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    • 专利摘要:
    Direct synthesis method of the material cu-silicoaluminato with zeolitic structure aei, and its catalytic applications The main objective of the present invention is to provide a new method for the preparation of the zeolitic aei structure in its silicoaluminate form containing copper atoms therein by means of a direct synthesis methodology. This new process involves the combination of an organometallic copper complex with an additional organic molecule capable of directing the crystallization of the zeolitic structure aei in its silicoaluminate form as organic structure directing agents (adeos). (Machine-translation by Google Translate, not legally binding)
    公开号:ES2586770A1
    申请号:ES201530513
    申请日:2015-04-16
    公开日:2016-10-18
    发明作者:Avelino Corma Canós；Manuel MOLINER MARÍN；Nuria MARTÍN GARCÍA
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；Universidad Politecnica de Valencia；
    IPC主号:
    专利说明:

    Technical Field
    The present invention relates to a new method for the preparation of the AEI zeolitic structure in its silicoaluminal form containing copper atoms in its interior by a direct synthesis methodology. This new methodology requires the combination of an organometallic copper complex and an organic molecule capable of directing the crystallization of the AE I zeolitic structure, as organic structure directing agents (ADEOs). The present invention also relates to the application of said Cu-silicoaluminate materials with the zeolitic structure AE I as catalysts in the selective catalytic reduction (ReS) of NOx among others.
    Background
    Zeolites are microporous materials formed by T04 tetrahedra (T = Si, Al, P, Ti, Ge, Sn ...) interconnected by oxygen atoms creating pores and cavities with uniform size and shape in the molecular range (3-15 A ).
    These microporous crystalline materials can be used as catalysts in numerous chemical processes. The use of a zeolite with specific physicochemical properties in a given chemical process will depend directly on the nature of the reagents and products involved in the process (such as size, shape, hydrophobicity ...) and also on the reaction conditions. On the one hand, the nature of the reagents and products will affect the diffusion of these molecules in the pores and cavities of the zeolite, and consequently, the choice of the zeolite with a suitable pore topology for the products involved in the reaction is essential . On the other hand, the zeolite must be chemically and structurally stable under the required reaction conditions.
    The formation of nitrogen oxides (NOx) during the combustion of fossil fuels has become a problem for society, since they are one of the largest atmospheric pollutants. Selective catalytic reduction (ReS) of NOx using
    Ammonia as a reducing agent has become a form of efficient control of these emissions (Brandenberger, et al. Catal. Rev. Sci. Eng., 2008, 50, 492).
    5 Recently, it has been described that silicoaluminate with AEI structure containing Cu bundles in its interior has a high catalytic activity and hydrothermal stability for the reduction of NO RCS, (Moliner et al. W02013159825; Moliner et al. Chem. Commun., 2012, 2012.48, 8264).
    1O The zeolitic structure AE I has a three-way system of small pores «4 A) interconnected by large cavities and also has double 6-member rings (DA6) as secondary construction units (Wagner, et al. J. Am. Chem. Soc., 2000, 122, 263).
    fifteen The silicoaluminate form of the zeolitic structure AEI can be synthesized using cyclic ammonium cations with alkyl substituents (Zones et al. USPatent 5958370; Cao et al. WO 2005/063624; Moliner et al. W02013159825), or tetraalkylphosphonium cations (Sano et al WO / 2015/005369) as ADEOs.
    20 25 For the preparation of the AEI zeolitic structure in its silicoaluminate form containing Cu bundles, the incorporation of the copper species is preferably carried out by post-synthetic metal ion exchange procedures on the previously synthesized and calcined material (Moliner et al. W02013159825 ; Sonada, et al. J. Mater. Chem. A, 2015, 3, 857). Following this methodology, several steps are required to achieve the final material, including the hydrothermal synthesis of silicoaluminate, calcination to eliminate ADEO, transformation to the ammonium form, exchange of the metal ion and finally, calcination to obtain the material in the Cu-form. desired silicoaluminate. All these steps contribute to increasing the total cost of the material preparation procedure.
    30 35 Therefore, the possibility of directly synthesizing the AEI zeolitic structure material in its silicoaluminate form containing copper bundles inside, could considerably improve the costs associated with its preparation, since it would avoid most of the steps described above, making these prepared materials directly very attractive to the industry.
    Description of the invention
    The main objective of the present invention is to provide a new method for the preparation of the AEI zeolitic structure in its silicoaluminate form containing copper atoms therein by means of a direct synthesis methodology. This new procedure involves the combination of an organometallic copper complex with an additional organic molecule capable of directing the crystallization of the AEI zeolitic structure in its silicoaluminate form as organic structure directing agents (ADEOs). The additional organic molecule can be, among others, any cyclic ammonium cation with alkyl substituents, such as N, N-dimethyl-3,5-dimethylpiperidonium.
    Following this synthesis procedure, it is possible to synthesize the zeolitic structure AEI in its silicoaluminate form containing copper atoms in its interior directly, avoiding the steps required to achieve said material by means of the traditional post-synthetic procedures of exchange with the metal ion.
    The present invention also relates to the use of materials with AEI zeolitic structure in its silicoaluminate form containing copper atoms obtained according to the described methodology, as catalysts.
    Therefore, the present invention relates to a process for the direct synthesis of the AEI zeolitic structure material in its silicoaluminate form containing copper atoms with high synthesis yields, comprising at least the following steps:
    (i) Preparation of a mixture containing at least one source of water, a source of copper, a polyamine to form the organometallic complex of Cu, a source of tetravalent element Y, a source of trivalent element X, an ammonium cation cyclic with alkyl substituents such as ADEO and a source of alkaline or alkaline earth cations (A), and where the synthesis mixture has the following molar composition:
    Y02: a X20 3: b ADEO: e A: d H20: e Cu: f Polyamine where a is in the range of 0.001 to 0.2, preferably between 0.005 a
    0.1, and more preferably between 0.01 to 0.07.b is in the range of 0.01 to 2; preferably between 0.1 to 1, andmore preferably between 0.1 to 0.6;
    e is in the range of O to 2; preferably between 0.001 to 1, andmore preferably between 0.01 to 0.8;d is in the range of 1 to 200; preferably between 1 to 50, andmore preferably between 2 to 20;e is in the range of 0.001 to 1; preferably between 0.001 a0.6, and more preferably between 0.001 to 0.5;f is in the range of 0.001 to 1; preferably between 0.001 a0.6, and more preferably between 0.001 to 0.5.
    (ii) Crystallization of the mixture obtained in (i) in a reactor.
    (iii) Recovery of the crystalline material obtained in (ii).
    (iv) According to the present invention, Y is a tetravalenle element that may be preferably selected from Si, Sn, Ti, Ge and combinations thereof, and more preferably is Si.
    The source of Si used may be selected from silicon oxide, silicon halide, colloidal silica, smoked silica, tetraalkylortosilicate, silicate, silicic acid, a previously synthesized crystalline material, a previously synthesized amorphous material and combinations thereof and, more preferably , is a material selected from a previously synthesized crystalline material, a previously synthesized amorphous material and combinations thereof, and more preferably, a previously synthesized crystalline material.
    According to the present invention, X is a trivalent element that may be preferably selected from Al, B, Fe, In, Ga and combinations thereof, and more preferably is Al.
    The source of Al used can be selected from any aluminum salt, any hydrated aluminum oxide, any aluminum alkoxide, a previously synthesized crystalline material, a previously synthesized amorphous material and combinations thereof, and more preferably, it is a selected material between a previously synthesized crystalline material, a previously synthesized amorphous material and combinations thereof, and more preferably, a previously synthesized crystalline material.
    According to a particular embodiment of the present invention, the crystalline material with the zeolitic structure FAU can be used in (i) as the sole source of Y and X,
    preferably silicon and aluminum, and which may have a Si / Al ratio preferably
    greater than 7.
    Therefore, according to a particular embodiment of the present invention, Y is Si and X is Al whereby the process for the direct synthesis of the AEI zeolitic structure material in its silicoaluminate form containing copper atoms with high synthesis yields, would comprise At least the following steps:
    (i) Preparation of a mixture containing at least one source of water, a source of copper, a polyamine to form the organometallic complex of Cu, a zeolite with the crystalline structure FAU, such as zeolite Y, as the sole source of silicon and aluminum, a cyclic ammonium cation with alkyl substituents such as ADEO and a source of alkaline or alkaline earth cations (A), and where the synthesis mixture has the following molar composition:
    Si02: a AI20 3: b ADEO: e A: d H20: e Cu: f Polyamine where a is in the range of 0.001 to 0.2, preferably between 0.005 a
    0.1, and more preferably between 0.01 to 0.07.b is in the range of 0.01 to 2; preferably between 0.1 to 1, andmore preferably between 0.1 to 0.6;c is in the range of O to 2; preferably between 0.001 to 1, andmore preferably between 0.01 to 0.8;d is in the range of 1 to 200; preferably between 1 to 50, andmore preferably between 2 to 20;e is in the range of 0.001 to 1; preferably between 0.001 a0.6, and more preferably between 0.001 to 0.5;f is in the range of 0.001 to 1; preferably between 0.001 a0.6, and more preferably between 0.001 to 0.5.
    (ii) Crystallization of the mixture obtained in (i) in a reactor.
    (iii) Recovery of the crystalline material obtained in (ii).
    According to the present invention, any source of Cu can be used in (i). Preferably, the copper source may be selected from nitrate, sulfate, oxalate salts, and combinations thereof, among others.
    According to the present invention, the mixture formed in (i) is free of any phosphorus source.
    According to a preferred embodiment of the present invention, the mixture formed in (i) may be free of any source of fluorine.
    According to a preferred embodiment of the present invention, the source of alkaline or alkaline earth cations may be any source of these elements, and may preferably be selected from a source of Na, K, and combinations thereof.
    According to the present invention, the ADEO required in step (i) can be any cyclic ammonium cation with some alkyl substituent, preferably a quaternary ammonium selected from N, N-dimethyl-3,5-dimethylpiperidinium (DMDMP), N, N- diethyl-2,6-dimethylpiperidinium (DEDMP), N, N-dimethyl-2,6-dimethylpiperidinium, N-ethyl-N-methyl-2,6-dimethylpiperidinium and combinations thereof, preferably N, N-dimethyl-3,5-dimethylpiperidinium.
    According to a particular embodiment, the process of the present invention may further comprise another ADEO called cooperative ADEO, which could also be present in step (i), and may be selected from any cyclic quaternary ammonium or any other organic molecule, as per example, any quaternary amine or ammonium.
    According to the present invention, any polyamine or mixtures of different polyamines capable of forming a complex with copper atoms can be used in (i), regardless of their form (cyclic, linear, branched ..), and regardless of the nature of the amine (primary, secondary or tertiary). Preferably said polyamine may be selected from tetraethylene pentamine, triethylenetetramine, 1,4,8,11-tetracycotetradecane, 1,4,8, 11-tetramethyl-1, 4,8, 11-tetraazacyclotetradecane, and combinations thereof, among others. Preferably the polyamine is tetraethylene pentamine.
    According to the present invention, the crystallization process described in (ii) is preferably carried out in autoclaves, under conditions that can be static or dynamic (for example by stirring the mixture) at a temperature selected between 100 and 200 ° C preferably between 130 and 200 ° C and more preferably between 130 and 175 ° C; And a crystallization time that can be between 6 hours and 50 days preferably between 1 and 20 days, and more preferably between 2 and 15 days. It should be borne in mind that the components of the synthesis mixture can come from different sources, which may vary the crystallization conditions described.
    According to a particular embodiment of the process of the present invention, it is possible to add AEI crystals to the synthesis mixture, which act as seeds favoring the described synthesis, in an amount up to 25% by weight with respect to the total amount of oxides. These crystals can be added before or during the crystallization process.
    According to the process of the present invention, after the crystallization described in (ii), the resulting solid is separated from the mother liquor and recovered. The recovery step (iii) can be carried out by different known separation techniques such as, for example, decantation, filtration, ultrafiltration, centrifugation or any other solid-liquid separation technique, and combinations thereof.
    The process of the present invention may further comprise the removal of the organic content contained inside the material by means of an extraction process.
    According to a particular embodiment, the removal of the organic compound contained inside the material can be carried out by heat treatment at temperatures above 25 ° C, preferably between 100 and 1000 ° C and for a period of time, preferably between 2 minutes and 25 hours.
    According to a particular embodiment of the present invention, in the process of obtaining the material described above, at least one metal can be introduced by post-synthesis processes such as impregnation, ion exchange or combinations thereof. These metals are preferably selected from precious metals, and more preferably from Pt, Pd and combinations thereof, preferably being located in extra-net positions.
    According to another particular embodiment of the present invention, in the process for obtaining the material described above, any metal oxide containing at least one precious metal, preferably selected from Pt, Pd, and combinations thereof, can be introduced.
    According to another particular embodiment, the material produced according to the present invention can be pelletized using any known technique.
    According to a preferred embodiment, the material obtained according to the present invention can be calcined. Therefore, the zeolitic material with AEI structure can have the following molar composition after being calcined:
    Y02: OX20 3: pA: rCu
    where or is in the range of 0.001 to 0.2; preferably between
    0.005 to 0.1, and more preferably between 0.01 to 0.07; where p is between the range of Oa 2, preferably between 0.001 to 1; And more preferably between 0.01 to 0.8;
    where r is between the interval 0.001 to 1; preferably between 0.001 to 0.6, and more preferably between 0.001 to 0.5.
    According to a particular embodiment, Y is Si and X is Al, therefore, the zeolitic material with AEI structure could have the following molar composition after being calcined: Si02. or AI20 3: p A. r Cu
    where or is in the range of 0.001 to 0.2; preferably between
    0.005 to 0.1, and more preferably between 0.01 to 0.07; where p is between the range of O to 2, preferably between 0.001 to 1; And more preferably between 0.01 to 0.8;
    where it remains between the interval 0.001 to 1; preferably between 0.001 to 0.6, and more preferably between 0.001 to 0.5.
    According to a preferred embodiment, the material obtained is Cu-SSZ-39.
    According to a particular embodiment of the present invention, the zeolitic material with AEI structure obtained can also comprise a precious metal preferably selected from Pd, Pt and combinations thereof.
    The present invention also relates to the use of the materials described above and obtained according to the process of the present invention as catalysts for the conversion of feeds formed by organic compounds into products of higher added value, or as a molecular sieve for the removal / separation of currents (eg gas mixtures) by contacting the feeds with the material obtained.
    According to a preferred embodiment, the material obtained in the present invention can be used as a catalyst in selective catalytic reduction (RCS) reactions of NOx (nitrogen oxide) in a gas stream. In particular, the NOx RCS will be carried out in the presence of reducing agents, preferably selected from ammonium, urea, hydrocarbons, and combinations thereof. According to this particular embodiment, the selective catalytic reduction (RCS) of NOx (nitrogen oxide) can be carried out using a monolith as a substrate and applying a layer of the zeolitic material obtained according to the present invention so that the gas stream can pass through it carrying out the desired reaction. In the same way, a layer of the zeolitic material obtained according to the present invention can be applied on other substrates, such as a filter through which the gas stream will pass.
    According to another particular embodiment of the present invention, the material synthesized according to the present invention and containing a precious metal, such as Pt or Pd, can be used as a catalyst for the selective oxidation of ammonia to nitrogen. According to this particular embodiment, the selective catalytic oxidation of ammonia to nitrogen can be carried out using a monolith as a substrate and applying a layer of the zeolitic material obtained according to the present invention so that the gas stream can pass through it carried out the desired reaction. In the same way, a layer of the zeolitic material obtained according to the present invention can be applied on other substrates such as a filter, among others, through which the gas stream will pass.
    According to another particular embodiment, the material described according to the present invention can be used in the conversion of methane to methanol (Wulfers, et al. Chem. Commun. 2015, 51, 4447).
    Throughout the description and the claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and features of the invention will be derived partly from the description and partly from the practice of the invention.
    Brief description of the figures Figure 1: PXRD patterns of the Cu-silicoaluminatos materials with AEI structure synthesized according to the present invention.
    Figure 2: UV-Vis spectrum of the Cu-silicoaluminate material with AEI structure synthesized according to Example 2 of the present invention.
    EXAMPLES
    Example 1: Synthesis of N, N-dimethyl-3,5-dimethylpiperidinium (DMDMP)
    10 9 of 3,5-dimethylpiperidine (Sigma-Aldrich, 2: 96% by weight) is mixed with 19.51 9 of potassium bicarbonate (KHC03, Sigma-Aldrich; 99.7% by weight) and dissolved in 140 ml of methanol. Then 54 ml of methyl iodide (CH31, Sigma-Aldrich, 2: 99% by weight) are added, and the resulting mixture is kept under stirring for 5 days at room temperature. After this time, the reaction mixture is filtered to remove potassium bicarbonate. The filtered solution is partially concentrated by rotary evaporator. Once the methanol has partially evaporated, the solution is washed with chloroform several times and magnesium sulfate (MgSO4, Sigma-Aldrich, 2: 99.5% by weight) is added. The mixture is then filtered to remove magnesium sulfate. The ammonium salt is obtained by precipitation with diethyl ether and subsequent filtration. The final yield of N, N-dimethyl-3,5-dimethylpiperidinium iodide is 85%.
    To prepare the hydroxide form of the above organic salt: 10.13 9 of the organic salt are dissolved in 75.3 9 of water. Next, 37.6 9 of an anion exchange resin (Dower SBR) are added, and the resulting mixture is kept under stirring for 24 hours. Finally, the solution is filtered and N, N-dimethyl-3,5-dimethylpiperidinium hydroxide is obtained (with an exchange rate of 94%).
    Example 2: Direct synthesis of Cu-silicoaluminato with AEI structure
    154.0 mg of a 20% by weight aqueous solution of copper sulfate (11) (CUS04, Alfa Aesar, 98%) are mixed with 31.2 mg of tetraethylenepentamine (TEPA, 98%, Sigma Aldrich) for the on-site preparation of the organometallic copper complex, keeping the resulting mixture under stirring for 2 hours. After this time, 3216.0 mg of a 7.4% by weight aqueous N, N-dimethyl-3,5-dimethylpiperidinium hydroxide solution are added, and 163.1 mg of a 20% by weight aqueous solution of sodium hydroxide, the resulting mixture being kept under stirring for 15 minutes. Finally, 235.3 mg of a zeolite with FAU structure (CBV-720, molar ratio Si02 / Ab03 = 21) is introduced into the synthesis mixture and the time required to evaporate excess water is maintained under stirring until the concentration of desired gel The final composition of the gel is Si02: 0.047 AI, 0 3: 0.046 Cu (TEPA) ": 0.2 DMDMP: 0.2 NaOH: 23 H, O. The resulting gel is transferred to an autoclave with a Teflon jacket. Crystallization is carried out. conducted at 135 ° C for 7 days under static conditions.The solid product is filtered, washed with plenty of water, dried at 100 ° C and finally calcined in air at 550 ° C for 4 h to remove organic debris. of solid achieved is greater than 90% (regardless of organic debris).
    The solid is characterized by powder X-ray diffraction, obtaining the characteristic peaks of the AEI structure (see Figure 1). The chemical analysis of the sample indicates a Si / Al ratio of 9.95 and a copper content of 3.3% by weight.
    The crystalline material obtained without calcining is characterized by UV-VIS spectroscopy to study the stability of the molecules of the organometallic copper complex after the crystallization of the zeolite. As seen in Figure 2, the UV-VIS spectrum shows a single band centered at -265 nm, which has been assigned to the presence of the intact CulEPA complex inside the zeolitic structure (Franco, et al. 2013 / 159828, 2012).
    Example 3: Direct synthesis of Cu-silicoaluminato with AEI structure
    75.1 mg of a 20% by weight aqueous solution of copper sulfate (11) (CUS04, Alfa Aesar, 98%) are mixed with 18.0 mg of tetraethylenepentamine (TEPA, 98%, Sigma Aldrich) for the on-site preparation of the organometallic copper complex, keeping the resulting mixture under stirring for 2 hours. After this time, 4049.0 mg of a 5.9% by weight aqueous N, N-dimethyl-3,5-dimethylpiperidinium hydroxide solution are added, and
    159.1 mg of a 20% by weight aqueous solution of sodium hydroxide, the resulting mixture being kept under stirring for 15 minutes. Finally, 285.2 mg of a zeolite with FAU structure (CBV-720 molar ratio Si02 / AI20 3 = 21) is introduced into the synthesis mixture and the time required to evaporate the excess water is maintained under stirring until the concentration of desired gel The final composition of the gel is Si02: 0.047 AI, 0 3: 0.019 Cu (TEPA) ": 0.3 DMDMP: 0.2 NaOH: 18 H, O. The resulting gel is transferred to an autoclave with a Teflon jacket. Crystallization is carried out. conducted at 135 ° C for 7 days under static conditions.The solid product is filtered, washed with plenty of water, dried at 100 ° C and finally calcined in air at 550 ° C for 4 h to remove organic debris. The solid obtained is greater than 90% (without taking into account the organic remains) The solid is characterized by X-ray powder diffraction, obtaining the characteristic peaks of the AEI structure (see Figure 1).
    Example 4: Direct synthesis of Cu-silicoaluminato with AEI structure
    112.2 mg of a 20% by weight aqueous solution of copper sulfate (11) (CUS04, Alfa Aesar, 98%) are mixed with 27.0 mg of tetraethylenepentamine (TEPA, 98%, Sigma Aldrich) for the on-site preparation of the organometallic copper complex, keeping the resulting mixture under stirring for 2 hours. After this time, 2416.0 mg of a 7.4% by weight aqueous N, N-dimethyl-3,5-dimethylpiperidinium hydroxide solution are added, and
    66.2 mg of a 20% by weight aqueous solution of sodium hydroxide, the resulting mixture being kept under stirring for 15 minutes. Finally, 196.2 mg of a zeolite with FAU structure (CBV-720 molar ratio Si02 / AI20 3 = 21) is introduced into the synthesis mixture and the time required to evaporate the excess water is maintained under stirring until the concentration of desired gel The final gel composition is Si02: 0.047 A1 20 3: 0.041 Cu (TEPA) 2+: 0.3 DMDMP: 0.1 NaOH: 21 H20. The resulting gel is transferred to an autoclave with a Teflon jacket. Crystallization is carried out at 135 ° C for 7 days under static conditions. The solid product is filtered, washed with plenty of water, dried at 100 ° C and finally calcined in air at 550 ° C for 4 h to remove organic debris. The solid yield achieved is greater than 90% (regardless of organic debris). The solid is characterized by powder X-ray diffraction, obtaining the characteristic peaks of the AEI structure.
    Example 5: Catalytic tests for the NOx ReS reaction
    The catalytic activity for the selective catalytic reduction of NOx is studied using a tubular, fixed-bed quartz reactor 1.2 cm in diameter and 20 cm long. In a typical experiment, the catalyst is compacted into particles between 0.25-0.42 mm in size, introduced into the reactor, and the temperature is increased to 550 ° C (see reaction conditions in Table 1); subsequently, that temperature is maintained for one hour under a flow of nitrogen. Once the desired temperature has been reached, the reaction mixture is fed. The NOx ReS is studied using NH3 as a reducer. The NOx present at the outlet of the gases from the reactor is analyzed in a way
    Continuous using a chemiluminescent detector (Thermo 62C). The catalytic results are summarized in Table 2.
    Table 1: Reaction conditions of the NOx RCS.
    Total gas flow (ml / min) 300
    Catalyst Load (mg) 40
    NO concentration (ppm) 500
    NH3 concentration (ppm) 530
    O2 concentration (%) 7
    H20 concentration (%) 5
    Temperature range studied rC) 170-550
    Table 2: Conversion (%) of NOx at different temperatures (200, 250, 300, 350, 400,
    450, 500 ° C) using the Cu-AEI catalyst synthesized following the methodology
    described in the present invention.
    Conversion ('lo) of NOx at different temperatures
    200 ° C 2500 e3000 e3500 e400 ° C450 ° C5000 e
    Example 2 71.798.499.699.897.196.985.1
    权利要求:
    Claims (36)
    [1]
    1. Process for the direct synthesis of a material with AEI zeolitic structure in its form
    silicoaluminate containing copper atoms comprising at least the following steps:
    (i) Preparation of a mixture containing at least one source of water, a source of copper, a polyamine, a source of telravalent element Y, a source of trivalenle element X, a cyclic ammonium cation with alkyl substituents such as ADEO and a source of alkaline or alkaline earth cations (A), and where the synthesis mixture has the following molar composition:
    Y02: a X20 3: b ADEO: e A: d H20: e Cu: f Polyamine
    where a is in the range of 0.001 to 0.2; b is in the range of 0.01 to 2; e is in the range of O to 2; d is in the range of 1 to 200; e is in the range of 0.001 to 1; f is in the range of 0.001 to 1.
    (ii) Crystallization of the mixture obtained in (i) in a reactor.
    (iii) Recovery of the crystalline material obtained in (ii).
    [2]
    2. Process for the direct synthesis of a material according to claim 1, characterized in that c is in the range of 0.001 to 1.
    [3]
    3. Process for the direct synthesis of a material according to claim 1, characterized in that Y is a tetravalent element selected from Si, Sn, Ti, Ge and combinations thereof.
    [4]
    Four. Process for the direct synthesis of a material according to claim 3, characterized in that it is Si and comes from a source selected from silicon oxide, silicon halide, colloidal silica, smoked silica, tetraalkylortosilicate, silicate, silicic acid, a
    previously synthesized crystalline material, a previously synthesized amorphous material and combinations thereof
    [5]
    5. Process for the direct synthesis of a material according to claim 4, characterized in that the source of Y is a previously synthesized crystalline material.
    [6]
    6. Process for the direct synthesis of a material according to claim 1, characterized in that X is selected from Al, B, Fe, In, Ga and combinations thereof.
    [7]
    7. Process for the direct synthesis of a material according to claim 6, characterized in that X is Al and comes from a source selected from aluminum salt, any hydrated aluminum oxide, any aluminum alkoxide, a previously synthesized crystalline material, a previously synthesized material amorphous and combinations thereof.
    [8]
    8. Process for the direct synthesis of a material according to claim 7, characterized in that the source of X is a previously synthesized crystalline material.
    [9]
    9. Process for the direct synthesis of a material according to the preceding claims, characterized in that a zeolite with FAU structure is the only source of Y and X.
    [10]
    10. Process for the direct synthesis of a material according to claim 1, characterized in that any source of copper can be used in step (i).
    [11]
    eleven. Process for the direct synthesis of a material according to claim 10, characterized in that the copper source is selected from nitrate, sulfate, oxalate salts, and combinations thereof.
    [12]
    12. Process for the direct synthesis of a material according to claim 1, characterized in that the cyclic ammonium cation used as ADEO is a quaternary ammonium selected from N, N-dimethyl-3,5-dimethylpiperidinium (DMDMP), N, N-diethyl-2 , 6-dimethylpiperidinium (DEDMP), N, N-dimethyl-2,6-dimethylpiperidinium, N-ethyl-N-methyl-2,6-dimethylpiperidinium and combinations thereof.
    [13]
    13. Process for the direct synthesis of a material according to claim 12, characterized in that the selected ADEO is N, N-dimethyl-3,5-dimethylpiperidinium.
    [14]
    14. Process for the direct synthesis of a material according to claim 1, characterized in that the polyamine of step (i) comprises primary, secondary, tertiary amines, or mixtures thereof.
    [15]
    fifteen. Process for the direct synthesis of a material according to claim 14, characterized in that the polyamine required in step (i) is selected from tetraethylenepentamine, triethylenetetramine, 1,4,8,11-tetraazacyclotetradecane, 1,4,8, 11-tetramethyl- 1, 4,8,11 tetracycotetradecane, or mixtures thereof.
    [16]
    16. Process for the direct synthesis of a material according to claim 15, characterized in that the polyamine used in step (i) is tetraethylenepentamine.
    [17]
    17. Process for the direct synthesis of a material according to claims 1 to 16, characterized in that the crystallization process described in (ii) is carried out in autoclaves, under static or dynamic conditions.
    [18]
    18. Process for the direct synthesis of a material according to claims 1 to 17, characterized in that the crystallization process described in (ii) is carried out at a temperature between 100 and 200 ° C.
    [19]
    19. Process for the direct synthesis of a material according to claims 1 to 18, characterized in that the crystallization time of the process described in (ii) is between 6 hours and 50 days.
    [20]
    twenty. Process for the direct synthesis of a material according to claims 1 to 19, characterized in that it further comprises adding AEI crystals as seeds to the synthesis mixture in an amount up to 25% by weight with respect to the total amount of oxides.
    [21]
    twenty-one. Process for the direct synthesis of a material according to claim 1, characterized in that the recovery step (iii) is carried out with a separation technique selected from decantation, filtration, ultrafiltration, centrifugation and combinations thereof.
    [22]
    22 Process for the direct synthesis of a material according to claims 1 to 21, characterized in that it also comprises the elimination of the organic content contained inside the material by means of an extraction process.
    [23]
    2. 3. Process for the direct synthesis of a material according to claims 1 to 22, characterized in that it also comprises the elimination of the organic content contained inside the material by means of a heat treatment at temperatures between 100 and 1000 ° C, for a period of time between 2 minutes and 25 hours.
    [24]
    24. Process for the direct synthesis of a material according to claims 1 to 23, characterized in that the material obtained is pelleted.
    [25]
    25. Process for the direct synthesis of a material according to claims 1 to 24, characterized in that it further comprises introducing at least one precious metal.
    [26]
    26. Process for the direct synthesis of a material according to claim 25, characterized in that the precious metal is selected from Pd, Pt and combinations thereof.
    [27]
    27. Zeolitic material with AEI structure obtained according to the process described in claims 1 to 26, characterized by the following molar composition after being calcined:
    Y02: OX20 3: pA: rCu
    where or is in the range of 0.001 to 0.2; where p is between the range of O to 2; where it remains between the interval 0.001 to 1.
    [28]
    28. Zeolitic material with AEI structure obtained according to claim 27, characterized in that y is Si and X is Al and by the following molar composition:
    Si02: or Ab03: p A: r Cuwhere or is in the range of 0.001 to 0.2;where p is between the range of O to 2;where r is between the interval 0.001 to 1.
    [29]
    29. Zeolitic material with AEI structure obtained according to claims 27 and 28, characterized in that the material is Cu-SSZ-39.
    [30]
    30 Zeolitic material with AEI structure obtained according to claims 27 to 29, characterized in that it further comprises a precious metal.
    [31]
    31. Zeolitic material with AEI structure obtained according to claim 30, characterized in that the precious metal is selected from Pd, Pt and combinations thereof.
    [32]
    32 Use of the zeolitic material with AEI structure described in claims 27 to 31, and obtained according to the process described in claims 1 to 26 in processes for the conversion of feeds formed by organic compounds into products of greater added value, or for their elimination / separation of the reactive current by contacting said feed with the described material.
    [33]
    33. Use of the zeolitic material with AEI structure according to claim 32, as a catalyst for the selective catalytic reduction (RCS) of nitrogen oxides (NOx) in a gas stream.
    [34]
    3. 4. Use of the zeolitic material with AEI structure according to claim 33, as a catalyst for the NOx RCS, characterized in that it is carried out in the presence of a reducing agent, selected from ammonia, urea, hydrocarbons, and combinations thereof.
    [35]
    35 Use of the zeolitic material with AEI structure according to claim 32, as catalyst in the conversion of methane into methanol.
    [36]
    36. Use of the zeolitic material with AEI structure according to claims 30 and 31, as a catalyst in the selective oxidation of ammonia to nitrogen.
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