WO2004039726A1 - Mesoporous structures having high catalytic activity in acid catalysis reactions and preparation method thereof - Google Patents

Mesoporous structures having high catalytic activity in acid catalysis reactions and preparation method thereof Download PDF

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WO2004039726A1
WO2004039726A1 PCT/ES2003/000544 ES0300544W WO2004039726A1 WO 2004039726 A1 WO2004039726 A1 WO 2004039726A1 ES 0300544 W ES0300544 W ES 0300544W WO 2004039726 A1 WO2004039726 A1 WO 2004039726A1
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solution
type material
obtaining
aluminosilicate type
material described
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PCT/ES2003/000544
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Spanish (es)
French (fr)
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Javier AGÚNDEZ RODRÍGUEZ
Isabel DÍAZ CARRETERO
Carlos MÁRQUEZ ÁLVAREZ
Joaquín PÉREZ PARIENTE
Enrique SASTRE DE ANDRÉS
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Consejo Superior De Investigaciones Científicas
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Priority to AU2003274160A priority Critical patent/AU2003274160A1/en
Publication of WO2004039726A1 publication Critical patent/WO2004039726A1/en

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C01B39/38—Type ZSM-5
    • C01B39/40—Type ZSM-5 using at least one organic template directing agent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation

Definitions

  • This invention relates to mesoporous aluminosilicate materials that possess a high catalytic activity in acid catalysis reactions, their preparation process and their use as a catalyst for hydrocarbon transformation reactions, such as cracking, isomerization, transalkylation, alkylation, dimerization and polymerization.
  • Zeolitic materials are widely used as catalysts in the refining and petrochemical industries and in the synthesis of chemical compounds of high added value. Its catalytic behavior is due to the presence in these materials of active centers of high acidity, which allow catalyzing a large number of reactions of industrial interest.
  • zeolites crystalline aluminosilicates
  • zeolitic materials in general have a crystalline structure in which there are cavities and channels
  • microporous whose access is limited by openings whose diameter is always less than 2.0 nm, and in most cases does not exceed 0.8 nm.
  • the size of the cavities and channels present in the structure of the zeolites and zeolitic materials is suitable for transforming or producing molecules that are small enough, for example to produce an isomer excluding other possible ones (property known as shape selectivity), it is a often too small to transform bulky molecules, which cannot access the interior of the microporous system. This implies a severe limitation for the use of zeolites and zeolitic materials in numerous chemical processes of industrial interest.
  • the Mobil Oil company announced the invention of a new family of ordered mesoporous materials, called M41S (WO Pat.
  • these materials are characterized by having a regular distribution of pores whose size, between 2.0 nm and 10.0 nm, is within the range of the mesopore, so they do not have the limitations of zeolites to process bulky molecules.
  • these materials are amorphous, that is, the inorganic skeleton is constituted by a network of tetrahedra of SiO 4 and AlO 4 linked together in a disorderly manner through oxygen atoms .
  • the acidity of these materials resembles that of amorphous silica-aluminas, being much lower than that of zeolites, as well as their catalytic activity.
  • This invention relates to new mesoporous materials with a chemical composition expressed by the following formula (in moles of oxides):
  • m is between 10 and 1000, preferably between
  • M represents the Na + or ⁇ cations, and the value of n is between 0.001 and 1, preferably between 0.01 and 1.
  • the present invention relates to the preparation of porous structures that have a lattice formed by the union of tetrahedra of SiO 4 and AlO 4 , with a molar ratio of silicon to aluminum between 5 and 500, which have a regular distribution of pores whose average diameter is between 2.0 nm and 10 nm, at least one X-ray diffraction peak corresponding to a spacing between 1.5 nm and 20.0 nm, a BET surface between 300 m 2 / g and 1400 m 2 / g, a total pore volume comprised between 0.2 cm 3 / g and 2.0 cm 3 / g, a catalytic activity in m-xylene transformation such that for a contact time value expressed as WF (gh / mol) between 0.5 and 1 the conversion of m-xylene at 400 ° C is at least 5%, and its use as catalysts for transformation reactions of organic molecules that are catalyzed by acid centers.
  • WF gh /
  • the process for obtaining the porous materials object of the present invention comprises a two step process.
  • a solution A called "colloidal ZSM-5 zeolite precursor solution” is prepared, whose main but not only feature is that it contains the tetrapropylammonium cation.
  • a solution B is prepared whose main but not the only characteristic is that it contains a cationic surfactant, which is mixed with solution A. It is characteristic of the present invention that solution A containing the tetrapropylammonium cation is a crystal precursor Colloidal size of the zeolite ZSM-5.
  • the preparation of this solution comprises the treatment of an aluminum source, such as aluminum hydroxide, with an aqueous solution of tetrapropylammonium hydroxide and optionally also with a sodium source, until the dissolution of the aluminum hydroxide is achieved.
  • an aluminum source such as aluminum hydroxide
  • an aqueous solution of tetrapropylammonium hydroxide and optionally also with a sodium source are sodium hydroxide and various soluble sodium salts, such as sodium chloride, sodium sulfate or sodium nitrate.
  • the aluminum hydroxide used in the invention can be advantageously prepared by precipitation from a solution of a soluble aluminum salt, such as aluminum sulfate or aluminum nitrate, by mixing it with a solution of a base, such as ammonium hydroxide.
  • a soluble aluminum salt such as aluminum sulfate or aluminum nitrate
  • a base such as ammonium hydroxide.
  • metallic aluminum can be dissolved in the tetrapropylammonium hydroxide solution.
  • the treatment of said hydroxide with the basic solution containing tetrapropylammonium and optionally a sodium source is carried out at a temperature between 10 ° C and 100 ° C, preferably between 20 ° C and 60 ° C, for a time between 5 minutes and 5 hours, preferably between 10 minutes and 1 hour.
  • the objective of this treatment is to achieve the complete dissolution of aluminum hydroxide.
  • the resulting solution is mixed with a source of silicon, non-limiting examples of which are colloidal silica, precipitated silica, pyrogenic silica, or silicon alkoxides, such as tetramethoxysilane and tetraethoxysilane.
  • the silicon source can be reacted with a part of the tetrapropylammonium hydroxide solution used in the preparation.
  • colloidal silica is used as a source of silicon, it can optionally be treated with a cation exchange resin in order to reduce the content of alkali cations, preferably sodium, which it contains.
  • the value of x in the composition of solution A is between 25 and 1000, preferably between 50 and 200.
  • solution A may contain one or more alcohols (ROH) having a number of carbon atoms between 1 and 6, may be linear or branched, and preferably methanol, ethanol or mixtures of both.
  • ROH alcohols
  • the values of y, z, w and v in the composition of solution A are such that the molar ratios y / x, z / x, w / xyv / x are within the following ranges: y / x between 0.05 and 1, preferably between 0.1 and 0.5. z / x between 0 and 1, preferably between 0.01 and 0.1. w / x between 5 and 100, preferably between 10 and 50. v / x between 0 and 50, preferably between 0.1 and 10.
  • solution A is prepared, it is aged at a temperature between 4 ° C and 150 ° C, preferably between 20 ° C and 110 ° C, for a time between 10 minutes and 7 days, preferably between 1 hour and 48 hours. It is characteristic of the present invention that the aging of solution A is carried out under conditions of temperature and time such that the formation of ZSM-5 crystals is not detected at the end of aging. For this reason, solution A is referred to herein as the "ZSM-5 colloidal zeolite precursor solution".
  • Solution B is prepared by dissolving one or more cationic surfactants in water, in an organic solvent or in a mixture of both.
  • Non-restrictive examples of this cationic surfactant they are hexadecyltrimethylammonium, dimethyldidodecylammonium and benzyltrimethylammonium.
  • This cation can be used in the form of salts, non-limiting examples of which are bromide and chloride, or as hydroxide, or mixture of both.
  • the solution B referred to in the invention may contain one or more of the surfactants described, and their proportion by weight with respect to the solvent is between 2 and 50%, preferably between 10% and 30%.
  • the preferred solvent for preparing solution B is water, but optionally an alcohol or mixture of two or more alcohols, or a mixture of alcohols with water.
  • solution B may contain tetramethylammonium and optionally also sodium, in a proportion not exceeding 90% of tetramethylammonium and 90% of sodium contained jointly in solutions A and B.
  • the molar ratio between the silicon of solution A, expressed as SiO 2 , and the cationic surfactant of solution B is between 0.1 and 15, preferably between 0.5 and 5.
  • Solution B it may contain a proportion of the total solvent used in the preparation between 1% and
  • the gel resulting from the mixture of solutions A and B is treated at a temperature between 4 ° C and 200 ° C, preferably between 20 ° C and 180 ° C, for a time between 30 minutes and 7 days, preferably between 1 hour and 48 hours.
  • the solid product obtained after this heating step is filtered, washed with deionized water and dried.
  • the product thus obtained is heated in air at temperatures between
  • the heat treatment can be carried out in an atmosphere of an inert gas, such as nitrogen, optionally followed by an air calcination.
  • the calcined material obtained by the process described in the present invention is characterized by having a chemical composition expressed by the following formula (in moles of oxides):
  • the porous material obtained according to the process described in the present invention is distinguished by having the following characteristics:
  • An average pore diameter (expressed as 4N / A) between 2.0 nm and 10 nm. 5)
  • a characteristic inherent to the material claimed in the present invention is its high catalytic activity in reactions that are catalyzed by acid solids.
  • catalytic activity is expressed by way of non-limiting example in the degree of conversion of m-xylene when a certain amount of this reagent is flowed into a tubular reactor through a bed containing a certain amount of the material heated to a certain temperature.
  • the material described in the invention can be used in a wide variety of hydrocarbon transformation reactions, among which are examples of catalytic cracking, isomerization, hydroisomerization, hydrocracking, alkylation, dimerization and polymerization, and among them, non-limiting example the conversion of m-xylene. DESCRIPTION OF THE FIGURES
  • Figure 1 X-ray diffractogram (CuK ⁇ radiation) of the calcined sample obtained according to the procedure described in example 1. The diffractogram in the region of values of 2 ⁇ between 4 ° is included in the box that appears inside the figure. and 40 °.
  • Example 1 illustrate the invention, without thereby constituting a limitation of the invention.
  • a solution A is prepared with the following composition:
  • a solution of 3.78 g of aluminum sulfate in 40 g of milliQ water is prepared.
  • the Al (OH) 3 is precipitated by adding 4.4 g of NH 4 OH (30% by weight aqueous solution), filtered and washed with deionized water.
  • the BET surface of the sample is 1,073 m 2 / g, its pore volume is 1.08 cm 3 / g and its average pore diameter is 4.0 nm.
  • the chemical composition of the solid (by weight) is: 98% SiO, 1.9% Al O 3 and 0.04% Na O.
  • Figure 2 shows the nitrogen adsorption isotherm of the calcined solid, in which the characteristic stage of filling the mesopores around a partial pressure p / p 0 of 0.35 is observed.
  • a solution A is prepared with the following composition:
  • Tetraethylorthosilicate The resulting gel is stirred an additional 30 minutes, and aged at a temperature of 80 ° C for 5 hours.
  • the dried solid is calcined at 550 ° C in N 2 flow for 1 h, followed by air at the same temperature for 6 h.
  • the X-ray diffraction diagram of the calcined solid has an intense peak at a spacing value of 3.5 nm; a BET area of 896 m 2 / g; a pore volume of 0.93 cm 3 / g and an average pore diameter of 4.2 nm.
  • the chemical composition of the solid by weight is 98% SiO 2 , 1.9% Al 2 O 3 and 0.03% Na 2 O.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
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Abstract

The invention relates to novel mesoporous aluminosilicate-type materials having a chemical composition with the following formula (in oxide moles): Al2O3: m SiO2: n M2O, wherein: m denotes a value of between 10 and 1000, preferably between 20 and 200; M denotes cations Na+ or H+; and n denotes a value of between 0.001 and 1, preferably between 0.01 and 1. The inventive materials comprise regularly-distributed pores having an average diameter of between 2 and 10 nm. Moreover, said materials also present a high catalytic activity in acid catalysis reactions. The invention also relates to the method of preparing said materials and to the use thereof as catalysts for hydrocarbon transformation reactions, such as cracking, isomerisation, transalkylation, alkylation, dimerisation and polymerisation.

Description

TITULOTITLE
ESTRUCTURAS MESOPOROSAS CON ELEVADA ACTIVIDADMESOPOROUS STRUCTURES WITH HIGH ACTIVITY
CATALÍTICA EN REACCIONES DE CATÁLISIS ACIDA Y SUCATALYTICS IN REACTIONS OF ACID CATALYSIS AND ITS
PROCEDIMIENTO DE PREPARACIÓNPREPARATION PROCEDURE
SECTOR DE LA TÉCNICASECTOR OF THE TECHNIQUE
Esta invención se refiere a materiales de tipo aluminosilicatos mesoporosos que poseen una elevada actividad catalítica en reacciones de catálisis acida, su procedimiento de preparación y su uso como catalizador de reacciones de transformación de hidrocarburos, tales como craqueo, isomerización, transalquilación, alquilación, dimerización y polimerización.This invention relates to mesoporous aluminosilicate materials that possess a high catalytic activity in acid catalysis reactions, their preparation process and their use as a catalyst for hydrocarbon transformation reactions, such as cracking, isomerization, transalkylation, alkylation, dimerization and polymerization.
ESTADO DE LA TÉCNICASTATE OF THE TECHNIQUE
Los materiales zeolíticos son ampliamente utilizados como catalizadores en las industrias de refino y petroquímica y en la síntesis de compuestos químicos de alto valor añadido. Su comportamiento catalítico se debe a la presencia en esos materiales de centros activos de elevada acidez, que permiten catalizar un gran número de reacciones de interés industrial.Zeolitic materials are widely used as catalysts in the refining and petrochemical industries and in the synthesis of chemical compounds of high added value. Its catalytic behavior is due to the presence in these materials of active centers of high acidity, which allow catalyzing a large number of reactions of industrial interest.
Tanto las zeolitas (aluminosilicatos cristalinos) como los materiales zeolíticos en general poseen una estructura cristalina en la que existen cavidades y canalesBoth zeolites (crystalline aluminosilicates) and zeolitic materials in general have a crystalline structure in which there are cavities and channels
* microporosos, cuyo acceso está limitado por aberturas cuyo diámetro es siempre inferior a 2,0 nm, y en la mayoría de los casos no excede de 0,8 nm. Aunque el tamaño de las cavidades y canales presentes en la estructura de las zeolitas y materiales zeolíticos es adecuado para transformar o producir moléculas que sean suficientemente pequeñas, por ejemplo producir un isómero excluyendo a otros posibles (propiedad conocida como selectividad de forma), es a menudo excesivamente pequeño para transformar moléculas voluminosas, que no pueden acceder al interior del sistema microporoso. Eso supone una severa limitación para el empleo de las zeolitas y materiales zeolíticos en numerosos procesos químicos de interés industrial. En el año 1992 la compañía Mobil Oil dio a conocer la invención de una nueva familia de materiales mesoporosos ordenados, denominada M41S (WO Pat. 91/11390 (1991)). Estos materiales se caracterizan por poseer una distribución regular de poros cuyo tamaño, entre 2,0 nm y 10,0 nm, está comprendido dentro del rango del mesoporo, por lo que no presentan las limitaciones de las zeolitas para procesar moléculas voluminosas. Sin embargo, y a pesar de poseer una distribución regular de mesoporos, estos materiales son amorfos, es decir, el esqueleto inorgánico está constituido por una red de tetraedros de SiO4 y AlO4 enlazados entre sí de manera desordenada a través de los átomos de oxígeno. Por este motivo, la acidez de estos materiales se asemeja a la de las sílices-alúminas amorfas, siendo muy inferior a la de las zeolitas, al igual que su actividad catalítica. Estos factores limitan severamente el empleo de los materiales mesoporosos ordenados en numerosos procesos de interés industrial. * microporous, whose access is limited by openings whose diameter is always less than 2.0 nm, and in most cases does not exceed 0.8 nm. Although the size of the cavities and channels present in the structure of the zeolites and zeolitic materials is suitable for transforming or producing molecules that are small enough, for example to produce an isomer excluding other possible ones (property known as shape selectivity), it is a often too small to transform bulky molecules, which cannot access the interior of the microporous system. This implies a severe limitation for the use of zeolites and zeolitic materials in numerous chemical processes of industrial interest. In 1992, the Mobil Oil company announced the invention of a new family of ordered mesoporous materials, called M41S (WO Pat. 91/11390 (1991)). These materials are characterized by having a regular distribution of pores whose size, between 2.0 nm and 10.0 nm, is within the range of the mesopore, so they do not have the limitations of zeolites to process bulky molecules. However, despite having a regular distribution of mesopores, these materials are amorphous, that is, the inorganic skeleton is constituted by a network of tetrahedra of SiO 4 and AlO 4 linked together in a disorderly manner through oxygen atoms . For this reason, the acidity of these materials resembles that of amorphous silica-aluminas, being much lower than that of zeolites, as well as their catalytic activity. These factors severely limit the use of mesoporous materials ordered in numerous processes of industrial interest.
Recientemente se ha descrito un método para obtener materiales mesoporosos a partir de disoluciones precursoras de cristales de la zeolita faujasita de tipo Y que contienen el catión tetrametilamonio y que poseen una elevada actividad catalítica en reacciones de catálisis acida. (Pat. ES 200201821)Recently, a method for obtaining mesoporous materials from precursor solutions of crystals of the Y-type zeolite faujasite containing the tetramethylammonium cation and having a high catalytic activity in acid catalysis reactions has been described. (Pat. ES 200201821)
DESCRIPCIÓN DE LA INVENCIÓN Descripción breveDESCRIPTION OF THE INVENTION Brief Description
Esta invención se refiere a nuevos materiales mesoporosos con una composición química expresada por la siguiente fórmula (en moles de óxidos):This invention relates to new mesoporous materials with a chemical composition expressed by the following formula (in moles of oxides):
Al2O3 : m SiO2 : n M2OAt 2 O 3 : m SiO 2 : n M 2 O
en donde el valor de m está comprendido entre 10 y 1000, preferentemente entrewherein the value of m is between 10 and 1000, preferably between
20 y 200; M representa los cationes Na+ o Ε , y el valor de n está comprendido entre 0,001 y 1, preferentemente entre 0,01 y 1.20 and 200; M represents the Na + or Ε cations, and the value of n is between 0.001 and 1, preferably between 0.01 and 1.
Estos materiales poseen una distribución regular de poros cuyo diámetro promedio está comprendido entre 2,0 nm y 10 nm. Presentan asimismo una elevada actividad catalítica en reacciones de catálisis acida. Se describe su procedimiento de preparación a partir de disoluciones precursoras de cristales de zeolita ZSM-5 de tamaño coloidal y su uso como catalizadores de reacciones de transformación de hidrocarburos, tales como craqueo, isomerización, transalquilación, alquilación, dimerización y polimerización. Descripción de la invención.These materials have a regular distribution of pores whose average diameter is between 2.0 nm and 10 nm. They also have a high catalytic activity in acid catalysis reactions. Its preparation process is described from precursor solutions of colloidal size ZSM-5 zeolite crystals and its use as catalysts for hydrocarbon transformation reactions, such as cracking, isomerization, transalkylation, alkylation, dimerization and polymerization. Description of the invention
La presente invención se refiere a la preparación de estructuras porosas que poseen un retículo formado por la unión de tetraedros de SiO4 y AlO4, con una relación molar de silicio a aluminio comprendida entre 5 y 500, que presentan una distribución regular de poros cuyo diámetro promedio está comprendido entre 2,0 nm y 10 nm, al menos un pico de difracción de rayos X correspondiente a un espaciado comprendido entre 1,5 nm y 20,0 nm, una superficie BET comprendida entre 300 m2/g y 1400 m2/g, un volumen total de poro comprendido entre 0,2 cm3/g y 2,0 cm3 /g, una actividad catalítica en la transformación de m-xileno tal que para un valor de tiempo de contacto expresado como W F (g h/mol) comprendido entre 0,5 y 1 la conversión de m-xileno a 400 °C es al menos del 5%, y a su empleo como catalizadores de reacciones de transformación de moléculas orgánicas que son catalizadas por centros ácidos.The present invention relates to the preparation of porous structures that have a lattice formed by the union of tetrahedra of SiO 4 and AlO 4 , with a molar ratio of silicon to aluminum between 5 and 500, which have a regular distribution of pores whose average diameter is between 2.0 nm and 10 nm, at least one X-ray diffraction peak corresponding to a spacing between 1.5 nm and 20.0 nm, a BET surface between 300 m 2 / g and 1400 m 2 / g, a total pore volume comprised between 0.2 cm 3 / g and 2.0 cm 3 / g, a catalytic activity in m-xylene transformation such that for a contact time value expressed as WF (gh / mol) between 0.5 and 1 the conversion of m-xylene at 400 ° C is at least 5%, and its use as catalysts for transformation reactions of organic molecules that are catalyzed by acid centers.
El procedimiento para la obtención de los materiales porosos objeto de la presente invención comprende un proceso en dos etapas. En la primera etapa, se prepara una disolución A, denominada "disolución precursora de zeolita ZSM-5 coloidal", cuya principal pero no única característica es que contiene el catión tetrapropilamonio. En una segunda etapa, se prepara una disolución B cuya principal pero no única característica es que contiene un surfactante catiónico, que se mezcla con la disolución A. Es característico de la presente invención que la disolución A que contiene el catión tetrapropilamonio es precursora de cristales de tamaño coloidal de la zeolita ZSM-5. Es bien conocido que la preparación de cristales de zeolita de tamaño coloidal requiere unas condiciones de síntesis que son diferentes de aquellas empleadas en la obtención de cristales no coloidales de zeolitas (Persson, A.E., Schoeman, B.J., Sterte, J., Otterstedt, J.E., Zeolites, 14 (1994) 557-567; Zeolites, 15 (1995) 611-619). Esta es una característica específica de la presente invención que la diferencia de otros procedimientos que hacen uso de simientes de ZSM-5 que no dan lugar a cristales coloidales de ZSM-5 (WO 01/92154 Al, Pinnavaia, TJ, Zhang, W.5 y Liu, Y.).The process for obtaining the porous materials object of the present invention comprises a two step process. In the first stage, a solution A, called "colloidal ZSM-5 zeolite precursor solution" is prepared, whose main but not only feature is that it contains the tetrapropylammonium cation. In a second stage, a solution B is prepared whose main but not the only characteristic is that it contains a cationic surfactant, which is mixed with solution A. It is characteristic of the present invention that solution A containing the tetrapropylammonium cation is a crystal precursor Colloidal size of the zeolite ZSM-5. It is well known that the preparation of colloidal-sized zeolite crystals requires synthesis conditions that are different from those used to obtain non-colloidal zeolite crystals (Persson, AE, Schoeman, BJ, Sterte, J., Otterstedt, JE , Zeolites, 14 (1994) 557-567; Zeolites, 15 (1995) 611-619). This is a specific feature of the present invention that the difference from other methods that make use of ZSM-5 seeds that do not give rise to colloidal crystals of ZSM-5 (WO 01/92154 Al, Pinnavaia, TJ, Zhang, W. 5 and Liu, Y.).
La composición química de la disolución A se representa mediante la fórmula (en moles):The chemical composition of solution A is represented by the formula (in moles):
Al2O3 : x SiO2 : y (TPA)2 O : z Na2O : w H2O : v ROH La preparación de esta disolución comprende el tratamiento de una fuente de aluminio, tal como el hidróxido de aluminio, con una disolución acuosa de hidróxido de tetrapropilamonio y opcionalmente también con una fuente de sodio, hasta lograr la disolución del hidróxido de aluminio. Ejemplos no limitantes de esa fuente de sodio son el hidróxido de sodio y diversas sales solubles de sodio, tales como el cloruro sódico, el sulfato sódico o el nitrato sódico. El hidróxido de aluminio empleado en la invención puede prepararse ventajosamente mediante su precipitación a partir de una disolución de una sal soluble de aluminio, tal como el sulfato de aluminio o el nitrato de aluminio, mediante mezclado de la misma con una disolución de una base, como por ejemplo el hidróxido amónico. Opcionalmente, se puede disolver aluminio metálico en la disolución de hidróxido de tetrapropilamonio.Al 2 O 3 : x SiO 2 : y (TPA) 2 O: z Na 2 O: w H 2 O: v ROH The preparation of this solution comprises the treatment of an aluminum source, such as aluminum hydroxide, with an aqueous solution of tetrapropylammonium hydroxide and optionally also with a sodium source, until the dissolution of the aluminum hydroxide is achieved. Non-limiting examples of that source of sodium are sodium hydroxide and various soluble sodium salts, such as sodium chloride, sodium sulfate or sodium nitrate. The aluminum hydroxide used in the invention can be advantageously prepared by precipitation from a solution of a soluble aluminum salt, such as aluminum sulfate or aluminum nitrate, by mixing it with a solution of a base, such as ammonium hydroxide. Optionally, metallic aluminum can be dissolved in the tetrapropylammonium hydroxide solution.
En el caso de que se emplee hidróxido de aluminio como fuente de aluminio, el tratamiento de dicho hidróxido con la disolución básica que contiene tetrapropilamonio y opcionalmente una fuente de sodio se realiza a una temperatura comprendida entre 10 °C y 100 °C, preferentemente entre 20 °C y 60 °C, durante un tiempo comprendido entre 5 minutos y 5 horas, preferentemente entre 10 minutos y 1 hora. El objetivo de este tratamiento es lograr la completa disolución del hidróxido de aluminio.In the case where aluminum hydroxide is used as an aluminum source, the treatment of said hydroxide with the basic solution containing tetrapropylammonium and optionally a sodium source is carried out at a temperature between 10 ° C and 100 ° C, preferably between 20 ° C and 60 ° C, for a time between 5 minutes and 5 hours, preferably between 10 minutes and 1 hour. The objective of this treatment is to achieve the complete dissolution of aluminum hydroxide.
Una vez disuelta la fuente de aluminio en la disolución de hidróxido de tetrapropilamonio, se mezcla la disolución resultante con una fuente de silicio, ejemplos no limitantes de la cual son la sílice coloidal, sílice precipitada, sílice pirogénica, o alcóxidos de silicio, tales como tetrametoxisilano y tetraetoxisilano. Opcionalmente, la fuente de silicio puede hacerse reaccionar con una parte de la disolución de hidróxido de tetrapropilamonio utilizado en la preparación. En caso de que se emplee sílice coloidal como fuente de silicio, ésta puede tratarse opcionalmente con una resina de intercambio catiónico con el objeto de disminuir el contenido de cationes alcalinos, preferentemente sodio, que contiene. El valor de x en la composición de la disolución A está comprendido entre 25 y 1000, preferentemente entre 50 y 200.Once the source of aluminum is dissolved in the tetrapropylammonium hydroxide solution, the resulting solution is mixed with a source of silicon, non-limiting examples of which are colloidal silica, precipitated silica, pyrogenic silica, or silicon alkoxides, such as tetramethoxysilane and tetraethoxysilane. Optionally, the silicon source can be reacted with a part of the tetrapropylammonium hydroxide solution used in the preparation. If colloidal silica is used as a source of silicon, it can optionally be treated with a cation exchange resin in order to reduce the content of alkali cations, preferably sodium, which it contains. The value of x in the composition of solution A is between 25 and 1000, preferably between 50 and 200.
Opcionalmente, la disolución A puede contener uno o más alcoholes (ROH) que posean un número de átomos de carbono comprendido entre 1 y 6, pueden ser lineales o ramificados, y preferentemente metanol, etanol o mezclas de ambos. Los valores de y, z, w y v en la composición de la disolución A son tales que las relaciones molares y/x, z/x, w/x y v/x están comprendidas dentro de los siguientes intervalos: y/x entre 0,05 y 1, preferentemente entre 0,1 y 0,5. z/x entre 0 y 1, preferentemente entre 0,01 y 0,1. w/x entre 5 y 100, preferentemente entre 10 y 50. v/x entre 0 y 50, preferentemente entre 0,1 y 10.Optionally, solution A may contain one or more alcohols (ROH) having a number of carbon atoms between 1 and 6, may be linear or branched, and preferably methanol, ethanol or mixtures of both. The values of y, z, w and v in the composition of solution A are such that the molar ratios y / x, z / x, w / xyv / x are within the following ranges: y / x between 0.05 and 1, preferably between 0.1 and 0.5. z / x between 0 and 1, preferably between 0.01 and 0.1. w / x between 5 and 100, preferably between 10 and 50. v / x between 0 and 50, preferably between 0.1 and 10.
Una vez preparada la disolución A, ésta se envejece a una temperatura comprendida entre 4 °C y 150 °C, preferentemente entre 20 °C y 110 °C, durante un tiempo comprendido entre 10 minutos y 7 días, preferentemente entre 1 hora y 48 horas. Es característico de la presente invención que el envejecimiento de la disolución A se realiza en condiciones de temperatura y tiempo tales que no se detecta la formación de cristales de ZSM-5 al finalizar el envejecimiento. Por este motivo, a la disolución A se la denomina en la presente invención "disolución precursora de zeolita ZSM-5 coloidal".Once solution A is prepared, it is aged at a temperature between 4 ° C and 150 ° C, preferably between 20 ° C and 110 ° C, for a time between 10 minutes and 7 days, preferably between 1 hour and 48 hours. It is characteristic of the present invention that the aging of solution A is carried out under conditions of temperature and time such that the formation of ZSM-5 crystals is not detected at the end of aging. For this reason, solution A is referred to herein as the "ZSM-5 colloidal zeolite precursor solution".
La disolución B se prepara mediante disolución de uno o más surfactantes catiónicos en agua, en un disolvente orgánico o en una mezcla de ambos. El surfactante catiónico empleado en la presente invención se representa mediante la fórmula NRiR^R-t , en donde R2, R3 y P pueden ser iguales o distintos, y representan grupos orgánicos que contienen entre 1 y 6 átomos de carbono, siendo la composición preferida aquella en la que R2 = R3 = P^ = CH3; Rt representa un grupo orgánico que contiene carbono e hidrógeno, saturado o insaturado, preferentemente una cadena alifática lineal o ramificada, que contiene un número de átomos de carbono comprendido entre 2 y 36, preferentemente entre 8 y 22. Ejemplos no restrictivos de este surfactante catiónico son el hexadeciltrimetilamonio, el dimetildidodecilamonio y el benciltrimetilamonio. Este catión puede emplearse bajo la forma de sales, ejemplos no limitantes de las cuales son el bromuro y el cloruro, o bien como hidróxido, o mezcla de ambos. La disolución B a la que hace referencia la invención puede contener uno o más de los surfactantes descritos, y su proporción en peso respecto al disolvente está comprendida entre el 2 y el 50%, preferentemente entre el 10% y el 30%. El disolvente preferido para preparar la disolución B es el agua, pero opcionalmente pueden emplearse un alcohol o mezcla de dos o más alcoholes, o una mezcla de alcoholes con agua. Los alcoholes empleados pueden contener un número de átomos de carbono comprendido entre 1 y 6, preferentemente metanol o etanol. Opcionalmente, la disolución B puede contener tetrametilamonio y opcionalmente también sodio, en una proporción no superior al 90% del tetrametilamonio y el 90% del sodio contenidos conjuntamente en las disoluciones A y B.Solution B is prepared by dissolving one or more cationic surfactants in water, in an organic solvent or in a mixture of both. The cationic surfactant used in the present invention is represented by the formula NRiR ^ Rt, wherein R 2 , R 3 and P may be the same or different, and represent organic groups containing between 1 and 6 carbon atoms, the preferred composition being one in which R 2 = R 3 = P ^ = CH 3 ; Rt represents an organic group containing carbon and hydrogen, saturated or unsaturated, preferably a linear or branched aliphatic chain, containing a number of carbon atoms between 2 and 36, preferably between 8 and 22. Non-restrictive examples of this cationic surfactant they are hexadecyltrimethylammonium, dimethyldidodecylammonium and benzyltrimethylammonium. This cation can be used in the form of salts, non-limiting examples of which are bromide and chloride, or as hydroxide, or mixture of both. The solution B referred to in the invention may contain one or more of the surfactants described, and their proportion by weight with respect to the solvent is between 2 and 50%, preferably between 10% and 30%. The preferred solvent for preparing solution B is water, but optionally an alcohol or mixture of two or more alcohols, or a mixture of alcohols with water. The alcohols used may contain a number of carbon atoms between 1 and 6, preferably methanol or ethanol. Optionally, solution B may contain tetramethylammonium and optionally also sodium, in a proportion not exceeding 90% of tetramethylammonium and 90% of sodium contained jointly in solutions A and B.
La relación molar entre el silicio de la disolución A, expresado como SiO2, y el surfactante catiónico de la disolución B (relación sílice/surfactante) está comprendida entre 0,1 y 15, preferentemente entre 0,5 y 5. La disolución B puede contener una proporción del total de disolvente empleado en la preparación comprendido entre 1% yThe molar ratio between the silicon of solution A, expressed as SiO 2 , and the cationic surfactant of solution B (silica / surfactant ratio) is between 0.1 and 15, preferably between 0.5 and 5. Solution B it may contain a proportion of the total solvent used in the preparation between 1% and
95%, preferentemente entre 10% y 50%.95%, preferably between 10% and 50%.
El gel resultante de la mezcla de las disoluciones A y B se trata a una temperatura comprendida entre 4°C y 200 °C, preferentemente entre 20°C y 180 °C, durante un tiempo comprendido entre 30 minutos y 7 días, preferentemente entre 1 hora y 48 horas. El producto sólido obtenido después de esta etapa de calentamiento se filtra, se lava con agua desionizada y se seca.The gel resulting from the mixture of solutions A and B is treated at a temperature between 4 ° C and 200 ° C, preferably between 20 ° C and 180 ° C, for a time between 30 minutes and 7 days, preferably between 1 hour and 48 hours. The solid product obtained after this heating step is filtered, washed with deionized water and dried.
El producto así obtenido se calienta en aire a temperaturas comprendidas entreThe product thus obtained is heated in air at temperatures between
400 °C y 800 °C, preferentemente entre 500 °C y 700 °C, con el fin de eliminar la materia orgánica que contiene. Opcionalmente, el tratamiento térmico puede llevarse a cabo en una atmósfera de un gas inerte, tal como nitrógeno, seguido opcionalmente de una calcinación en aire.400 ° C and 800 ° C, preferably between 500 ° C and 700 ° C, in order to remove the organic matter it contains. Optionally, the heat treatment can be carried out in an atmosphere of an inert gas, such as nitrogen, optionally followed by an air calcination.
El material calcinado obtenido mediante el procedimiento descrito en la presente invención se caracteriza por tener una composición química expresada por la siguiente fórmula (en moles de óxidos):The calcined material obtained by the process described in the present invention is characterized by having a chemical composition expressed by the following formula (in moles of oxides):
Al2O3 : m SiO2 : n M2OAt 2 O 3 : m SiO 2 : n M 2 O
en donde el valor de m está comprendido entre 10 y 1000, preferentemente entre 20 y 200; M representa los cationes Na+ o H"1", y el valor de n está comprendido entre 0,001 y 1, preferentemente entre 0,01 y 0,9. Además de su composición química, el material poroso obtenido según el procedimiento descrito en la presente invención se distingue por poseer las siguientes características:wherein the value of m is between 10 and 1000, preferably between 20 and 200; M represents the Na + or H "1" cations, and the value of n is between 0.001 and 1, preferably between 0.01 and 0.9. In addition to its chemical composition, the porous material obtained according to the process described in the present invention is distinguished by having the following characteristics:
1) Al menos un pico de difracción de rayos X correspondiente a un valor de espaciado comprendido entre 1,5 nm y 20 nm.1) At least one X-ray diffraction peak corresponding to a spacing value between 1.5 nm and 20 nm.
2) Un volumen total de poro (N) comprendido entre 0,2 cm3/g y 2,0 cm3 /g.2) A total pore volume (N) between 0.2 cm 3 / g and 2.0 cm 3 / g.
3) Una superficie BET (A) comprendida entre 300 m2/g y 1.400 m2/g.3) A BET surface (A) between 300 m 2 / g and 1,400 m 2 / g.
4) Un diámetro medio de poro (expresado como 4N/A) comprendido entre 2,0 nm y 10 nm. 5) Una característica inherente al material que se reivindica en la presente invención es su elevada actividad catalítica en reacciones que son catalizadas por sólidos ácidos. En la presente invención esa actividad catalítica se expresa a modo de ejemplo no limitante en el grado de conversión del m-xileno cuando una cierta cantidad de este reactivo se hace fluir en un reactor tubular a través de un lecho que contiene una cierta cantidad del material calentado a una cierta temperatura. Más específicamente, es una característica inherente del material el hecho de que en un reactor tubular de lecho fijo empleando nitrógeno como gas portador (relación molar Ν2/m-xileno = 4), a un tiempo de contacto W/F (W/F se expresa en gramos de catalizador por hora y por mol de m-xileno) comprendido entre 0,5 y 1 y a una temperatura de 400 °C, permite obtener una conversión de m-xileno igual o superior al 5%.4) An average pore diameter (expressed as 4N / A) between 2.0 nm and 10 nm. 5) A characteristic inherent to the material claimed in the present invention is its high catalytic activity in reactions that are catalyzed by acid solids. In the present invention that catalytic activity is expressed by way of non-limiting example in the degree of conversion of m-xylene when a certain amount of this reagent is flowed into a tubular reactor through a bed containing a certain amount of the material heated to a certain temperature. More specifically, the fact that in a fixed bed tubular reactor using nitrogen as a carrier gas (molar ratio Ν 2 / m-xylene = 4), at a contact time W / F (W / F, is a characteristic of the material It is expressed in grams of catalyst per hour and per mole of m-xylene) between 0.5 and 1 and at a temperature of 400 ° C, allows to obtain a conversion of m-xylene equal to or greater than 5%.
Es característico del material obtenido según el procedimiento descrito en la presente invención el poseer simultáneamente todas las características indicadas anteriormente, lo que lo distingue de otros materiales descritos anteriormente en la bibliografía que pueden poseer una o más, pero no todas, las características del material reivindicado en la presente invención.It is characteristic of the material obtained according to the process described in the present invention to simultaneously possess all the characteristics indicated above, which distinguishes it from other materials described above in the literature that may possess one or more, but not all, the characteristics of the claimed material. in the present invention.
El material descrito en la invención puede emplearse en una amplia variedad de reacciones de transformación de hidrocarburos, entre las que se pueden mencionar como ejemplos el craqueo catalítico, la isomerización, hidroisomerización, hidrocraqueo, alquilación, dimerización y polimerización, y entre ellas cabe destacar como ejemplo no limitante la conversión de m-xileno. DESCRIPCIÓN DE LAS FIGURASThe material described in the invention can be used in a wide variety of hydrocarbon transformation reactions, among which are examples of catalytic cracking, isomerization, hydroisomerization, hydrocracking, alkylation, dimerization and polymerization, and among them, non-limiting example the conversion of m-xylene. DESCRIPTION OF THE FIGURES
Figura 1. Difractograma de rayos X (radiación CuKα) de la muestra calcinada obtenida según el procedimiento descrito en el ejemplo 1. En el recuadro que aparece en el interior de la figura se incluye el difractograma en la región de valores de 2Θ entre 4° y 40°.Figure 1. X-ray diffractogram (CuKα radiation) of the calcined sample obtained according to the procedure described in example 1. The diffractogram in the region of values of 2Θ between 4 ° is included in the box that appears inside the figure. and 40 °.
Figura 2. Isoterma de adsorción-desorción de nitrógeno (-196 °C) de la muestra calcinada obtenida según el procedimiento descrito en el ejemplo 1Figure 2. Nitrogen adsorption-desorption isotherm (-196 ° C) of the calcined sample obtained according to the procedure described in Example 1
EJEMPLOS DE REALIZACIÓNEXAMPLES OF REALIZATION
Los siguientes ejemplos ilustran la invención, sin que constituyan por ello una limitación de la invención. Ejemplo 1The following examples illustrate the invention, without thereby constituting a limitation of the invention. Example 1
Se prepara una disolución A con la siguiente composición:A solution A is prepared with the following composition:
Al2O3: 100 SiO2 : 12 (TPA)2O: 0,40 Na2O: 2120 H2O : 400 ETOHAt 2 O 3 : 100 SiO 2 : 12 (TPA) 2 O: 0.40 Na 2 O: 2120 H 2 O: 400 ETOH
Para ello, se prepara una disolución de 3,78 g de sulfato de aluminio en 40 g de agua milliQ. Se precipita el Al(OH)3 añadiendo a la disolución 4,4 g de NH4OH (disolución acuosa al 30% en peso), se filtra y se lava con agua desionizada.For this, a solution of 3.78 g of aluminum sulfate in 40 g of milliQ water is prepared. The Al (OH) 3 is precipitated by adding 4.4 g of NH 4 OH (30% by weight aqueous solution), filtered and washed with deionized water.
Se introducen en un bote de polipropileno (PP) 32,83 g de TPAOH (disolución acuosa al 42,2% en peso), 84,92 g de agua milliQ y 0,09 g de NaOH. Se agita durante 15 minutos y a continuación se añade el Al(OH)3. Se agita hasta disolver totalmente el hidróxido de aluminio, lo que ocurre en 20 minutos. Se añaden entonces 59,02 g de tetraetilortosilicato. Se agita el gel resultante 30 minutos más, y se envejece a una temperatura de 80 °C durante 5 horas.32.83 g of TPAOH (42.2% aqueous solution by weight), 84.92 g of milliQ water and 0.09 g of NaOH are introduced into a polypropylene (PP) canister. Stir for 15 minutes and then add Al (OH) 3 . It is stirred until the aluminum hydroxide is completely dissolved, which occurs in 20 minutes. Then 59.02 g of tetraethylorthosilicate are added. The resulting gel is stirred an additional 30 minutes, and aged at a temperature of 80 ° C for 5 hours.
Al cabo de este tiempo, se deja enfriar hasta temperatura ambiente y se añadenAfter this time, allow to cool to room temperature and add
17,55 g de una disolución acuosa de bromuro de cetiltrimetilamonio (CTAB) (20% en peso), denominada disolución B. La mezcla resultante se mantiene a una temperatura de 25 °C durante 3 horas. Al cabo de este tiempo, se filtra la suspensión resultante, y el sólido se lava y se seca. El producto sólido seco se calcina a una temperatura de 550 °C en flujo de N2 durante 1 h, seguido de aire a la misma temperatura durante 6 h.17.55 g of an aqueous solution of cetyltrimethylammonium bromide (CTAB) (20% by weight), called solution B. The resulting mixture is maintained at a temperature of 25 ° C for 3 hours. After this time, the resulting suspension is filtered, and the solid is washed and dried. The dried solid product is calcined at a temperature of 550 ° C in a flow of N 2 for 1 h, followed by air at the same temperature for 6 h.
El diagrama de difracción de rayos X del sólido calcinado se presenta en la figura 1, en el que se puede observar la presencia de un pico intenso que corresponde a un valor de espaciado d = 3,9 nm. La superficie BET de la muestra es de 1.073 m2/g, su volumen de poro de 1,08 cm3/g y su diámetro promedio de poro de 4,0 nm. La composición química del sólido (en peso) es: 98 % de SiO , 1,9% de Al O3 y 0,04 % de Na O. La figura 2 muestra la isoterma de adsorción de nitrógeno del sólido calcinado, en la que se observa la etapa característica de llenado de los mesoporos alrededor de una presión parcial p/p0 de 0,35. En la reacción de transformación de m-xileno, a 400 °C, para una relación molar nitrógeno/m-xileno de 4 y a un tiempo de contacto (expresado como W/F (mol g/h)) de 0,70 esta muestra produce una conversión del reactivo del 15 %.The X-ray diffraction diagram of the calcined solid is presented in Figure 1, in which the presence of an intense peak corresponding to a spacing value d = 3.9 nm can be observed. The BET surface of the sample is 1,073 m 2 / g, its pore volume is 1.08 cm 3 / g and its average pore diameter is 4.0 nm. The chemical composition of the solid (by weight) is: 98% SiO, 1.9% Al O 3 and 0.04% Na O. Figure 2 shows the nitrogen adsorption isotherm of the calcined solid, in which the characteristic stage of filling the mesopores around a partial pressure p / p 0 of 0.35 is observed. In the m-xylene transformation reaction, at 400 ° C, for a nitrogen / m-xylene molar ratio of 4 and at a contact time (expressed as W / F (mol g / h)) of 0.70 this sample produces a reagent conversion of 15%.
Ejemplo 2Example 2
Se prepara una disolución A con la siguiente composición:A solution A is prepared with the following composition:
Al2O3: 100 SiO2: 12 (TPA)2O: 0,40 Na2O: 2120 H2O: 400 ETOHAt 2 O 3 : 100 SiO 2 : 12 (TPA) 2 O: 0.40 Na 2 O: 2120 H 2 O: 400 ETOH
Para ello, se prepara una disolución de 7,56 g de sulfato de aluminio en 80 g de agua milliQ. Se precipita el Al(OH)3 añadiendo a la disolución 8,8 g de NIL4OH (30%), se filtra y se lava con agua desionizada.For this, a solution of 7.56 g of aluminum sulfate in 80 g of milliQ water is prepared. The Al (OH) 3 is precipitated by adding 8.8 g of NIL 4 OH (30%) to the solution, filtered and washed with deionized water.
Se introducen en un bote de polipropileno (PP) 65,66 g de TPAOH (disolución acuosa al 42,2% en peso), 169,84 g de agua milliQ y 0,18 g de NaOH. Se agita durante 15 minutos y a continuación se añade el Al(OH)3. Se agita hasta disolver totalmente el hidróxido de aluminio, lo que ocurre en 20 minutos. Se añaden entonces 118,04 g de65.66 g of TPAOH (42.2% aqueous solution by weight), 169.84 g of milliQ water and 0.18 g of NaOH are introduced into a polypropylene (PP) canister. Stir for 15 minutes and then add Al (OH) 3 . It is stirred until the aluminum hydroxide is completely dissolved, which occurs in 20 minutes. Then 118.04 g of
Tetraetilortosilicato. Se agita el gel resultante 30 minutos más, y se envejece a una temperatura de 80 °C durante 5 horas.Tetraethylorthosilicate. The resulting gel is stirred an additional 30 minutes, and aged at a temperature of 80 ° C for 5 hours.
Al cabo de este tiempo, se deja enfriar hasta temperatura ambiente y se añaden 35,1 g de una disolución acuosa de bromuro de cetiltrimetilamonio (CTAB) (20% en peso), denominada disolución B. La mezcla resultante se calienta a una temperatura de 80 °C durante 3 horas. Al cabo de este tiempo, se filtra la suspensión resultante, y el sólido se lava y se seca.After this time, it is allowed to cool to room temperature and 35.1 g of an aqueous solution of cetyltrimethylammonium bromide (CTAB) (20% by weight), called solution B, is added. The resulting mixture is heated to a temperature of 80 ° C for 3 hours. After this time, the resulting suspension is filtered, and the solid is washed and dried.
El sólido seco se calcina a 550 °C en flujo de N2 durante 1 h, seguido de aire a la misma temperatura durante 6 h. El diagrama de difracción de rayos X del sólido calcinado presenta un pico intenso a un valor de espaciado de 3,5 nm; un área BET de 896 m2/g; un volumen de poro de 0,93 cm3/g y un diámetro medio de poro de 4,2 nm. La composición química del sólido en peso es de 98 % de SiO2, 1,9 % de Al2O3 y 0,03% de Na2O. En la reacción de transformación de m-xileno, a 400 °C, para una relación molar nitrógeno/hidrocarburo de 4 y a un tiempo de contacto (expresado como W/F (mol g/h)) de 0,62, esta muestra produce una conversión del reactivo del 8 %. The dried solid is calcined at 550 ° C in N 2 flow for 1 h, followed by air at the same temperature for 6 h. The X-ray diffraction diagram of the calcined solid has an intense peak at a spacing value of 3.5 nm; a BET area of 896 m 2 / g; a pore volume of 0.93 cm 3 / g and an average pore diameter of 4.2 nm. The chemical composition of the solid by weight is 98% SiO 2 , 1.9% Al 2 O 3 and 0.03% Na 2 O. In the m-xylene transformation reaction, at 400 ° C, for a nitrogen / hydrocarbon molar ratio of 4 and at a contact time (expressed as W / F (mol g / h)) of 0.62, this sample produces a reagent conversion of 8%.

Claims

REIVINDICACIONES
1) Un material de tipo aluminosilicato mesoporoso que posee una alta actividad en reacciones de transformación de moléculas orgánicas catalizadas por centros ácidos, y caracterizado porque posee la composición química expresada por la siguiente fórmula (en moles de óxidos):1) A mesoporous aluminosilicate type material that has a high activity in transformation reactions of organic molecules catalyzed by acid centers, and characterized in that it has the chemical composition expressed by the following formula (in moles of oxides):
Al2O3 : m SiO2 : n M2O en donde el valor de m está comprendido entre 10 y 1000, preferentemente entre 20 y 200; M representa los cationes Na+ o ϊÚ , y el valor de n está comprendido entre 0,001 y 1, preferentemente entre 0,01 y 1, y que se caracteriza además por presentar las siguientes propiedades: a) al menos un pico de difracción de rayos X correspondiente a un valor de espaciado comprendido entre 1,5 nm y 20 nm, b) un volumen total de poro comprendido entre 0,2 cm /g y 2,0 cm /g, c) una superficie BET comprendida entre 300 m /g y 1.400 m /g, d) un diámetro medio de poro comprendido entre 2,0 nm y 10 nm, e) una actividad catalítica en la transformación de m-xileno tal que para un valor de W/F (g.h/mol) comprendido entre 0,5 y 1 la conversión de m-xileno es al menos el 5%.At 2 O 3 : m SiO 2 : n M 2 O where the value of m is between 10 and 1000, preferably between 20 and 200; M represents the Na + or ϊÚ cations, and the value of n is between 0.001 and 1, preferably between 0.01 and 1, and which is further characterized by having the following properties: a) at least one ray diffraction peak X corresponding to a spacing value between 1.5 nm and 20 nm, b) a total pore volume between 0.2 cm / g and 2.0 cm / g, c) a BET surface area between 300 m / g 1,400 m / g, d) an average pore diameter between 2.0 nm and 10 nm, e) a catalytic activity in m-xylene transformation such that for a value of W / F (gh / mol) between 0.5 and 1 the conversion of m-xylene is at least 5%.
2) Un procedimiento para la obtención del material de tipo aluminosilicato mesoporoso descrito en la reivindicación 1 caracterizado porque se realiza mediante la mezcla de una disolución A denominada "disolución precursora de zeolita ZSM-5 coloidal", y una disolución B, caracterizada porque contiene un surfactante catiónico.2) A process for obtaining the mesoporous aluminosilicate type material described in claim 1, characterized in that it is carried out by mixing a solution A called "colloidal zeolite ZSM-5 precursor solution", and a solution B, characterized in that it contains a cationic surfactant.
3) Un procedimiento de obtención del material de tipo aluminosilicato poroso descrito en la reivindicación 1 según la reivindicación 2 caracterizado por los siguientes pasos: a) calentamiento del gel resultante de la mezcla de las disoluciones A y B a una temperatura comprendida entre 4 °C y 200 °C, preferentemente entre 20 °C y3) A process for obtaining the porous aluminosilicate type material described in claim 1 according to claim 2 characterized by the following steps: a) heating the gel resulting from the mixture of solutions A and B at a temperature between 4 ° C and 200 ° C, preferably between 20 ° C and
180 °C, durante un tiempo comprendido entre 30 minutos y 7 días, preferentemente entre 1 hora y 48 horas, b) el producto sólido obtenido en a) se filtra, se lava con agua desionizada y se seca, y c) el producto así obtenido se calienta en aire a temperaturas comprendidas entre 400 °C y 800 °C, con el fin de eliminar la materia orgánica que contiene. Opcionalmente, el tratamiento térmico puede llevarse a cabo en una atmósfera de un gas inerte, tal como nitrógeno, que opcionalmente puede continuarse con una calcinación en aire.180 ° C, for a time between 30 minutes and 7 days, preferably between 1 hour and 48 hours, b) the solid product obtained in a) is filtered, washed with deionized water and dried, and c) the product thus obtained is heated in air at temperatures between 400 ° C and 800 ° C, in order to eliminate the organic matter it contains. Optionally, the heat treatment can be carried out in an atmosphere of an inert gas, such as nitrogen, which can optionally be continued with an air calcination.
4) Un procedimiento de obtención del material de tipo aluminosilicato poroso descrito en la reivindicación 1 caracterizado porque la preparación de la disolución A según las reivindicaciones 2 y 3 consiste en los siguientes pasos: a) tratamiento de una fuente de aluminio, tal como el hidróxido de aluminio, o sales solubles de aluminio, tales como el sulfato de aluminio o el nitrato de aluminio, o aluminio metálico, con una disolución acuosa de hidróxido de tetrapropilamonio que opcionalmente puede contener además una fuente de sodio, como por ejemplo hidróxido sódico, cloruro sódico o sulfato sódico, hasta obtener una disolución, b) mezcla de la disolución de a) con una fuente de silicio, como por ejemplo sílice coloidal, sílice precipitada, sílice pirogénica o alcóxidos de silicio como por ejemplo tetrametoxisilano y tetraetoxisilano, y c) envejecimiento de la disolución así obtenida a una temperatura comprendida entre 4 °C y 150 °C, preferentemente entre 20 °C y 110 °C, durante un tiempo comprendido entre 10 minutos y 7 días, preferentemente entre 1 hora y 48 horas.4) A process for obtaining the porous aluminosilicate type material described in claim 1, characterized in that the preparation of solution A according to claims 2 and 3 consists of the following steps: a) treatment of an aluminum source, such as hydroxide of aluminum, or soluble salts of aluminum, such as aluminum sulfate or aluminum nitrate, or metallic aluminum, with an aqueous solution of tetrapropylammonium hydroxide which may optionally also contain a source of sodium, such as sodium hydroxide, chloride sodium or sodium sulfate, until a solution is obtained, b) mixing the solution of a) with a source of silicon, such as colloidal silica, precipitated silica, pyrogenic silica or silicon alkoxides such as tetramethoxysilane and tetraethoxysilane, and c) aging of the solution thus obtained at a temperature between 4 ° C and 150 ° C, preferably between 20 C and 110 ° C, for a time between 10 minutes and 7 days, preferably 1 hour to 48 hours.
5) Un procedimiento para la obtención del material de tipo aluminosilicato mesoporoso descrito en la reivindicación 1 preparado como se describe en las reivindicaciones 2 a 4 caracterizado porque la composición química de la disolución A se representa mediante la fórmula (en moles):5) A process for obtaining the mesoporous aluminosilicate type material described in claim 1 prepared as described in claims 2 to 4 characterized in that the chemical composition of solution A is represented by the formula (in moles):
Al2O3 : x SiO2 : y (TPA)2 O : z Na2O : w H2O : v ROHAl 2 O 3 : x SiO 2 : y (TPA) 2 O: z Na 2 O: w H 2 O: v ROH
en la que el valor de x está comprendido entre 20 y 1000 y los valores de y, z, w y v son tales que las relaciones molares y/x, z/x, w/x y v/x están comprendidas dentro de los siguientes intervalos: a) y/x entre 0,05 y 1, preferentemente entre 0,1 y 0,5. b) z/x entre 0 y 1, preferentemente entre 0,01 y 0,1. c) w/x entre 5 y 100, preferentemente entre 10 y 50. d) v/x entre 0 y 50, preferentemente entre 0,1 y 10.in which the value of x is between 20 and 1000 and the values of y, z, w and v are such that the molar ratios y / x, z / x, w / xyv / x fall within the following intervals: a ) and / x between 0.05 and 1, preferably between 0.1 and 0.5. b) z / x between 0 and 1, preferably between 0.01 and 0.1. c) w / x between 5 and 100, preferably between 10 and 50. d) v / x between 0 and 50, preferably between 0.1 and 10.
6) Un procedimiento de obtención del material de tipo aluminosilicato poroso descrito en la reivindicación 1 preparado como se describe en las reivindicaciones 2 a 5 caracterizado porque la disolución A puede contener uno o más alcoholes lineales o ramificados, representados por la expresión ROH en la fórmula de la reivindicación 5, que contengan un número de átomos de carbono comprendido entre 1 y 6. 7) Un procedimiento de obtención del material de tipo aluminosilicato poroso descrito en la reivindicación 1 preparado como se describe en las reivindicaciones 2 a 6 caracterizado porque la disolución B se prepara mediante la disolución de uno o más surfactantes catiónicos en agua, en un disolvente orgánico o en una mezcla de ambos; de forma general los surfactantes catiónicos empleados se representan mediante la fórmula NRiR^ i, en donde R2, R y t pueden ser iguales o distintos, y representan grupos orgánicos que contienen entre 1 y 6 átomos de carbono, siendo la composición preferida aquella en la que R = R3 ^ i = CH3; R\ representa un grupo orgánico que contiene carbono e hidrógeno, saturado o insaturado, preferentemente una cadena alifática lineal o ramificada, que contiene un número de átomos de carbono comprendido entre 2 y 36.6) A process for obtaining the porous aluminosilicate type material described in claim 1 prepared as described in claims 2 to 5 characterized in that the solution A may contain one or more linear or branched alcohols, represented by the expression ROH in the formula of claim 5, containing a number of carbon atoms between 1 and 6. 7) A process for obtaining the porous aluminosilicate type material described in claim 1 prepared as described in claims 2 to 6 characterized in that the solution B is prepared by dissolving one or more cationic surfactants in water, in an organic solvent or in a mixture of both; in general, the cationic surfactants used are represented by the formula NRiR ^ i, where R 2 , R and t may be the same or different, and represent organic groups containing between 1 and 6 carbon atoms, the preferred composition being that in the that R = R 3 ^ i = CH 3 ; R \ represents an organic group containing carbon and hydrogen, saturated or unsaturated, preferably a linear or branched aliphatic chain, containing a number of carbon atoms between 2 and 36.
8) Un procedimiento de obtención del material de tipo aluminosilicato poroso descrito en la reivindicación 1 preparado según la reivindicación 7 caracterizado porque el surfactante catiónico se selecciona, entre otros, del siguiente grupo: hexadeciltrimetilamonio, dimetildidodecilamonio, benciltrimetilamonio, sales de dichos cationes, entre otros, sales de bromuro, cloruro, o bien como hidróxido, o mezcla de ambos.8) A process for obtaining the porous aluminosilicate type material described in claim 1 prepared according to claim 7, characterized in that the cationic surfactant is selected, among others, from the following group: hexadecyltrimethylammonium, dimethyldidodecylammonium, benzyltrimethylammonium, salts of said cations, among others , bromide salts, chloride, or as hydroxide, or mixture of both.
9) Un procedimiento de obtención del material de tipo aluminosilicato poroso descrito en la reivindicación 1 según las reivindicaciones 7 y 8 caracterizado porque la disolución B puede contener uno o más de los surfactantes descritos, y la proporción en peso de éstos respecto al disolvente está comprendida entre el 2 % y el 50%.9) A process for obtaining the porous aluminosilicate type material described in claim 1 according to claims 7 and 8, characterized in that the solution B may contain one or more of the surfactants described, and the proportion by weight of these relative to the solvent is comprised between 2% and 50%.
10) Un procedimiento de obtención del material de tipo aluminosilicato poroso descrito en la reivindicación 1 preparado según las reivindicaciones 2 a la 9 caracterizado porque la relación molar entre el silicio, expresado como SiO2, y el surfactante catiónico (sílice/surfactante) está comprendida entre 0,1 y 15.10) A process for obtaining the porous aluminosilicate type material described in claim 1 prepared according to claims 2 to 9 characterized because the molar ratio between silicon, expressed as SiO 2 , and the cationic surfactant (silica / surfactant) is between 0.1 and 15.
11) Un procedimiento de obtención del material de tipo aluminosilicato poroso descrito en la reivindicación 1 preparado según las reivindicaciones 2 a 10 caracterizado porque la disolución B puede contener una proporción del total de disolvente empleado en la preparación comprendida entre el 1% y el 95%.11) A process for obtaining the porous aluminosilicate type material described in claim 1 prepared according to claims 2 to 10, characterized in that the solution B can contain a proportion of the total solvent used in the preparation between 1% and 95% .
12) Un procedimiento de obtención del material de tipo aluminosilicato poroso descrito en la reivindicación 1 preparado según las reivindicaciones 2 a 11 caracterizado porque el disolvente empleado para preparar la disolución B puede ser agua, uno o más alcoholes o una mezcla de agua y alcoholes; estos alcoholes pueden ser lineales o ramificados, y pueden contener un número de átomos de carbono comprendido entre 1 y 6.12) A process for obtaining the porous aluminosilicate type material described in claim 1 prepared according to claims 2 to 11, characterized in that the solvent used to prepare solution B can be water, one or more alcohols or a mixture of water and alcohols; These alcohols can be linear or branched, and can contain a number of carbon atoms between 1 and 6.
13) Un procedimiento de obtención del material de tipo aluminosilicato poroso descrito en la reivindicación 1 preparado según las reivindicaciones 2 a 12 caracterizado porque la disolución B puede contener tetrapropilamonio y opcionalmente también sodio, en una proporción no superior al 90% del tetrapropilamonio y el 90% del sodio contenido en total en las disoluciones A y B.13) A process for obtaining the porous aluminosilicate type material described in claim 1 prepared according to claims 2 to 12, characterized in that solution B may contain tetrapropylammonium and optionally also sodium, in a proportion not exceeding 90% of tetrapropylammonium and 90 % of sodium contained in total in solutions A and B.
14) Utilización del material de tipo aluminosilicato poroso según la reivindicación 1 obtenido según el procedimiento descrito en las reivindicaciones 2 a 13, como catalizador de reacciones de transformación de hidrocarburos, tales como craqueo, isomerización, transalquilación, alquilación, dimerización y polimerización.14) Use of the porous aluminosilicate type material according to claim 1 obtained according to the process described in claims 2 to 13, as a catalyst for hydrocarbon transformation reactions, such as cracking, isomerization, transalkylation, alkylation, dimerization and polymerization.
15) Utilización del material de tipo aluminosilicato poroso según la reivindicación 1 obtenido según el procedimiento descrito en las reivindicaciones 2 a 13, como catalizador en la reacción de transformación de xilenos. 15) Use of the porous aluminosilicate type material according to claim 1 obtained according to the process described in claims 2 to 13, as a catalyst in the xylenes transformation reaction.
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CN101829552A (en) * 2010-06-08 2010-09-15 浙江大学 Preparation method of mesoporous alumina catalyst
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