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    • 专利摘要:
    CHA/AEI intergrowth synthesis, synthesis procedure and its use in catalytic applications. In the present invention, a new procedure for the synthesis of the intergrown CHA/AEI material in its zeolitic form is described using a single organic structure directing agent (ADEO), much simpler than the mixtures described so far, and in the absence of anions fluoride in the synthesis medium. The present invention also describes the material obtained with said procedure and its use as a catalyst in various catalytic processes, such as methanol to olefins, and the selective catalytic reduction (SCR) of different nitrogen oxides (NOx) in gaseous emissions. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2829385A1
    申请号:ES202130276
    申请日:2021-03-29
    公开日:2021-05-31
    发明作者:Jurado Estefania Bello；Carrizo Cecilia Gertrudis París；Koda Daniel Schwalbe；Leshkov Yuriy Roman；Canós Avelino Corma；Bombarelli Rafael Gómez；Marin Manuel Moliner
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；Universidad Politecnica de Valencia；Massachusetts Institute of Technology；
    IPC主号:
    专利说明:

    [0002] SYNTHESIS OF THE CHA / AEI INTERGROWTH. SYNTHESIS PROCEDURE AND
    [0004] The present invention refers to a new process for the synthesis of a zeolitic material formed by the intergrowth of the CHA / AEI phases, as well as the use as a catalyst of the zeolitic material synthesized according to the present synthesis process.
    [0006] BACKGROUND OF THE INVENTION
    [0007] Zeolites are crystalline microporous materials with channels and cavities of uniform size and shape in the molecular range, and whose structures are formed by TO4 tetrahedra, where traditionally T are Si and Al atoms, which are interconnected by oxygen atoms. Although the definition of zeolite was initially limited to silicoaluminates, in recent years it has been extended to the preparation of other silica materials that have other T heteroatoms in their structure in addition to Si and Al (eg T = Ge, B, Ti, Sn, among others). These materials have application in various fields, highlighting their use as catalysts, adsorbents or ion exchangers.
    [0009] In addition to zeolites (silicoaluminates or siliceous materials), there is a family of materials known as aluminophosphates (AlPOs) that are crystallographically analogous to zeolites, but whose structural composition is defined by the presence of phosphorus and aluminum atoms in alternating distribution in the crystal lattice (Wilson, et al. J. Am Chem. Soc. 1982, 104, 1146). Silicoaluminophosphates (SAPOs) are a particular case of AlPOs, where a small amount of the structure's atoms are partially replaced by silicon atoms (Chen, et al. J. Phys. Chem., 1994, 98, 10216).
    [0011] Zeolites can be classified according to the size of their channels and pores. In this sense, zeolites with channels limited by 8-T atoms are called “small pore zeolites” (openings around 4 A), zeolites with channels limited by 10-T atoms are “medium pore zeolites” (openings around 5.5 Á), those whose channels are limited by 12-T atoms are “large pore zeolites” (openings around 7 Á) and finally, those zeolites whose channels are limited by more than 12-T atoms are called "extra-large pore zeolites" (with openings greater than 7A).
    [0013] Of the 250 or so zeolitic structures accepted by the International Zeolite Association (IZA), more than 80 have a small pore topology. Of all these small pore zeolites, the chabazite (CHA) crystalline structure is possibly one of the most interesting given that it presents the application of various chemical processes, standing out as a heterogeneous catalyst in the transformation of methanol to olefins (MTO) and selective catalytic reduction. (RCS) of NOx. The crystal structure of CHA is formed by a three-way system of small pores interconnected by large cavities.
    [0015] The synthesis of the CHA structure has been described in the form of various chemical compositions, highlighting as zeolite or silicoaluminate ("SSZ-13"; Zones, US Patent 4544538, 1985, assigned to Chevron) or SAPO ("SAPO-34"; Lok et al. US Patent 4440871, 1984, assigned to UOP). In general, it can be said that zeolites or silicoaluminates have greater hydrothermal stability and better acid properties than homologous SAPOs (Wang et al., Nat. Commun. 2019, 10, 1137; Katada et al. J. Phys. Chem. C, 2011, 115, 22505).
    [0017] The first syntheses of the CHA structure in the laboratories were carried out using exclusively alkali cations as inorganic structure directing agents (ADEI), resulting in the formation of CHA with low Si / AI ~ 1-2 ratios (J. Chem. Soc. 1956, 2822). However, zeolites with low Si / AI ratios (e.g. less than 4) have limited hydrothermal stability, making it necessary to increase said Si / AI ratios for most applications.
    [0019] The incorporation of organic molecules as organic structure directing agents (ADEOs) allowed the preparation of the CHA zeolite with higher Si / AI ratios. The first ADEOs described for the synthesis of the CHA zeolite were N, N, N-trialkyl-1-adamantylammonium, N-alkyl-3-quinuclidol and / or N, N, N-trialkylbicyclo [2.2.1] heptan-2- ammonium (Zones, US Patent 4544538, 1985, assigned to Chevron), being the cation N, N, N-trimethydamantan-1-ammonium (TMAdA) the preferred for the synthesis of the zeolite CHA. This ADEO is a relatively complex molecule, presenting a high preparation cost, which is an important drawback in the commercial preparation of CHA zeolite.
    [0021] Subsequently, other ADEOs have been described for the synthesis of CHA zeolite, such as benzyltrimethylammonium (Miller et al., US Patent 8007764, 2011, assigned to Chevron), trialkylcyclohexylammoniums (Cao et al., US Patent 2008/0045767, 2008 , assigned to ExxonMobil; Feyen et al., WO2013 / 182974, 2013, assigned to BASF), N, N- dimethylpiperidinium (Yilmaz et al. WO2013 / 035054, 2013, assigned to BASF), N- alkyl-1,4 cations -diazabicyclo [2.2.2] octane and derivatives (Zones, W02010 / 114996, 2010, assigned to Chevron), tetraethylammonium (Martin et al., Chem. Commun., 2015, 51, 9965) or choline (Chen et al., Environ. Sci. Technol., 2014, 48, 13909).
    [0023] In addition to the small-pore zeolitic material with the CHA structure, another small-pore material that has received a lot of attention in recent years is the AEI structure, which is also made up of a three-way system of small pores interconnected by large cavities. As in the case of CHA, the synthesis of the AEI structure has been described in the form of various chemical compositions, standing out as zeolite or silicoaluminate ("SSZ-39"; Zones, et al. US Patent 5958370, 1999, assigned a Chevron) or SAPO ("SAPO-18"; Chen et al. J. Phys. Chem.
    [0024] 1994, 98, 10216).
    [0026] The synthesis of the zeolitic structure AEI in its silicoaluminate form preferably uses as ADEOs cyclic quaternary ammoniums with alkyl substituents in the ring, such as N, N-diethyl-2,6-dimethylpiperidinium or N, N-dimethyl-3, 5-dimethylpiperidinium, among others (Zones, et al. US Patent 5958370, 1999). In general, the use of cyclic ammoniums substituted with alkyl groups tends to present certain problems: on the one hand, they tend to increase the cost of the preparation process, and, on the other hand, alkyl substituents can induce the presence of enantiomeric mixtures, which can modify nucleation / crystallization processes (Dusselier et al., Chem. Mater. 2015, 27, 2695). Recently, the use of tetraethylphosphonium cations as ADEO for the synthesis of zeolite AEI has also been described (Maruo, et al. Chem. Lett., 2014, 43, 302-304). However, the use of ADEOs derived from phosphines presents some important disadvantages. On the one hand, organic molecules derived from phosphines show serious problems for the environment and health, inevitably associated with their use. While, on the other hand, the complete elimination of the phosphorous species trapped inside the Zeolitic cavities is very complicated, especially in small pore zeolites, and its elimination process requires calcination stages at very high temperatures and hydrogen atmospheres for the complete decomposition / elimination of said species (Sonoda, et al. J. Mater. Chem. A, 2015, 3, 857).
    [0028] Zeolitic structures are usually built from building units, which are periodically arranged in three dimensions. However, certain disorders in the crystal lattice can sometimes occur, such as the presence of intergrowths, where building units of more than one crystalline phase are present, such as CHA and AEI.
    [0030] In the case of the CHA zeolitic structure, the building unit is a sheet formed by double rings of six (DA6). There are two types of plates: "a" and "b", which are identical from a structural point of view, but one is the mirror image of the other. When the same type of sheets "aaaaaa" or "bbbbbb" are packaged, the crystal structure CHA is formed. On the contrary, when they are packaged alternately, "ababab", the structure that is formed in this case is the AEI. In the particular case of CHA / AEI intergrowth, regions with the classical packaging sequences of the CHA structure and other regions with the packaging sequences of the AEI structure are observed. It is important to highlight that the CHA and AEI structures present different X-ray diffraction patterns (XRD, see Figure 1). Taking this into account, a suitable analysis of the CHA / AEI intergrowth can be made by comparing the experimentally obtained XRD pattern with the intergrowth patterns calculated using programs or algorithms designed to simulate zeolitic intergrowths (see Figure 1 and simulated XRD patterns for the CHA / AEI family in “Collection of simulated XRD powder patterns for zeolites” de Treacy and Higgins, 2007).
    [0032] The synthesis of the CHA / AEI intergrowth has been widely described in its silicoaluminophosphate (SAPO) form, formed by the intergrowth of the materials SAPO-34 and SAPO-18 (Janssen et al., US20020165089, assigned to ExxonMobil). Interestingly, the intergrowths obtained show special catalytic properties compared to the pure crystalline phases, as in the case of the SAPO-34 / SAPO-18 intergrowth for the reaction of methanol to olefins (MTO) (Smith et al., Appl. Catal. A, 2015, 505, 1). However, as has been commented previously, zeolites or silicoaluminates have greater hydrothermal stability and better acid properties than homologous SAPOs (Wang et al., Nat. Commun. 2019, 10, 1137; Katada et al. J. Phys. Chem. C, 2011, 115, 22505). Therefore, the preparation of the CHA / AEI intergrowth in its zeolitic form is of great interest for its application in catalytic processes.
    [0034] It is important to note that the extrapolation of the synthesis of crystalline materials such as silicoaluminophosphate (SAPO) in its zeolitic form (eg silicoaluminate) cannot be considered direct, since in addition to the chemical composition being different, the required synthesis means are completely different, an acidic medium being normally required in the synthesis of SAPOs and normally a basic medium in the case of zeolites. Therefore, the nucleation and crystallization mechanisms that govern each synthesis process of the same crystalline structure, but in its SAPO or zeolitic form, will be completely different. In fact, there are crystalline materials whose preparation has not been achieved as SAPO (e.g. BEA or MFI), and other crystalline structures whose preparation has not been achieved as zeolite (e.g. AVE).
    [0036] The preparation of the CHA / AEI intergrowth in zeolitic or silicoaluminate form has been exclusively described thanks to the use of a physical mixture of two ADEOs in the synthesis medium, where one of them is specific for the AEI structure and the other is specific for the CHA structure. (Cao et al., US7094389, 2006, assigned to ExxonMobil; Cao et al., US7670589, 2010, assigned to ExxonMobil). In particular, these two patents describe the use of W, W-diethyl-2,6-dimethylpiperidinium (DEDMP) as specific ADEO of the AEI and W, W, W-trimethylatedmantan-1-ammonium (TMAdA) or W -ethyl, W, W-dimethylcyclohexanammonium (DMDECHA) as specific ADEOs for CHA. It is important to highlight that all the examples described of the CHA / AEI intergrowth using said ADEOs mixtures have been obtained in a fluoride medium.
    [0038] The presence of fluorine in the synthesis medium and / or in the synthesized crystalline material is not recommended for its possible industrial application. The reason is the high corrosivity and danger that hydrofluoric acid or fluorinated derivatives present when they are used as a reactive source, or as a by-product formed in post-synthetic stages (for example, in the calcination stage). Thus, development is required of new efficient synthesis methodologies of the CHA / AEI intergrowth in its zeolitic form in media free of fluoride anions.
    [0040] Recently, another methodology for the synthesis of CHA / AEI intergrowth has been described, also based on the mixture of two specific ADEOs, one to stabilize the AEI phase (W, W-dimethyl-3,5-dimethylpiperidinium) and the other for the CHA phase. (TMAda) (Shi et al., CN110422856A, 2019).
    [0042] It should be noted that the use of mixtures of specific ADEOs of different crystalline phases is a known methodology in the synthesis of intergrown zeolites with small pores and large cavities and relatively high Si / AI ratios (greater than 5). For example, the synthesis of CHA / AFX intergrowth has been described using the mixture of TMAda (ADEO for CHA) and 1,1 '- (butan-1,4-diyl) bis (1,4-diazabicyclo [2.2.2] octan-1-io) (Dab-42 +, ADEO for AFX). However, this methodology based on the use of co-ADEOs has two serious drawbacks: 1) the use of two fairly specific, and usually expensive, ADEOs for each of the materials that must be part of the intergrowth; and 2) the use of mixtures of specific ADEOs requires a very fine adjustment of the synthesis parameters in order to avoid the crystallization of the two crystalline phases independently.
    [0044] DESCRIPTION OF THE INVENTION
    [0046] The present invention describes a new procedure for the synthesis of a zeolitic material formed by the intergrowth of the CHA / AEI phases, which requires a single ADEO in the absence of fluoride anions. The present invention also describes the material obtained by said process, as well as the use of said zeolitic material as a catalyst in various catalytic processes, such as methanol to olefins, and the selective catalytic reduction (SCR) of NOx in gaseous emissions.
    [0048] A first aspect of the present invention refers to a new procedure for the synthesis of a zeolitic material formed by the intergrowth of the CHA / AEI phases characterized in that it comprises the following steps:
    [0049] i) preparing a mixture comprising at least one source of water, at least one source of a tetravalent element "Y", optionally at least a source of an alkali or alkaline earth cation "A", optionally at least one source of a trivalent element "X", and an organic structure directing agent "ADE01" with structure selected from [R1R2R3R4N +] Q- or [R5R6CycloN +] Q- ,
    [0050] where R1 and R5 are an isopropyl or te / Y-butyl group, R2 is a linear alkyl chain comprised between 1-3 carbon atoms, R3, R4 and R6 can be a straight or branched alkyl chain comprised between 1-4 carbon atoms carbon, while the CycloN group is a nitrogenous heterocycle that can be formed by an alkyl chain of between 4-7 carbon atoms, linear or branched, joined at the ends to the N, and where Q- is an anion; where the molar composition of the mixture is:
    [0051] n X203: Y02: a A: m ADE01: z H20
    [0052] where
    [0053] n is comprised between the range of 0 to 0.12, preferably between 0.005 to 0.12; and more preferably between 0.01 to 0.10;
    [0054] a is in the range 0 to 2, preferably 0 to 1; and more preferably between 0.1 to 0.8;
    [0055] m is comprised between the range of 0.01 to 2, preferably between 0.05 to 1; and more preferably between 0.05 to 0.6;
    [0056] z is in the range 1 to 200, preferably 1 to 50, and more preferably 2 to 20;
    [0057] ii) crystallizing the mixture obtained in i) in a reactor; Y
    [0058] ni) recovering the crystalline material obtained in ii).
    [0059] In the present invention, "intergrowth of the CHA / AEI phases or intergrowth CHA / AEI or CHA / AEI crystals" is understood to be all materials in which regions within the same crystal are observed with the classical packaging sequences of the structure. CHA (where the same type of sheets "aaaaaa" or "bbbbbb" are packaged) and other regions with the packaging sequences of the AEI structure (where they are packaged alternately, "ababab"). It is important to highlight that the CHA and AEI structures present different X-ray diffraction patterns (XRD, see Figure 1).
    [0061] In the present invention, the term "Cyclo" refers to a linear alkyl chain of 4-7 carbon atoms, optionally substituted with an alkyl of 1 to 3 carbon atoms, preferably a methyl, the terminal carbons of which are N-linked to the corresponding quaternary ammonium, so that said linear alkyl chain, together with the N atom they form a heterocycle.
    [0063] The advantage associated with the presence of “ADE01” is that it avoids the use of mixtures of specific ADEOs for each of the crystalline phases (CHA and AEI) that are part of the intergrown material, which are normally expensive, and, in addition, require a very fine adjustment of the synthesis parameters in order to avoid the crystallization of the two crystalline phases independently.
    [0065] According to a particular embodiment, the tetravalent element Y can be selected from silicon, tin, titanium, zirconium, germanium, and combinations thereof, preferably from silicon, tin, titanium, zirconium, and combinations thereof. Most preferably, element Y is silicon which can come from a source selected from silicon oxide, silicon halide, colloidal silica, fumed silica, tetraalkyl orthosilicate, silicate, silicic acid, an amorphous silica, a zeolite and combinations of the themselves, and more preferably between an amorphous silica, a zeolite, and combinations thereof.
    [0067] According to a particular embodiment, the amorphous silica or the zeolite may also contain other heteroatoms in its structure. Examples might be FAU, Beta, MFI, or LTL zeolites, or amorphous ordered mesoporous materials, such as MCM-41. These previously synthesized materials could also contain other heteroatoms in their structure, such as aluminum.
    [0069] According to a particular embodiment, the source of element Y can be faujasite (FAU), and it could contain heteroatoms in its structure, such as aluminum.
    [0071] According to a particular embodiment, the trivalent element X can be selected from aluminum, boron, iron, indium, gallium and combinations thereof, preferably from aluminum, boron and combinations thereof, and more preferably is aluminum.
    [0073] According to a particular embodiment, the trivalent element X is aluminum and comes from a source that can be selected from, at least, any aluminum salt (for example, aluminum nitrate), aluminum alkoxides, or any hydrated aluminum oxide and combinations thereof.
    [0074] According to a particular embodiment, the synthesis mixture contains a source of alkali or alkaline earth metal (A). Preferably, the alkali or alkaline earth cation is preferably selected from sodium, potassium, calcium, and combinations thereof. More preferably, it is selected from sodium and potassium, and combinations thereof. The source of the alkali and alkaline earth metals can be any salt. By way of example, the source of sodium can be a sodium salt, such as NaCl, NaBr, or NaNÜ3; sodium hydroxide or sodium aluminate. The source of potassium can be potassium hydroxide or potassium halide, such as KCI or KBr, or potassium nitrate.
    [0076] According to a particular embodiment, when the source of the alkali or alkaline earth cation (A) is a source of hydroxide ions [A (OH)], for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, the ratio of A (OH) / Si will not be higher than 0.64.
    [0078] According to a particular embodiment of the present invention, ADE01 is defined by the structures [R1R2R3R4N +] or [R5R6CycloN +], where:
    [0079] - R1 and R5 are an isopropyl or te / f-butyl group, and preferably isopropyl. - R2 is a linear alkyl chain comprised between 1-3 carbon atoms, and preferably methyl or ethyl.
    [0080] - R3 and R4 can be a straight or branched alkyl chain comprised between 1-4 carbon atoms, and preferably, it is a methyl, ethyl, propyl, isopropyl, sec-butyl or fe / f-butyl, and more preferably, ethyl, isopropyl or tert - butyl, and even more preferably ethyl or isopropyl.
    [0081] - R6 can be a straight or branched alkyl chain comprised between 1-4 carbon atoms, and is preferably methyl, ethyl, propyl, isopropyl, sec-butyl or fe / f-butyl, and more preferably, methyl, ethyl or isopropyl, and even more preferably methyl or ethyl.
    [0082] - while the Cyclo group can be formed by a chain between 4-7 linear or branched carbon atoms, linked at the ends to the N, preferably, the Cyclo group and the N to which it is attached form a pyrrolidine, piperidine or azepane, and more preferably, pyrrolidine.
    [0084] According to a particular preferred embodiment of the present invention, the ADE01 can be selected from N-ethyl-N-isopropyl-N-methylpropan-2-ammonium; N, N-diethyl-N isopropylpropan-2-ammonium; N, N, N-triethylpropan-2-ammonium; N- (tert-butyl) -N-ethyl-N, 2-dimethylpropan-2-ammonium; N- (tert-butyl) -N, N-diethyl-2-methylpropan-2-ammonium; N- (tert-butyl) -N, N, 2-trimethylpropan-2-ammonium; N-ethyl-N-isopropyl-N, 2-dimethylpropan-2-ammonium; N, N-diethyl-N-isopropyl-2-methylpropan-2-ammonium; N-isopropyl-N, N, 2-trimethylpropan-2-ammonium; 1.1- diisopropylpyrrolidin-1-io; 1-ethyl-1-isopropylpyrrolidin-1-io; 1-isopropyl-1-methylpyrrolidin-1-io; 1- (tert-butyl) -1-ethylpyrrolidin-1-io; 1- (tert-butyl) -1-methylpyrrolidin-1-io, preferably from N-ethyl-N-isopropyl-N-methylpropan-2-ammonium; N, N-diethyl-N-isopropylpropan-2-ammonium; N, N, N-triethylpropan-2-ammonium; 1,1-diisopropylpyrrolidin-1-io; 1-ethyl-1-isopropylpyrrolidin-1-io; 1-isopropyl-1-methylpyrrolidin-1-io and more preferably between N- ethyl-N-isopropyl-N-methylpropan-2-ammonium; N, N-diethyl-N-isopropylpropan-2-ammonium; 1-ethyl-1-isopropylpyrrolidin-1-io; 1-isopropyl-1-methylpyrrolidin-1-io.
    [0086] In another preferred embodiment of the process of the present invention, step i) further comprises at least one second directing agent with an organic structure selected from N-ethyl-N-isopropyl-N-methylpropan-2-ammonium; N, N-diethyl-N-isopropylpropan-2-ammonium; N, N, N-triethylpropan-2-ammonium; N- (tert-butyl) -N-ethyl-N, 2-dimethylpropan-2-ammonium; N- (tert-butyl) -N, N-diethyl-2-methylpropan-2-ammonium; N- (tert-butyl) -N, N, 2-trimethylpropan-2-ammonium; N-ethyl-N-isopropyl-N, 2-dimethylpropan-2-ammonium; N, N-diethyl-N-isopropyl-2-methylpropan-2-ammonium; N-isopropyl-N, N, 2-trimethylpropan-2-ammonium; 1.1- diisopropylpyrrolidin-1-io; 1-ethyl-1-isopropylpyrrolidin-1-io; 1-isopropyl-1-methylpyrrolidin-1-io; 1- (tert-butyl) -1-ethylpyrrolidin-1-io; 1- (tert-butyl) -1-methylpyrrolidin-1-io, and any combination of the above, preferably between N-ethyl-N-isopropyl-N-methylpropan-2-ammonium; N, N-diethyl-N-isopropylpropan-2-ammonium; N, N, N-triethylpropan-2-ammonium; 1,1-diisopropylpyrrolidin-1-io; 1-ethyl-1-isopropylpyrrolidin-1-io; 1-isopropyl-1-methylpyrrolidin-1-io, and any combination of the above and more preferably between N-ethyl-N-isopropyl-N-methylpropan-2-ammonium; N, N-diethyl-N-isopropylpropan-2-ammonium; 1-ethyl-1-isopropylpyrrolidin-1-io; 1-isopropyl-1-methylpyrrolidin-1-io and any combination of the above.
    [0088] The ADEOs listed above are not specific molecules for the CHA material in its zeolite form or for the AEI material in its zeolite form, but are biselective for the intergrowth of CHA / AEI, with which the possibility of using a mixture of them it would not present the problems of crystallization of mixtures of the two zeolitic phases CHA or AEI independently.
    [0089] According to the present invention, the crystallization process described in ii) can be carried out preferably in autoclaves, under conditions that can be static or dynamic at a temperature selected between 100 and 200 ° C, preferably between 130 and 175 ° C and more preferably between 150 and 175 ° C and a crystallization time that can be between 6 hours and 50 days, preferably between 1 and 14 days, and more preferably between 2 and 10 days. It must be taken into account that the components of the synthesis mixture can come from different sources, which can cause the crystallization conditions described to vary.
    [0091] According to a particular embodiment of the process of the present invention, it is possible to add crystals of CHA, AEI or CHA / AEI to the synthesis mixture of step i), which act as seeds favoring the synthesis described, in an amount up to 25% in weight with respect to the total amount of oxides. These crystals can be added before or during the crystallization process.
    [0093] According to the process described, after the crystallization described in ii), the resulting solid is separated from the mother liquor and recovered. Recovery step iii) can be carried out by different known separation techniques such as decantation, filtration, ultrafiltration, centrifugation or any other solid-liquid separation technique and combinations thereof.
    [0095] The process of the present invention may further comprise a step (iv) for the elimination of the organic content contained within the material obtained in (iii) by means of an extraction process.
    [0097] According to another particular embodiment, the process of the present invention also comprises a step (iv) for eliminating the organic compound contained within the material obtained in (iii) by means of a heat treatment at temperatures above 25 ° C, preferably between 200 and 1000 ° C and for a period of time preferably between 2 minutes and 25 hours.
    [0099] According to another particular embodiment, the material produced according to the present invention can be sieved or pelleted using any known technique.
    [0101] In the process described above, any cation present in the material can be exchanged by ion exchange for other cations using conventional techniques, such as through ion exchange processes in solution or impregnation processes followed by heat treatments. Thus, depending on the X2O3 / YO2 molar ratio of the synthesized material, any compensating cation (or extra-lattice) present in the material can be exchanged, at least in part, by ion exchange. These exchange cations are preferably selected from metals, protons, proton precursors (such as ammonium ions) and mixtures thereof, more preferably said cation is a metal selected from rare earths, metals from groups IIA, IIIA, IVA, VA , IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII and combinations thereof.
    [0103] According to a particular embodiment, the exchange cation is a metal and can be selected from copper, iron, palladium, platinum, rhodium, gold, silver, iridium, ruthenium, cerium, and combinations thereof; preferably, they are selected from copper, iron, palladium, platinum, cerium, and combinations thereof; and more preferably, between copper, iron, palladium, platinum, and combinations thereof.
    [0105] The transition metals can be included in the synthesis mixture of step (i) as simple salts or as complexes that protect the transition metal from precipitation under the alkaline conditions dictated by the reaction mixture. Especially, polyamine complexes are useful for protecting copper, platinum or palladium transition metal ions during preparation. In this way, transition metal ions can be introduced into the zeolitic material during crystallization. In one embodiment of the present invention, the reaction mixture may further comprise copper tetraethylenepentamine (Cu-TEPA) to introduce copper into the molecular sieve during crystallization.
    [0107] According to a particular embodiment, the synthesis mixture of step (i) can also contain fillers in addition to ADE01, which can help in the preparation of the zeolitic material. Such pore fillers could be amines or simple ammonium cations. The amounts are not particularly limited and could range from 0 to about 1, preferably from 0 to about 0.5 based on silica (mol / mol).
    [0109] A second aspect of the present invention relates to a zeolitic material that presents the intergrowth of the CHA / AEI phases obtained according to the process described above and which can have the following molar composition
    [0110] o X203: Y 02: p A: q ADE01: rH20
    [0111] where
    [0112] X is a trivalent element;
    [0113] Y is a tetravalent element;
    [0114] A is an alkali or alkaline earth cation;
    [0115] or it is comprised between the range of 0 to 0.12, preferably between 0.005 to 0.12; and more preferably between 0.01 to 0.10;
    [0116] p is in the range 0 to 1, preferably 0 to 0.8; and more preferably between 0 to 0.5;
    [0117] q is comprised between the range of 0.01 to 1, preferably between 0.01 to 0.5; and more preferably between 0.01 to 0.3;
    [0118] The remainder is comprised between the range of 0 to 2, preferably between 0 to 1.5; and more preferably between 0 to 1;
    [0120] The use of "ADE01" as the only organic directing agent instead of two specific molecules for the CHA and AEI phases respectively, would not only present an economic benefit for the material obtained by facilitating the synthesis, but would also facilitate a more controlled distribution and / or homogeneous heteroatoms throughout the intergrown material obtained. Also the absence of fluoride anions in the material obtained, prevents the generation of corrosive fluorinated products during the activation processes (e.g. calcination).
    [0121] According to a preferred embodiment, the material obtained according to the present invention can be calcined. Thus, the zeolitic material that presents the intergrowth of the CHA / AEI phases can have the following molar composition after being calcined:
    [0122] o X 2 O 3 '■ Y02
    [0123] where
    [0124] X is a trivalent element;
    [0125] Y is a tetravalent element; Y
    [0126] or it is comprised between the range 0 and 0.12, preferably between 0.005 to 0.12; and more preferably between 0.01 to 0.10.
    [0128] According to a particular embodiment, the tetravalent element Y of the zeolitic material presenting the intergrowth of the CHA / AEI phases can be selected preferably from silicon, tin, titanium, zirconium, germanium, and combinations thereof. Most preferably of silicon, tin, titanium, and zirconium, and combinations thereof, more preferably it is silicon.
    [0130] On the other hand, the trivalent element X of the zeolitic material exhibiting the intergrowth of the CHA / AEI phases according to the present invention, can preferably be selected from aluminum, boron, iron, indium, gallium and combinations thereof. Most preferably aluminum, boron and combinations thereof and most preferably Al.
    [0132] The material of the present invention obtained according to the process described above, is formed by the intergrowth of the CHA / AEI phases.
    [0134] According to a particular embodiment, the material obtained is substantially free of the presence of phosphorus in the crystal lattice.
    [0136] A third aspect of the present invention also refers 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 with greater added value, or as molecular sieves for the elimination / separation of reactive streams (eg gas mixtures) by contacting the feeds with the material obtained.
    [0138] According to a preferred embodiment, the material obtained according to the present invention can be used in the production of olefins after putting it in contact with an oxygenated organic compound under certain reaction conditions, for example, temperatures between 200 and 800 ° C and pressures between 0.1 kPa and 10 MPa. In particular, when feeding methanol, the obtained definitions are mostly ethylene and propylene. Ethylene and propylene are molecules of high commercial interest, since they can be polymerized to form polymers and copolymers, such as polyethylene and polypropylene.
    [0140] According to another preferred embodiment, the material obtained in the present invention can be used as a catalyst in selective catalytic reduction (SCR) reactions of NOx (nitrogen oxides) in a gas stream. In particular, the RCS of NOx will be carried out in the presence of reducing agents, such as ammonia, urea and / or hydrocarbons. Especially useful for this use are materials into which copper atoms have been introduced according to any of the known techniques.
    [0142] According to another preferred embodiment, the material obtained in the present invention can be used as a passive adsorbent to treat the exhaust gases of an internal combustion engine, which comprises the adsorption of NOx at low temperatures, preferably less than 200 ° C, and its subsequent thermal desorption at temperatures higher than that of adsorption, the removal of desorbed NOx being possible on a catalyst located after the passive adsorbent, preferably on a RCS catalyst. Especially useful for this use are materials to which palladium atoms have been introduced according to any of the known techniques.
    [0144] According to another preferred embodiment, the material obtained in the present invention can be used as a catalyst in combustion reactions of alkanes, such as, for example, methane. Especially useful for this use are materials to which palladium atoms have been introduced according to any of the known techniques.
    [0146] A fourth aspect of the present invention is the catalytic process for the conversion of organic compounds into higher value-added products characterized in that it comprises the following stages:
    [0147] a) contacting the material described above and obtained according to the process of the present invention with feeds of organic compounds, preferably oxygenated organic compound, more preferably methanol; Y
    [0148] b) heating the mixture from step a), preferably at temperatures between 200 and 800 ° C; under pressure conditions between 0.1 kPa and 10MPa.
    [0149] c)
    [0150] A fifth aspect of the present invention is the process for the selective catalytic reduction (SCR) of NOx (nitrogen oxide) in a gas stream characterized in that it comprises the following step:
    [0151] a) contacting the material described above and obtained according to the process of the present invention in a gas stream comprising nitrogen oxide, preferably in the presence of agents reducing agents, more preferably selected from ammonium, urea and / or hydrocarbons.
    [0153] In a preferred embodiment the catalyst material described above comprises copper atoms.
    [0155] A sixth aspect of the present invention is the process for passive adsorption of exhaust gases from an internal combustion engine characterized in that it comprises the following stages:
    [0156] a) contacting the material described above and obtained according to the process of the present invention in the gas outlet of an internal combustion engine, where said gases are at a temperature lower than 200 ° C.
    [0158] In a preferred embodiment of the process, it additionally comprises a subsequent step of desorption of the nitrogen oxide adsorbed in step (a) at a temperature higher than that of adsorption.
    [0160] In a more preferred embodiment the material described above comprises palladium atoms.
    [0162] A seventh aspect of the present invention is the catalytic process for alkane combustion reactions characterized in that it comprises contacting the material described above and obtained according to the process of the present invention with alkanes, preferably methane, during its combustion.
    [0164] In a more preferred embodiment of the process the material described above comprises palladium atoms.
    [0166] Throughout the description and claims the word "comprise" 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 characteristics of the invention will emerge in part from the description and in part from the practice of the invention.
    [0167] Throughout the description and claims the word "comprise" 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 characteristics of the invention will emerge in part from the description and in part from the practice of the invention. The following examples and figures are provided by way of illustration, and are not intended to be limiting of the present invention.
    [0169] BRIEF DESCRIPTION OF THE FIGURES
    [0171] Figure 1: X-ray diffraction pattern (XRD) of different intergrowths of CHA / AEI simulated from the DIFFaX software.
    [0173] Figure 2: X-ray diffraction pattern (XRD) of the uncalcined sample obtained according to Example 4 of the present invention.
    [0175] Figure 3: X-ray diffraction pattern (XRD) of the calcined sample obtained according to Example 4 of the present invention
    [0177] EXAMPLES
    [0179] The present invention is illustrated by the following examples which are not intended to be limiting thereof.
    [0181] Example 1: Synthesis of W-ethyl-W-isopropyl-W-methylpropan-2-ammonium hydroxide (EIMP)
    [0182] In a round bottom flask, 0.278 mole of W-ethyl-W-isopropylpropan-2-amine (35.94 g) is dissolved in 150 ml of ethyl ether. The resulting solution is cooled in an ice bath and, under continuous stirring, 0.707 moles of methyl iodide (100.32 g) are added dropwise in three aliquots over a 24 h period. Then, the solution is allowed to react for a week at room temperature with stirring. When the reaction is complete, W-ethyl-W-isopropyl-W-methylpropan-2-ammonium iodide (EIMP) precipitates as a white solid. The product is isolated by filtration and dried.
    [0184] Subsequently, 50.0 mmol of W-ethyl-W-isopropyl-W-methylpropan-2-ammonium iodide is dissolved in 110 ml of water. Then 100 g of resin are added exchange (Amberlite IRN-78) to the previous solution and keep stirring for 24 hours. Finally, the solution is collected by filtration and the hydroxide form of N-ethyl-N-isopropyl-N-methylpropan-2-ammonium [EIMP (OH)] has an exchange efficiency of at least 95%.
    [0186] Example 2: Synthesis of N, N-diethyl-N-isopropylpropan-2-ammonium hydroxide (DEIP)
    [0187] 0.438 moles of N-ethyl-N-isopropylpropan-2-amine (56.58 g) are dissolved in 120 ml of chloroform. The resulting solution is cooled in an ice bath, and subsequently 1.094 moles of iodoethane (170.69 g) are added dropwise and under constant stirring. Once the mixture reaches room temperature, it is slowly heated to 45 ° C and allowed to react for 7 days. After completion of the reaction, the solvent is evaporated, and the product is precipitated by adding ethyl ether. Filter under vacuum to remove the compound and finally dry under vacuum and heat. N, N-diethyl-N-isopropylpron-2-ammonium iodide (DEIP) is obtained as a white solid.
    [0189] Subsequently, 50.0 mmol of the N, N-diethyl-N-isopropylpronan-2-ammonium iodide is dissolved in 110 ml of water. Next, 100 g of anion exchange resin (Amberlite IRN-78) are added to the previous solution and it is kept stirring for 24 hours. Finally, the solution is collected by filtration and the hydroxide form of N, N-diethyl-N-isopropylpronan-2-ammonium [DEIP (OH)] has an exchange efficiency of at least 95%.
    [0191] Example 3: Synthesis of 1-ethyl-1-isopropylpyrrolidin-1-io hydroxide (ElPir)
    [0192] The preparation of 1-ethyl-1-isopropylpyrrolin-1-io hydroxide (ElPir) was carried out by three synthetic steps.
    [0194] 3.1: Synthesis of 1-isopropylpyrrolidin-1-io bromide
    [0195] 0.10 moles of pyrrolidine (7.11 g) are dissolved in 100 ml of 2-propanol and then, under stirring, 0.25 moles (30.75 g) of 2-bromopropane are added through small aliquots. The resulting solution is heated to 70 ° C and allowed to react for 24 h. At the end of this time and once the reaction mixture reaches room temperature, an ethyl acetate-acetone mixture is added to favor the precipitation of the organic salt. Finally, the compound is isolated by filtration, recrystallized, and characterized by NMR. 1-isopropylpyrrolidin-1-io bromide it is obtained as a white precipitate.
    [0197] 3.2: Synthesis of 1-isopropylpyrrolidine
    [0198] 0.074 moles of 1-isopropylpyrrolidin-1-io bromide (14.38 g) are dissolved in 100 ml of distilled water, and 0.074 moles of sodium hydroxide (2.96 g) are added with stirring. The resulting solution is allowed to react at room temperature for one hour. A biphasic mixture is obtained, in which 1-isopropylpyrrolidine is formed on top of it. The compound is separated by decantation and on the remaining aqueous phase, a liquid-liquid extraction is carried out with chloroform (2 x 50 ml) to recover part of the amine that was dissolved. The two organic parts are combined, dried over anhydrous magnesium sulfate, filtered to remove the inorganic salt and finally the solvent is evaporated. 1-Isopropylpyrrolidine is obtained as a thick yellow liquid.
    [0200] 3.3: Synthesis of 1-ethyl-1-isopropylpyrrolidin-1-io iodide
    [0201] 0.071 moles of 1-isopropylpyrrolidine (8.03 g) are dissolved in 60 ml of anhydrous methanol and an excess of iodoethane (0.176 moles, 27.5 g) is added dropwise, under constant stirring and at room temperature. The resulting mixture is slowly heated to 60 ° C and allowed to react for 72 h. After the reaction, the solvent is evaporated and the compound is precipitated by adding ethyl ether. The product is separated by vacuum filtration and dried under vacuum and heat. 1-Ethyl-1-isopropylpyrrolidin-1-io iodide (ElPir) is obtained as a white precipitate.
    [0203] Finally, 50.0 mmol of 1-ethyl-1-isopropylpyrrolidin-1-io iodide (ElPir) is dissolved in HOml of water. Next, 100g of anion exchange resin (Amberlite IRN-78) are added to the previous solution and it is kept stirring for 24 hours. Finally, the solution is collected by filtration and the hydroxide form of 1-ethyl-1-isopropylpyrrolidin-1-io: [EIPir (OH)] has an exchange efficiency of at least 95%.
    [0205] Example 4: Synthesis of CHA / AEI intergrowth
    [0206] 1.43 g of FAU (CBV720, Si / AI ~ 14, Zeolyst, Lot no: 72004003128) are mixed with 10.34 g of an aqueous solution of EIMP hydroxide (9.37% by weight, prepared according to Example 1 of the present invention), keeping the resulting mixture stirred for 10 minutes for homogenization. Then 0.41 is added g of a 40% by weight aqueous solution of sodium hydroxide (NaOH, Sigma-Aldrich, 98%). The mixture is kept under stirring until the desired concentration is achieved. The final gel composition is Si02 / 0.036 Al203 / 0.3 EIMP (OH) / 0.2 NaOH / 15 H20. This gel is transferred to a steel autoclave with a Teflon jacket and heated at 140 ° C for 5 days. After this time, the product obtained is recovered by filtration, washed with plenty of water and, finally, dried at 100 ° C. By X-ray diffraction it is observed that the solid obtained in its uncalcined form presents the characteristic peaks of the intergrowth of the CHA / AEI phases (see Figure 2). The material is calcined at 580 ° C for 5 h in an air atmosphere to eliminate the organic matter confined inside.
    [0208] The X-ray diffraction pattern of the calcined sample is observed in Figure 3, showing an intergrowth of the CHA / AEI phases of approximately 50% -50%. The chemical composition of the CHA / AEI intergrown material obtained in the present example shows Si / AI and Na / AI molar ratios of 11.0 and 0.37, respectively. The average particle size is -200 nm.
    [0210] Example 5: Synthesis of CHA / AEI intergrowth
    [0211] 1.43 g of FAU (CBV720, Si / AI ~ 14, Zeolyst, Lot no: 72004003128) are mixed with 10.40 g of an aqueous solution of EIMP hydroxide (9.37% by weight, prepared according to Example 1 of the present invention), keeping the resulting mixture stirred for 10 minutes for homogenization. Then 0.84 g of a 40% by weight aqueous solution of sodium hydroxide (NaOH, Sigma-Aldrich, 98%) is added. The mixture is kept under stirring until the desired concentration is achieved. The final gel composition is Si02 / 0.036 Al203 / 0.30 EIMP (OH) / 0.42 NaOH / 14.69 H20. This gel is transferred to a steel autoclave with a Teflon jacket and heated at 140 ° C for 5 days. After this time, the product obtained is recovered by filtration, washed with plenty of water and, finally, dried at 100 ° C. By means of X-ray diffraction, it is observed that the solid obtained presents the characteristic peaks of the intergrowth of the CHA / AEI phases. The material is calcined at 580 ° C for 5 h in an air atmosphere to eliminate the organic matter confined inside.
    [0213] Example 6: Synthesis of CHA / AEI intergrowth
    [0214] 1.38 g of FAU (CBV760, Si / AI ~ 25, PQIndustries) are mixed with 10.36 g of a EIMP hydroxide aqueous solution (9.37% by weight, prepared according to Example 1 of the present invention), keeping the resulting mixture stirred for 10 minutes for homogenization. Subsequently, 0.81 g of a 40% by weight aqueous solution of sodium hydroxide (NaOH, Sigma-Aldrich, 98%) is added. The mixture is kept under stirring until the desired concentration is achieved. The final gel composition is Si02 / 0.02 Al203 / 0.30 EIMP (OH) / 0.41 NaOH / 15.13 H20. This gel is transferred to a steel autoclave with a Teflon jacket and heated at 140 ° C for 5 days. After this time, the product obtained is recovered by filtration, washed with plenty of water and, finally, dried at 100 ° C. By X-ray diffraction it is observed that the solid obtained presents the characteristic peaks of the intergrowth of the CHA / AEI phases. The material is calcined at 580 ° C for 5 h in an air atmosphere to eliminate the organic matter confined inside. The chemical composition of the CHA / AEI intergrown material obtained in the present example shows Si / AI and Na / AI molar ratios of 8.9 and 0.67, respectively.
    [0216] Example 7: Synthesis of CHA / AEI intergrowth
    [0217] To 1.85 g of an aqueous solution of EIMP hydroxide (6.6% by weight, prepared according to Example 1 of the present invention) are added 60 mg of FAU (CBV720, Si / AI-14, Zeolyst, Lot no. : 72004003128), 128 mg of a colloidal suspension of amorphous silica (40% by weight, Ludox HS-40, Sigma-Aldrich) and 6 mg of aluminum hydroxide [AI (OH) 3, Alpha Aesar, 76.5% min . Al203], keeping the resulting mixture under stirring for 30 minutes to homogenize it. Subsequently, 130 mg of a 20% by weight aqueous solution of sodium hydroxide (NaOH, Sigma-Aldrich, 98%) are added. The mixture is kept under stirring until the desired concentration is achieved. The final gel composition is Si02 / 0.043 Al203 / 0.35 EIMP (OH) / 0.38 NaOH / 23.51 H20. This gel is transferred to a steel autoclave with a Teflon jacket and heated at 140 ° C for 7 days. After this time, the product obtained is recovered by filtration, washed with plenty of water and, finally, dried at 100 ° C. By means of X-ray diffraction, it is observed that the solid obtained presents the characteristic peaks of the intergrowth of the CHA / AEI phases. The material is calcined at 580 ° C for 5 h in an air atmosphere to eliminate the organic matter confined inside.
    [0219] Example 8: Synthesis of CHA / AEI intergrowth
    [0220] To 1.84 g of an aqueous solution of EIMP hydroxide (6.6% by weight, prepared according to Example 1 of the present invention) 66 mg of FAU (CBV712, Si / AI-25, PQ Industries) are added, 117 mg of a colloidal suspension of amorphous silica (40% by weight, Ludox HS-40, Sigma-Aldrich) and 6 mg of aluminum hydroxide [AI (OH) 3, Alfa Aesar, 76.5% min. AI2O3], keeping the resulting mixture under stirring for 30 minutes to homogenize it. Then 104 mg of a 20% by weight aqueous solution of sodium hydroxide (NaOH, Sigma-Aldrich, 98%) are added. The mixture is kept under stirring until the desired concentration is achieved. The final gel composition is Si02 / 0.071 AI2O3 / 0.35 EIMP (OH) / 0.32 NaOH / 24.96 H20. This gel is transferred to a steel autoclave with a Teflon jacket and heated at 140 ° C for 7 days. After this time, the product obtained is recovered by filtration, washed with plenty of water and, finally, dried at 100 ° C. By means of X-ray diffraction, it is observed that the solid obtained presents the characteristic peaks of the intergrowth of the CHA / AEI phases. The material is calcined at 580 ° C for 5 h in an air atmosphere to eliminate the organic matter confined inside.
    [0222] Example 9: Synthesis of CHA / AEI intergrowth
    [0223] 178 mg of FAU (CBV720, Si / AI ~ 14, Zeolyst, Lot no: 72004003128) are mixed with 1.14 g of an aqueous solution of DEIP hydroxide (11.6% by weight, prepared according to Example 2 of the present invention), keeping the resulting mixture under stirring for 10 minutes to homogenize it. Then 219 mg of a 20% by weight aqueous solution of sodium hydroxide (NaOH, Sigma-Aldrich, 98%) are added. The mixture is kept under stirring until the desired concentration is achieved. The final gel composition is Si02 / 0.036 AI2Ü3 / 0.30 DEIP (OH) / 0.44 NaOH /14.88 H20. This gel is transferred to a steel autoclave with a Teflon jacket and heated at 140 ° C for 7 days. After this time, the product obtained is recovered by filtration, washed with plenty of water and, finally, dried at 100 ° C. By X-ray diffraction it is observed that the solid obtained in its uncalcined form presents the characteristic peaks of the intergrowth of the CHA / AEI phases. The material is calcined at 580 ° C for 5 h in an air atmosphere to eliminate the organic matter confined inside.
    [0225] Example 10: Synthesis of CHA / AEI intergrowth
    [0226] 178 mg of FAU (CBV760, Si / AI ~ 25, PQIndustries) are mixed with 1.15 g of a DEIP hydroxide aqueous solution (11.6% by weight, prepared according to Example 2 of the present invention), keeping the resulting mixture stirred for 10 minutes to homogenize it. Then 213 mg of a 20% by weight aqueous solution of sodium hydroxide (NaOH, Sigma-Aldrich, 98%) are added. The mixture is kept under stirring until the desired concentration is achieved. The final gel composition is Si02 / 0.02 Al203 / 0.30 DEIP (OH) / 0.42 NaOH / 14.55 H20. This gel is transferred to a steel autoclave with a Teflon jacket and heated at 140 ° C for 7 days. After this time, the product obtained is recovered by filtration, washed with plenty of water and, finally, dried at 100 ° C. By X-ray diffraction it is observed that the solid obtained in its uncalcined form presents the characteristic peaks of the intergrowth of the CHA / AEI phases. The material is calcined at 580 ° C for 5 h in an air atmosphere to eliminate the organic matter confined inside.
    [0228] Example 11: Synthesis of CHA / AEI intergrowth
    [0229] 0.181 g of FAU (CBV720, Si / AI ~ 14, Zeolyst, Lot no: 72004003128) are mixed with 1.84 g of an aqueous solution of ElPir hydroxide (6.5% by weight, prepared according to Example 3 of the present invention), keeping the resulting mixture under stirring for 10 minutes for homogenization. Then 0.13 g of a 20% by weight aqueous solution of sodium hydroxide (NaOH, Sigma-Aldrich, 98%) is added. The mixture is kept under stirring until the desired concentration is achieved. The final gel composition is Si02 / 0.036 Al203 / 0.30 EIPir (OH) / 0.25 NaOH / 14.74 H20. This gel is transferred to a steel autoclave with a Teflon jacket and heated at 135 ° C for 10 days. After this time, the product obtained is recovered by filtration, washed with plenty of water and, finally, dried at 100 ° C. By means of X-ray diffraction, it is observed that the solid obtained presents the characteristic peaks of the intergrowth of the CHA / AEI phases. The material is calcined at 580 ° C for 5h in an air atmosphere to eliminate the organic matter confined inside.
    [0231] Example 12: Synthesis of CHA / AEI intergrowth
    [0232] 0.189 g of FAU (CBV720, Si / AI ~ 14, Zeolyst, Lot no: 72004003128) are mixed with 1.86 g of an aqueous solution of ElPir hydroxide (6.5% by weight, prepared according to Example 3 of the present invention), keeping the resulting mixture under stirring for 10 minutes for homogenization. Then add 0.23 g of a 20% by weight aqueous solution of sodium hydroxide (NaOH, Sigma-Aldrich, 98%). The mixture is kept under stirring until the desired concentration is achieved. The final gel composition is Si02 / 0.036 Al203 / 0.29 EIPir (OH) / 0.44 NaOH / 13.80 H20. This gel is transferred to a steel autoclave with a Teflon jacket and heated at 135 ° C for 10 days. After this time, the product obtained is recovered by filtration, washed with plenty of water and, finally, dried at 100 ° C. By means of X-ray diffraction, it is observed that the solid obtained presents the characteristic peaks of the intergrowth of the CHA / AEI phases. The material is calcined at 580 ° C for 5h in an air atmosphere to eliminate the organic matter confined inside.
    [0234] Example 13: Synthesis of CHA / AEI intergrowth
    [0235] To 1.82 g of an aqueous solution of EIMP hydroxide (6.6% by weight, prepared according to Example 1 of the present invention) are added 369 mg of a colloidal suspension of amorphous silica (40% by weight, Ludox HS -40, Sigma-Aldrich) and 5 mg of aluminum hydroxide [AI (OH) 3, Alfa Aesar, 76.5% min. Al203], keeping the resulting mixture under stirring for 30 minutes to homogenize it. Next, 216 mg of a 20% by weight aqueous solution of sodium hydroxide (NaOH, Sigma-Aldrich, 98%) are added. To this mixture, 14 mg of the solid from Example 4 (without calcining) are added. The mixture is kept under stirring until the desired concentration is achieved. The final gel composition is Si02 / 0.017 Al203 / 0.29 EIMP (OH) / 0.41 NaOH / 13.75 H20. This gel is transferred to a steel autoclave with a Teflon jacket and heated at 140 ° C for 7 days. After this time, the product obtained is recovered by filtration, washed with plenty of water and, finally, dried at 100 ° C. By means of X-ray diffraction, it is observed that the solid obtained presents the characteristic peaks of the intergrowth of the CHA / AEI phases. The material is calcined at 580 ° C for 5h in an air atmosphere to eliminate the organic matter confined inside.
    [0237] Example 14: Synthesis of CHA zeolite prepared with comparative effects 3.79 g of FAU (CBV720, Si / AI ~ 14, Zeolyst, Lot no: 72004003128) are mixed with 15.27 g of an aqueous hydroxide solution of TMAda ( 25% by weight, Sachem), keeping the resulting mixture stirred for 10 minutes to homogenize. Then, 2.42 g of a 20% by weight aqueous solution of sodium hydroxide (NaOH, Sigma-Aldrich, 98%) are added. The mixture is kept in stirring until the desired concentration is achieved. The final gel composition is SÍO2 / 0.036 AI2O3 / 0.3 TMAda (OH) / 0.2 NaOH / 15 H20. This gel is transferred to a steel autoclave with a Teflon jacket and heated at 160 ° C for 10 days. After this time, the product obtained is recovered by filtration, washed with plenty of water and, finally, dried at 100 ° C. By X-ray diffraction it is observed that the solid obtained presents the characteristic peaks of the pure CHA crystalline phase. The material is calcined at 580 ° C for 5h in an air atmosphere to eliminate the organic matter confined inside. The chemical composition has Si / AI and Na / AI molar ratios of 9.6 and 0.38, respectively. The average particle size is -200 nm.
    [0239] Example 15: Preparation of the intergrown material CHA / AEI exchanged with Cu (Cu-CHA / AEI)
    [0240] The synthesized and calcined sample according to the method set forth in Example 6, is exchanged with a 2 M aqueous solution of ammonium nitrate (NH4NO3, Sigma-Aldrich, 99% by weight) with a liquid / solid ratio of 10, maintaining the mixture at 80 ° C for 2 hours. After this time, the solid is recovered by filtration. Next, 28.27 mg of copper acetate [(CH3C00) 2Cu-H20, Probus, 99%) are dissolved in 30 g of water, and 300 mg of the previously exchanged zeolite are added. The suspension is kept stirred for 24 h at 80 ° C. After this time, the product obtained is recovered by filtration and washed with plenty of water. Finally, the material is calcined in air at 550 ° C for 4h, obtaining the Cu-CHA / AEI catalyst. Chemical analysis indicates 2.9% Cu (by weight).
    [0242] To prepare the catalyst aged with steam at 750 ° C (Cu-CHA / AEI_750C), 100 mg of the Cu-CHA / AEI catalyst are introduced into a fixed-bed reactor passing a flow rate of 300 mL / min with 10% of water, 10% O2 and equilibrated with nitrogen for 13 hours at 750 ° C.
    [0244] Example 16: Preparation of the CHA material exchanged with Cu (Cu-CHA) The synthesized and calcined sample according to the method set forth in Example 14, is exchanged with a 2 M aqueous solution of ammonium nitrate (NH4NO3, Sigma-Aldrich, 99% by weight) with a liquid / solid ratio of 10, keeping the mixture at 80 ° C for 2 hours. After this time, the solid is recovered by filtration.
    [0245] Next, 28.27 mg of copper acetate [(CH3C 00) 2CuH20, Probus, 99%) are dissolved in 30 g of water, and 300 mg of the previously washed zeolite are added. The suspension is kept stirred for 24 h at 80 ° C. After this time, the product obtained is recovered by filtration and washed with plenty of water. Finally, the material is calcined in air at 550 ° C for 4 hours, obtaining the Cu-CHA catalyst. The chemical analysis indicates 2.5% Cu (by weight).
    [0247] To prepare the catalyst aged with steam at 750 ° C (Cu-CHA _750C), 100 mg of the Cu-CHA catalyst are introduced into a fixed bed reactor, passing a flow rate of 300 mL / min with 10% water, 10% 02 and equilibrated with nitrogen for 13 hours at 750 ° C.
    [0249] Example 17: Catalytic test for the reaction of methanol to olefins
    [0250] The activity of the samples prepared according to Examples 4 and 14 of the present invention has been studied in the transformation of methanol to olefins. Prior to their catalytic study, both samples have been exchanged with a 2 M solution of NH4NO3 at 80 ° C for two hours, setting a liquid / solid ratio of 10. After this treatment, the solids are recovered by filtration, being washed abundantly with water, and dried at 100 ° C. The exchanged samples are finally calcined at 540 ° C for 3 hours in air.
    [0252] The methanol-to-defined reaction is carried out in a fixed-bed isothermal reactor under the following reaction conditions: WHSV = 0.8 h-1, atmospheric pressure, reaction temperature = 350 ° C, catalyst = 50 mg pelletized between 0.2 and 0.4 mm. The methanol is vaporized by bubbling with 30 ml / min of nitrogen in a tank of methanol at -17 ° C. The catalyst is diluted in 1.95 g of inert silica (0.1-0.2 mm) and placed in a 10 mm diameter glass reactor. The reaction temperature is constantly regulated by a type K thermocouple and a PID controller associated with a heating furnace. The reactor outlet is controlled at 150 ° C and the products are analyzed in two gas chromatographs, first in a PONA 50 m 0.25 mm internal diameter capillary column to separate hydrocarbons from C1 to Ci2 with a temperature of 37 ° C and second in a 30 m and 0.53 mm internal diameter PLOT-alumina column with a temperature program from 50 to 180 ° C to separate C2-C4 hydrocarbons and determine hydrogen transfer. The detectors used are of flame ionization. Conversion is defined as the sum of the hydrocarbon weight yields.
    [0254] The catalytic results obtained for the catalysts obtained according to Examples 4 and 14 of the present invention are shown in Table 1:
    [0256] Selectivity ratios (%) to X95
    [0257] olefins to X95
    [0258] Time of life
    [0259] Sample c2 = c3 = c4 = Cz ~ IC2 ~ Ci ~ IC2 ~
    [0260] X95 (min)
    [0262] Example 4 788 39.8 42.6 15.7 1.10 0.40
    [0263] Example 14 552 46.2 37.8 12.5 0.82 0.27 Table 1: Life time of the catalysts described in Examples 4 and 14 of the present invention for the reaction of Methanol to Olefins (calculated as time in which the conversion is maintained above 95%), as well as the selectivity to light olefins for a methanol conversion of 95% (X95)
    [0265] Comparing the results, it is observed that the catalyst based on CHA / AEI intergrowth obtained according to the claims of the present invention (Example 4) has a considerably longer life time than the catalyst based on zeolite CHA obtained according to its traditional synthesis methodology. (Comparative Example 14 in Table 1). The life time has been calculated as the reaction time in which the methanol conversion remains above 95%). Furthermore, the selectivity towards the light olefins propylene and butenes, which in general are olefins of higher value than ethylene, increases with the CHA / AEI intergrowth.
    [0267] Example 18: Catalytic test for the RCS reaction of NOx
    [0268] The catalytic activity of the sample Cu-CHA / AEI and Cu-CHA synthesized according to Examples 15 and 16, respectively, of the present invention for the selective catalytic reduction of NOx is studied using a 1.2 cm fixed bed quartz tubular reactor in diameter and 20 cm long. In a typical experiment, 40 mg of the catalyst together with 1.2 g of SiC, is introduced into the fixed bed reactor, and the temperature is increased until reaching 550 ° C with a ramp of 10 ° C / min, in a flow of nitrogen 300 ml / min. Subsequently, that temperature is maintained for one hour under the same nitrogen flow. Once the desired temperature has been reached, the reaction mixture is fed (see the reaction conditions in Table 2):
    [0272] Table 2: Reaction conditions for the SCR of NOx.
    [0274] The RCS of NOx is studied using NH3 as a reducing agent. The NOx present at the exit of the reactor gases is analyzed continuously by means of a chemiluminescent detector CLD8xx analyzer (ECO PHYSICS).
    [0276] The aging of both samples are carried out by hydrothermal treatment at 750 ° C using a total flow of 300 ml / min with the following composition: 10% water, 10% oxygen and balanced with nitrogen for 13 hours.
    [0278] The catalytic results of the Cu-CHA / AEI and Cu-CHA catalysts prepared according to Examples 15 and 16 of the present invention are summarized in Table 3:
    [0280]
    [0281]
    [0283] Table 3: Conversion (%) of NOx at different temperatures (210, 250, 300, 350, 400, 450, 500 and 550 ° C) using the catalysts described according to Examples 15 and 16 of the present invention both in their fresh form as after being aged with steam at 750 ° C for 13h.
    [0285] It can be seen that the results obtained with the Cu-CHA / AEI catalyst prepared according to Example 15 of the present invention exceed the catalytic activity obtained with the Cu / CHA catalyst prepared according to Example 16, both in its fresh and aged form after be treated with steam at 750 ° C.
    权利要求:
    Claims (32)
    [1]
    1. Synthesis procedure of a zeolitic material formed by the intergrowth of the CHA / AEI phases characterized in that it comprises the following steps:
    i) preparation of a mixture comprising at least one source of water, at least one source of a tetravalent element "Y", optionally at least one source of an alkali or alkaline earth cation "A", optionally at least one source of an element trivalent "X", and an organic structure directing agent "ADE01" with structure selected from [R1R2R3R4N +] Q- or [R5R6CycloN +] Q-, where R1 and R5 are an isopropyl or te / f-butyl group, R2 is a chain linear alkyl comprised between 1-3 carbon atoms, R3, R4 and R6 is a linear or branched alkyl chain comprised between 1-4 carbon atoms, the CycloN group is a nitrogenous heterocycle that is formed by an alkyl chain of between 4- 7 carbon atoms, straight or branched, end-linked to the N, and where Q- is an anion; where the molar composition of the mixture is:
    n X203: Y02: a A: m ADE01: z H20
    where
    n is comprised between the range from O to 0.12;
    a is between the range of 0 to 2;
    m is comprised between the range of 0.01 to 2;
    z is comprised between the range from 200 to 200;
    ii) crystallizing the mixture obtained in i) in a reactor; Y
    iv) recovering the crystalline material obtained in ii).
    [2]
    2. Process according to claim 1, characterized in that the tetravalent element Y is selected from silicon, tin, titanium, zirconium, germanium, and combinations thereof.
    [3]
    3. Process according to claim 2, characterized in that the tetravalent element Y is silicon and comes from a source selected from silicon oxide, silicon halide, colloidal silica, fumed silica, tetraalkylorthosilicate, silicate, silicic acid, an amorphous silica, a zeolite and combinations thereof.
    [4]
    4. Process according to claim 3, characterized in that the silicon source is selected from an amorphous silica, a zeolite and combinations thereof.
    [5]
    Process according to any of the preceding claims, characterized in that the trivalent element X is selected from aluminum, boron, iron, indium, gallium and combinations thereof.
    [6]
    Process according to claim 5, characterized in that characterized in that the tetravalent element X is Al and comes from a source selected from any aluminum salt, aluminum alkoxides, any hydrated aluminum oxide and combinations thereof.
    [7]
    7. Process according to any of the preceding claims, characterized in that the ADE01 is selected from N-ethyl-N-isopropyl-N-methylpropan-2-ammonium; N, N-diethyl-N-isopropylpropan-2-ammonium; N, N, N-triethylpropan-2-ammonium; N- (tert-butyl) -N-ethyl-N, 2-dimethylpropan-2-ammonium; N- (tert-butyl) -N, N-diethyl-2-methylpropan-2-ammonium; N- (tert - butyl) -N, N, 2-trimetilpropan-2-ammonium; N-ethyl-N-isopropyl-N, 2-dimethylpropan-2-ammonium; N, N-diethyl-N-isopropyl-2-methylpropan-2-ammonium; N-isopropyl-N, N, 2-trimethylpropan-2-ammonium; 1,1-diisopropylpyrrolidin-1-io; 1-ethyl-1-isopropylpyrrolidin-1-io; 1-isopropyl-1-methylpyrrolidin-1-io; 1- (tert-butyl) -1-ethylpyrrolidin-1-io; 1- (tert-butyl) -1-methylpyrrolidin-1-io.
    [8]
    8. Process according to claim 7, characterized in that said ADE01 is selected from N-ethyl-N-isopropyl-N-methylpropan-2-ammonium; N, N-diethyl-N-isopropylpropan-2-ammonium; N, N, N-triethylpropan-2-ammonium; 1,1-diisopropylpyrrolidin-1-io; 1-ethyl-1-isopropylpyrrolidin-1-io; 1-isopropyl-1-methylpyrrolidin-1-io.
    [9]
    9. Process according to claim 8, characterized in that said ADE01 is selected from N-ethyl-N-isopropyl-N-methylpropan-2-ammonium; N, N-diethyl-N-isopropylpropan-2-ammonium; 1-ethyl-1-isopropylpyrrolidin-1-io; 1-isopropyl-1-methylpyrrolidin-1-
    10.
    [10]
    10. Process according to any of the preceding claims, characterized in that the crystallization process described in ii) is carried out in autoclaves, under static or dynamic conditions.
    [11]
    Process according to any of the preceding claims, characterized in that the crystallization process described in ii) is carried out at a temperature between 100 and 200 ° C.
    [12]
    12. Process according to any of the preceding claims, characterized in that the crystallization time of the process described in ii) is between 6 hours and 50 days.
    [13]
    Process according to any of the preceding claims, characterized in that it further comprises adding crystals of CHA, AEI or CHA / AEI as seeds to the synthesis mixture of step i) in an amount up to 25% by weight with respect to the total amount of oxides.
    [14]
    Process according to claim 13, characterized in that the CHA, AEI or CHA / AEI crystals are added before the crystallization process or during the crystallization process.
    [15]
    Process according to any of the preceding claims, characterized in that the recovery step iii) is carried out with a separation technique selected from decantation, filtration, ultrafiltration, centrifugation and combinations thereof.
    [16]
    16. Process according to any of the preceding claims, characterized in that it further comprises a step (iv) for eliminating the organic content contained within the material obtained in (iii) by means of an extraction process.
    [17]
    17. Process according to any of claims 1 to 15, characterized in that it also comprises a step (iv) for the elimination of the organic content confined inside the material obtained in (iii) by calcination by a heat treatment at temperatures between 200 and 1000 ° C for a period of time between 2 minutes and 25 hours.
    [18]
    18. Process according to any of the preceding claims, characterized in that the material obtained is sieved or pelleted.
    [19]
    19. Process according to any of the preceding claims, characterized in that any cation present in the material can be exchanged by ion exchange for other cations.
    [20]
    20. Process according to claim 19, characterized in that the exchange cation is selected from metals, protons, proton precursors and mixtures thereof.
    [21]
    21. Process according to claim 20, characterized in that the exchange cation is a metal selected from rare earths, metals from groups IIA, IIIA, IVA, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII and combinations thereof.
    [22]
    22. Process according to claim 21, characterized in that the metal is copper, iron, palladium, platinum, rhodium, gold, silver, iridium, ruthenium, cerium, and combinations thereof.
    [23]
    23. Process according to claim 22, characterized in that the metal is copper, iron, palladium, platinum, cerium, and combinations thereof.
    [24]
    24. Zeolitic material formed by the intergrowth of the CHA / AEI phases obtained according to the process described in any of claims 1 to 23, characterized in that it has the following molar composition
    o X203: Y 02: p A: q ADE01: rH 20
    where
    X is a trivalent element;
    Y is a tetravalent element;
    A is an alkali or alkaline earth element;
    or is comprised between the range from O to 0.12;
    p is comprised between the range from O to 1;
    q is between the range of 0.01 to 1; and
    subtraction between the interval 0a2.
    [25]
    25. - Zeolitic material formed by the intergrowth of the CHA / AEI phases according to claim 24, characterized in that it has the following molar composition after being calcined:
    n X203: Y02
    where
    X is a trivalent element;
    Y is a tetravalent element; Y
    n is between the range 0 and 0.12.
    [26]
    26. Zeolitic material formed by the intergrowth of the CHA / AEI phases according to any of claims 24 and 25, characterized in that the tetravalent element Y is selected from silicon, tin, titanium, zirconium, germanium, and combinations thereof.
    [27]
    27. Zeolitic material formed by the intergrowth of the CHA / AEI phases according to any of claims 24 to 26, characterized in that the trivalent element X is selected from aluminum, boron, iron, indium, gallium and combinations thereof.
    [28]
    28. Use of a zeolitic material formed by the intergrowth of the CHA / AEI phases described in any of claims 24 to 27 and obtained according to the process described in any of claims 1 to 23 as a catalyst or absorbent.
    [29]
    29. Use of a zeolitic material formed by the intergrowth of the CHA / AEI phases according to claim 28, as a catalyst for the production of olefins after putting it in contact with an oxygenated organic compound.
    [30]
    30. Use of a zeolitic material formed by the intergrowth of the CHA / AEI phases according to claim 28 for the selective catalytic reduction (SCR) of NOx (nitrogen oxides) in a gas stream.
    [31]
    31. Use of a zeolitic material formed by the intergrowth of the CHA / AEI phases according to claim 28 as a passive adsorbent for NOx at temperatures below 200 ° C, and subsequently capable of desorbing said NOx at temperatures above 200 ° C .
    [32]
    32. Use of a zeolitic material formed by the intergrowth of the CHA / AEI phases according to claim 28, for the combustion of alkanes.
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    引用文献:
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