, wherein in (3), the zeolitic material obtained in (2) is directly subjected to ion exchange with one or more metal cations M, and no ion exchange step is carried out prior to the ion exchange of the zeolitic material obtained in (2) with one or more metal cations M.

[0116] 40. The one or more metal cations M are selected from the group consisting of Sr, Zr, Cr, Mg, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Sc, and mixtures of two or more thereof, preferably selected from the group consisting of Sr, Zr, Cr, Mg, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more thereof, more preferably Sr, Cr, Mg, Mo, Fe, Co, Ni, Cu , Zn, Ag, and mixtures of two or more thereof, more preferably selected from the group consisting of Cr, Mg, Mo, Fe, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, more preferably selected from the group consisting of Mg, Mo, Fe, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, more preferably selected from the group consisting of Mg, Mo, Fe, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, more preferably the one or more cations M comprise Cu and / or Fe, preferably comprise Cu, even more preferably the one or more cations M consist of Cu and / or Fe, preferably consist of Cu.

[0117] 41. The method according to any one of embodiments 37 or 40, wherein the one or more metal cations M are provided as a salt, preferably as one or more salts selected from the group consisting of halides, sulfates, nitrates, phosphates, acetates, and mixtures of two or more thereof, more preferably from the group consisting of sulfates, nitrates, acetates, and mixtures of two or more thereof, more preferably the one or more metal cations M used to prepare the mixture according to (1) are provided as nitrates and / or acetates, more preferably as acetates.

[0118] 42. After (2) and before (3), (i) optionally isolating the zeolitic material obtained in (2), preferably by filtration; and / or, preferably, and (ii) optionally washing the zeolitic material obtained in (2) or (i), preferably with distilled water; and / or, preferably, and (iii) optionally drying the zeolitic material obtained in (2), (i), or (ii); and / or, preferably, and The method of any one of embodiments 37 to 41, comprising (iv) optionally calcining the zeolitic material obtained in (2), (i), (ii), or (iii).

[0119] 43. The method of embodiment 42, wherein the calcination in (iv) is carried out for a duration in the range of 0.5 to 15 hours, preferably 1 to 10 hours, more preferably 1.5 to 8 hours, more preferably 2 to 6 hours, more preferably 2.5 to 5.5 hours, more preferably 3 to 5 hours, more preferably 3.5 to 4.5 hours.

[0120] 44. The method according to embodiment 42 or 43, wherein the calcination in (iv) is carried out at a temperature in the range of 300 to 900°C, preferably 350 to 800°C, more preferably 400 to 750°C, more preferably 450 to 700°C, more preferably 500 to 650°C, more preferably 560 to 600°C.

[0121] 45. The one or more SiO sources 2 are selected from the group consisting of silicon-containing zeolites having a FAU, FER, GIS, MOR, LTA, TON, MTT, BEA, and / or MFI framework structure, silica, silicates, silicic acid, and combinations of two or more thereof, preferably selected from the group consisting of silicon-containing zeolites having a FAU, GIS, BEA, and / or MFI framework structure, silica, alkali metal silicates, silicic acid, and combinations of two or more thereof, more preferably selected from the group consisting of silicon-containing zeolites having a FAU, BEA, and / or MFI framework structure, fumed silica, colloidal silica, The method according to any one of embodiments 16 to 44, wherein the one or more SiO sources 2 are selected from the group consisting of silica, reactive amorphous solid silica, silica gel, pyrogenic silica, lithium silicate, sodium silicate, potassium silicate, silicic acid, and combinations of two or more thereof, more preferably selected from the group consisting of silicon-containing zeolite having a FAU framework structure, colloidal silica, fumed silica, silica gel, pyrogenic silica, and combinations of two or more thereof, more preferably selected from the group consisting of silicon-containing zeolite having a FAU framework structure, colloidal silica, and / or fumed silica.

[0122] 46. ​​The zeolite having an FAU type framework structure is selected from the group consisting of ZSM-3, faujasite, [Al-Ge-O]-FAU, CSZ-1, ECR-30, zeolite X, zeolite Y, LZ-210, SAPO-37, ZSM-20, Na-X, US-Y, Na-Y, [Ga-Ge-O]-FAU, Li-LSX, [Ga-Al-Si-O]-FAU, and [Ga-Si-O]-FAU (including mixtures of two or more thereof), Preferably, from the group consisting of ZSM-3, faujasite, CSZ-1, ECR-30, zeolite X, zeolite Y, LZ-210, ZSM-20, Na-X, US-Y, Na-Y, and Li-LSX (including mixtures of two or more thereof); More preferably, it is selected from the group consisting of faujasite, zeolite X, zeolite Y, Na-X, US-Y, and Na-Y (including mixtures of two or more thereof), more preferably, it is selected from the group consisting of faujasite, zeolite X, and zeolite Y (including mixtures of two or more thereof), The method according to embodiment 45, wherein the zeolite having an FAU-type framework structure comprises zeolite X and / or zeolite Y, preferably zeolite Y, more preferably the zeolite having an FAU-type framework structure is zeolite X and / or zeolite Y, preferably zeolite Y.

[0123] 47. Zeolites with the BEA-type framework structure include zeolite beta, tsarnikite, [B-Si-O]- * BEA, CIT-6, [Ga-Si-O]- * BEA, beta polymorph B, SSZ-26, SSZ-33, beta polymorph A, [Ti-Si-O]- * From the group consisting of BEA, and pure silica beta (including mixtures of two or more thereof), Preferably, it is selected from the group consisting of zeolite beta, CIT-6, beta polymorph B, SSZ-26, SSZ-33, beta polymorph A, and pure silica beta (including mixtures of two or more thereof); More preferably, the zeolite having a BEA-type framework structure comprises zeolite beta, preferably zeolite beta obtained from synthesis without the use of organic templates; More preferably, the zeolite having a BEA-type framework structure is zeolite beta, preferably zeolite beta obtained from an organic template-mediated synthesis or from a synthesis without using an organic template, more preferably zeolite beta obtained from an organic template-free synthesis.

[0124] 48. Zeolites having an MFI type framework structure are selected from the group consisting of silicalite, ZSM-5, [Fe-Si-O]-MFI, [Ga-Si-O]-MFI, [As-Si-O]-MFI, AMS-1B, AZ-1, Bor-C, Encilite, Boralite C, FZ-1, LZ-105, Mucinite, NU-4, NU-5, TS-1, TSZ, TSZ-III, TZ-01, USC-4, USI-108, ZBH, ZKQ-1B, ZMQ-TB, MnS-1, and FeS-1 (including mixtures of two or more thereof); Preferably, it is selected from the group consisting of silicalite, ZSM-5, AMS-1B, AZ-1, Encilite, FZ-1, LZ-105, Mucinite, NU-4, NU-5, TS-1, TSZ, TSZ-III, TZ-01, USC-4, USI-108, ZBH, ZKQ-1B, and ZMQ-TB (including mixtures of two or more thereof); More preferably, the zeolite having an MFI type framework structure comprises silicalite and / or ZSM-5, preferably ZSM-5; The method according to any one of embodiments 45 to 47, wherein the zeolite having an MFI-type framework structure is more preferably the zeolite silicalite and / or ZSM-5, preferably ZSM-5.

[0125] 49. The method according to any one of embodiments 16 to 48, wherein the one or more B2O3 sources are selected from the group consisting of boric acid, borates, borate esters, and mixtures of two or more thereof, preferably from the group consisting of boric acid, borates, triethyl borate, trimethyl borate, boron esters, and mixtures of two or more thereof, more preferably the one or more B2O3 sources comprise boric acid and / or borates, preferably boric acid, more preferably the one or more B2O3 sources consist of boric acid and / or borates, preferably boric acid.

[0126] 50. The method according to any one of embodiments 16 to 49, wherein the one or more AlO sources 3 comprise one or more compounds selected from the group consisting of aluminum-containing zeolites having a FAU framework structure and aluminum salts, preferably the one or more AlO sources 3 comprise an aluminum-containing zeolite having a FAU framework structure or aluminum nitrate, more preferably the one or more AlO sources 3 consist of an aluminum-containing zeolite having a FAU framework structure or aluminum nitrate.

[0127] 51. The method according to any one of embodiments 16 to 50, wherein the one or more SiO2 sources and the one or more Al2O3 sources comprise a silicon- and aluminum-containing zeolite having a FAU framework structure, preferably the one or more SiO2 sources and the one or more Al2O3 sources consist of a silicon- and aluminum-containing zeolite having a FAU framework structure.

[0128] 52. The method of any one of embodiments 16-51, wherein the solvent system is selected from the group consisting of optionally branched chain (C1-C4) alcohols, distilled water, and mixtures thereof, preferably from the group consisting of optionally branched chain (C1-C3) alcohols, distilled water, and mixtures thereof, more preferably from the group consisting of methanol, ethanol, distilled water, and mixtures thereof, more preferably the solvent system comprises distilled water, more preferably the solvent system consists of distilled water.

[0129] 53. The method of any one of embodiments 16 to 52, wherein the mixture prepared in (1) and crystallized in (2) contains 5% by weight or less, preferably 3% by weight or less, more preferably 1% by weight or less, more preferably 0.5% by weight or less, more preferably 0.1% by weight or less, more preferably 0.05% by weight or less, more preferably 0.01% by weight or less, more preferably 0.005% by weight or less, more preferably 0.001% by weight or less, more preferably 0.0005% by weight or less, and more preferably 0.0001% by weight or less, calculated as an element, with the mixture prepared in (1) being 100% by weight.

[0130] 54. The method according to any one of embodiments 16 to 53, wherein the mixture prepared in (1) comprises seed crystals, the seed crystals comprising one or more zeolitic materials having in their framework structure a zeolitic material comprising SiO2, B2O3, and Al2O3, obtained according to the method according to any one of embodiments 15 to 59, preferably the one or more zeolitic materials of the seed crystals are obtainable and / or obtained according to the method according to any one of embodiments 15 to 59.

[0131] 55. A zeolitic material having an AEI-type framework structure, preferably according to any one of embodiments 1 to 15, which is obtainable and / or obtainable according to the method according to any one of embodiments 16 to 54.

[0132] 56. NO by selective catalytic reduction x A method for treating (A) providing a gas stream containing one or more nitrogen oxides; (B) contacting the gas stream provided in step (A) with the zeolitic material of any one of embodiments 1 to 15 and 55; A method comprising:

[0133] 57. The method of embodiment 56, wherein the gas stream provided in (A) further comprises one or more reducing agents, the reducing agents preferably comprising ammonia and / or urea.

[0134] 58. The method according to embodiment 56 or 57, wherein the gas stream provided in (A) comprises one or more waste gases, preferably one or more waste gases from one or more industrial processes, more preferably the waste gas stream comprises one or more waste gas streams obtained in a process for combusting nitrogen-containing substances, including in a process for producing adipic acid, nitric acid, hydroxylamine derivatives, caprolactam, glyoxal, methyl-glyoxal, glyoxylic acid, or a mixture of waste gas streams from two or more of the above-mentioned processes, even more preferably the waste gas stream comprises one or more waste gas streams obtained in a process for producing adipic acid and / or nitric acid.

[0135] 59. The method of any one of embodiments 56-58, wherein the gas stream provided in (A) comprises one or more waste gases from an internal combustion engine, preferably a diesel engine or a lean-burn gasoline engine.

[0136] 60. The method according to any one of embodiments 56 to 59, wherein the contacting of the gas stream with the zeolitic material in (B) is carried out at a temperature comprised within the range of 250 to 550°C, preferably 300 to 500°C, more preferably 325 to 450°C, more preferably 350 to 425°C, more preferably 380 to 420°C, even more preferably 390 to 410°C.

[0137] 61. NO x 56. An apparatus for the treatment of a gas stream containing a zeolitic material according to any one of embodiments 1 to 15 and 55, comprising a catalyst bed provided in fluid contact with the gas stream to be treated, the catalyst bed comprising the zeolitic material according to any one of embodiments 1 to 15 and 55.

[0138] 62. The apparatus of embodiment 61, wherein the catalyst bed is a fixed bed catalyst or a fluidized bed catalyst, preferably a fixed bed catalyst.

[0139] 63. The apparatus of embodiment 61 or 62, further comprising one or more devices provided upstream of the catalyst bed for injecting one or more reducing agents into the gas stream, the reducing agents preferably comprising ammonia and / or urea.

[0140] 64. Use of the zeolitic material according to any one of embodiments 1 to 15 and 55 as a molecular sieve, as an adsorbent, for ion exchange, as a catalyst or a precursor thereof and / or as a catalyst support or a precursor thereof, preferably as a catalyst or a precursor thereof and / or as a catalyst support or a precursor thereof, more preferably as a catalyst ... x for selective catalytic reduction (SCR) of CO2, for storage and / or adsorption of CO2, for oxidation of NH3, in particular for oxidation of NH3 slip in diesel systems, for decomposition of N2O, as catalysts, as additives in fluid catalytic cracking (FCC) processes, and / or in organic conversion reactions, preferably in the conversion of alcohols to olefins, more preferably in the catalysis of methanol to olefins (MTO), more preferably in the catalysis of nitrogen oxides NO x More preferably, for selective catalytic reduction (SCR) of nitrogen oxides NO in exhaust gases from a combustion engine, preferably from a diesel engine or from a lean-burn gasoline engine. x as a catalyst for selective catalytic reduction (SCR). EXAMPLES

[0141] Experimental Section Reference Example 1: Inductively Coupled Plasma (ICP) Elemental analysis was performed with an inductively coupled plasma atomic emission spectrometer (ICP-AES, Shimadzu ICPE-9000).

[0142] Reference Example 2: Scanning Electron Microscopy (SEM) FE-SEM images were obtained on a Hitachi S-5200 microscope operating at 1 kV.

[0143] Reference Example 3: Measurement of X-ray diffraction data (XRD) Powder X-ray diffraction (XRD) patterns were collected on a Rigaku Ultima III diffractometer using CuKα radiation (40 kV, 40 mA).

[0144] Reference Example 4: Determination of average aspect ratio and average grain size To determine the aspect ratio of the primary crystallites of the zeolitic material, primary zeolitic crystallites oriented perpendicular to the electron probe were manually selected in the SEM images for evaluation. Both available dimensions for a given crystallite (i.e., width and height of the crystallite) were measured and recorded for each particle. This procedure was performed for as many SEM images displaying different parts of the surface of the sample as necessary to obtain values ​​for at least 120 different particles, preferably at least 150 different particles, more preferably at least 200 different particles. The average of the aspect ratios obtained for all of the measured particles, i.e., the ratio of the width to the height of each particle, constituted the average aspect ratio of the sample. The average width (largest dimension) of the primary crystallites obtained in the above manner constituted the average particle size of the primary crystallites of the sample.

[0145] Reference Example 5: Synthesis of N,N-dimethyl-3,5-dimethylpiperidinium hydroxide (DMPOH) First, 24 g of 3,5-dimethylpiperidine (TCI, 98%, cis-trans mixture) was mixed with 220 mL of methanol (Wako, 99.9%) and 42 g of potassium carbonate (Wako, 99.5%). Then, 121 g of methyl iodide (Wako, 99.5%) was added dropwise, and the resulting mixture was maintained under reflux for 1 day. After partial removal of methanol by evaporation, chloroform was added, stirred, and then filtered to remove potassium carbonate. This step was repeated to completely remove methanol and potassium carbonate. Then, ethanol was added to perform recrystallization, and diethyl ether was added to precipitate the iodide salt. After filtration, the solid product was dried and mixed with hydroxide ion exchange resin (DIAION SA10AOH, Mitsubishi) and distilled water. After 1 day, the resin was removed by filtration to obtain an aqueous DMPOH solution (35.1 wt%).

[0146] Comparative Example 1: Preparation of a zeolite material with an AEI-type framework structure using tetraethylphosphonium as a template agent First, tetraethylphosphonium hydroxide (TEPOH) aqueous solution was mixed with 8M NaOH aqueous solution (Wako) and distilled water. Then, boric acid (Wako) was added to the above solution and stirred for 1 h. Then, HY zeolite (CBV720 with Si / Al=15, Zeolyst) was added to the above solution and stirred for 1 h. The molar composition of the obtained gel was 1 SiO2:0-0.2 H3BO3:0.067 Al:0.2 TEPOH:0.1 NaOH:5 H2O. The mother gel thus prepared was crystallized under tumbling conditions (40 rpm) in an autoclave at 170 °C for 5 days. The solid product was collected by centrifugation, washed with distilled water and dried overnight at 100 °C under air. As can be seen from the XRD of the obtained materials shown in Figure 1, zeolite materials exhibiting AEI framework type structure were obtained, respectively. SEM images of the obtained materials are shown in Figure 3.

[0147] Using TEPOH as the OSDA, the as-synthesized SSZ-39 and [B,Al]-AEI zeolites (0.5 g) were calcined at 600 °C for 6 h in a flow of hydrogen / nitrogen mixture (H2: 15 mL / min, N2: 60 mL / min) to remove the template.

[0148] The calcined Na-type zeolite (1 g) was ion-exchanged twice with 100 mL of 2.5 M NH4NO3 aqueous solution at 80° C. for 3 h. The solid product was collected by filtration, washed with distilled water, dried in air at 100° C., and calcined in air at 600° C. for 5 h to obtain H-type zeolite.

[0149] The average particle size of the zeolite obtained without boron and the samples obtained with SiO2:H3BO3 molar ratios of 20, 10, and 5, respectively, were obtained according to the method of Reference Example 4. Thus, the zeolite obtained without boron and the zeolite obtained with SiO2:H3BO3 molar ratios of 20 and 10, respectively, showed an average particle size of 140 nm, while the zeolite obtained with a SiO2:H3BO3 molar ratio of 5 showed an average particle size of 800 nm.

[0150] Thus, larger crystal sizes are only obtained when a large amount of boron is used in the starting gel, as can be seen from the average particle size measurements reflected in the SEM image of the zeolitic material in Figure 3. When less boron or no boron is used in the starting gel, only very small crystals are obtained.

[0151] Example 1: Preparation of zeolitic materials with AEI-type framework structure using N,N-dimethyl-3,5-dimethylpiperidinium as template agent First, 0.7555 g of DMPOH aqueous solution obtained according to Reference Example 5 was mixed with 0.82 g of 8M NaOH aqueous solution (Wako) and distilled water. Then, 0.033 g of boric acid (Wako) was added to the above solution and stirred for 1 h. Then, 0.6665 g of HY zeolite (CBV760 with Si / Al=30, Zeolyst) was added to the above solution and stirred for 1 h. The molar composition of the obtained gel was 1 SiO2:0.05 H3BO3:0.033 Al:0.155 DMPOH:0.48 NaOH, where the molar ratio of H2O:SiO2 of the gel varied between 20 and 40. The mother gel thus prepared was crystallized in an autoclave at 150 °C for 3 days under tumbling conditions (30 rpm). The solid products were collected by filtration, washed with distilled water and dried overnight at 100° C. under air. Zeolite materials exhibiting AEI framework type structure were obtained, respectively, as can be seen from the XRD of the obtained materials shown in Figure 2. SEM images of the obtained materials are shown in Figure 4.

[0152] The as-synthesized SSZ-39 and [B,Al]-AEI zeolites were then calcined at 600 °C for 6 h in air to remove the template using DMPOH as the OSDA.

[0153] The calcined Na-type zeolite (1 g) was ion-exchanged twice with 100 mL of 2.5 M NH4NO3 aqueous solution at 80° C. for 3 h. The solid product was collected by filtration, washed with distilled water, dried in air at 100° C., and calcined in air at 600° C. for 5 h to obtain H-type zeolite.

[0154] The average aspect ratios and average particle sizes of the zeolites obtained using H2O:SiO2 molar ratios of 20, 30, and 40 were obtained according to the method of Reference Example 4. Thus, the average particle size of the zeolites obtained using a H2O:SiO2 molar ratio of 20 gave an average particle size of 1.5 μm and an average aspect ratio of 4.3, the zeolites obtained using a H2O:SiO2 molar ratio of 30 gave an average particle size of 1.0 μm and an average aspect ratio of 3.0, and the zeolites obtained using a H2O:SiO2 molar ratio of 40 gave an average particle size of 1.0 μm and an average aspect ratio of 2.0.

[0155] Thus, even with a low amount of boron in the starting gel, large crystal sizes can be achieved, as can be seen from the measurements of the average particle size reflected in the SEM image of the zeolitic material in Figure 4. Thus, larger crystals containing a relatively high concentration of catalytically active Al sites can be obtained compared to the results achieved according to Comparative Example 1, where isomorphous replacement of Al sites by boron occurs to a much greater extent, compared to the larger crystals obtained according to Comparative Example 1.

[0156] In addition to the aforementioned advantages, the method of the invention allows the use of starting gels with a much higher amount of water compared to the starting gel according to Comparative Example 1. As a result, better crystallinity can be achieved. Furthermore, the starting gel according to the method of the invention shows a much higher degree of resistance to contaminants due to the higher dilution, as a result of the method of the invention allowing the recycling of template and / or unreacted materials to a much greater extent than is possible when using the method according to Comparative Example 1.

[0157] Finally, whereas the method of Comparative Example 1 requires an elaborate procedure for the removal of the phosphorus-containing template, namely calcination under a reducing atmosphere, but nevertheless does not result in a product completely free of phosphorus-containing residues, the method of the present invention allows the quantitative removal of the organic template used by calcination in air alone.

[0158] Example 2: Preparation of zeolitic materials with AEI-type framework structure using N,N-dimethyl-3,5-dimethylpiperidinium as template agent Zeolitic materials with AEI-type framework structure were prepared according to the procedure based on the method of Example 1, using N,N-dimethyl-3,5-dimethylpiperidinium as template agent, starting gel composition of 1 SiO2:0-0.2 H3BO3:0.033 Al:0.155 DMPOH:0.1 NaOH:20-31 H2O, and varying the molar ratio of Si:B used in the starting gel between 5 and 20. Zeolitic materials showing AEI-type framework structure were obtained, respectively, as can be seen from the XRD of the obtained materials shown in Figure 5. SEM images of the obtained materials are shown in Figure 6.

[0159] The resulting zeolite material was subjected to elemental analysis by ICP, giving the results shown in the table below.

[0160] [Table 1]

[0161] As can be seen from the SEM image of the zeolitic material in Figure 6, by increasing the amount of boron in the starting gel, a further increase in the crystal size of the resulting zeolitic material can be achieved compared to Example 1, which used a molar ratio of Si:B of 20 in the starting gel. However, as can be seen from the comparison with the results shown in Figure 3 for Comparative Example 1, much less boron is required with the method of the present invention to obtain a crystal size comparable to that obtained according to the Comparative Example. Thus, again, as shown above in the discussion of the results of Example 1, even with a relatively low amount of boron in the starting gel, large crystal sizes can be achieved that contain a relatively high concentration of catalytically active Al sites, compared to the larger crystals obtained according to Comparative Example 1, where isomorphous replacement of Al sites by boron occurs to a much greater extent. [Brief description of the drawings]

[0162] [Figure 1] FIG. 2 shows the XRD pattern of the as-prepared [B,Al]-AEI zeolite obtained according to Comparative Example 1. [Diagram 2] FIG. 2 shows the XRD pattern of the as-prepared [B,Al]-AEI zeolite obtained according to Example 1. [Diagram 3] FIG. 2 shows an SEM image of the as-prepared [B,Al]-AEI zeolite obtained according to Comparative Example 1. [Figure 4] FIG. 2 shows an SEM image of the as-prepared [B,Al]-AEI zeolite obtained according to Example 1. [Diagram 5] FIG. 2 shows the XRD pattern of the as-prepared [B,Al]-AEI zeolite obtained according to Comparative Example 2. [Figure 6] FIG. 2 shows an SEM image of the as-prepared [B,Al]-AEI zeolite obtained according to Example 2.

[0163] References -U.S. Patent No. 5,958,370 -Moliner,M.et al.in Chem.Commun.2012,48,pages 8264-8266 -Maruo,T.et al.in Chem.Lett.2014,43,page 302-304 -Martin,N.et al.in Chem.Commun.2015,51,11030-11033 -Dusselier,M.et al.in ACS Catal.2015,5,10,6078-6085 -U.S. Patent Application Publication No. 2015 / 0118150A1 -International Patent Application Publication No. 2016 / 149234A1 -Ransom,R.et al.in Ind.Eng.Chem.Res.2017,56,4350-4356 -International Patent Application Publication No. 2018 / 113566A1 -Patent Publication No. 2018-087105A

Claims

1. SiO ２ , Al ２ O ３ , and B ２ O ３ wherein the zeolite material has an Al:B molar ratio within a range of 10 to 50, a Si:B molar ratio within a range of 180 to 220, the zeolite material exhibits a Si:(Al+B) molar ratio within a range of 5 to 10, a Si:Al molar ratio within a range of 6 to 25, an average particle size of primary crystals of the zeolite material within a range of 0.5 to 4.0 μm, and the primary crystals of the zeolite material exhibit an average aspect ratio of 1.4 to 5.

0.

2. 2. The zeolitic material of claim 1, wherein the zeolitic material comprises one or more metal cations M selected from the group consisting of Sr, Zr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Sc, and mixtures of two or more thereof.

3. 2. The zeolitic material of claim 1, wherein the zeolitic material having an AEI-type framework structure is selected from the group consisting of SSZ-39, SAPO-18, and SIZ-8 (including mixtures of two or more thereof).

4. SiO according to claim 1 ２ , Al ２ O ３ , and B ２ O ３ 1. A method for preparing the zeolitic material having an AEI-type framework structure comprising: (1) One or more organic templates as structure-directing agents, one or more SiO ２ Source, one or more B ２ O ３ source, one or more Al ２ O ３ preparing a mixture comprising a source, optionally a seed crystal, and a solvent system, wherein the one or more SiO ２ a source and said one or more Al ２ O ３ the source comprises a silicon and aluminum containing zeolite having a FAU framework structure; (1) The molar ratio of silicon to boron (Si:B), each calculated as an element, in the mixture prepared according to (1) is in the range of 4 to 25; (1) The molar ratio of silicon to boron (Si:Al), each calculated as an element, in the mixture prepared according to (1) is in the range of 15 to 50; (2) Extracting SiO from the mixture ２ , B ２ O ３ , and Al ２ O ３ heating the mixture obtained in (1) to crystallize a zeolitic material comprising Including, The one or more organic templates are N,N-di(C １ ~C ２ ) alkyl-3,5-di(C １ ~C ２ ) alkylpiperidinium compounds, N,N-di(C １ ~C ２ ) alkyl-2,6-di(C １ ~C ２ ) alkyl piperidinium compounds, and mixtures of two or more thereof.

5. The mixture prepared in (1) contains seed crystals, and the amount of seed crystals contained in the mixture prepared in (1) is SiO ２ 5. The method of claim 4, wherein the Si content is in the range of 0.1 to 15 wt. %, based on 100 wt. % of Si in the mixture calculated as:

6. 5. A zeolitic material having an AEI-type framework structure, said zeolitic material being obtainable and / or obtainable according to the method of claim 4.

7. NO by selective catalytic reduction ｘ A method for treating (A) providing a gas stream containing one or more nitrogen oxides; (B) contacting the gas stream provided in step (A) with the zeolitic material of any one of claims 1 to 3 and 6; A method comprising:

8. NO ｘ 10. An apparatus for the treatment of a gas stream containing a compound according to claim 1, wherein the apparatus comprises a catalyst bed provided in fluid contact with the gas stream to be treated, the catalyst bed comprising the zeolitic material according to any one of claims 1 to 3 and 6.

9. Use of the zeolitic material according to any one of claims 1 to 3 and 6 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 for the removal of CO ２ for storage and / or adsorption of NH ３ for the oxidation of NH, especially in diesel systems ３ For oxidation of slip, N ２ Use as an additive in fluid catalytic cracking (FCC) processes for the cracking of O and / or as a catalyst in organic conversion reactions.

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