• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Synthesis of the MFI zeolite in its nanocrystalline form, synthesis procedure and its use in catalytic applications. The present invention relates to a new synthesis process of a crystalline material having the zeolitic structure MFI in its nanocrystalline form, and which may comprise, at least, the following steps: i) Preparation of a mixture comprising at least one source of 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 one organic molecule (ADEO1), where ADEO1 is preferably a monocyclic quaternary ammonium with the structure R1R2CycloN+ . The molar composition of the mixture is: n X2O3 : YO2 : a A: m ADEO1: z H2O; ii) Crystallization of this mixture in a reactor; and iii) Recovery of the crystalline material obtained.
    公开号:ES2692859A1
    申请号:ES201730770
    申请日:2017-06-05
    公开日:2018-12-05
    发明作者:Eva María GALLEGO SÁNCHEZ；Cecilia Gertrudis PARIS CARRIZO；Luis-joaquín MARTÍNEZ TRIGUERO；Manuel MOLINER MARÍN；Avelino Corma Canos
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；Universidad Politecnica de Valencia；
    IPC主号:
    专利说明:

    SYNTHESIS OF THE ZEOLITE MFI IN ITS NANOCRISTALINE FORM,SYNTHESIS PROCEDURE AND ITS USE IN CATALYTIC APPLICATIONS
    5The present invention relates to a new method of synthesis of zeolite withMFI crystalline structure in its nanocrystalline form, as well as the use as a catalystof the zeolitic material synthesized according to the present synthesis procedure. 10 BACKGROUND OF THE INVENTION
    The synthesis of zeolite with MFI structure was described for the first time in its aluminosilicate form using the organic tetrapropylammonium molecule (TPA) as the directing agent of organic structure (ADEO) (Argauer et al., US Patent 3702886, 1972). The
    15 MFI structure presents two interconnected channel systems, delimited by 10 atoms, and whose pore opening is ~ 5-5.5 Å (Kokotailo et al., Nature, 1978, 272, 437).
    The use of the TPA cation as ADEO also allows the preparation of the MFI structure
    20 with other chemical compositions, such as in its galosilicate form (Lalik et al., J. Phys. Chem., 1992, 96, 805), borosilicate (Coudurier et al., J. Catal., 1987, 108, 1 ), titanosilicate (Taramasso et al., US Patent 4410501, 1983), or stañosilicate (Mal et al., J. Chem. Soc., Chem. Commun., 1994, 1933), among others. The possibility of preparing the MFI zeolitic structure with various compositions gives it
    25 interesting catalytic properties in a large number of chemical processes, both petrochemical and fine chemistry (Tabak et al., Catal. Today, 1990, 6, 307; Notari, Catal. Today, 1993, 18, 163).
    The synthesis of zeolites in their nanocrystalline form, that is, with very large crystal sizes
    30 small (<100 nm), has received great attention in recent years, since this type of materials allow to improve the efficiency of catalytic processes that require the presence of reagents and / or bulky products, greatly favoring their diffusion through of crystals, and minimizing deactivation processes (Zheng et al. J. Mater. Chem. A, 2016, 4, 16756). However, the
    35 preparation of a certain zeolite in its nanocrystalline form in a way


    Efficient and general, that is, with wide ranges of chemical composition, good synthesis yields (> 80%), and presenting homogeneous particle sizes with an average particle size below 50 nm, it is a complicated task.
    5 The synthesis of the MFI structure in its nanocrystalline form has been studied using TPA as ADEO (Micropor. Mesopor. Mater., 2000, 39, 135). The final particle size, chemical composition and synthesis performance of the MFI zeolite in its nanocrystalline form, are clearly influenced by the source of aluminum used, the pH of synthesis, dilution of the medium, or the presence of alkali cations, among others
    10 factors
    Other synthesis methodologies have been described in the literature using TPA as ADEO, including its synthesis confined within ordered supports (Madsen et al., Chem. Commun., 1999, 673), using microwave radiation (Hu et al., 15 Micropor. Mesopor. Mater., 2009, 119, 306), using alcoholic media (Persson et al., Zeolites, 1994, 14, 557; Majano et al., Adv. Mater., 2006, 18, 2440), or introducing surfactants or polymers in the synthesis medium (Zhu et al., J. Colloid Interface Sci., 2009, 331, 432; Xin et al., Chem. Commun., 2009, 7590), among others. Unfortunately, all these synthesis methodologies introduce limitations
    20 important economic for the industrial scale preparation of the MFI material in nanocrystalline form.
    The use of bulky dicationic organic molecules has been described as efficient ADEOs to synthesize the MFI structure with very small particle sizes, with good synthesis yields and wide ranges of chemical composition. For example, Ryoo et al. have used dicationic ADEOs with long aliphatic chains (> C16), such as C22H45íN + (CH3) 2íC6H12íN + (CH3) 2íC6H13 (Choi et al., Nature 2009, 461, 246; Kim et al., Chem. Mater. 2017, 29, 1752). Other authors have used similar bulky molecules with long aliphatic chains (> C16) 30 capable of self-assembling and acting as bulky dimers to direct the formation of the MFI structure with very small particle sizes (Xu et al., Nat. Commun., 2014, 5 (4262): 1). On the other hand, Burton also employs bulky dicationic ADEOs derived from alkylpyrrolidines for the synthesis of the nanocrystalline MFI structure (Burton, WO2014 / 099261, 2014). These synthetic procedures with 35 bulky ADEs require the use of long aliphatic chains and / or the use of


    different stages of synthesis, which may make the preparation of ADEO more expensive for the synthesis of the MFI structure in its nanocrystalline form.
    Recently, Tsapatsis et al. have been able to synthesize the crystalline structure
    5 MFI in its nanocrystalline form, using the tetrabutyl phosphonium cation as ADEO (Renet al., Angew. Chem. Int. Ed. 2015, 54, 10848). Unfortunately, thisprocedure requires the use of phosphine-derived ADEOs, which presentsSome important disadvantages. On the one hand, organic molecules derived fromphosphines show serious problems for the environment and health, associated
    10 inevitably to its use. On the other hand, the complete elimination of the phosphorous species trapped inside the zeolitic cavities is very complicated, especially in small pore zeolites, and their elimination process requires calcination stages at very high temperatures and hydrogen atmospheres for the complete decomposition / elimination of these species.
    15 Thus, there is a need for the chemical industry to find simpler organic molecules, such as monocathionic ADEOs that are not based on phosphine derivatives, and that are capable of directing the formation of the MFI structure in its nanocrystalline form with glass sizes less than 50 nm,
    20 with wide ranges of chemical composition and good synthesis yields (> 90%).
    Despite the advances shown in the synthesis of the MFI structure in its nanocrystalline form, there is a clear need for the chemical industry to improve
    Its synthesis for its subsequent application in various catalytic processes, and more particularly for its use as a catalyst in the processes of methanol to propene, alkylation-transalkylation of alkyl aromatics and catalytic cracking and hydrocracking, among others. 30 DESCRIPTION OF THE INVENTION
    The present invention relates to a new method of synthesis of the zeolite with MFI structure in its nanocrystalline form, which uses a monocathionic ADEO not derived from phosphines to obtain high synthesis yields (> 80%) and a smaller average crystal size 35 50 nm The present invention also relates to


    subsequent use of said synthesized material as a catalyst in various catalytic processes, preferably as a catalyst in the process of methanol to olefins (MTO).
    In a first aspect, the present invention relates to a new method of synthesis of a crystalline material that has the MFI zeolitic structure in its nanocrystalline form and which can comprise at least the following steps:
    i) Preparation of a mixture comprising at least one source of 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 one organic molecule (ADEO1) with the structure R1R2CycloN +,
    where ADEO1 is a monocyclic quaternary ammonium with the structure R1R2CycloN +, where the Cyclo group can comprise between 3-7 carbon atoms, and the R1 and R2 groups can be linear alkyl chains comprised between 1-4 and 3-6 carbon atoms respectively. The molar composition of the mixture is:
    n X2O3: YO2: a A: m ADEO1: z H2O
    where n is in the range of 0 to 0.5, preferably 0.003 to 0.1; and more preferably between 0.005 to 0.05; a is in the range of 0 to 2, preferably 0 to 1; and more preferably between 0 to 0.8; m is in the range of 0.01 to 2, preferably 0.1 to 1; and more preferably between 0.1 to 0.6; and z is in the range of 1 to 200, preferably 1 to 50, and more preferably 2 to 20;
    ii) Crystallization of the mixture obtained in i) in a reactor; Yiii) Recovery of the crystalline material obtained in ii).
    In the present invention, the term "Cyclo" refers to a linear alkyl chain of between 4-7 carbon atoms, optionally substituted by an alkyl of between 1 and 3 carbon atoms, preferably a methyl, whose terminal carbons are attached to the N of the corresponding quaternary ammonium, so that said alkyl chain


    linear next to the N atom make up a heterocycle.
    According to a particular embodiment, the tetravalent element Y may be selected from silicon, tin, titanium, zirconium, germanium, and combinations thereof. From
    5 preferred way, the source of element Y is a source of silicon that can beselected from, silicon oxide, silicon halide, colloidal silica, silicasmoked, tetraalkylortosilicate, silicate, silicic acid, a material previouslycrystalline synthesized, a previously synthesized amorphous material and combinations ofthe same.
    According to a particular embodiment, the source of silicon may be selected from a previously synthesized crystalline material, a previously synthesized amorphous material and combinations thereof and optionally also contain other heteroatoms in its structure. Some examples could be faujasite type zeolites
    15 (FAU), type L (LTL) and mesoporous amorphous materials, such as MCM-41. These previously synthesized materials could also contain other heteroatoms in their structure, such as aluminum.
    According to a preferred embodiment, the trivalent element X may be selected from
    20 between aluminum, boron, iron, indium, gallium and combinations thereof; preferably from aluminum, boron and combinations thereof; and more preferably it is aluminum.
    According to a particular embodiment, the trivalent element X is aluminum. This source of
    Aluminum may be selected from at least any aluminum salt (for example aluminum nitrate), or any hydrated aluminum oxide.
    According to a particular embodiment of the present invention, ADEO1 may be selected from alkyl azetidiniums, alkyl pyrrolidiniums, alkyl piperidiniums, and
    30 combinations thereof. Preferably said ADEO1 may be selected from N-propyl-N-methylazetidinium, N-butyl-N-methylazetidinium, N-pentyl-Nmethylazetidinium, N-propyl-N-methylpyrrolidinium, N-butyl-N-methylpyrrolidinium, N-pentyl -Nmethylpyrrolidinium, N-butyl-N-ethylpyrrolidinium, N, N-dibutyl-pyrrolidinium, and combinations thereof. Preferably said ADEO1 is N-butyl-N-methylpyrrolidinium.


    According to the present invention, the crystallization process described in ii) can preferably be carried out in autoclaves, under conditions that can be static or dynamic at a selected temperature of between 80 and 200 ° C, preferably between 120 and 175 ° C and more preferably between 130 and 175 ° C and a time of
    5 crystallization that can be between 6 hours and 50 dayspreferably between 1 and 14 days, and more preferably between 2 and 10 days.Keep in mind that the components of the synthesis mixture cancome from different sources what can vary the conditions ofcrystallization described.
    According to a particular embodiment of the process of the present invention, it is possible to add MFI crystals to the synthesis mixture, which act as seeds favoring the described synthesis, in an amount up to 25% by weight with respect to the total amount of the oxides corresponding to the sources of X and Y introduced in the middle the
    15 stage i). These crystals can be added before or during the crystallization process.
    According to the described procedure, 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.
    The process of the present invention may further comprise the removal of the organic content contained within the material by any technique of
    25 known removal / extraction.
    According to a particular embodiment, the removal of the organic compound contained inside the material can be carried out by means of a heat treatment at temperatures above 25 ° C, preferably between 100 and 1000 ° C and during a
    30 period of time preferably between 2 minutes and 25 hours.
    According to another particular embodiment, the material produced according to the present invention can be pelletized using any known technique.
    According to a preferred embodiment, any cation present in the material can be


    exchanged by ion exchange for other cations using conventional techniques. Thus, 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 ion exchange. These cations can be
    5 preferably selected from metals, protons, proton precursors and mixtures thereof; and more preferably 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.
    Another aspect of the invention relates to a zeolitic material with an MFI structure obtained according to the procedure described above and characterized by having the following molar composition:
    or X2O3: YO2: p A: q ADEO1: r H2Owhere
    15 X is a trivalent element; And it is a tetravalent element; A is an alkaline or alkaline earth cation;
    or is in the range of 0 to 0.5, preferably 0.003 to 0.1; and more preferably between 0.005 to 0.05;
    20 p is in the range of 0 to 2, preferably 0 to 1; and more preferably between 0 to 0.8; q is in the range of 0.01 to 2, preferably between
    0.1 to 1 and more preferably between 0.1 to 0.6;
    r is in the range of 0 to 2, preferably 0 to 25 1.5; and more preferably from 0 to 1;
    According to a preferred embodiment, the material obtained according to the present invention can be calcined. Thus, the zeolitic material with MFI structure can have the following molar composition after being calcined:
    30 or X2O3: YO2: p A where X is a trivalent element; And it is a tetravalent element; A is an alkaline or alkaline earth cation;
    35 or is between the range 0 and 0.5, preferably between 0.003 to 0.1; Y


    more preferably between 0.005 to 0.05;p is in the range of 0 to 2, preferably 0 to 1; Ymore preferably from 0 to 0.8.
    5 As mentioned above, in the procedure described above, any cation present in the material can be exchanged by ion exchange for other cations using conventional techniques. Thus, 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 ion exchange.
    10 These exchange cations are preferably selected from metals, protons, proton precursors (such as ammonium ions) and mixtures thereof, more preferably said cation is a metal selected from rare earths, metals of groups IIA, IIIA, VAT, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII and combinations thereof, and subsequently heat treated.
    The crystalline material of the present invention can also be intimately combined 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 lead to
    20 carried out in the crystallization stage ii), 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.
    In the zeolitic material with MFI structure described, the tetravalent element Y may be selected from silicon, tin, titanium, zirconium, germanium, and combinations thereof, preferably it is silicon, and the trivalent element X may be selected from aluminum , boron, iron, indium, gallium and combinations thereof, preferably between alumino and boron and more preferably is alumino.
    A third aspect of the invention relates to the use of the materials described above and obtained according to the process of the present invention as catalysts for the conversion of feeds formed by organic compounds into products of higher added value, or as a molecular sieve for
    35 elimination / separation of reactive currents (eg gas mixtures)


    contacting the feeds with the material obtained.
    According to a preferred embodiment, the material obtained according to the present invention can be used in the production of olefins after contacting it with a
    5 oxygenated organic compound under certain reaction conditions. In particular, when feeding methanol, the olefins obtained are mostly ethylene and propylene. Ethylene and propylene can be polymerized to form polymers and copolymers, such as polyethylene and polypropylene.
    According to a preferred embodiment, the material obtained according to the present invention can be used as a catalyst in aromatic acylation processes, where the alkylatable aromatic compound can be selected from benzene, biphenyl, naphthalene, anthracene, phenanthrene, thiophene, benzothiophene, substituted derivatives of them and combinations thereof, and the alkylating agent is selected from
    15 olefins, alcohols, polyalkylated aromatic compounds and combinations thereof. The material obtained, containing or not containing hydrogenating dehydrogenating components, can be used in aromatic alkyl dealkylation processes, alkylaromatic transalkylation, aromatic alkyl isomerization, or in combined alkylaromatic dealkylation and transalkylation processes.
    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, within the range of gasoline or diesel.
    According to a preferred embodiment, the material obtained according to the present invention can be used as a catalyst in catalytic cracking processes of hydrocarbon fractions to increase the production of olefins.
    Throughout the description and claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and features of the invention will be derived partly from the description and partly from the practice of the invention.

    BRIEF DESCRIPTION OF THE FIGURES
    FIG. 1: Diffraction patterns of the materials obtained according to Examples 3-11 of the present invention.
    5FIG. 2: SEM images of the materials obtained according to Examples 3, 4 and 10 ofThe present invention.FIG. 3: TEM image of the material obtained according to Example 3 hereininvention.
    10 FIG. 4: Conversion values of methanol at 450 ° C and WHSV = 10 h-1, obtained using as catalysts the materials synthesized according to Examples 3 and 9 of the present invention.
    The present invention is illustrated by the following examples that are not intended to be limiting thereof. EXAMPLES
    The invention will now be illustrated by tests carried out by the inventors, which demonstrates the effectiveness of the product of the invention. Example 1: Synthesis of 1-butyl-1-methylpyrrolidinium (1B1M)
    In a glass balloon, 15 g of 1-butylpyrrolidine (0.118 mol) and 200 ml of chloroform are added. The ball is placed in an ice bath (0 ° C) and allowed to cool while maintaining constant agitation. Then 33.47 g of iodomethane (0.236 mol) are gradually added. Once the system reaches room temperature, it is allowed to react for 72 hours. After the reaction, the solvent is evaporated, added
    30 a mixture of ethanol-ethyl acetate to crystallize the product. The crystals formed of the 1-butyl-1-methylpyrrolidinium iodide are filtered off, obtaining 27.6 g (0.1025 mol) of product.
    To prepare the hydroxide form of the above organic salt: 15 g of the organic salt are dissolved in 75 g of water. Next, 38 g of a resin of


    anion exchange (Dower SBR), and the resulting mixture is kept under stirring for 24 hours. Finally, the solution is filtered and 1-butyl-1-methylpyrrolidinium hydroxide is obtained (with an exchange rate of 95%). 5 Example 2: Synthesis of triethylbutylammonium (TEBA).
    20.24 g (0.20 mol) of ethylisobutylamine are dissolved in 200 ml of chloroform. The solution is transferred to a two-mouth ball connected to refrigeration. The mixture is cooled in an ice bath. Anhydrous K2CO3 (13.82 g; 0.10 mol) is added and allowed to react for one hour under constant stirring. Using a compensated pressure funnel, the iodoethane (93.58 g; 0.60 mol) is added slowly. It is then heated to 50 ° C and allowed to react for 24 h. It is cooled to room temperature, a new aliquot of iodoethane (31 g, 0.20 moles) is added and allowed to react another 48 h. After the reaction time, the solvent and the residue are evaporated
    15 obtained is dissolved in dichloromethane. The crude is filtered to separate inorganic salts, reserving the supernatant. Finally, the solvent is evaporated and the product is crystallized by the addition of ethyl acetate.
    To prepare the hydroxide form of the above organic salt: 15 g of the salt are dissolved
    20 organic in 75 g of water. Next, 38 g of an anion exchange resin (Dower SBR) are added, and the resulting mixture is kept under stirring for 24 hours. Finally, the solution is filtered and triethylbutylammonium hydroxide is obtained (with an exchange rate of 95%). 25 Example 3: Synthesis of nanocrystalline silicoaluminate with MFI structure
    23.9 g of a 6.7% by weight aqueous solution of 1B1M hydroxide (obtained according to Example 1) are mixed with 0.065 g of alumina [Al (OH) 3, Sigma-Aldrich]. The mixture is kept under stirring for 20 minutes. Subsequently, 3.730 g of a 40% by weight aqueous solution of colloidal silica (Ludox HS-40, Sigma-Aldrich) are added and the mixture is kept under stirring until the desired concentration is achieved. The final composition of the gel is SiO2 / 0.0167 Al2O3 / 0.4 1B1M / 10 H2O. This gel is transferred to a steel autoclave with a Teflon jacket and heated at 150 ° 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. He


    solid obtained is calcined in air at 550 ° C for 5 hours. The solid yield obtained is greater than 90%.
    X-ray diffraction confirms that the solid obtained has the peaks
    5 characteristics of the MFI structure (see Example 3 in Figure 1). The compositionThe chemistry of the final sample has a Si / Al ratio of 33.2. Crystal sizeaverage is 10-15 nm (see images of SEM and TEM in Figures 2 and 3). TheTextural properties of the synthesized material according to Example 3 of the presentinvention have been calculated by adsorption / desorption of N2, obtaining 514 m2 / g,
    10 320 m2 / g, and 194 m2 / g, for the total BET area, micropore area and external area, respectively.
    Example 4: Synthesis of nanocrystalline silicoaluminate with MFI structure
    18.4 g of a 6.7% by weight aqueous solution of 1B1M hydroxide (obtained according to Example 1) are mixed with 0.01 g of alumina [Al (OH) 3, Sigma-Aldrich]. The mixture is kept under stirring for 20 minutes. Subsequently, 1.64 g of a 40% by weight aqueous solution of colloidal silica (Ludox HS-40, Sigma-Aldrich) are added and the mixture is kept under stirring until concentration is achieved.
    20 desired. The final gel composition is SiO2 / 0.005 Al2O3 / 0.4 1B1M / 10 H2O. This gel is transferred to a steel autoclave with a Teflon jacket and heated at 150 ° 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 5 hours. Performance
    25 of solid obtained is greater than 90%.
    X-ray diffraction confirms that the solid obtained has the characteristic peaks of the MFI structure (see Example 4 in Figure 1). The chemical composition of the final sample has an Si / Al ratio of 83.3. Crystal size
    30 average is 15-20 nm (see SEM images in Figure 2).
    Example 5: Synthesis of nanocrystalline silicoaluminate with MFI structure
    1.37 g of a 6.7% by weight aqueous solution of 1B1M 35 hydroxide (obtained according to Example 1) are mixed with 0.072 g of a 20% by weight aqueous solution


    of sodium hydroxide (NaOH, Sigma-Aldrich, 98%) and 0.006 g of alumina [Al (OH) 3,Sigma-Aldrich]. The mixture is kept under stirring for 20 minutes.Subsequently, 0.35 g of a 40% aqueous solution of colloidal silica is added.by weight (Ludox HS-40, Sigma-Aldrich) and the mixture is kept under stirring until5 achieve the desired concentration. The final gel composition is SiO2 / 0.0167 Al2O3 /0.15 NaOH / 0.25 1B1M / 10 H2O. This gel is transferred to a steel autoclave withTeflon shirt and heated at 150 ° C for 14 days in static conditions.After this time, the product obtained is recovered by filtration,washing with plenty of water, and drying at 100 ° C. The solid obtained is calcined in
    10 air at 550 ° C for 5 hours. The solid yield obtained is greater than 90%.
    X-ray diffraction confirms that the solid obtained has the characteristic peaks of the MFI structure (see Example 5 in Figure 1). The chemical composition of the final sample has a Si / Al ratio of 35.1. Crystal size
    15 average is 15-20 nm.
    Example 6: Synthesis of nanocrystalline silicoaluminate with MFI structure
    1.37 g of a 6.7% by weight aqueous solution of 1B1M hydroxide are mixed
    20 (obtained according to Example 1) with 0.074 g of a 20% by weight aqueous solution of sodium hydroxide (NaOH, Sigma-Aldrich, 98%) and 0.006 g of alumina [Al (OH) 3, Sigma-Aldrich]. The mixture is kept under stirring for 20 minutes. Subsequently, 0.34 g of a 40% by weight aqueous solution of colloidal silica (Ludox HS-40, Sigma-Aldrich) is added and the mixture is kept under stirring until
    25 achieve the desired concentration. The final composition of the gel is SiO2 / 0.0167 Al2O3 / 0.15 NaOH / 0.25 1B1M / 50 H2O. This gel is transferred to a steel autoclave with a Teflon jacket and heated at 150 ° 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
    30 air at 550 ° C for 5 hours. The solid yield obtained is greater than 80%.
    X-ray diffraction confirms that the solid obtained has the characteristic peaks of the MFI structure (see Example 6 in Figure 1). The chemical composition of the final sample has a Si / Al ratio of 31. The crystal size
    35 average is 20-25 nm.


    Example 7: Synthesis of nanocrystalline silicoaluminate with MFI structure
    1.38 g of a 6.7% by weight aqueous solution of 1B1M hydroxide are mixed
    5 (obtained according to Example 1) with 0.095 g of a 20% by weight aqueous solution of potassium hydroxide (KOH, Sigma-Aldrich, 98%) and 0.012 g of alumina [Al (OH) 3, Sigma-Aldrich]. The mixture is kept under stirring for 20 minutes. Subsequently, 0.35 g of a 40% by weight aqueous solution of colloidal silica (Ludox HS-40, Sigma-Aldrich) is added and the mixture is kept under stirring until
    10 achieve the desired concentration. The final composition of the gel is SiO2 / 0.033 Al2O3 / 0.15 KOH / 0.25 1B1M / 10 H2O. This gel is transferred to a steel autoclave with a Teflon jacket and heated at 150 ° 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
    15 air at 550 ° C for 5 hours. The solid yield obtained is greater than 80%.
    X-ray diffraction confirms that the solid obtained has the characteristic peaks of the MFI structure (see Example 7 in Figure 1). The chemical composition of the final sample has a Si / Al ratio of 19.2. Crystal size
    20 average is 20-25 nm.
    Example 8: Synthesis of nanocrystalline borosilicate with MFI structure
    9.09 g of a 6.7% by weight aqueous solution of 1B1M hydroxide are mixed
    25 (obtained according to Example 1 of the present invention) with 0.43 g of a 5% aqueous boric acid solution [H3BO3, Sigma-Aldrich]. The mixture is kept under stirring for 20 minutes. Subsequently, 1.52 g of a 40% by weight aqueous solution of colloidal silica (Ludox HS-40, Sigma-Aldrich) is added and the mixture is kept under stirring until the desired concentration is achieved. The final composition of the
    30 gel is SiO2 / 0.0167 B2O3 / 0.4 1B1M / 10 H2O. This gel is transferred to a steel autoclave with a Teflon jacket and heated at 150 ° 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 5 hours. The solid yield obtained is superior
    35 to 85%.


    X-ray diffraction confirms that the solid obtained has the characteristic peaks of the MFI structure. The chemical composition of the final sample has a Si / B ratio of 29.3. The average crystal size is ~ 10-15 nm.
    Example 9: Synthesis of silicoaluminate with MFI structure using tetrapropylammonium as ADEO
    13.02 g of a 20% by weight aqueous solution of the hydroxide of
    10 tetrapropylammonium with 0.084 g of alumina [Al (OH) 3, Sigma-Aldrich]. The mixture is kept under stirring for 20 minutes. Subsequently, 4.8 g of a 40% by weight aqueous solution of colloidal silica (Ludox HS-40, Sigma-Aldrich) are added and the mixture is kept under stirring until the desired concentration is achieved. The final gel composition is SiO2 / 0.0167 Al2O3 / 0.4 TPAOH / 10 H2O. This gel is
    15 transferred to a steel autoclave with a Teflon jacket and heated at 150 ° 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 5 hours. The solid yield obtained is ~ 70%.
    20 By X-ray diffraction it is confirmed that the solid obtained has the characteristic peaks of the MFI structure (see Example 9 in Figure 1). The chemical composition of the final sample has a Si / Al ratio of 31.8. The average crystal size is 200 nm (see SEM image in Figure 2). The properties
    Textural materials of the synthesized material according to Example 9 of the present invention have been calculated by adsorption / desorption of N2, obtaining 360 m2 / g, 349 m2 / g, and 11 m2 / g, for the total BET area, micropore area and external area, respectively. This example shows that the use of TPA as ADEO results in the crystallization of the MFI zeolite with an average crystal size considerably larger than
    Those obtained in Examples 3-7 of the present invention, as also show the lower values of BET and external area obtained (compare with Example 3).
    Example 10: Synthesis of silicoaluminate with MFI structure using tetrapropylammonium as ADEO


    13.02 g of a 20% by weight aqueous solution of tetrapropylammonium hydroxide are mixed with 0.026 g of alumina [Al (OH) 3, Sigma-Aldrich]. The mixture is kept under stirring for 20 minutes. Subsequently, 4.83 g of a 40% by weight aqueous solution of colloidal silica (Ludox HS-40, Sigma-Aldrich) are added and the mixture is kept under stirring until the desired concentration is achieved. The final composition of the gel is SiO2 / 0.005 Al2O3 / 0.4 TPAOH / 10 H2O. This gel is transferred to a steel autoclave with a Teflon jacket and heated at 150 ° C for 14 days under static conditions. After this time, the product obtained is
    10 recovered by filtration, washing with plenty of water, and dried at 100 ° C. The solid obtained is calcined in air at 550 ° C for 5 hours. The solid yield obtained is ~ 50%.
    X-ray diffraction confirms that the solid obtained has the peaks
    15 characteristic of the MFI structure (see Example 10 in Figure 1). The chemical composition of the final sample has a Si / Al ratio of 91.3.
    Example 11: Synthesis using triethylbutylammonium (TEBA) as ADEO
    2.01 g of a 8.0% by weight aqueous solution of TEBA hydroxide (obtained according to Example 2 of the present invention) are mixed with 0.006 g of alumina [Al (OH) 3, Sigma-Aldrich]. The mixture is kept under stirring for total homogenization for 20 minutes. 0.349 g of a 40% by weight aqueous solution of colloidal silica (Ludox HS-40 colloidal silica, are added to the mixture,
    25 Sigma-Aldrich) and the mixture is kept under stirring until the desired concentration is achieved. The final composition of the gel is SiO2 / 0.0167 Al2O3 / 0.4 TEBA / 10 H2O. This gel is transferred to a steel autoclave with a Teflon jacket and heated at 150 ° C for 14 days under static conditions. After this time, the product obtained is recovered by filtration, washed with plenty of water, and dried to
    30 100 ° C. The solid obtained is calcined in air at 550 ° C for 5 hours.
    X-ray diffraction confirms that the solid obtained has the characteristic peaks of the MFI structure (see Example 11 in Figure 1). The chemical composition of the final sample has an Si / Al ratio of 32.4. The average crystal size 35 is ~ 100 nm. This example shows that the absence of a cyclic group


    in the ADEO, together with the combination of linear alkyl groups of different sizes (in this case, one butyl and three ethyl), it results in the crystallization of the MFI with an average size of significantly larger crystals. 5 Example 12: Catalytic test for the reaction of methanol to olefins
    The activity of the samples has been tested in the transformation of methanol to olefins in a fixed bed isothermal reactor under the following reaction conditions: WHSV = 10 h-1, atmospheric pressure, reaction temperature = 450 ° C, catalyst = 50 10 mg pelletized between 0.2 and 0.4 mm. The methanol is vaporized by bubbling with 20 ml min-1 of nitrogen in a methanol tank at 23 ° C. The catalyst is diluted in 1.95g of inert silica (0.1-0.2mm) and placed in a 10mm diameter glass reactor. The reaction temperature is constantly regulated by a type K thermocouple and a PID controller associated with a heating oven. The reactor outlet is controlled at 150 ° C and the products are analyzed in two gas chromatographs, first in a PONA 50m 0.25 mm capillary column with internal diameter to separate hydrocarbons from C1 to C12 with a temperature program of 35 to 250 ° C and second in a column PLOT-alumina of 30 m and 0.53 mm internal diameter with a temperature program of 50 to 180 ° C to separate C2-C4 hydrocarbons and determine
    20 hydrogen transfer. The detectors used are flame ionization. The conversion is defined as the sum of the weight yields of hydrocarbons.
    The catalytic results obtained for the catalysts obtained according to Examples 3 and 9 of the present invention are shown in Table 1. Comparing the results of the two materials presented in Table 1, it is concluded that the catalyst based on the MFI zeolite obtained according to Example 3 it is much more active than the MFI zeolite-based catalyst obtained according to Example 9, presenting a much slower deactivation (see Figure 4). The smaller crystal size of the catalyst obtained according to Example 3 explains this considerable increase in
    30 life time. In addition, it is shown that the reduction in crystal size causes a higher yield to olefins with a lower production of unwanted paraffins, ethylene and aromatics (see Table 1).
    Table 1: Yields to hydrocarbons in the reaction of methanol to olefins at 35 450 ° C and WHSV = 10 h-1 at reaction time of 250 minutes


    Yields in% weight Example 3Example 9
    Paraffins
    C1 0.682.07
    C2 0.110.27
    C3 2.335.21
    C4 3.908.12
    C5 2.293.53
    C6 2.172.27
    C7 1.581.12
    C8 0.550.48
    OLEFINS
    C2 8.4113.80
    C3 38.4926.88
    C4 24.2715.99
    C5 6.434.01
    C6 0.960.60
    C7 0.310.26
    AROMATICS
    C6 0.230.57
    C7 1.173.33
    C8 2.457.99
    C9 1.942.11
    C10 0.280.26
    C11 0.050.06
    C12 0.010.09
    NAFTENS
    C5 0.320.28
    C6 0.560.41
    C7 0.400.24
    C8 0.080.06

    TOTALS
    OLEFINS 78.8861.53
    Paraffins 13.6123.07
    AROMATICS 6.1414.41
    NAFTENS 1.380.99
    权利要求:
    Claims (24)
    [1]
    1. Method of synthesis of a zeolitic material with the MFI structure in its nanocrystalline form, characterized in that it comprises at least the following steps:
    i) Preparation of a mixture comprising at least one source of 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 one organic molecule (ADEO1) with the structure R1R2CycloN +,
    where ADEO1 is a quaternary ammonium of structure R1R2CycloN +, where the Cyclo group comprises between 4-7 carbon atoms, group R1 is a linear alkyl chain of between 1 to 4 carbon atoms, group R2 is a linear alkyl chain of between 3 to 6 carbon atoms; and the molar composition of the mixture is:
    n X2O3: YO2: a A: m ADEO1: z H2O
    where n is in the range of 0 to 0.5; a is in the range of 0 to 2; m is in the range of 0.01 to 2; z is in the range of 1 to 200; and ii) Crystallization of the mixture obtained in i) in a reactor; and iv) Recovery of the crystalline material obtained in ii).
    [2]
    2.  Method according to claim 1, characterized in that the tetravalent element Y is selected from silicon, tin, titanium, zirconium, germanium, and combinations thereof.
    [3]
    3.  Method according to claim 2, characterized in that the source of the tetravalent element Y is a source of silicon is selected from silicon oxide, silicon halide, colloidal silica, smoked silica, tetraalkylortosilicate, silicate, silicic acid, a previously synthesized crystalline material , a previously synthesized amorphous material and combinations thereof.

    [4]
    4. Method according to claim 3, characterized in that the source of silicon is selected from a previously synthesized crystalline material, a previously synthesized amorphous material and combinations thereof.
    5. Method according to claim 4, characterized in that the materialspreviously synthesized contain other heteroatoms in their structure.
    [6]
    6. Method according to claim 1, characterized in that the element
    Trivalent X is selected from aluminum, boron, iron, indium, gallium and combinations thereof.
    [7]
    7. Method according to claim 1, characterized in that the ADEO1 is selected from alkyl azetidiniums, alkyl pyrrolidiniums, alkyl piperidiniums, and combinations thereof.
    [8]
    Method according to claim 7, characterized in that the ADEO1 is selected from N-propyl-N-methylazetidinium, N-butyl-N-methylazetidinium, N-pentyl-N-methylazetidinium, N-propyl-N-methylpyrrolidinium, N-butyl -N-methylpyrrolidinium, N-pentyl-Nmethylpyrrolidinium, N-butyl-N-ethylpyrrolidinium, N, N-dibutyl-pyrrolidinium, and combinations of the
    20 same.
    [9]
    9. Method according to claim 8, characterized in that said ADEO1 is N-butyl-N-methylpyrrolidinium.
    Method according to claims 1 to 9, characterized in that the crystallization process described in ii) is carried out in autoclaves, under static conditions
    or dynamic
    [11]
    11. Method according to any of the preceding claims,
    30 characterized in that the crystallization stage described in ii) is carried out at a temperature between 80 and 200 ° C.
    [12]
    12. Method according to any of the preceding claims, characterized
    because the crystallization time of step ii) is between 6 hours and 50 days.

    [13]
    13. Method according to any of the preceding claims, characterized in that it further comprises adding MFI crystals to the synthesis mixture in an amount of up to 25% by weight with respect to the total amount of the sources of X and Y
    5 introduced in stage i).
    [14]
    14. Method according to claim 13, characterized in that the MFI crystals are added before the crystallization process or during the crystallization process of step ii).
    [15]
    15. Method according to any of the preceding claims, characterized in that the recovery step iii) is carried out by a separation technique selected from decantation, filtration, ultrafiltration, centrifugation and combinations thereof.
    [16]
    16. Method according to any of the preceding claims, characterized in that it further comprises eliminating the organic content contained within the material.
    Method according to claim 16, characterized in that the process of eliminating the organic content contained inside the material is carried out by means of a heat treatment at temperatures between 100 and 1000 ° C for a period of time between 2 minutes and 25 hours
    Method according to any of the preceding claims, characterized in that the material obtained is pelletized.
    [19]
    19. Method according to any of the preceding claims, characterized
    because any cation present in the material is exchanged by ion exchange for other cations.
    [20]
    20. Method according to claim 19, characterized in that the exchange cation is selected from metals, protons, proton precursors, and mixtures thereof.

    [21]
    21. Method according to claims 18 and 19, characterized in that the exchange cation is a metal selected from rare earths, metals of groups IIA, IIIA, VAT, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII, and combinations thereof.
    5 22. Zeolitic material with MFI structure obtained according to the procedure described inclaims 1 to 21, characterized in that it has the following molar composition
    or X2O3: YO2: p A: q ADEO1: r H2OwhereX is a trivalent element;
    10 Y is a tetravalent element; A is an alkaline or alkaline earth element;
    or is in the range of 0 to 0.5;p is in the range of 0 to 2;q is in the range of 0.01 to 2; Y
    15 r is in the range of 0 to 2.
    [23]
    23. Zeolitic material with MFI structure according to claim 22, characterized in that it has the following molar composition after being calcined:
    or X2O3: YO2: p A
    20 where X is a trivalent element; And it is a tetravalent element; and A is an alkaline or alkaline earth element;
    or is in the range between 0 and 0.5; and 25 p is in the range of 0 to 2.
    [24]
    24. Zeolitic material with MFI structure according to claims 22 and 23, characterized in that the tetravalent element Y is selected from silicon, tin, titanium, zirconium, germanium, and combinations thereof.
    [25]
    25. MFI structure zeolitic material according to claims 22 and 23, characterized in that the trivalent element X is selected from aluminum, boron, iron, indium, gallium and combinations thereof.
    Use of a zeolitic material with MFI structure described in claims 22

    to 25 and obtained according to the method described in claims 1 to 21 in processes 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 contacting said feed with the material described
    [27]
    27. Use of a zeolitic material with MFI structure according to claim 26, for the production of olefins after contacting it with an oxygenated organic compound.
    Use of a zeolitic material with an MFI structure according to claim 26, for the production of alkylated aromatic molecules upon contact with an alkylatable aromatic molecule and an alkylating agent.
    [29]
    29. Use of a zeolitic material with MFI structure according to claim 26 in
    15 processes of aromatic alkyl dealkylation, transalkylamic transalkylation, aromatic alkyl isomerization, or in combined processes of alkyl aromatic dealkylation and transalkylation.
    [30]
    30. Use of a zeolitic material with MFI structure according to claim 26, for the
    20 production of synthetic liquid fuels, within the range of gasoline or diesel, after contacting said material with light olefins.
    [31]
    31. Use of a zeolitic material with MFI structure according to claim 26 in
    Catalytic cracking processes of hydrocarbon fractions to increase the production of olefins.

    DRAWINGS
    FIGURE 1

    FIGURE 2
    FIGURE 3

    FIGURE 4
    类似技术:
    公开号 | 公开日 | 专利标题
    US3972983A|1976-08-03|Crystalline zeolite ZSM-20 and method of preparing same
    KR102003088B1|2019-07-23|Synthesis of mse-framework type molecular sieves
    US4963337A|1990-10-16|Zeolite SSZ-33
    US4021331A|1977-05-03|Organic compound conversion by zeolite ZSM-20 catalysts
    CA2699155C|2014-08-12|Synthesis of high activity zsm-48
    US5512267A|1996-04-30|Zeolite CIT-1
    CA2049035A1|1991-07-27|Zeolite ssz-31
    AU2009330725B2|2016-01-21|High activity MTT framework type molecular sieves
    ES2692859B2|2020-01-15|SYNTHESIS OF ZEOLITE MFI IN ITS NANOCRISTALINE FORM, SYNTHESIS PROCEDURE AND ITS USE IN CATALYTIC APPLICATIONS
    EP2961528A2|2016-01-06|Zeolite ssz-57 having enhanced large pore selectivity
    JP5670320B2|2015-02-18|Method for producing crystalline metallosilicate
    ES2692818B2|2019-11-28|SYNTHESIS OF ZEOLITE BETA IN ITS NANOCRISTALINE FORM, SYNTHESIS PROCEDURE AND ITS USE IN CATALYTIC APPLICATIONS
    ES2291484T3|2008-03-01|ZEOLITA SSZ-60.
    JP2006512273A|2006-04-13|Molecular sieve SSZ-63
    ES2739646B2|2021-01-18|PROCEDURE FOR THE SYNTHESIS OF MWW MATERIAL IN ITS NANOCRISTALINE FORM AND ITS USE IN CATALYTIC APPLICATIONS
    CN107531587B|2020-11-24|Hydrocarbon conversion using UZM-53
    ES2698700B2|2019-11-21|SYNTHESIS OF ZEOLITE CHA IN ITS NANOCRISTALINE FORM, SYNTHESIS PROCEDURE AND ITS USE IN CATALYTIC APPLICATIONS
    RU2498853C1|2013-11-20|Zeolite-containing catalyst, method for production thereof and method of converting straight-run gasoline to high-octane gasoline component with low benzene content
    CN107531498B|2020-05-19|UZM-53 as MTT Zeolite
    Wang et al.2022|Zeolite nanosheets for catalysis
    ES2296989T3|2008-05-01|ZEOLITA SSZ-58.
    EP0483222A1|1992-05-06|Zeolite |ssz-24
    ES2715008A1|2019-05-31|Zeolitic material with Ferrierite structure in its nanocrystalline form, procedure for its synthesis and use of said material |
    CS271488B2|1990-10-12|Method of xylene raw material&#39;s catalytic isomerization
    同族专利:
    公开号 | 公开日
    US20200207631A1|2020-07-02|
    EP3636596A4|2021-03-03|
    ES2692859B2|2020-01-15|
    WO2018224711A1|2018-12-13|
    EP3636596A1|2020-04-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR2936791A1|2008-10-07|2010-04-09|Inst Francais Du Petrole|Preparing MFI structural type zeolite, useful e.g. as catalyst support, adsorbent or separation agent, comprises mixing source of tetravalent element and quaternary amine compound in aqueous medium and hydrothermal treatment of mixture|
    US3702886A|1969-10-10|1972-11-14|Mobil Oil Corp|Crystalline zeolite zsm-5 and method of preparing the same|
    IT1127311B|1979-12-21|1986-05-21|Anic Spa|SYNTHETIC, CRYSTALLINE, POROUS MATERIAL CONSTITUTED BY SILICON AND TITANIUM OXIDES, METHOD FOR ITS PREPARATION AND ITS USES|
    DE3361440D1|1982-12-30|1986-01-16|Asahi Chemical Ind|A crystalline aluminosilicate, a process for producing the same, and a catalyst comprising the crystalline aluminosilicate|
    RU2177468C2|1994-11-23|2001-12-27|Эксон Кемикэл Пейтентс Инк.|Method of converting hydrocarbons using zeolite-bound zeolite catalyst|
    US9475041B2|2012-04-24|2016-10-25|Basf Se|Zeolitic materials and methods for their preparation using alkenyltrialkylammonium compounds|
    EP2935101B1|2012-12-21|2016-12-21|ExxonMobil Chemical Patents Inc.|Synthesis of zsm-5|CN113454027A|2019-02-27|2021-09-28|雪佛龙美国公司|Molecular sieve SSZ-115, its synthesis and use|
    US11103859B2|2020-01-06|2021-08-31|Uop Llc|UZM-54 and transalkylation process using same|
    法律状态:
    2018-12-05| BA2A| Patent application published|Ref document number: 2692859 Country of ref document: ES Kind code of ref document: A1 Effective date: 20181205 |
    2020-01-15| FG2A| Definitive protection|Ref document number: 2692859 Country of ref document: ES Kind code of ref document: B2 Effective date: 20200115 |
    优先权:
    申请号 | 申请日 | 专利标题
    ES201730770A|ES2692859B2|2017-06-05|2017-06-05|SYNTHESIS OF ZEOLITE MFI IN ITS NANOCRISTALINE FORM, SYNTHESIS PROCEDURE AND ITS USE IN CATALYTIC APPLICATIONS|ES201730770A| ES2692859B2|2017-06-05|2017-06-05|SYNTHESIS OF ZEOLITE MFI IN ITS NANOCRISTALINE FORM, SYNTHESIS PROCEDURE AND ITS USE IN CATALYTIC APPLICATIONS|
    EP18814418.2A| EP3636596A4|2017-06-05|2018-06-01|Synthesis of nanocrystalline mfi zeolite, synthesis method and use thereof in catalytic applications|
    US16/619,011| US20200207631A1|2017-06-05|2018-06-01|Synthesis of Nanocrystalline MFI Zeolite, Synthesis Method and use Thereof in Catalytic Applications|
    PCT/ES2018/070399| WO2018224711A1|2017-06-05|2018-06-01|Synthesis of nanocrystalline mfi zeolite, synthesis method and use thereof in catalytic applications|
    [返回顶部]