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    • 专利摘要:
    Synthesis of zeolite cha in its nanocrystalline form, synthesis procedure and its use in catalytic applications. The present invention relates to a synthesis process of silicoaluminate with zeolitic CHA structure in its nanocrystalline form, which may comprise, at least, the following steps: i) Preparation of a mixture containing at least water, a zeolite with the FAU crystal structure, such as zeolite Y, as the sole source of silicon and aluminum, and an organic molecule capable of directing the formation of the zeolite CHA (ADEO1) wherein ADEO1 can be any organic molecule capable of directing the crystallization of the CHA zeolite, and where the molar composition of the synthesis mixture can be as follows: SiO2 : a Al2 O3 : b ADEO1: c H2 O; ii) Crystallization of the mixture obtained in (i) in a reactor; and iii) Recovery of the crystalline material obtained in (ii). (Machine-translation by Google Translate, not legally binding)
    公开号:ES2698700A1
    申请号:ES201731010
    申请日:2017-08-04
    公开日:2019-02-05
    发明作者:Sánchez Eva María Gallego；Carrizo Cecilia Gertrudis Paris；Triguero Luis Joaquin Martínez；Marin Manuel Moliner；Canós Avelino Corma；Chengeng Li
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；Universidad Politecnica de Valencia；
    IPC主号:
    专利说明:

    [0001]
    [0002]
    [0003]
    [0004] The present invention relates to a new hydrothermal synthesis process of silicoaluminates with zeolitic structure of the CHA type in nanocrystalline form, from other crystalline zeolitic silicoaluminates and organic structure directing agents, and their use as a catalyst.
    [0005]
    [0006] BACKGROUND OF THE INVENTION
    [0007]
    [0008] Zeolites or molecular sieves are described as materials formed by TO4 tetrahedra (T = Si, Al, P, Ge, B, Ti, Sn ...), interconnected by oxygen atoms, creating pores and cavities of size and shape uniform in the molecular range. These zeolitic materials have important applications as catalysts, adsorbents or ion exchangers among others.
    [0009]
    [0010] 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 Á), 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 7 A) (Corma et al., Nature, 2006, 443, 842; Sun et al., Nature, 2009, 458, 1154).
    [0011]
    [0012] Among the more than 200 zeolitic structures accepted by the International Zeolite Association (IZA), the chabazite crystalline structure is one of the most interesting due to its use in very diverse applications, standing out as a heterogeneous catalyst in the methanol to olefins (MTO) processes and the selective catalytic reduction (SCR) of NOx.
    [0013]
    [0014] The IZA has granted the CHA code to the chabazite molecular sieve, which presents a crystalline structure formed by a tridirectional system of small pores interconnected by large cavities (Dent et al., Nature, 1958, 181, 1794). The CHA structure has been synthesized with various chemical compositions, highlighting as aluminosilicate ("SSZ-13", Zones, US Patent 4544538, 1985, assigned to Chevron) or silicoaluminophosphate ("SAPO-34", Lok et al., US Patent 4440871, 1984, assigned to UOP). In general, it can be said that aluminosilicates have greater hydrothermal stability and better acid properties than homologous silicoaluminophosphates (Katada et al., J. Phys. Chem. C, 2011, 115, 22505).
    [0015]
    [0016] Chabazite is a natural zeolite with the following chemical composition Ca6Al12Si2 4 O 7 2. In addition to the natural form of chabazite, this zeolitic structure has been synthesized in the laboratory using different inorganic alkali cations as inorganic structure directing agents (ADE) . Thus, the synthesis of KG zeolite has been described (Breck et al., J. Chem. Soc. 1956, 2822), which is a chabazite synthesized in the presence of potassium cations and having a Si / Al ratio of 1.1. -2.1; zeolite D (Barrer et al., British Patent 868846, 1961), which is a chabazite synthesized in the presence of sodium-potassium cations and which has a Si / Al ratio of 2.2-2.5; and zeolite R (Milton et al., US Patent 3030181, 1962, assigned to Union Carbide) and having a Si / Al ratio of 1.7-1.8.
    [0017]
    [0018] Possibly, the first use of organic structure directing agents (ADEO) in the synthesis of chabazite zeolite was described by Tsitsishrili et al. (Soobsch, Akad, Nauk, Cruz, SSR, 1980, 97, 621), which shows the presence of tetramethylammonium cations (TMA) in the reactive mixture K2O-Na2O-SiO2-Al2O3-H2O. However, the Si / Al ratio obtained in the final solid is very low (Si / Al ~ 2.1). In the article it is described that the presence of the TMA in the synthesis medium seems to influence the crystallization of the CHA, but said organic molecule is not incorporated in the synthesized material.
    [0019]
    [0020] In general, aluminosilicates with low Si / Al ratio (less than 5) have a lower hydrothermal stability. Thus, with the aim of increasing said Si / Al ratio in the synthesis of CHA, more bulky ADEOs were introduced into the synthesis medium, such as N, N, N-trialkyl-1-adamantylammonium, N-alkyl-3 -quinuclidol and / or N, N, -trialkyl-exoaminonorbornane (Zones, US Patent 4544538, 1985, assigned to Chevron). Using these ADEOs, the CHA zeolite is obtained with Si / Al ratios between 4-25, which is called SSZ-13.
    [0021]
    [0022] The preferred procedure for the synthesis of SSZ-13 zeolite uses the N, N, N-trimethyl-1-adamantammonium cation (TMAdA) in the presence of sodium in the synthesis medium, using aluminum hydroxide and silica as amorphous sources of aluminum and silicon (Zones, US Patent 4544538, 1985, assigned to Chevron). Following this methodology of synthesis, zeolite SSZ-13 crystallizes with an average crystal size between 2-5 qm, as confirmed by the "IZA Synthesis Commission" (see SSZ-13 at http: //www.iza -online.org/synthesis/).
    [0023]
    [0024] The synthesis of zeolites in their nanocrystalline form, that is, with crystal sizes <100 nm, is highly desirable, given that this type of materials allow to improve the efficiency of the catalytic processes, decreasing the problems associated with the diffusion of reagents and products , as well as the deactivation of the catalyst due to molecules formed through consecutive reactions of the intermediate and final products of the reaction (Zheng et al., J. Mater, Chem. A, 2016, 4, 16756). However, the preparation of a certain zeolite in its nanocrystalline form, in an efficient and general manner, ie with broad ranges of chemical composition, such as wide Si / Al ranges, good synthesis yields (> 80%) , and with homogeneous particle sizes with an average particle size below 100 nm, is a complicated task.
    [0025]
    [0026] In the particular case of CHA silicoaluminate, the synthesis has been described in its nanocrystalline form (with sizes between 50 and 100 nm), using TMAda as ADEO in the presence of sodium in the synthesis medium, and using amorphous aluminum and silicon sources. (aluminum hydroxide and silica, respectively) (Zones et al, US 6,709,644, 2004, assigned to Chevron). According to example 1 of said patent, the synthesis gel has the following final composition: SiO2: 0.02 Al2O3: 0.2 NaOH: 0.2 ADEO: 12 H2O. According to said molar composition, the theoretical Si / Al ratio in the synthesis gel would be ~ 25, while the solid obtained according to the procedure described in Example 1 of said patent has a Si / Al ratio of ~ 11. The difference between the Si / Al ratios in the synthesis medium and in the final solid would indicate a low synthesis yield, with values less than 50% by weight with respect to the initial inorganic oxides introduced in the preparation of the material.
    [0027] Recently, the synthesis of CHA zeolite in its nanocrystalline form has also been described by introducing a surfactant, cetyltrimethylammonium (CTMA) into the traditional CHA synthesis medium (Li et al., Catal.Sci. Technol., 2016, 6, 5856). The synthesis gel has the following molar ratios: SiO2: 0.025 Al2O3: 0.2 NaOH: 0.2 TMAda: 0.12 CTMA: 44 H2O. The resulting material presents a good synthesis yield, with similar Si / Al values in the synthesis gel and in the final solid (20 and 17, respectively), but with a crystal size distribution in a wide range, from 50 at 200 nm.
    [0028]
    [0029] Finally, the synthesis of CHA silicoaluminate has been described with average crystal sizes close to 100 nm in certain Si / Al ratios (between 39 and 60), using the zeolitic FAU structure as a source of silicon and aluminum in the presence of sodium and TMAda in the synthesis medium (Takata et al., Micropor, Mesopor, Mater., 2016, 225, 524). Unfortunately, when the Si / Al ratio is less than 35, the average crystal size of the CHA-type materials synthesized is always greater than 100 nm.
    [0030]
    [0031] As shown, there are very few examples in the literature where the synthesis of zeolite CHA in its silicoaluminate form with small average particle sizes is efficiently described. In addition, and in a relevant manner, all of them show the presence of sodium in the synthesis medium. As it has been observed, the methodology described by Zones et al, using sources of amorphous silicon and aluminum in the presence of sodium, results in crystalline materials with low synthesis yields (Zones et al, US 6,709,644, 2004, assigned to Chevron). On the other hand, the methodology described by Li et al., Introducing a surfactant into the synthesis medium in the presence of alkaline cations, does not allow to control the average particle size in values lower than 100 nm (Li et al., Catal. Sci. Technol., 2016, 6, 5856). While the use of the FAU zeolite as a source of silicon and aluminum in the presence of alkaline cations, results in crystal sizes greater than 100 nm when the Si / Al ratios are less than 35 (Takata et al., Micropor. Mater., 2016, 225, 524), relationships that are usually desired for the application of acid zeolites as catalysts in most chemical processes.
    [0032]
    [0033] In addition, the use of alkaline cations in the synthesis medium results in materials zeolitics with alkaline cations in extra-net positions compensating the negative charge introduced by the aluminum atoms in tetrahedral coordination. Since their presence limits the acidic properties of the materials, post-synthetic exchange processes are required in order to replace said inorganic cations with protons. For this, the preferred process is an exchange with an ammonium salt, and its subsequent thermal treatment at high temperature to generate the acid centers. Therefore, the preparation of a zeolitic material, synthesized directly in the absence of alkaline or alkaline earth cations, will make it possible to avoid the need for the post-synthetic steps required to be able to eliminate the inorganic cations from the zeolitic.
    [0034]
    [0035] With all this, there is a need to find an efficient procedure that allows the synthesis of the zeolitic CHA structure in its silicoaluminate form in the absence of alkaline cations, with average crystal sizes less than 100 nm and good synthesis yields (> 80%) .
    [0036]
    [0037] The efficient preparation of zeolite CHA in its silicoaluminate form with controlled crystal sizes and less than 100 nm in the absence of alkaline cations is shown in this report, giving rise to catalysts with catalytic behaviors superior to those described up to now in certain catalytic processes, such as for the selective production of light olefins from methanol in the methanol to olefins (MTO) process.
    [0038]
    [0039] DESCRIPTION OF THE INVENTION
    [0040]
    [0041] The present invention relates to a new process for the synthesis of silicoaluminate with zeolitic structure CHA in its nanocrystalline form, using a zeolite with the crystalline structure FAU as the sole source of silicon and aluminum, under conditions essentially free of alkali cations. The resulting solid has high synthesis yields (> 80%) and an average crystal size of less than 100 nm. The present invention also relates to the subsequent use of said synthesized material as a catalyst in various catalytic processes, preferably as a catalyst in the process of converting methanol into light olefins (MTO).
    [0042]
    [0043] The present invention relates to a new method of synthesis of a material zeolitic with the CHA structure in its nanocrystalline form under alkaline or alkaline earth metal-free conditions and which may comprise, at least, the following steps:
    [0044] i) Preparation of a mixture containing at least water, a zeolite with the FAU crystal structure, such as zeolite Y, as the sole source of silicon and aluminum, and an organic molecule capable of directing the formation of the zeolite CHA (ADEO1), and where the synthesis mixture can have the following molar composition:
    [0045]
    [0046] SiO2: a Al2O3: b ADEO1: c H2O
    [0047] where a is between the range of 0.001 to 0.2, preferably between 0.005 to 0.1, and more preferably between 0.015 to 0.07;
    [0048] where b is comprised between the range of 0.01 to 2, preferably between 0.1 to 1, and more preferably between 0.1 to 0.6;
    [0049] where c is comprised between the range of 1 to 200, preferably between 1 to 50, and more preferably between 2 to 30;
    [0050] ii) Crystallization of the mixture obtained in (i) in a reactor; Y
    [0051] iii) Recovery of the crystalline material obtained in (ii).
    [0052]
    [0053] According to the present invention, the crystalline material with the zeolitic structure FAU which is used in (i) as the sole source of silicon and aluminum is zeolite Y. Preferably, the zeolite used has a Si / Al ratio greater than 7.
    [0054]
    [0055] One of the advantages of the present invention is that the reactive mixture prepared in step (i) is preferably free of alkali and alkaline earth cations.
    [0056]
    [0057] According to the present invention, the ADEO required in step (i), ADEO1, can be any organic molecule capable of directing the crystallization of the CHA zeolite, preferably, it is selected from a cyclic quaternary ammonium, a quaternary ammonium with at least a cyclic substituent group in its structure and combinations thereof. According to a particular embodiment, the ADEO required in step (i) can be a quaternary ammonium and preferably be selected from N, N, N-trimethyl-1-adamantammonium, 3,3,6,6-tetramethyl-3-azabicyclo [ 3.1.0] hexan-3-io, (4R, 7S) -2,2-dimethyl-2,3,3a, 4,7,7a-hexahydro-1H-4,7-ethanoisoindole-2-io, N, N, N-trimethylcyclohexylammonium, N, N, N-trimethylbenzylammonium, 1-methylquinuclidin-1-io, and combinations of them.
    [0058]
    [0059] According to a particular embodiment, the ADEO required in step (i) is N, N, N-trimethyl-1-adamantammonium.
    [0060]
    [0061] According to another particular embodiment, the ADEO required in step (i) is 3,3,6,6-tetramethyl-3-azabicyclo [3.1.0] hexan-3-io.
    [0062]
    [0063] According to another particular embodiment, the ADEO required in step (i) is (4R, 7S) -2,2-dimethyl-2,3,3a, 4,7,7a-hexahydro-1H-4,7-ethanoisoindole-2 -io.
    [0064]
    [0065] 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), being able to be selected from any organic molecule, preferably selected from amine or quaternary ammonium.
    [0066]
    [0067] According to a preferred embodiment, the cooperative ADEO is an ammonium cation, preferably it is a cyclic ammonium cation.
    [0068]
    [0069] According to another particular embodiment, the cooperative ADEO is an amine.
    [0070]
    [0071] According to the present invention, the crystallization step described in (ii) can be carried out preferably in autoclaves, under conditions that can be static or dynamic at a selected temperature preferably between 80 and 200 ° C, more preferably between 120 and 175 ° C, and more preferably between 130 and 175 ° C, and a crystallization time which may be between 6 hours and 30 days, preferably between 1 and 20 days, and more preferably between 1 and 14 days. It must be taken into account that the components of the synthesis mixture can come from different sources which can vary the crystallization conditions described.
    [0072]
    [0073] According to a particular embodiment of the process of the present invention, it is possible to add crystals of CHA to the synthesis mixture, which act as seeds favoring the synthesis described, 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.
    [0074] According to the described process, 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 separation techniques known as for example decanting, filtration, ultrafiltration, centrifugation or any other solid-liquid separation technique and combinations thereof.
    [0075]
    [0076] The process of the present invention may further comprise the removal of the organic content contained within the material by any known removal / extraction technique.
    [0077]
    [0078] According to a particular embodiment, the removal of the organic compound contained inside the material can be carried out by a heat treatment at temperatures above 25 ° C, preferably between 100 and 1000 ° C and for a period of time preferably comprised between 2 and minutes and 25 hours.
    [0079]
    [0080] According to another particular embodiment, the material produced according to the present invention can be pelletized using any known technique.
    [0081]
    [0082] According to a preferred embodiment, depending on the SiO2 / Al2O3 ratio of the material, cations can be introduced into the final calcined material using conventional techniques. Said exchange cation may be selected from metals, protons, proton precursors and mixtures thereof.
    [0083]
    [0084] According to a particular embodiment, the exchange cation is a metal that can be selected from rare earths, metals of groups IIA, IIIA, IVA, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII and combinations of the same.
    [0085]
    [0086] According to a preferred embodiment, the ion exchange cation is copper.
    [0087]
    [0088] The present invention also relates to a zeolitic material with CHA structure obtained according to the process described above and having the following molar composition:
    [0089] SiO2: o Al2O3: p ADEO1: q H2O
    [0090] where
    [0091] or is comprised between the range of 0.001 to 0.2, preferably between 0.005 to 0.1; and more preferably between 0.015 to 0.07,
    [0092] p is between the range of 0.01 to 1, preferably between 0.01 to 0.5; and more preferably between 0.01 to 0.3,
    [0093] q is comprised in the range of 0 to 2, preferably between 0 to 1.5, and more preferably between 0 to 1.
    [0094]
    [0095] According to a preferred embodiment, the material obtained according to the present invention can be calcined. Thus, the zeolitic material with CHA structure can have the following molar composition after being calcined:
    [0096] SiÜ 2 : o Al2O3
    [0097] where
    [0098] where o is between the range 0.001 and 0.2, preferably between 0.005 to 0.1; and more preferably between 0.015 to 0.07.
    [0099]
    [0100] The material of the present invention obtained according to the process described above has the network structure of the CHA zeolite.
    [0101]
    [0102] According to a particular embodiment, the crystalline material obtained is preferably free of the presence of alkaline or alkaline earth cations.
    [0103]
    [0104] According to a preferred embodiment, the material obtained according to the present invention can be exchanged ionically with a metal source selected preferably from rare earths, metals of groups IIA, IIIA, IVA, VA, IB, IIB, IIIB, IVB, VB, VIB , VIIB, VIII and combinations thereof. Thus, the zeolitic material with CHA structure can have the following molar composition after introducing the metal (M):
    [0105] SiO 2 : o Al 2 O 3 : r M
    [0106] where o is between the range 0.001 and 0.2, preferably between 0.005 to 0.1; and more preferably between 0.01 to 0.07,
    [0107] where r is comprised between the interval 0.001 and 1, preferably between 0.001 to 0.6; and more preferably between 0.001 to 0.5.
    [0108]
    [0109] According to a particular embodiment, the metal (M) is preferably copper.
    [0110] The crystalline material of the present invention can also be intimately combined with hydrogenating-dehydrogenating components such as, for example, platinum, palladium, nickel, rhenium, cobalt, tungsten, molybdenum, vanadium, chromium, manganese, iron and combinations thereof. These elements can be introduced in their cationic form and / or from salts or other compounds that by decomposition generate the metal component or oxide in its proper catalytic form.
    [0111]
    [0112] The present invention also relates to the use of the materials described above and obtained according to the synthesis method 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 elimination / separation of reactive currents (for example mixtures of gases) putting the feeds in contact with the material obtained.
    [0113]
    [0114] 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. Said oxygenated compound may be preferably selected from methanol, ethanol, or mixtures thereof.
    [0115]
    [0116] In particular, when feeding methanol the olefins obtained are mostly ethylene and propylene. Ethylene and propylene can be used for the preparation of polymers and co-polymers, such as polyethylene and polypropylene.
    [0117]
    [0118] 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 NOx SCR will be carried out in the presence of reducing agents, such as ammonium, urea and / or hydrocarbons. Especially useful for this use are the materials to which copper, iron or combinations thereof have been introduced, according to any of the known techniques.
    [0119]
    [0120] Throughout the description and the claims the word "comprises" and its variants do not intend to exclude other technical characteristics, additives, components or steps. For experts in the field, other objects, advantages and characteristics of the invention will be inferred in part from the description and in part from the practice of the invention.
    [0121]
    [0122] BRIEF DESCRIPTION OF THE FIGURES
    [0123]
    [0124] FIG. 1 Some examples of organic molecules used as organic structure directing agents (ADEOs) in the present invention.
    [0125]
    [0126] FIG. 2 Diffraction patterns of the materials obtained in Examples 4-13 of the present invention.
    [0127]
    [0128] FIG. 3 SEM images of the materials obtained according to Examples 4-13 of the present invention.
    [0129]
    [0130] FIG. 4 Conversion values of methanol at 350 ° C and WHSV = 0.8 h "1, obtained using as catalysts the materials synthesized according to Examples 4, 6, 11, 12 and 13 of the present invention.
    [0131]
    [0132] The present invention is illustrated by the following examples which are not intended to be limiting thereof.
    [0133]
    [0134] EXAMPLES
    [0135]
    [0136] Example 1: Synthesis of N, N, N-trimethyl-1-adamantammonium (TMAda)
    [0137]
    [0138] 29.6 g of 1-Adamantamine (Sigma-Aldrich) are mixed with 64 g of potassium carbonate (Sigma-Aldrich) and dissolved in 320 ml of chloroform. Then, 75 g of methyl iodide (Sigma-Aldrich) are added, and the resulting mixture is kept under stirring for 5 days at room temperature. After this time, the reactive mixture is filtered to eliminate the inorganic salts. The organic salt of the quaternary ammonium is obtained by precipitation, and subsequent washing, with diethyl ether. The final yield of N, N, N-trimetill-1-adamantammonium iodide is 85%.
    [0139]
    [0140] To prepare the hydroxide form of the above organic salt: 51.3 mmol of the organic salt are dissolved in water. Then 51 g of an exchange resin are added anionic (Amberlite IRN-78), and the resulting mixture is kept under stirring for 24 hours. Finally, the solution is filtered and the N, N, N-trimethyl-1-adamantammonium hydroxide is obtained (with an exchange percentage of 95%).
    [0141]
    [0142] Example 2: Synthesis of 3,3,6,6-tetramethyl-3-azabicyclo [3.1.0] hexan-3-io (TTMAH)
    [0143]
    [0144] 10 g (90.8 mmol) of 6,6-dimethyl-3-azabicyclo [3.1.0] hexane are dissolved in 200 ml of methanol. The solution is cooled to 0 ° C in an ice bath. Then add 6.3 g of anhydrous potassium carbonate (45.4 mmol) and allow it to react for a few minutes. Finally, 77.3 g of methyl iodide (54.6 mmol) are added dropwise. Once the resulting mixture reaches room temperature, it is left to react for 48 h. After the reaction, the solvent is evaporated, obtaining a solid residue. 200 ml of chloroform are added to dissolve the organic quaternary ammonium salt and filtered to separate the product from the inorganic salts. Finally, 3,3,6,6-tetramethyl-3-azabicyclo [3.1.0] hexane-3-iodide is obtained by recrystallization from diethyl ether, with a yield of 87%.
    [0145]
    [0146] To prepare the hydroxide form of the above organic salt: 50 mmol of the organic salt is dissolved in water. Then 50 g of an anion exchange resin (Amberlite IRN-78) are added, and the resulting mixture is kept stirring for 24 hours. Finally, the solution is filtered and the hydroxide of 3,3,6,6-tetramethyl-3-azabicyclo [3.1.0] hexan-3-io is obtained (with an exchange percentage of 96%).
    [0147]
    [0148] Example 3: Synthesis of (4R, 7S) -2,2-dimethyl-2,3,3a, 4,7,7a-hexahydro-1H-4,7-ethanoisoindole-2-io (DMHHE)
    [0149]
    [0150] 12 g (150 mmol) of 1,3-cyclohexadiene and 16.7 g (150 mmol) of N-methylmaleimide are dissolved in 300 ml of toluene, the mixture being refluxed for 4 days. After cooling, the solvent is evaporated, obtaining a solid residue. The reaction product is obtained by precipitation with a mixture of 90:10 ethyl hexanoacetate. The resulting precipitate is filtered and washed with hexane to obtain the Diels-Alder adduct.
    [0151]
    [0152] To a suspension of 8.3 g of LiAlH4 (218 mmol) in 450 ml of anhydrous tetrahydrofuran (THFanh) at -10 ° C and under N2, the Diels-Alder adduct is slowly added. (16.6 g, 87 mmol) dissolved in 150 ml of THFanh. When the addition is complete, the stirring mixture is allowed to stabilize and reach room temperature. Then it is heated to reflux for 8 h and, subsequently, it is left at room temperature overnight. The mixture is again cooled to -10 ° C, and the reaction is stopped by very slow and controlled addition of H 2 O (10 ml), a 15% (w / w) aqueous solution of NaOH (10 ml) and finally , distilled water (10 ml). After stirring for 1 hour at room temperature, the mixture is filtered to remove the inorganic salts, the solvent is partially evaporated, and the mixture is extracted with dichloromethane. The combined organic extracts are washed with brine and dried with anhydrous MgSO 4. Finally, the solvent is evaporated, providing the corresponding reduced product (89% yield).
    [0153]
    [0154] To a chloroform solution (300 ml) of the amine (12.6 g, 77.4 mmol) obtained in the previous step, CH3I (43.7 g, 308 mmol) is gradually added. The mixture is kept under stirring for 4 days at room temperature. The solvent is evaporated and the desired quaternary salt is obtained by precipitation with a mixture of ethyl acetate-diethyl ether.
    [0155]
    [0156] To prepare the hydroxide form of the above organic salt: 30 mmol of the organic salt is dissolved in water. Then 50 g of an anion exchange resin (Amberlite IRN-78) are added, and the resulting mixture is kept stirring for 24 hours. Finally, the solution is filtered and the hydroxide of (4R, 7S) -2,2-dimethyl-2,3,3a, 4,7,7a-hexahydro-1H-4,7-ethanoisoindole-2-io is obtained ( with an exchange rate of 94%).
    [0157]
    [0158] Example 4: Synthesis using TMAda as ADEO and FAU as a source of silicon and aluminum, in the absence of alkaline cations
    [0159]
    [0160] 23.9 g of an aqueous solution at 6.7% by weight of the hydroxide of TMAda (obtained according to Example 1) and 2.27 g of zeolite Y (CBV720, Si / Al ~ 14, Zeolyst) are mixed. The mixture is kept under stirring until the desired concentration is achieved. The final composition of the gel is: SiO2 / 0.036 Al2O3 / 0.4 TMAda / 5 H2O. This gel is transferred to a teflon-coated steel autoclave and heated at 175 ° C for 14 days under static conditions. After this time, the product obtained is recovered by filtration, washed with plenty of water, and dried at 100 ° C. The obtained solid is calcined in air at 550 ° C for 6 hours. The yield of solid obtained is greater than 90%.
    [0161]
    [0162] By X-ray diffraction, it is confirmed that the solid obtained has the characteristic peaks of the CHA structure (see Example 4 in Figure 2). The chemical composition of the final sample has a Si / Al ratio of 14.2. The average crystal size is 50-70 nm (see the SEM image in Figure 3).
    [0163]
    [0164] Example 5: Synthesis using TMAda as ADEO and FAU as source of silicon and aluminum, in the absence of alkaline cations
    [0165]
    [0166] 1.06 g of a 13.24% by weight aqueous solution of the TMAda hydroxide (obtained according to Example 1) and 0.104 g of Y zeolite (CBV760, Si / Al ~ 26, Zeolyst) are mixed. The mixture is kept under stirring until the desired concentration is achieved. The final composition of the gel is: SiO2 / 0.019 Al2O3 / 0.4 TMAda / 5 H2O. This gel is transferred to a teflon-coated steel autoclave and heated at 175 ° C for 14 days under static conditions. After this time, the product obtained is recovered by filtration, washed with plenty of water, and dried at 100 ° C. The solid obtained is calcined in air at 550 ° C for 6 hours. The yield of solid obtained is greater than 90%.
    [0167]
    [0168] By X-ray diffraction, it is confirmed that the solid obtained has the characteristic peaks of the CHA structure (see Example 5 in Figure 2). The chemical composition of the final sample presents a Si / Al ratio of 24.1. The average crystal size is 60-80 nm (see SEM image in Figure 3).
    [0169]
    [0170] Example 6: Synthesis using TTMAH as ADEO and FAU as a source of silicon and aluminum, in the absence of alkaline cations
    [0171]
    [0172] 15.57 g of a 7.3% by weight aqueous solution of 3,3,6,6-tetramethyl-3-azabicyclo [3.1.0] hexan-3-io hydroxide (TTMAH, obtained according to Example 2) and 1.2 are mixed. g of Y zeolite (CBV720, Si / Al ~ 14, Zeolyst). The mixture is kept under stirring until the desired concentration is achieved. The final composition of the gel is: SiO2 / 0.036 Al2O3 / 0.2 TTMAH / 3 H2O. This gel is transferred to a teflon-coated steel autoclave and heated at 175 ° C for 14 days under static conditions. Passed At this time, the product obtained is recovered by filtration, washed with abundant water, and dried at 100 ° C. The solid obtained is calcined in air at 550 ° C for 6 hours. The yield of solid obtained is greater than 90%.
    [0173]
    [0174] By X-ray diffraction, it is confirmed that the solid obtained has the characteristic peaks of the CHA structure (see Example 6 in Figure 2). The chemical composition of the final sample has a Si / Al ratio of 14.2. The average crystal size is 60-80 nm (see SEM image in Figure 3).
    [0175]
    [0176] Example 7: Synthesis using DMHHE as ADEO and FAU as source of silicon and aluminum, in the absence of alkaline cations
    [0177]
    [0178] 7.04 g of a 10.4% by weight aqueous solution of DMHHE hydroxide (obtained according to Example 3) and 0.6 g of Y zeolite (CBV720, Si / Al-14, Zeolyst) are mixed. The mixture is kept under stirring until the desired concentration is achieved. The final composition of the gel is: SiO2 / 0.036 Al2O3 / 0.4 DMHHE / 3 H2O. This gel is transferred to a teflon-coated steel autoclave and heated at 175 ° C for 14 days under static conditions. After this time, the product obtained is recovered by filtration, washed with plenty of water, and dried at 100 ° C. The solid obtained is calcined in air at 550 ° C for 6 hours.
    [0179]
    [0180] By X-ray diffraction, it is confirmed that the solid obtained has the characteristic peaks of the CHA structure (see Example 7 in Figure 2). The chemical composition of the final sample presents a Si / Al ratio of 14.5. The average crystal size is 60-80 nm (see SEM image in Figure 3).
    [0181]
    [0182] Example 8: Synthesis using TMAda as ADEO and FAU as a source of silicon and aluminum, in the presence of alkaline cations
    [0183]
    [0184] As a reference, a synthesis was carried out in the presence of alkali ions. 3.39 g of an 11.4% by weight aqueous solution of the TMAda hydroxide (obtained according to Example 1) are mixed with 0.22 g of a 20% by weight aqueous solution of sodium hydroxide (NaOH, Sigma-Aldrich). Next, 0.47 g of zeolite Y (CBV720, Si / Al ~ 14, Zeolyst) are added, and the resulting mixture is kept under stirring until the desired concentration is reached. The final composition of the gel is: SiO2 / 0.036 Al2O3 / 0.25 TMAda / 0.15 NaOH / 5 H2O. This gel is transferred to a teflon-coated steel autoclave and heated at 175 ° C for 14 days under static conditions. After this time, the product obtained is recovered by filtration, washed with plenty of water, and dried at 100 ° C. The solid obtained is calcined in air at 550 ° C for 6 hours. The yield of solid obtained is greater than 85%.
    [0185]
    [0186] By X-ray diffraction, it is confirmed that the solid obtained has the characteristic peaks of the CHA structure (see Example 8 in Figure 2). The chemical composition of the final sample has a Si / Al ratio of 14.0. The average crystal size is 200-250 nm (see SEM image in Figure 3).
    [0187]
    [0188] This example clearly shows that the presence of alkaline cations in a synthesis medium comparable to that presented above in Example 4 favors the crystallization of a CHA zeolite with considerably larger crystal sizes.
    [0189]
    [0190] Example 9: Synthesis using TMAda as ADEO and sources of amorphous silicon and aluminum, in the absence of alkaline cations
    [0191]
    [0192] 14.83 g of an 11.4% by weight aqueous solution of the TMAda hydroxide (obtained according to Example 1) are mixed with 1.2 g of fumed silica (Sigma-Aldrich) and 0.11 g of aluminum hydroxide [Al (OH) 3, 63 % by weight of Al2O3, Sigma-Aldrich]. The mixture is kept under stirring until the desired concentration is achieved. The final composition of the gel is: SiO2 / 0.033 Al2O3 / 0.4 TMAda / 5 H2O. This gel is transferred to a teflon-coated steel autoclave and heated at 175 ° C for 14 days under static conditions. After this time, the product obtained is recovered by filtration, washed with plenty of water, and dried at 100 ° C. The solid obtained is calcined in air at 550 ° C for 6 hours. The yield of solid obtained is greater than 90%.
    [0193]
    [0194] By X-ray diffraction it is confirmed that the solid obtained has the characteristic peaks of the CHA structure (see Example 9 in Figure 2). The chemical composition of the final sample has a Si / Al ratio of 14.2. The sample has an average crystal size of ~ 1 μm (see the SEM image in Figure 3).
    [0195]
    [0196] This example clearly shows that the use of amorphous silicon and aluminum sources, Although alkaline cations are not present in the synthesis medium, it also promotes the crystallization of the CHA zeolite with considerably larger crystal sizes than those obtained in Example 4. It should be noted that the synthesis conditions of the present example are comparable to those carried out in Example 4, only by changing the initial sources of silicon and aluminum. Therefore, the combination of Examples 4 and 9, clearly show the need to use zeolite Y as a source of silicon and aluminum in a medium substantially free of alkali cations, in order to obtain the silicoaluminate CHA in its nanocrystalline form with excellent synthesis yields.
    [0197]
    [0198] Example 10: Synthesis using TTMAH as ADEO and sources of amorphous silicon and aluminum, in the absence of alkaline cations
    [0199]
    [0200] 15.57 g of a 7.3% by weight aqueous solution of 3,3,6,6-tetramethyl-3-azabicyclo [3.1.0] hexan-3-io hydroxide (TTMAH, obtained according to Example 2) are mixed with 0.11. g of aluminum hydroxide [Al (OH) 3, 63% by weight of Al2O3, Sigma-Aldrich]. The mixture is kept under stirring for 20 minutes. Subsequently, 3.0 g of an aqueous solution of colloidal silica at 40% by weight (Ludox HS-40, Sigma-Aldrich) are added, and the resulting gel is kept under stirring until the desired concentration is reached. The final composition of the gel is: SiO 2 / 0.034 Al 2 O 3 / 0.2 TTMAH / 3H2O. This gel is transferred to a teflon-coated steel autoclave and heated at 175 ° C for 14 days under static conditions. After this time, the product obtained is recovered by filtration, washed with plenty of water, and dried at 100 ° C.
    [0201]
    [0202] By X-ray diffraction, it is observed that the solid obtained has a characteristic pattern of an amorphous material (see Example 10 in Figure 2).
    [0203]
    [0204] In this particular case, the synthesis conditions are analogous to those used in Example 6 of the present invention, observing that the use of amorphous silicon and aluminum sources, unlike the Y zeolite as the initial source of silicon and aluminum, does not they allow the crystallization of the zeolite CHA, again showing the unique capacity of the zeolite Y in a synthesis medium substantially free of alkaline cations to direct the crystallization of the zeolite CHA in its nanocrystalline form with excellent synthesis yields (see Example 6).
    [0205] Example 11: Synthesis using TMAda as ADEO and sources of amorphous silicon and aluminum, in the presence of alkaline cations
    [0206]
    [0207] According to the procedure described in the original Zones patent (U.S. Patent 4544538, 1985, assigned to Chevron), the silicoaluminate of the zeolite CHA is synthesized in its conventional form. For this, 23.9 g of an aqueous solution at 6.7% by weight of the TMAda hydroxide (obtained according to Example 1) are mixed with 0.065 g of sodium hydroxide (NaOH, Sigma-Aldrich). Next, 2.27 g of fumed silica (Sigma_Aldrich) and 0.17 g of aluminum hydroxide [Al (OH) 3, 63% by weight of Al2O3, Sigma-Aldrich] are introduced, keeping the resulting mixture under stirring until the desired concentration is achieved (adding water if necessary). The final composition of the gel is: SiO2 / 0.025 Al2O3 / 0.2 TMAda / 0.2 NaOH / 44 H2O. This gel is transferred to a teflon-coated steel autoclave and heated at 160 ° C for 6 days under static conditions. After this time, the product obtained is recovered by filtration, washed with plenty of water, and dried at 100 ° C. The solid obtained is calcined in air at 580 ° C for 3 hours. The yield of solid obtained is greater than 90%.
    [0208]
    [0209] In order to eliminate the sodium cations that may be confined inside the synthesized zeolite, 0.5 g of the calcined solid is exchanged with 5 ml of a 1 M aqueous solution of ammonium chloride (NH4Cl, Sigma-Aldrich), maintaining a relationship solid / liquid of 10 g / at room temperature for 10 h. Subsequently, the dry solid obtained after filtering and washing with water, is calcined in air at 500 ° C for 3 hours.
    [0210]
    [0211] By X-ray diffraction, it is confirmed that the solid obtained has the characteristic peaks of the CHA structure (see Example 11 in Figure 2). The chemical composition of the final sample presents a Si / Al ratio of 15.3. The average crystal size is 1.5-2.5 pm (see SEM image in Figure 3).
    [0212]
    [0213] Following the classical procedure described in the literature for the synthesis of zeolite SSZ-13 with high Si / Al ratios (Zones, US Patent 4544538, 1985, assigned to Chevron), a solid with very large crystal sizes is obtained, such that as also Lobo and Schreyeck reproduced for the "Commission of synthesis of the IZA" (see SSZ-13 at http://www.iza-online.org/synthesis/).
    [0214]
    [0215] Example 12: Synthesis of zeolite SSZ-13 in its nanocrystalline form using a surfactant and alkali cations
    [0216]
    [0217] According to the procedure described in the work (Li et al., Catal. Sci. Technol., 2016, 6, 5856), the nanocrystalline form of the zeolite CHA is synthesized using a surfactant and alkaline cations. 23.9 g of a 6.7% by weight aqueous solution of the TMAda hydroxide (obtained according to Example 1) are mixed with 0.031 g of sodium hydroxide (NaOH, Sigma-Aldrich). Next, 2.27 g of silica (Sigma-Aldrich) and 0.15 g of aluminum hydroxide [Al (OH) 3, 63% by weight of Al2O3, Sigma-Aldrich] are introduced, the resulting gel being maintained in agitation until concentration is achieved desired (adding water if necessary). The final composition of the gel is: SiO2 / 0.025 Al2O3 / 0.2 TMAda / 0.2 NaOH / 44 H2O. This gel is transferred to a teflon-coated steel autoclave and heated at 160 ° C for 1 day under static conditions. After this time, 3.31 g of cetyltrimethylammonium bromide (CTAB, Sigma-Aldrich) is introduced and the product obtained is recovered by filtration, washed with abundant water, and dried at 100 ° C. The solid obtained is calcined in air at 580 ° C for 3 hours. The yield of solid obtained is greater than 90%.
    [0218]
    [0219] In order to eliminate the sodium cations that may be confined inside the synthesized zeolite, 0.5 g of the calcined solid is exchanged with 5 ml of a 1 M aqueous solution of ammonium chloride (NH4Cl, Sigma-Aldrich), maintaining a relationship solid / liquid of 10 g / at room temperature for 10 h. Subsequently, the dry solid obtained after filtering and washing with water, is calcined in air at 500 ° C for 3 hours.
    [0220]
    [0221] By X-ray diffraction, it is confirmed that the solid obtained has the characteristic peaks of the CHA structure (see Example 12 in Figure 2). The chemical composition of the final sample has a Si / Al ratio of 17.0. The average crystal size is 50-200 nm (see SEM image in Figure 3).
    [0222]
    [0223] Example 13: Synthesis of nanocrystalline zeolite SSZ-62 (CHA) using amorphous silicon and aluminum sources, and alkaline cations in the synthesis medium According to the procedure described in the original Zones patent (Zones et al, US 6709644, 2004, assigned to Chevron), CHA zeolite is synthesized in its nanocrystalline form using amorphous silicon and aluminum sources, and alkaline cations in the synthesis medium . For this, 25 g of a 13.5% by weight aqueous solution of the TMAda hydroxide (obtained according to Example 1) are mixed with 1.28 g of sodium hydroxide (NaOH, Sigma-Aldrich). Then, 0.44 g of aluminum hydroxide [Al (OH) 3, 63% by weight of Al2O3, Sigma-Aldrich], and 12.02 g of an aqueous colloidal silica solution at 40% by weight (Ludox HS-40) are added. , Sigma-Aldrich), and the resulting gel, is maintained in agitation until achieving the desired concentration (adding water if necessary). The final composition of the gel is: SiO2 / 0.033 Al2O3 / 0.2 TMAda / 0.4 NaOH / 20 H2O. This gel is transferred to a teflon-coated steel autoclave and heated at 160 ° C for 2 days under static conditions. After this time, the product obtained is recovered by filtration, washed with plenty of water, and dried at 100 ° C. The solid obtained is calcined in air at 580 ° C for 3 hours. The yield of solid obtained is less than 50%.
    [0224]
    [0225] In order to eliminate the sodium cations that may be confined inside the synthesized zeolite, 0.5 g of the calcined solid is exchanged with 5 ml of a 1 M aqueous solution of ammonium chloride (NH4Cl, Sigma-Aldrich), maintaining a relationship solid / liquid of 10 g / at room temperature for 10 h. Subsequently, the dry solid obtained after filtering and washing with water, is calcined in air at 500 ° C for 3 hours.
    [0226]
    [0227] By X-ray diffraction, it is confirmed that the solid obtained has the characteristic peaks of the CHA structure (see Example 13 in Figure 2). The chemical composition of the final sample has a Si / Al ratio of 8.6. The average crystal size is 20-30 nm (see the SEM image in Figure 3).
    [0228]
    [0229] This synthesis methodology presents a low synthesis yield of nanocrystalline CHA material, with efficiencies lower than 50%.
    [0230]
    [0231] Example 14: Catalytic test for the reaction of methanol to olefins
    [0232]
    [0233] The activity of the samples has been tested in the transformation of methanol to olefins in an isothermal fixed-bed 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 methanol reservoir 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 K-type thermocouple and a PID controller associated with a heating furnace. The output of the reactor is controlled at 150 ° C and the products are analyzed in two gas chromatographs, first in a capillary column PONA 50m 0.25 mm internal diameter to separate hydrocarbons from C1 to C12 at a temperature of 37 ° C and second in a PLOT-alumina column 30 m and 0.53 mm internal diameter with temperature program from 50 to 180 ° C to separate C2-C4 hydrocarbons and determine hydrogen transfer. The detectors used are flame ionization. The conversion is defined as the sum of the yields by weight of hydrocarbons.
    [0234]
    [0235] The catalytic results obtained for the catalysts obtained according to Examples 4, 6, 11, 12 and 13 of the present invention are shown in Figure 4 and Table 1. Comparing the results of the materials presented in Figure 4, it is concluded that the catalysts based on the CHA zeolite obtained according to the claims of the present invention (Examples 4 and 6) are significantly much more active than other catalysts based on CHA zeolite obtained according to other synthesis methodologies, including CHA catalysts with large crystal sizes ( Example 11), and CHA with small crystal sizes synthesized in the presence of alkaline cations (Examples 12 and 13). If we consider the lifetime of each catalyst as the time during which the conversion of methanol is higher than 95% (X95), it can be seen that the catalysts synthesized according to the present invention, Examples 4 and 6, present times of life much higher, 1085 and 1011 minutes, respectively, than the other catalysts with CHA structure synthesized in the presence of alkaline cations, Examples 11, 12 and 13, with life times of 212, 472, and 397 minutes, respectively. These results show that the preparation of the CHA zeolite in its silicoaluminate form using the FAU zeolite as sole source of silicon and aluminum, in the absence of alkaline cations, not only allows the crystallization of said zeolite in its nanocrystalline form (<100 nm) with excellent synthesis yields, but also the catalytic activity observed for the MTO reaction is five times higher than the classic SSZ-13 zeolite (Example 11), and more than twice as active as other nanocrystalline zeolites with CHA structure synthesized with alkaline cations (Examples 12 and 13).
    [0236] Table 1: Yields to hydrocarbons in the reaction of methanol to olefins at 350 ° C and WHSV = 0.8 h -1 at the reaction time of 200 minutes.
    [0237]
    权利要求:
    Claims (33)
    [1]
    1. Process of synthesis of a zeolitic material with the structure CHA in its nanocrystalline form under conditions free of alkaline or alkaline earth cations, characterized in that it comprises, at least, the following steps:
    i) Preparation of a mixture containing at least water, a zeolite with the crystal structure FAU, as the sole source of silicon and aluminum, and an organic molecule (ADEO1), and where the molar composition of the mixture is:
    SiO 2 : a Al 2 O 3 : b ADEO1: c H 2 O
    where a is between the range of 0.001 to 0.2;
    where b is between the range of 0.01 to 2; Y
    where c is between the range of 1 to 200;
    ii) Crystallization of the mixture obtained in (i) in a reactor; Y
    iii) Recovery of the crystalline material obtained in (ii).
    [2]
    2. Synthesis process according to claim 1, characterized in that the zeolite with crystal structure FAU is zeolite Y.
    [3]
    Synthesis process according to claim 1, characterized in that the ADEO1 is selected from a cyclic quaternary ammonium, a quaternary ammonium with at least one cyclic substituent group in its structure and combinations thereof.
    [4]
    4. Synthesis process according to claim 3, characterized in that the ADEO1 is a quaternary ammonium selected from N, N, N-trimethyl-1-adamantammonium, 3,3,6,6-tetramethyl-3-azabicyclo [3.1.0] hexan-3-io, (4R, 7S) -2,2-dimethyl-2,3,3a, 4,7,7a-hexahydro-1H-4,7-ethanoisoindole-2-io, N, N, N- trimethylcyclohexylammonium, N, N, N-trimethylbenzylammonium, 1-methylquinuclidin-1-io, and combinations thereof.
    [5]
    5. Synthesis process according to claim 4, characterized in that the ADEO1 is N, N, N-trimethyl-1-adamantammonium.
    [6]
    6. The synthesis process according to claim 4, characterized in that the ADEO1 is 3,3,6,6-tetramethyl-3-azabicyclo [3.1.0] hexan-3-io.
    [7]
    7. Synthesis process according to claim 4, characterized in that the ADEO1 is (4R, 7S) -2,2-dimethyl-2,3,3a, 4,7,7a-hexahydro-1H-4,7-ethanoisoindole-2 -io.
    [8]
    8. The synthesis process according to claim 1, characterized in that it also comprises another cooperative ADEO present in step (i), which is selected from any organic molecule.
    [9]
    9. The synthesis process according to claim 8, characterized in that the cooperative ADEO is an ammonium cation.
    [10]
    10. The synthesis process according to claim 9, characterized in that the cooperative ADEO is a cyclic ammonium cation.
    [11]
    11. The synthesis process according to claim 8, characterized in that the cooperative ADEO is an amine.
    [12]
    The synthesis process according to any of the preceding claims, characterized in that the crystallization step described in (ii) is carried out in autoclaves, in static or dynamic conditions.
    [13]
    The synthesis process according to any of the preceding claims, characterized in that the crystallization process described in (ii) is carried out at a temperature between 80 and 200 ° C.
    [14]
    The synthesis 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 30 days.
    [15]
    The synthesis process according to any of the preceding claims, characterized in that it also comprises adding CHA zeolite crystals as seeds to the synthesis mixture in an amount up to 25% by weight with respect to the total amount of oxides.
    [16]
    The synthesis process according to claim 15, characterized in that the CHA crystals are added before the crystallization process or during the crystallization process.
    [17]
    The synthesis process according to any of the preceding claims, characterized in that the recovery step (iii) is carried out with a separation technique selected from settling, filtration, ultrafiltration, centrifugation and combinations thereof.
    [18]
    The synthesis process according to any of the preceding claims, characterized in that it also comprises the elimination of the organic content contained inside the material.
    [19]
    The synthesis process according to claim 17, characterized in that the process of removing the organic content contained inside the material is carried out by a thermal treatment at temperatures between 100 and 1000 ° C for a period of time comprised between 2 minutes and 25 minutes. hours.
    [20]
    20. Synthesis process according to any of the preceding claims, characterized in that the material obtained is pelletized.
    [21]
    21. Synthesis process according to any of the preceding claims, characterized in that cations can be introduced into the final calcined material using conventional techniques.
    [22]
    22. The synthesis process according to claim 21, characterized in that the exchange cation is selected from metals, protons, proton precursors and mixtures thereof.
    [23]
    23. Synthesis process according to any of claims 21 or 22, characterized in that the exchange cation is a metal selected from rare earths, metals of groups IIA, IIIA, IVA, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII and combinations thereof.
    [24]
    24. Synthesis process according to claim 23, characterized in that the metal is copper.
    [25]
    25. Zeolitic material with CHA structure obtained according to the process described in any of claims 1 to 24, characterized in that it has the following molar composition
    SiO2: o Al2O3: p ADEO1: q H2O
    where
    or is comprised in the range of 0.001 to 0.2;
    p is comprised in the range of 0.01 to 1;
    q is in the range of 0 to 2.
    [26]
    26. Zeolitic material with CHA structure according to claim 25, characterized in that it has the following molar composition after being calcined:
    SiO 2 : o Al 2 O 3
    where
    or is comprised in the range 0.001 to 0.2.
    [27]
    27. Zeolitic material with CHA structure according to any of claims 25 or 26, characterized in that it also comprises a metal selected from rare earths, metals of groups IIA, IIIA, IVA, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII and combinations thereof.
    [28]
    28. Zeolitic material with CHA structure according to claim 27, characterized in that it has the following molar composition after introducing the metal (M):
    SiO 2 : o A ^ O 3 : r M
    where:
    or is between the range 0.001 and 0.2;
    r is between the interval 0.001 and 1.
    [29]
    29. Zeolitic material with CHA structure according to any of claims 27 or 28, characterized in that the metal (M) is copper.
    [30]
    30. Use of a zeolitic material with CHA structure described in claims 25 to 29 for the conversion of feeds formed by organic compounds into products of higher added value, or for their elimination / separation of the reactive current by putting said feed in contact with the described material.
    [31]
    31. Use of a zeolitic material with CHA structure according to claim 30, for the production of olefins after putting it in contact with an oxygenated organic compound under certain reaction conditions.
    [32]
    32. Use of a zeolitic material with CHA structure according to claim 31, wherein the oxygenate is methanol, ethanol, or mixtures thereof.
    [33]
    33. Use of a zeolitic material with CHA structure according to claim 30 for the selective catalytic reduction (SCR) of NOx (nitrogen oxides) in a stream.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP1485323B1|2002-03-15|2007-01-03|ExxonMobil Chemical Patents Inc.|High silica chabazite, its synthesis and its use in the conversion of oxygenates to olefins|
    US20150132215A1|2009-11-24|2015-05-14|Basf Se|Process For The Preparation Of Zeolites Having CHA Structure|
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