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    • 专利摘要:
    Zeolitic material with ferrierite structure in its nanocrystalline form, procedure for its synthesis and use of said material. Zeolitic material with the ferrierite structure in its nanocrystalline form and its synthesis method comprising at least: i) preparing a mixture comprising: water, a source of a tetravalent element Y, a source of a trivalent element X, a source of an alkaline or alkaline earth metal cation (A), and two organic compounds (ADEO1 and ADEO2), wherein ADEO1 is selected from a monocyclic quaternary ammonium salt where at least one of the substituents attached to the nitrogen is a linear alkyl chain formed by 6 - 22 carbon atoms, and ADEO2 is selected from an amine, an ammonium ammonium salt or combinations thereof, ii) synthesis of the zeolite starting from the mixture obtained in i) and iii) recovery of the crystalline material (zeolite ferrierite) obtained in ii). (Machine-translation by Google Translate, not legally binding)
    公开号:ES2715008A1
    申请号:ES201731377
    申请日:2017-11-30
    公开日:2019-05-31
    发明作者:Canos Avelino Corma；Rey María Del Rocío Díaz；Benavent Vicente Juan Margarit；Sanchez María Cristina Martínez；Villalba María Teresa Navarro
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；Universidad Politecnica de Valencia；
    IPC主号:
    专利说明:

    [0001]
    [0002] Zeolitic material with Ferrierite structure in its nanocrystalline form, procedure for its synthesis and use of said material
    [0003]
    [0004] The present invention relates to a new zeolite with a Ferrierite crystalline structure in its nanocrystalline form, to its synthetic procedure, as well as to the use of said zeolite as a catalyst.
    [0005]
    [0006] BACKGROUND OF THE INVENTION
    [0007]
    [0008] Zeolites, natural or synthetic, are aluminosilicates with crystalline structures formed by a three-dimensional system of TO4 tetrahedra (mainly T = Si or Al) joined together through common oxygen atoms, which are arranged forming pores and cavities of dimensions molecular (3-15 A) uniform in size and shape. The structure of a zeolite containing only SiO4 tetrahedra is electronically neutral. The isomorphic substitution of Si4 + by Al3 + creates a formal charge defect that is compensated by the presence of certain cations, which are not part of the network and that are housed inside the pores of the zeolite. The International Association of Zeolites (IZA) has accepted more than 230 zeolites (http://www.iza-online.org) with different topology, zeolites that can be classified according to the size of their pores, whose openings or windows are delimited for a T number of atoms in tetrahedral coordination. Thus, small pore zeolites have windows delimited by 8 T atoms, medium pore zeolites have windows delimited by 10 T atoms, medium pore zeolites have windows delimited by 12 T atoms, and extra large pore zeolites have windows delimited by more than 12 atoms.
    [0009]
    [0010] Thanks to this great variety of structures and the possibility of modifying the chemical composition of most zeolites, these materials have numerous applications in adsorption processes, ion exchange and as heterogeneous catalysts in the refining, petrochemical and environmental fields (Davis, Nature 2002, 417, 813; Martinez et al., Coord. Chem. Rev. 2011, 255, 1558).
    [0011]
    [0012] In its application as heterogeneous catalysts, the presence of pores and cavities of molecular dimensions gives zeolites the so-called selectivity of form, exerted by its structure to reactants, transition states or products involved in the reaction. However, the reduced dimensions of these channel systems can also cause diffusion problems to more bulky molecules, which will have direct consequences on the activity, selectivity and deactivation rate of the zeolltic material and will imply an underuse of it. For these reasons it may be convenient to decrease the length of the pores of the zeolite and, therefore, the length of the diffusional paths. There are different proposals to reduce the length of the channels, such as the generation of intra-crystalline mesoporosity by direct slithering in the presence of rigid materials used as a template ("hard templating" methods) or by post-slhesis demetallization treatments (Perez-Ramirez et al. Chem. Soc. Rev. 2008, 37, 2530; Janssen et al., Microporous and Mesoporous Mater. 2003, 65, 59) Another alternative to decrease the length of the pores is to reduce the crystal size of the zeolites from microscopic dimensions to nanoscopic dimensions (Mintova et al., Chem. Soc. Rev. 2015, 44, 7207-7233.).
    [0013]
    [0014] Ferrierite zeolite [FER] is a zeolite with a bi-directional microporous structure formed by medium-sized pores (10 T atoms, 4.2 x 5.4 A) and small-sized pores (8 T atoms, 3.5 x 4.8 A) interconnected. A small cavity is formed along the small-sized channels, accessible only through the windows of 8 T atoms, known as the FER box (Baerlocher et al., Atlas of Zeolite Framework Types (6th Ed.), Elsevier Science BV, Amsterdam, 2007, pp. 142). Due to the reduced size of its channels delimited by 8 T atoms, zeolite ferrite is considered a monodirectional zeolite of medium pore in terms of its application as a heterogeneous catalyst.
    [0015]
    [0016] Zeolite ferrierite can be prepared using different methods of synthesis and different organic structure directing agents (ADEOs), and with different chemical composition, defined by its Si / Al ratio (Moliner et al., Angew. Chem. Int. Ed. 2015 , 54, 3560). It has a high thermal, hydrothermal and chemical stability, and is used as a catalyst in different processes, such as the isomerization of nbutenes (Vermeiren et al., Top. Catal. 2009, 52, 31) or oleic acid (Ngo, et al. , Eur. J. Lipid Sci. Technol. 2007, 109, 214). As a catalyst it is very selective, but the monodirectional nature of its structure limits the reaction to the active centers closest to the surface of the crystal and contributes to rapid deactivation due to the blockage of its pores by bulky precursor molecules of the formation of coke. Therefore, the decrease in pore length in zeolite ferrite would be highly recommended.
    [0017]
    [0018] In recent years, different research groups have described the synthesis of nanocrystalline zeolite ferrierite. Using pyrrolidine as the structure directing agent (ADE) it has been possible to synthesize ferrierite with average sizes in the range of 40-60 nm (Chu et al., Microporous and Mesoporous Materials 2017, 240, 189), and therefore nanocrystalline. However, recent studies have shown that reducing the crystal size from 40 nm to values below 15 nm is an important benefit from the point of view of catalyst life when nanozeolites are used as catalysts in industrially relevant processes such as olefin oligomerization and the alkylation of benzene with propylene (Gallego et al., Chem. Sci. 2017, 8 (12), 8138). Used as ADEO choline, ferrierite nano-needles were obtained, with sizes of 10 x 100 nm (Lee et al., ACS Catalysis 2013, 3, 617). In this case, the needles grow in the crystallographic direction [001], along which the medium-sized channels (10 T atoms) run. Therefore, the length of these pores, of 100 nm, is not the one that has been reduced to a greater extent. The combination of piperidine and TMAOH results in the synthesis of aggregates of ferrierite nanocrystals (Xue et al., RSC Advances 2015, 5, 12131), and the joint utilization of pyrrolidine and an organosilane directed the synthesis of crystallization of nanolamines. with ferrite structure (Wuamprakhon et al., Microporous and Mesoporous Materials 2016, 219, 1). In none of these cases the external surface exceeds 200 m2 / g, and the materials with greater external surface are not very crystalline as evidenced by their low micropore volume, less than 0.05 cm3 / g.
    [0019] As the background found in the bibliography and described in the previous paragraphs demonstrates, there is a clear need by the chemical industry to improve the synthesis of zeolite ferrierite in its nanocrystalline form, and in particular to synthesize nanoferrierites with morphologies in which it is reduced the crystal size in the crystallographic direction [001], parallel to the channels of 10 T atoms, for its subsequent application as a catalyst in various catalytic processes, and more particularly for use in oligomerization processes of light olefins for production of fuels synthetic liquids.
    [0020]
    [0021] This invention therefore proposes a new zeolite material with a crystalline Ferrierite structure in its nanocrystalline form, as! as its synthesis procedure that allows obtaining it.
    [0022] DESCRIPTION OF THE INVENTION
    [0023]
    [0024] The present invention relates to a zeolltic crystalline material with Ferrierite structure, also called Ferrierite zeolite, in its nanocrystalline form. The size of the crystals of said zeoltic material along the crystallographic direction [001] is in the range of 5 to 15 nm. The crystallographic direction [001] is the direction along which the pores of medium size (10 T atoms) run through which the molecules diffuse when the zeolite ferrite is used as a heterogeneous catalyst.
    [0025]
    [0026] The present invention also relates to the method of synthesis of said material.
    [0027]
    [0028] In a first aspect, the present invention relates to a zeolltic material with ferrite structure. The size of the crystals of said zeoltic material along the crystallographic direction [001] is in the range of 5 to 100 nm, preferably between 5 and 15 nm.
    [0029]
    [0030] The crystallographic direction [001] is the direction along which the pores of medium size (10 T atoms) run through which the molecules diffuse when the zeolite ferrite is used as a heterogeneous catalyst.
    [0031]
    [0032] In a preferred embodiment of the material of the present invention, the size of the crystals of said zeoltic material along the crystallographic direction [010] is in the range of 5 to 100 nm, more preferably between 5 and 15 nm.
    [0033] In a preferred embodiment of the material of the present invention, the size of the crystals of said zeoltic material along the crystallographic direction [100] is in the range of 2 to 100 nm, more preferably between 2 and 10 nm.
    [0034] In a more preferred embodiment, the size of the crystals of said zeoltic material along the crystallographic direction [001] is in the range of 5 to 15 nm, along the crystallographic direction [010] is comprised in the range of 5 to 15 nm, and along the crystallographic direction [100] is in the range of 2 to 10 nm,
    [0035] In a preferred embodiment, the material of the present invention has the following molar composition:
    [0036] or X2O3: YO2: p ADEO1: q ADEO2: r A ': z H2O where
    [0037] X is a trivalent element;
    [0038] And it is a tetravalent element;
    [0039] A ’is an alkaline or alkaline earth element;
    [0040] ADEO1 is a monocyclic quaternary ammonium salt where at least one of the nitrogen-linked substituents is a linear alkyl chain consisting of between 6-22 carbon atoms,
    [0041] ADEO2 is selected from an amine, an ammonium salt or combinations thereof
    [0042] or is in the range of 0 to 0.5, preferably between 0.003 to 0.1; and more preferably between 0.01 to 0.075;
    [0043] p is in the range of 0.001 to 1, preferably between 0.001 to 0.5; and more preferably between 0.001 to 0.2;
    [0044] q is in the range of 0.01 to 2, preferably between 0.05 to 1; and more preferably between 0.1 to 0.6;
    [0045] r is in the range of 0 to 2, preferably 0 to 1; and more preferably between 0 to 0.8;
    [0046] z is in the range of 0 to 2, preferably 0 to 1; and more preferably between 0 to 0.8.
    [0047]
    [0048] In a preferred embodiment of the invention, the tetravalent element Y is selected from silicon, tin, titanium, zirconium, germanium, and combinations thereof, more preferably Y is silicon.
    [0049]
    [0050] According to a preferred embodiment, the trivalent element X may be selected from aluminum, boron, iron, indium, gallium and combinations thereof, preferably between aluminum, boron and combinations thereof and more preferably aluminum.
    [0051]
    [0052] According to a particular embodiment of the present invention, the organic compound ADEO1 is a monocyclic quaternary ammonium salt comprising the structure R1R2CycloN + (the N linked to R1, R2 and the cycle), where the groups R1 and R2 are linear alkyl chains comprised between 1-6 and 6-22 carbon atoms, respectively and the "Cycle" refers to a linear aiquliic chain of between 4-7 carbon atoms, whose terminal carbons are attached to the N of the corresponding quaternary ammonium, so that said linear alkyl chain next to the N atom forms a heterocycle.
    [0053]
    [0054] Preferably ADEO1 are halides (F-, Cl-, Br-, I-) or ammonium hydroxides (OH-). The cycle may preferably be a pyrrolidinium or piperidinium.
    [0055]
    [0056] R1 is preferably a methyl or an ethyl and R2 is preferably a hexadecyl or heptadethyl.
    [0057]
    [0058] In a more preferred embodiment, ADEO1 is the compound of the following formula (it is hexadecylmethylpiperidinium):
    [0059]
    [0060]
    [0061]
    [0062]
    [0063] ADEO2 may be selected from any amine or ammonium salt that directs the synthesis towards the crystallization of zeolite with ferrite structure, and combinations thereof. The condition that the organic compound ADEO2 must meet is that in its presence the synthesis of zeolite ferrite is favored. Some of the organic compounds that meet this condition are cyclic amines such as piperidine, cyclic diamines such as DABCO, or non-cyclic amines such as ethylenediamine. Other molecules are the benzylmethylpyrrolidinium salt, quinuclidine, 1-6 bis (N-methylpyrrolidinium) hexane, cyclohexylamine, choline and tetramethylammonium.
    [0064]
    [0065] ADEO1 and ADEO2 are different and the presence of both is necessary to obtain the nanocrystalline Ferririte zeolite.
    [0066]
    [0067] ADEO2 may be selected from mono-amines, diamines or primary, secondary or tertiary polyamines, or salts of mono-ammonium, diamonium, quaternary polyammonium, and combinations thereof.
    [0068]
    [0069] According to a particular embodiment of the present invention, ADEO2 may be selected from N-alkyl pyrrolidines, N-alkyl piperidines, N-alkyl-Nhexamethyleneimines, N-alkyl-N.heptamethyleneimines, N-alkyl-pyrrolidiniums, Nalkylpiperidiniums, Nalkyl-N-hexamethylene ammoniums, N-alkyl-Nheptamethyleneammoniums and combinations thereof, where the alkyl groups are preferably C1-C8 alkyls, linear or branched.
    [0070]
    [0071] Preferably A ’is sodium or potassium.
    [0072]
    [0073] According to a preferred embodiment, the zeoltic material with ferrite structure has the following molar composition:
    [0074] or X2O3: YO2: r A '
    [0075] where
    [0076] X is a trivalent element;
    [0077] And it is a tetravalent element;
    [0078] A ’is an alkaline or alkaline earth element;
    [0079] or is in the range of 0 to 0.5, preferably between 0.003 to 0.1; and more preferably between 0.01 to 0.075;
    [0080] r is in the range of 0 to 2, preferably 0 to 1; and more preferably between 0 to 0.8;
    [0081]
    [0082] In a preferred embodiment of the invention, the tetravalent element Y is selected from silicon, tin, titanium, zirconium, germanium, and combinations thereof, more preferably Y is silicon.
    [0083]
    [0084] According to a preferred embodiment, the trivalent element X may be selected from aluminum, boron, iron, indium, gallium and combinations thereof, preferably from aluminum, boron and combinations thereof and more preferably aluminum.
    [0085]
    [0086] Preferably A ’is sodium or potassium.
    [0087]
    [0088] A second aspect of the invention relates to the method of synthesizing a zeoltic material with the Ferrierite structure in its nanocrystalline form as described in the first aspect of the invention. Said procedure comprises at least the following steps:
    [0089] i) Preparation of a mixture, also called a synthesis gel, comprising at least: water, at least one source of an element tetravalent Y, at least one source of a trivalent element X, at least one source of an alkaline or alkaline earth cation (A), and at least two organic compounds (ADEO1 and ADEO2), where ADEO1 is a monocyclic quaternary ammonium salt where at At least one of the substituents bound to nitrogen is a linear alkyl chain consisting of between 6-22 carbon atoms, and ADEO2 is selected from an amine, an ammonium salt or combinations thereof, where the molar composition of the mixture, expressed in the form of the equivalent oxides of the elements present therein, it is:
    [0090] l X2O3: YO2: m ADEO1: n ADEO2: a A: and H2O
    [0091]
    [0092] l is in the range of 0 to 0.5, preferably between 0.003 to 0.1; and more preferably between 0.01 to 0.075;
    [0093] m is in the range of 0.001 to 1, preferably between 0.001 to 0.5; and more preferably between 0.001 to 0.2;
    [0094] n is in the range of 0.01 to 2, preferably between 0.05 to 1; and more preferably between 0.1 to 0.6;
    [0095] a is in the range of 0 to 2, preferably 0 to 1; and more preferably between 0 to 0.8;
    [0096] and is in the range of 2 to 200, preferably between 5 to 150, and more preferably between 7 to 100;
    [0097] ii) synthesis of the zeolite starting from the mixture obtained in i) in a reactor at a temperature in the range of 80-200 ° C for a period of time in the range of 6 hours to 50 days,
    [0098] iii) recovery of the crystalline material (zeolite) obtained in ii).
    [0099]
    [0100] In a preferred embodiment of the invention, the tetravalent element Y is selected from silicon, tin, titanium, zirconium, germanium, and combinations thereof, more preferably Y is silicon.
    [0101]
    [0102] Preferably, the source of element Y is an oxide, an alkoxide, a halide or a salt (silicate, germanate, titanate ...) of element Y.
    [0103]
    [0104] More preferably, the source of element Y is a source of silicon which may be selected from silicon oxide, silicon alkoxide (for example tetraalkyl ortho-silicate) silicon halide, colloidal silica, smoking silica, a silicate, sillcic acid, a previously synthesized crystalline zeolite type material, a previously synthesized amorphous material and combinations thereof.
    [0105]
    [0106] According to a particular embodiment, the source of Si may be selected from a previously synthesized crystalline material, a previously synthesized amorphous material and combinations thereof, and which may also contain other heteroatoms in its structure. Some examples could be zeolites type faujasita (FAU), type L (LTL) and mesoporous materials ordered amorphous, such as MCM-41.
    [0107]
    [0108] According to a preferred embodiment, the trivalent element X may be selected from aluminum, boron, iron, indium, gallium and combinations thereof, preferably from aluminum, boron and combinations thereof and more preferably aluminum.
    [0109]
    [0110] Preferably, the source of element X is an oxide, a hydroxide, a halide, a nitrate, a sulfate, an alkoxide, or a sodium or potassium salt of element X. In a more preferred embodiment, the source of aluminum may be selected from at least any aluminum salt (for example aluminum nitrate), or any hydrated aluminum oxide.
    [0111]
    [0112] According to a particular embodiment of the present invention, the organic compound ADEO1 is a monocyclic quaternary ammonium salt comprising the structure R1R2CycloN + (the N linked to R1, R2 and the cycle), where groups R1 and R2 are linear alkyl chains comprised between 1-6 and 6-22 carbon atoms, respectively and the "Cycle" refers to a linear alkyl chain of 4-7 carbon atoms, whose terminal carbons are attached to the N of the corresponding quaternary ammonium, so that said linear alkyl chain next to the atom of N make up a heterocycle.
    [0113]
    [0114] Preferably ADEO1 are halides (F-, Cl-, Br-, I-) or ammonium hydroxides (OH-).
    [0115]
    [0116] Preferably, ADEO1 is the compound of the following formula (hexadecylmethylpiperidinium).
    [0117]
    [0118]
    [0119]
    [0120] According to a particular embodiment of the present invention, ADEO2 may be selected from any amine or ammonium salt that directs the synthesis towards the crystallization of zeolite with ferrite structure, and combinations thereof. The condition that the organic compound ADEO2 must meet is that in its presence the zeolite ferrite fermentation is favored. Some of the organic compounds that meet this condition are tic amines such as piperidine, tic diamines such as DABCO, or non-tic amines such as ethylenediamine. Other molecules are the benzylmethylpyrrolidinium salt, quinuclidine 1-6 bis (N-methylpyrrolidinium) hexane, cyclohexylamine, choline and tetramethylammonium.
    [0121] ADEO1 and ADEO2 are different and the presence of both is necessary to obtain the nanocrystalline Ferririte zeolite.
    [0122]
    [0123] ADEO2 may be selected from mono-amines, diamines or primary, secondary or tertiary polyamines, or salts of mono-ammonium, diamonium, quaternary polyammonium, and combinations thereof.
    [0124]
    [0125] According to a particular embodiment of the present invention, ADEO2 may be selected from N-alkyl-pyrrolidines, N-alkyl-piperidines, N-alkyl-N-hexamethyleneimines, Nalkyl-N.heptamethyleneimines, N-alkyl-pyrrolidines, N-alkylpiperidiniums, Nalkyl-N-hexamethylene ammonia, N-alkyl-N-heptamethylene ammonia and combinations thereof, where the alkyl groups are preferably C1-C8, linear or branched alkyls.
    [0126]
    [0127] Preferably, ADEO2 may be pyrrolidine, piperidine or hexamethyleneimine or combinations thereof.
    [0128]
    [0129] In a preferred embodiment of the invention, the source of an alkali or alkaline earth cation (A) is selected from oxides, hydroxides and salts of said alkaline or alkaline earth element.
    [0130]
    [0131] In a preferred embodiment of the invention, the alkaline or alkaline earth element is sodium or potassium.
    [0132] According to the present invention, the mixture obtained in step i) is subjected to a stage of synthesis of the zeolite (crystalline material) in a reactor or autoclave. The zeolite synthesis step described in ii) can preferably be carried out in autoclaves, under conditions that can be static or dynamic at a temperature selected between 80 and 200 ° C, preferably between 90 and 185 ° C and more preferably between 100 and 175 ° C and a crystallization time that can be between 6 hours and 50 days, preferably between 1 and 35 days, and more preferably between 2 and 25 days. It should be borne in mind that the components of the synthesis mixture can come from different sources, which may vary the synthesis or crystallization conditions of the zeolite described.
    [0133]
    [0134] According to a particular embodiment of the process of the present invention, it is possible to add ferrite crystals to the synthesis mixture, which act as seeds favoring the described synthesis, in an amount of up to 25% by weight with respect to the total amount of X and And introduced into the synthesis medium, expressed as oxides equivalent to the sources of X and Y. These crystals can be added before or during stage ii).
    [0135]
    [0136] According to the process described, after step ii), the resulting solid (nanocrystalline ferrierite zeolite) is separated from the mother liquor and recovered. The recovery step iii) can be carried out by different known separation techniques such as, for example, decantation, filtration, ultrafiltration, centrifugation or any other solid-liquid separation technique and combinations thereof.
    [0137]
    [0138] The method of the present invention may further comprise the elimination of the organic content contained within the material by any known removal / extraction technique. The elimination of the organic content contained inside the material is carried out after stage iii) of material recovery.
    [0139]
    [0140] According to a particular embodiment, the removal of the organic compound contained inside the material can be carried out by means of a thermal treatment or calcination at temperatures above 25 ° C, preferably between 100 and 1000 ° C, more preferred between 300 and 700 ° C and for a period of time preferably between 2 minutes and 25 hours, more preferred between 1 hour and 15 hours.
    [0141] After calcination (elimination of organic compounds), the material obtained would have the formula: o X2O3: YO2: r A ', which has been described in the first aspect of the invention.
    [0142] According to another particular embodiment, the zeolltic material produced according to the present invention, whether calcined or not, can be pelletized using any known technique. Preferably it is pelletized at a particle size between 0.25 and 0.42 mm (length), which is the fraction of particles recovered between two sieves with meshes of 60 and 40 apertures per linear inch (MESH), respectively.
    [0143]
    [0144] According to a preferred embodiment, any cation present in the zeolltic material produced according to the present invention can be exchanged by ion exchange for other cations using conventional techniques. Ace! therefore, depending on the X2O3 / YO2 molar ratio of the synthesized material, any cation present in the material can be exchanged, at least in part, by ionic exchange for any of the procedures described in the State of the Art. By way of example, the ion exchange is carried out by suspending the synthesized zeolitic material in an aqueous solution containing the cations to be exchanged, at a temperature between 20 and 100 ° C for a time between 10 minutes to 100 hours. At the end of the exchange, the solid is recovered by filtration or centrifugation. Said cations may preferably be selected from metals, protons, proton precursors and mixtures thereof, and more preferably the exchange cation is a proton or a proton precursor and combinations thereof.
    [0145]
    [0146] The crystalline material of the present invention can also be combined intimately with hydrogenating-dehydrogenating components such as platinum, palladium, nickel, rhenium, cobalt, tungsten, molybdenum, vanadium, chromium, manganese, iron and combinations thereof. The introduction of these elements can be carried out in the crystallization stage, by exchange (if applicable), and / or by impregnation or by physical mixing. 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 appropriate catalytic form.
    [0147]
    [0148] A third aspect of the invention relates to the use of the materials described above and obtained according to the method of synthesis of the present invention as catalysts for the conversion of feeds formed by organic compounds, such as for example olefins, n-paraffins, aromatics or alcohols , in products of higher added value, such as liquid fuels (gasoline, diesel, kerosene), xylenes, and in particular p-xylene, or short chain alkenes such as propylene, or as a molecular sieve for the elimination / separation of streams formed by hydrocarbon mixtures (for example gas mixtures) by contacting the feeds with the material obtained.
    [0149]
    [0150] According to a preferred embodiment, the material obtained according to the present invention can be used as a catalyst in oligomerization processes of light olefins, such as, for example, propene, butene, or pentene, for the production of synthetic liquid fuels, such as gasoline, kerosene or diesel
    [0151]
    [0152] According to a preferred embodiment, the material obtained according to the present invention, containing or not containing hydrogenating-dehydrogenating components, can be used as a catalyst in aromatic alkylation processes, in aromatic alkyl dealkylation processes, alkylaromatic transalkylation, aromatic alkyl isomerization, or in combined processes of dealkylation and transalkylation of alkylaromatics, for the production of aromatics of higher added value such as, for example, benzene, p-xylene or isopropylbenzene.
    [0153]
    [0154] According to a preferred embodiment, the material obtained according to the present invention can be used as a catalyst in isomerization and / or hydroisomerization processes of linear paraffins, as for example in isomerization processes of butene to isobutene, in isomerization processes of n-paraffins belonging to the fraction of gasoline to the corresponding isoparaffins, or in isomerization processes of long-chain n-paraffins (dewaxing or isodewaxing processes).
    [0155]
    [0156] According to a preferred embodiment, the material obtained according to the present invention can be used as a catalyst in hydrocarbon cracking processes, for the production of light olefins or in processes of converting methanol to hydrocarbons, such as propylene, to light olefins or hydrocarbons. belonging to the gasoline fraction.
    [0157]
    [0158] Throughout the description and the claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and characteristics of the invention will be derived partly from the description and partly from the practice of the invention.
    [0159] BRIEF DESCRIPTION OF THE FIGURES
    [0160]
    [0161] FIG. 1: X-ray diffraction patterns of the materials obtained in Examples 2-5 of the present invention.
    [0162]
    [0163] FIG. 2: Stock electronic microscopla emission scanning field (FESEM, the English Field emission scanning electron microscopy) (left) and electronic microscopla transmission (TEM, the English Transmission electron microscopy) (right) of the materials obtained according to the Examples 2 (fig. 2A), 4 (fig. 2B) and 5 (fig. 2C) of the present invention.
    [0164]
    [0165] EXAMPLES
    [0166]
    [0167] The invention will be illustrated below by tests carried out by the inventors, which shows the effectiveness of the product of the invention.
    [0168]
    [0169] Example 1: Synthesis of ADEO hexadecylmethylpiperidinium (C16MPip) as ADEO1
    [0170] For the synthesis of hexadecylmethylpiperidinium bromide (C16MPip, Mw = 404.51 g / mol) 0.1 mol of 1-bromohexadecane (Acros Organics, 97%, Mw = 305.34 g / mol) and 0.12 mol are added of N-methylpiperidine (Sigma-Aldrich, 99%, Mw = 99.18 g / mol) to 400 mL of acetonitrile. The solution is heated to 80 ° C and maintained at this temperature for 24 h. After the reaction, the solution is concentrated in a rotary evaporator and the product is precipitated with diethyl ether, filtered and washed with more diethyl ether. A white solid is obtained which is dried under vacuum and at 50 ° C for 5 hours to completely eliminate the solvents. The yield is 92%.
    [0171]
    [0172] Example 2: Synthesis of nanocrystalline ferrierite of molar ratio SiO2 / Al2O3 = 30 in the gel at a temperature of 150 ° C.
    [0173]
    [0174] In a first step, 9,429 g of distilled water are added to 3.2 g of a 10% solution of NaOH (source of element A) (810-3 mol) previously prepared. Next, and under vigorous agitation, 3,005 g of colloidal silica (Ludox AS-40, 0.02 mol) is added as the source of element Y, followed by 0.405 g of ADEO1 C16MPip (110-3 mol). Once ADEO1 is dissolved, 0.444 g of Al2 (SO4) 3-18H2O (Panreac, 6.6710-4 mol) are added as a source of element X, and stirring is maintained until its total dissolution. At that time 0.341 g of piperidine are added as ADEO2 (Sigma-Aldrich, 4-10'3 mol) dropwise, and the resulting gel is vigorously stirred for 4 hours at room temperature. The gel, with a final composition 0.2 Na2O: 1 SiO2: 0.033 Al2O3: 0.2 Piperidine: 0.05 C16MPip: 40 H2O, is transferred to a steel autoclave with a teflon jacket and kept at a temperature of 150 ° C for 7 days, under agitation conditions. After that time, the product obtained is recovered by filtration, washed with plenty of water until the pH is reduced below 9 and dried at 100 ° C. The solid obtained is calcined in air at 550 ° C for 10 h. The calcined solid is exchanged with a 2.5 M solution of NH4Cl for 2 h at 80 ° C, using a liquid-solid ratio of 10: 1. After washing with distilled water until the absence of chlorides, the solid is dried at 100 ° C and calcined at 550 ° C for 4 hours to obtain the zeolite in its acid form.
    [0175]
    [0176] By X-ray diffraction, it is confirmed that the solid obtained presents the characteristic peaks of the ferrierite zeolite (see Example 2 in Figure 1). The chemical composition of the final sample has a Si / Al ratio of 11.9. The textural properties of the synthesized material according to Example 2 of the present invention have been calculated by adsorption / desorption of N2, obtaining 398 m2 / g, 241 m2 / g, and 157 m2 / g, for the total BET area, area of micropore and external area, respectively. The material synthesized according to Example 2 has nanocrystals with two different morphologies, isotropic morphologies and sizes of 5-15 nm, and laminar morphology nanocrystals (see TEM image in Figure 2). In crystals of isotropic morphology and dimensions of 5-15 nm, the length of the channels of 10 atoms T, parallel to the direction [001], is about 5-15 nm. The high values of BET area and external area are due to the small size of the ferrierite nanocrystals obtained according to the present example.
    [0177]
    [0178] Example 3: Synthesis of nanocrystalline ferrierite of molar ratio SiO 2 / Al 2 O 3 = 60 in the gel at a temperature of 150 ° C.
    [0179]
    [0180] In a first step, 9.537 g of ultrapure distilled water are added to 3.2 g of a 10% solution of NaOH (source of element A) (810-3 mol) previously prepared. Then, and under vigorous agitation, 3,005 g of colloidal silica (Ludox AS-40, 0.02 mol) are added as a source of element Y, followed by 0.405 g of ADEO1 C16MPip (110-3 mol). Once ADEO1 is dissolved, 0.222 g of Al2 (SO4) 318H2O (Panreac, 3.3310-4 mol) are added as a source of element X, and stirring is maintained until completely dissolved. At that time 0.341 g of Piperidine as ADEO2 (Sigma-Aldrich, 410-3 mol) dropwise, and the resulting gel is vigorously stirred for 4 hours at room temperature. The gel, with a final composition 0.2 Na2O: 1 SiO2: 0.017 Al2O3: 0.2 Piperidine: 0.05 C16MPip: 40 H2O, is transferred to a steel autoclave with a teflon jacket and kept at a temperature of 150 ° C for 7 days, under agitation conditions. After that time, the product obtained is recovered by filtration, washed with plenty of water until the pH is reduced below 9 and dried at 100 ° C. The solid obtained is calcined in air at 550 ° C for 10 h. The calcined solid is exchanged with a 2.5 M solution of NH4Cl for 2 h at 80 ° C, using a liquid-solid ratio of 10: 1. After washing with distilled water until the absence of chlorides, the solid is dried at 100 ° C and calcined at 550 ° C for 4 hours to obtain the zeolite in its acid form.
    [0181] X-ray diffraction confirms that the solid obtained presents the characteristic peaks of the zeolite ferrierite (see Example 3 in Figure 1). The chemical composition of the final sample has a Si / Al ratio of 18.2. The textural properties of the synthesized material according to Example 3 of the present invention have been calculated by adsorption / desorption of N2, obtaining 366 m2 / g, 231 m2 / g, and 135 m2 / g, for the total BET area, area of micropore and external area, respectively.
    [0182]
    [0183] Example 4: Synthesis of nanocrystalline ferrierite of molar ratio SiO 2 / Al 2 O 3 = 30 in the gel at a temperature of 120 ° C.
    [0184]
    [0185] In a first step, 9,429 g of ultrapure distilled water are added to 3.2 g of a 10% solution of NaOH (source of element A) (810-3 mol) previously prepared. Then, and under vigorous stirring, 3.005 g of colloidal silica (Ludox AS-40, 0.02 mol) is added as a source of element Y, followed by 0.405 g of ADEO1 C16MPip (110-3 mol). Once ADEO1 is dissolved, 0.444 g of Al2 (SO4) 3-18H2O (Panreac, 6.6710-4 mol) is added as a source of element X and stirring is maintained until completely dissolved. At that time, 0.341 g of piperidine is added as ADEO2 (Sigma-Aldrich, 410-3 mol) dropwise, and the resulting gel is vigorously stirred for 4 hours at room temperature. The gel, of final composition 0.2 Na2O: 1 SiO2: 0.033 Al2O3: 0.2 Piperidine: 0.05 C16MPip: 40 H2O, is transferred to a steel autoclave with teflon jacket and kept at a temperature of 120 ° C for 17 days, under conditions of agitation. After that time, the product obtained is recovered by filtration, washed with plenty of water until the pH is reduced below 9 and dried at 100 ° C. The solid obtained is calcined in air at 550 ° C for 10 h. The calcined solid is exchanged with a 2.5 M solution of NH4Cl for 2 h at 80 ° C, using a liquid-solid ratio of 10: 1. After washing with distilled water until the absence of chlorides, the solid is dried at 100 ° C and calcined at 550 ° C for 4 hours to obtain the zeolite in its acid form.
    [0186]
    [0187] By X-ray diffraction, it is confirmed that the solid obtained presents the characteristic peaks of the zeolite ferrite (see Example 4 in Figure 1). The chemical composition of the final sample has a Si / Al ratio of 10.5. The textural properties of the synthesized material according to Example 4 of the present invention have been calculated by adsorption / desorption of N2, obtaining 447 m2 / g, 187 m2 / g, and 262 m2 / g, for the total BET area, area of micropore and external area, respectively. The material synthesized according to Example 4 has nanocrystals with two different morphologies, isotropic morphologies and sizes of 5-15 nm, and laminar morphology nanocrystals (see TEM image in Figure 2). Figure 2 clearly shows that the proportion of laminar nanocrystals in the sample obtained according to Example 4 is much smaller than in the sample obtained according to Example 2. The higher values of BET area and external area are due to the greater proportion of nanocrystals with isotropic morphology and sizes of 5-15 nm present in the ferrierite obtained according to the present example, crystals in which the length of the channels of 10 atoms T, parallel to the direction [001], will be 5-15 nm.
    [0188]
    [0189] Example 5: Synthesis of microcrystalline ferrierite of molar ratio SiO 2 / Al 2 O 3 = 30 in the gel at a temperature of 150 ° C. (comparative)
    [0190]
    [0191] To synthesize microcrystalline ferrite, 8,795 g of ultrapure distilled water are added to 3,888 g of a 10% solution of NaOH (source of element A) (0.0972 mol). Next, and under vigorous agitation, 3,005 g of colloidal silica (Ludox AS-40, 0.02 mol) is added as a source of element Y, followed by 0.444 g Al2 (SO4) 318H2O (Panreac, 6.6710-4 mol ) as a source of element X. After adding 0.760 g of piperidine as ADEO2 (Sigma-Aldrich, 0.0089 mol), the resulting gel is vigorously stirred for 4 hours at room temperature. The final composition gel 0.243 Na2O: 1 SiO2: 0.033 Al2O3: 0.446 Piperidine: 40 H2O is transferred to a steel autoclave with a Teflon jacket and kept at a temperature of 150 ° C for 5 days, under stirring conditions . After that time, the product obtained is recovered by filtration, washed with plenty of water until the pH is reduced below 9 and dried at 100 ° C. The solid obtained is calcined in air at 550 ° C for 10 h. The calcined solid is exchanged with a 2.5 M solution of NH4Cl for 2 h at 80 ° C, using a liquid-solid ratio of 10: 1. After washing with distilled water until the absence of chlorides, the solid is dried at 100 ° C and calcined at 550 ° C for 4 hours to obtain the zeolite in its acid form.
    [0192] By X-ray diffraction, it is confirmed that the solid obtained presents the characteristic peaks of the zeolite ferrite (see Example 5 in Figure 1). The chemical composition of the final sample has a Si / Al ratio of 8.9. The textural properties of the synthesized material according to Example 5 of the present invention have been calculated by adsorption / desorption of N2, obtaining 319 m2 / g, 302 m2 / g, and 17 m2 / g, for the total BET area, area of micropore and external area, respectively. The material synthesized according to Example 5 has crystals in the form of sheets, with dimensions of 0.6 x 1.0 ^ m in the plane bc and sheet thickness of 40-100 nm. (see TEM image in Figure 2). The length of the channels of 10 atoms T, parallel to the direction [001] will therefore be about 1000 nm. Figure 2 clearly shows the larger crystal size of the sample obtained according to Example 5 compared to the crystal sizes of the samples obtained according to Examples 2, 3 and 4. As a consequence of this larger size of crystal, the sample obtained according to Example 5 has lower values of total BET area and external area than the samples obtained according to Examples 2, 3 and 4.
    [0193]
    [0194] Example 6: Catalytic test for the oligomerization reaction of 1-pentene using the material synthesized according to Example 2.
    [0195]
    [0196] The material synthesized according to Example 2 has been pelletized by selecting the particle size between 0.25 and 0.42 mm, to carry out the oligomerization reaction of 1-pentene. The zeolite ferrite (0.260 g) is diluted with silicon carbide (0.59-0.84 mm) to a total catallotic bed volume of 4.0 ml. The diluted catalyst is introduced into a tubular steel reactor of 1 cm of internal diameter, and is activated by rising at a temperature of 520 ° C in nitrogen flow (200 ml / min), and keeping at this temperature in air flow ( 200 ml / min) for 5 hours. Then, the temperature is lowered to the reaction temperature, 200 ° C, and the system is pressurized with N2 to the working pressure of 40 bar. At that time the reactor is quenched and the reactant mixture (1-pentene: n-heptane, in a 60:40 molar ratio) is fed through a parallel conduction until a constant flow and composition is achieved, at which time the feed is passed again through the reactor, and that is considered the start of the reaction. The spatial velocity used, WHSV (Weight Hour Space Velocity) referred to 1-pentene, has been 7.7 h-1. In these experimental conditions the mixture is in the Kquida phase.
    [0197]
    [0198] At the outlet of the reactor the product stream is depressurized and vaporized to be analyzed in line on a Varian 3800 gas chromatograph, equipped with a 25 m CP-Sil 5CB column, a flame ionization detector (FID), and using n-heptane, inert in our experimental conditions, as an internal standard.
    [0199]
    [0200] In addition, the mixture of C5 + products is condensed and analyzed by simulated distillation (excluding n-heptane from the gasoline fraction), for the determination of selectivity in liquid products. The cut-off points for the fractions considered are the following:
    [0201]
    [0202] - Naphtha: C5 - 173.9 ° C.
    [0203] - Diesel: 173.9 - 391.1 ° C.
    [0204] - Heavy fraction: 391.1 - 1000 ° C.
    [0205] The catalytic results of the synthesized material according to Example 2 of the present invention are summarized in Table 1 (see the table at the end of the examples).
    [0206]
    [0207] Example 7: Catalytic test for the oligomerization reaction of 1-pentene using the material synthesized according to Example 4.
    [0208]
    [0209] The material synthesized according to Example 4 has been pelletized by selecting the particle size between 0.25 and 0.42 mm, to carry out the oligomerization reaction of 1-pentene, following the same procedure described in Example 6.
    [0210]
    [0211] The catalytic results obtained with the material synthesized according to Example 4, of the present invention are shown in Table 1.
    [0212]
    [0213] Example 8: Catalytic test for the oligomerization reaction of 1-pentene using the material synthesized according to Example 5.
    [0214]
    [0215] The microcrystalline ferrierite zeolite, synthesized according to Example 5, has been pelletized by selecting the particle size between 0.25 and 0.42 mm, to carry out the 1-pentene oligomerization reaction, following the same procedure described in the Example 6.
    [0216]
    [0217] The catalytic results obtained are shown in Table 1.
    [0218] Comparing the results of the three materials presented in Table 1, it is concluded that the catalysts based on the nanocrystalline zeolite ferrierite obtained according to Examples 2 and 4, are much more active than the microcrystalline zeolite ferrierite based catalyst obtained according to Example 5 for 1-pentene oligomerization reaction. Thus, the average conversion of olefin at a spatial speed, WHSV, of 7.7 h-1, in the reaction time interval (TOS) of 0-3 hours, is 99, 97 and 81%, respectively. The advantages derived from the smaller crystal size in synthesized nanocrystalline ferrierites according to Examples 2 and 4 become more evident at higher reaction times (TOS). In fact, the average conversion of olefin in the TOS range of 3-6 h is maintained at values close to 91% in the case of Example 2, at values of 97% in the case of Example 4, and decreases to values of 29% in the case of microcrystalline ferrierite, synthesized according to Example 5. In addition to the greater activity and greater stability against deactivation with the reaction time, the nanocrystalline ferrierites synthesized according to examples 2 and 4 of this The invention is much more selective to the fraction diesel (50 and 48.6% weight), the fuel with the highest demand in Europe, than the microcrystalline ferrite synthesized according to Comparative Example 5 (18.9% weight).
    [0219]
    [0220] Comparing the results obtained with the nanocrystalline ferrierites synthesized according to Examples 2 and 4, it is concluded that the two catalysts have a conversion comparable to short reaction times (conversions of 98 and 97%, respectively, at TOS = 0-3 h ), but the catalyst corresponding to Example 4, which has a higher proportion of isotropic morphology nanocrystals with sizes in the range of 5-15 nm, has greater stability against deactivation than the catalyst corresponding to Example 2, which has greater proportion of crystals with laminar morphology (conversions of 97 and 91%, respectively, in the range of TOS = 3-6 h).
    [0221]
    [0222] The improvement obtained by using as a catalyst for the oligomerization of light olefins a zeolite ferrierite in its nanocrystalline form is demonstrated, characterized in that the size of its crystals along the crystallographic direction [001] is in the range of 5 to 15 nm, synthesized according to the present invention. In addition to the greater activity and the greater stability against deactivation with the reaction time, the nanocrystalline ferrierites synthesized according to Examples 2 and 4 of the present invention are more selective to the fraction diesel, the fuel with the highest demand in Europe, than the microcrystalline ferrite synthesized according to Example 5.
    [0223]
    权利要求:
    Claims (39)
    [1]
    1. Zeolltic material with Ferrierite structure, characterized in that the size of the crystals of said zeoltic material along the crystallographic direction [001] is in the range of 5 to 100 nm.
    [2]
    2. Material, according to claim 1, wherein the size of the crystals of said zeolltic material along the crystallographic direction [001] is in the range of 5 to 15 nm.
    [3]
    3. Material, according to any one of the preceding claims 1-2, wherein the size of the crystals of said zeoltic material along the crystallographic direction [010] is in the range of 5 to 100 nm,
    [4]
    4. Material, according to claim 3, wherein the size of the crystals of said zeoltic material along the crystallographic direction [010] is in the range of 5 to 15 nm.
    [5]
    5. Material, according to any one of the preceding claims 1-4, wherein the size of the crystals of said zeoltic material along the crystallographic direction [100] is in the range of 2 to 100 nm,
    [6]
    6. Material, according to claim 5, wherein the size of the crystals of said zeolitic material along the crystallographic direction [100] is in the range 2 to 10 nm.
    [7]
    7. Material according to any of the preceding claims 1-6, characterized in that it has the following molar composition
    or X2O3: YO2: p ADEO1: q ADEO2: r A ': z H2O
    where
    X is a trivalent element;
    And it is a tetravalent element;
    A ’is an alkaline or alkaline earth element;
    ADEO1 is a monocyclic quaternary ammonium salt where at least one of the nitrogen-linked substituents is a linear alkyl chain consisting of between 6-22 carbon atoms,
    ADEO2 is selected from an amine, an ammonium salt or combinations thereof
    or is in the range of 0 to 0.5, preferably between 0.003 to 0.1; and more preferably between 0.01 to 0.075;
    p is in the range of 0.001 to 1, preferably between 0.001 to 0.5; and more preferably between 0.001 to 0.2;
    q is in the range of 0.01 to 2, preferably between 0.05 to 1; and more preferably between 0.1 to 0.6;
    r is in the range of 0 to 2, preferably 0 to 1; and more preferably between 0 to 0.8;
    z is in the range of 0 to 2, preferably 0 to 1; and more preferably between 0 to 0.8.
    [8]
    8. Material according to claim 7, wherein ADEO1 is a monocyclic quaternary ammonium salt comprising the structure R1R2CycloN + where the "Cycle" refers to a linear alkyl chain of 4-7 carbon atoms, whose terminal carbons are attached to the N of the corresponding quaternary ammonium, so that said linear alkyl chain next to the N atom forms a heterocycle and the R1 and R2 groups are linear alkyl chains comprised between 1-6 and 6-22 carbon atoms, respectively.
    [9]
    9. Material according to any of claims 7-8 wherein ADEO1 is the compound of the following formula:

    [10]
    10. Material according to any of claims 7-9 wherein ADEO2 is selected from mono-amines, diamines or primary, secondary or tertiary polyamines, mono-ammonium, diamonium, quaternary polyammonium salts, or combinations thereof.
    [11]
    11. Material according to any of claims 7-10 wherein ADEO2 is selected from N-alkyl pyrrolidines, N-alkyl piperidines, N-alkyl-Nhexamethyleneimines, N-alkyl-N.heptamethylenimines, N-alkyl-pyrrolidiniums, N-alkylpiperidiniums, Nalkyl-N-hexamethylene ammoniums, N-alkyl-N-heptamethylenamoniums or combinations thereof.
    [12]
    12. Material according to any of the preceding claims 1-6, characterized in that it has the following molar composition:
    or X2O3: YO2: r A '
    where
    X is a trivalent element;
    And it is a tetravalent element; Y
    A ’is an alkaline or alkaline earth element;
    or is in the range 0 and 0.5;
    r is in the range of 0 to 2.
    [13]
    13. Material according to any of the preceding claims 7-12, wherein the tetravalent element Y is selected from silicon, stan, titanium, zirconium, germanium and combinations thereof.
    [14]
    14. Material according to any of claims 7-13, wherein the trivalent element X is selected from aluminum, boron, iron, indium, gallium and combinations thereof.
    [15]
    15. Material according to any of claims 7-14, characterized in that A ’is sodium or potassium.
    [16]
    16. Method of synthesis of a zeoltic material with Ferrierite structure in its nanocrystalline form as described in any of the preceding claims, characterized in that said method because it comprises at least the following steps:
    i) Preparation of a mixture, also called a synthesis gel, comprising at least: water, at least one source of a tetravalent element Y, at least one source of a trivalent element X, at least one source of an alkaline or alkaline earth cation (A), and at least two organic compounds ADEO1 and ADEO2, where ADEO1 is a monocyclic quaternary ammonium salt where at least one of the nitrogen-linked substituents is a linear alkyl chain formed between 6-22 carbon atoms, and ADEO2 is selected from an amine, an ammonium salt or combinations thereof, where the molar composition of the mixture, expressed in the form of the equivalent oxides of the elements present therein, is:
    l X2O3: YO2: m ADEO1: n ADEO2: a A: and H2O
    l is in the range of 0 to 0.5, preferably between 0.003 to 0.1; and more preferably between 0.01 to 0.075;
    m is in the range of 0.001 to 1, preferably between 0.001 to 0.5; and more preferably between 0.001 to 0.2;
    n is in the range of 0.01 to 2, preferably between 0.05 to 1; and more preferably between 0.1 to 0.6;
    a is in the range of 0 to 2, preferably 0 to 1; and more preferably between 0 to 0.8;
    and is in the range of 2 to 200, preferably between 5 to 150, and more preferably between 7 to 100;
    ii) synthesis of the zeolite starting from the mixture obtained in i) in a reactor at a temperature in the range of 80-200 ° C for a period of time in the range of 6 hours to 50 days;
    iii) recovery of the zeolltic crystalline material with Ferrierite structure obtained in ii).
    [17]
    17. Method according to claim 16 wherein the tetravalent element Y is selected from silicon, tin, titanium, zirconium, germanium, and combinations thereof.
    [18]
    18. Method according to claim 17 wherein the tetravalent element Y is silicon.
    [19]
    19. Method according to claim 18 wherein the source of silicon is selected from silicon oxide, silicon alkoxide, silicon halide, colloidal silica, smoking silica, a silicate, syphilic acid, a previously synthesized crystalline material, a previously synthesized amorphous material and combinations thereof.
    [20]
    20. Method according to any of the preceding claims 16-19, wherein the trivalent element X is selected from aluminum, boron, iron, indium, gallium and combinations thereof.
    [21]
    21. Method according to any of the preceding claims 16-20, wherein the organic compound ADEO1 is a monocyclic quaternary ammonium salt comprising the structure R1R2CycloN + where the "Cycle" refers to a linear alkyl chain of 4-7 carbon atoms , whose terminal carbons are attached to the N of the corresponding quaternary ammonium, so that said linear alkyl chain next to the atom of N forms a heterocycle and the groups R1 and R2 are linear alkyl chains comprised between 1-6 and 6-22 carbon atoms respectively.
    [22]
    22. Method according to claim 21 wherein ADEO1 is the compound of the following formula:

    [23]
    23. Method according to any of the preceding claims 16-22, wherein the organic compound ADEO2 is selected from mono-amines, diamines, primary, secondary or tertiary polyamines, or quaternary mono-ammonium, diamonium or polyammonium salts and combinations thereof .
    [24]
    24. The method according to any of the preceding claims 16-23, wherein ADEO2 is selected from N-alkyl-pyrrolidines, N-alkyl-piperidines, N-alkyl-N-hexamethyleneimines, Nalkyl-N.heptamethyleneimines, N-alkyl-pyrrolidines, N-alkylpiperidiniums, N-alkyl-N-hexamethylene diamonds, N-alkyl-N-heptamethylene ammoniums or combinations thereof.
    [25]
    25. Method according to any of the preceding claims 16-23, wherein ADEO2 is selected from pyrrolidine, piperidine, hexamethyleneimine or combinations thereof.
    [26]
    26. Method according to any of the preceding claims 16-25, wherein step ii) is carried out in an autoclave.
    [27]
    27. Method according to any of the preceding claims 16-26, wherein step ii) is carried out between 100 and 175 ° C.
    [28]
    28. A method according to any of the preceding claims 16-27, which comprises the addition of zeolite ferrite crystals as seeds to the synthesis mixture in an amount up to 25% by weight with respect to the total amount of oxides before or during the stage ii).
    [29]
    29. Method according to any of the preceding claims 16-28 wherein the recovery stage iii) is carried out with a separation technique selected from decantation, filtration, ultrafiltration, centrifugation and combinations thereof.
    [30]
    30. The method according to any of the preceding claims 16-29, further comprising a stage of elimination of the organic content contained within the material obtained in stage iii).
    [31]
    31. Procedure according to revindication 30 where the process of eliminating the organic content contained inside the material is carried out by means of a thermal treatment at temperatures between 100 and 1000 ° C for a period of time between 2 minutes and 25 hours.
    [32]
    32. Method according to any of the preceding claims 16-31 wherein the zeoltic material with Ferrierite structure is pelletized.
    [33]
    33. Method according to any of the preceding claims 16-32 characterized in that any cation present in the zeolltic material with Ferrierite structure is exchanged by ionic exchange for H + or an H + precursor.
    [34]
    34. Use of a zeolltic material with Ferrierite structure described in claims 1 to 15 as a catalyst in processes for the conversion of feeds formed by organic compounds into products of higher added value, or as a molecular sieve for their removal / separation of the reactive current .
    [35]
    35. Use according to claim 34, for the production of illiquid synthetic fuels selected from gasoline or diesel from light olefins.
    [36]
    36. Use according to claim 34, for that of alkylation, dealkylation, transalkylation, isomerization or combinations thereof of aromatic compounds
    [37]
    37. Use according to claim 34, for isomerization, hydroisomerization processes or combinations thereof of linear paraffins.
    [38]
    38. Use according to claim 34, for the production of light olefins by catalytic cracking processes.
    [39]
    39. Use according to claim 34, for the conversion of methanol to hydrocarbons.
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    申请号 | 申请日 | 专利标题
    ES201731377A|ES2715008B2|2017-11-30|2017-11-30|Zeolitic material with Ferrierite structure in its nanocrystalline form, procedure for its synthesis and use of said material|ES201731377A| ES2715008B2|2017-11-30|2017-11-30|Zeolitic material with Ferrierite structure in its nanocrystalline form, procedure for its synthesis and use of said material|
    PCT/ES2018/070761| WO2019106215A1|2017-11-30|2018-11-28|Nanocrystalline zeolite material with a ferrierite structure, method for synthesising same and use of said material|
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