WO2013110838A1 - Itq-38 material, the method for the production thereof and the use thereof - Google Patents

Itq-38 material, the method for the production thereof and the use thereof Download PDF

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WO2013110838A1
WO2013110838A1 PCT/ES2013/070014 ES2013070014W WO2013110838A1 WO 2013110838 A1 WO2013110838 A1 WO 2013110838A1 ES 2013070014 W ES2013070014 W ES 2013070014W WO 2013110838 A1 WO2013110838 A1 WO 2013110838A1
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material according
value
procedure
infinity
obtaining
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Spanish (es)
French (fr)
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Manuel MOLINER MARÍN
Jorge GONZÁLEZ GONZÁLEZ
Avelino Corma Canos
Fernando REY GARCÍA
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Consejo Superior De Investigaciones Científicas (Csic)
Universidad Politécnica De Valencia
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    • 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
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/065—Galloaluminosilicates; Group IVB- metalloaluminosilicates; Ferroaluminosilicates
    • 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
    • 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
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
    • 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
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/12—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the replacing atoms being at least boron atoms
    • 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
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent

Definitions

  • This patent refers to the synthesis of a new porous crystalline material, ITQ-38, its method of preparation and its use in the catalytic conversion of organic compounds.
  • Zeolites are porous crystalline aluminosilicates that have found important applications as catalysts, adsorbents and ion exchangers. Many of these zeolitic materials have well-defined structures that form channels and cavities inside them of uniform size and shape that allow the adsorption of certain molecules, while preventing the passage into the glass of other molecules of size too large to diffuse through of the pores. This characteristic gives these materials molecular sieve properties. These molecular sieves can include in the Si network and other elements of group IIIA of the periodic system, all of them tetrahedrally coordinated, the tetrahedra being joined by their vertices through oxygen forming a three-dimensional network.
  • the negative charge generated by the elements of group IIIA in network positions is compensated by the presence in the cation crystal, such as alkaline or alkaline earth.
  • cation crystal such as alkaline or alkaline earth.
  • One type of cation can be totally or partially exchanged for another type of cations by ion exchange techniques, thus being able to vary the properties of a given silicate by selecting the desired cations.
  • zeolites have been synthesized in the presence of an organic molecule that acts as a structure directing agent.
  • Organic molecules that act as structure directing agents can contain nitrogen, phosphorus or PN bonds in their composition, and can lead to stable organic cations in the reaction medium.
  • the mobilization of the silica can be carried out in the presence of groups y ⁇ and basic medium, which can be introduced as hydroxide of the same ADE, such as for example tetrapropylammonium hydroxide in the case of the zeolite ZSM-5.
  • a new ITQ-38 porous crystalline material which, both in its calcined and synthesized form without calcining, has a powder X-ray diffraction pattern that is different from other known zeolitic materials and whose diffraction lines are more important are given in Table 1 for the calcined form and in Table 2 for the uncalcined form.
  • Table 1 Table 1
  • X-ray diffractograms were obtained with a Panalytical X'Pert Pro diffractometer equipped with a fixed divergence slit using radiation K a of copper.
  • the diffraction data was recorded by a 2 ⁇ step of 0.01 ° in which ⁇ is the Bragg angle and a count time of 10 seconds per step.
  • crystallographic changes may include small variations in the parameters of the unit cell and / or changes in the symmetry of the crystal, without a change in structure. These modifications, which also include changes in relative intensities, may also be due to differences in the type and amount of compensation cations, network composition, crystal size and shape thereof, preferred orientation or the type of thermal or hydrothermal treatments suffered .
  • ITQ-38 has a molar composition in its calcined and anhydrous state that is given by the equation:
  • X is a trivalent element selected from Al, B, Fe, In, Ga, Cr, or mixtures thereof;
  • Y is a tetravalent element selected from Ti, Sn, Zr, V or mixtures thereof, preferably from Ti, Sn, Zr, or mixtures thereof;
  • Z is a tetravalent element selected from Si, Ge or mixtures thereof, preferably Si;
  • z / y is between 5 and infinity, preferably between 10 and infinity, and more preferably between 10 and 150.
  • the value of x can be equal to zero, so it can have a chemical composition:
  • the value of z / y is between 5 and infinity, preferably between 10 and infinity, and more preferably between 10 and 150.
  • the value of y can be equal to zero, so it can have a chemical composition:
  • the value of z / x is between 9 and infinity, preferably between 20 and infinity.
  • the microporous crystalline material may have a chemical composition:
  • R is a structure directing agent, preferably selected from an amine, a tetraalkylammonium salt, an organic molecule containing P, or an organic molecule containing P-N bonds and combinations thereof;
  • n / (x + y + z) is between 3 and 0.000, preferably between 1 and 0.001, and more preferably between 1 and 0.05,
  • the structure directing agent is a tetraalkylammonium salt, and is preferably 1, l-dimethyl-4- (1-methylpyrrolidino-1-yl) piperidine hydroxide (ADE1).
  • the value of x can be zero whereby the crystalline material can have the following chemical composition:
  • n / (y + z) is between 3 and 0.000, preferably between 1 and 0.001, and more preferably between 1 and 0.05; the value of z / y is between 5 and infinity, preferably between 10 and infinity, and more preferably between 10 and 150.
  • the crystalline material could have the following chemical composition:
  • the value of z / x is between 9 and infinity, more preferably between 20 and infinity;
  • n / (x + z) is between 3 and 0.000, preferably between 1 and 0.001, and more preferably between 1 and 0.05.
  • the organic component of the Structure Director Agent can be removed, for example, by extraction or by heat treatment by heating at a temperature above 250 ° C for a period of time between 2 minutes and 25 hours, preferably between 1 hour and 8 hours.
  • the compensation cations in the material in its uncalcined form, or after thermal treatment can be exchanged in the case of being present, by other cations such as metal ions, H + and H + precursors such as NH + .
  • cations that can be introduced by ion exchange those that can have a positive role in the activity of the material as a catalyst are preferred, and more specifically cations such as H + , rare earth cations, and group VIII metals are preferred, as well as of the group HA, IIIA, VAT, VA, IB, IIB, IIIB, IVB, VB, VIIB of the periodic table of the elements.
  • the described crystalline material can also be combined intimately with hydrogenating-dehydrogenating components preferably selected from platinum, palladium, nickel, rhenium, cobalt, tungsten, molybdenum, vanadium, chromium, manganese, iron and combinations thereof.
  • hydrogenating-dehydrogenating components preferably selected from platinum, palladium, nickel, rhenium, cobalt, tungsten, molybdenum, vanadium, chromium, manganese, iron and combinations thereof.
  • the introduction of these elements can be carried out in the crystallization stage, by exchange (if place), 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.
  • the present invention also relates to the method of preparing the ITQ-38 crystalline material described above.
  • a method of preparing the material may comprise at least the following steps: a) preparation of a mixture containing at least 3 ⁇ 40, an oxide or other source of the tetravalent material Z, a structure directing agent (R); a source of the trivalent element X, an oxide or other source of the tetravalent material Y, where the synthesis mixture has a molar composition of oxides in the following ranges:
  • X is a trivalent element selected from Al, B, Fe, In, Ga, Cr, or mixtures thereof;
  • Y is a tetravalent element selected from Ti, Sn, Zr, V or mixtures thereof, preferably from Ti, Sn,
  • Z is a tetravalent element selected from Si, Ge or mixtures thereof, preferably Si;
  • R is a structure directing agent, preferably selected from an amine, a tetraalkylammonium salt, an organic molecule containing P, or an organic molecule containing PN bonds and combinations thereof, preferably it is a salt of tetraalkylammonium, and more preferably it is 1, l-dimethyl-4- (1-methylpyrrolidino-l-yl) piperidine hydroxide
  • the value of z / y is between 5 and infinity, preferably between 10 and infinity, and more preferably between 10 and 150;
  • n / (x + y + z) is between 3 and 0.000, preferably between 1 and 0.001, and more preferably between 1 and 0.05.
  • the range Si02 / GeC> 2 would be greater than 1, preferably greater than 2.
  • the value of x can be zero whereby the crystalline material obtained with the process of the present invention can have the following chemical composition:
  • n / (y + z) is between 3 and 0.000, preferably between 1 and 0.001, and more preferably between 1 and 0.05;
  • z / y is between 5 and infinity, preferably between 10 and infinity, and more preferably between 10 and 150.
  • the crystalline material obtained with the process of the present invention could have the following chemical composition:
  • the value of z / x is between 9 and infinity, more preferably between 20 and infinity;
  • the ITQ-38 crystalline material can be prepared from a reaction mixture containing 3 ⁇ 40, optionally an oxide or a source of the trivalent element X, such as Al and / or B, an oxide or a source of the tetravalent element or elements Z, such as Si; a source of Ge, such as GeC> 2, and an organic structure directing agent (R) generally a quaternary ammonium salt, preferably the hydroxide.
  • Organic structure directing agents (R) containing P or PN bonds, can also be introduced into the reaction mixture.
  • the crystallization of ITQ-38 can be carried out in static or stirring, in autoclaves at a temperature between 80 and 200 ° C, at times sufficient to achieve crystallization, for example between 12 hours and 60 days.
  • ITQ-38 crystals are separated from the mother liquors, and recovered. It should be taken into account that the components of the synthesis mixture can come from different sources, and depending on these, crystallization times and conditions may vary.
  • ITQ-38 crystals can be added as seeds, in amounts of up to 25% by weight with respect to the total oxides, to the synthesis mixture. These can be added before or during the crystallization of ITQ-38.
  • the process of obtaining the crystalline material may comprise a step of calcining said crystalline material that can be carried out at a temperature selected between 200 and 1000 ° C.
  • the calcined crystalline material may undergo a washing process that may comprise at least:
  • a solution is selected from an aqueous, alcoholic, organic solution or mixture thereof.
  • This washing step can preferably be carried out at a temperature between 0 and 200 ° C.
  • the calcined ITQ-38 material or the calcined and washed ITQ-38 material may be subjected to one or more post-synthesis treatments.
  • said post-synthesis treatment may comprise at least: a) suspend in a solution containing at least one trivalent element X selected from Al, Ga, B, Cr, Fe,
  • said solution is selected from an aqueous, alcoholic, organic solution or mixture of both.
  • steps a and b of the post-synthesis treatment are carried out at a temperature between 0 and 200 ° C.
  • the present invention also relates to the use of ITQ-38 material for the conversion of organic compounds.
  • the material described above and obtained according to the method of obtaining described above can be used for the transformation of organic compounds, preferably to convert feeds formed by organic compounds into products of greater added value.
  • the ITQ-38 material can be used in hydrocarbon catalytic cracking processes.
  • the ITQ-38 material can be used in alkylation processes of aromatic compounds with alcohols or olefins.
  • the material described according to the present invention can be pelletized according to known techniques, and can be used as a cracking catalyst component.
  • Example 1 Synthesis of the structure directing agent: 1, l-dimethyl-4- (1-methylpyrrolidino-l-yl) piperidinium hydroxide (ADE1)
  • the quaternization of the diamine is carried out as follows: on a solution of 10.4 g of diamine in 80 ml of MeOH 42.2 g of methyl iodide are added. The mixture is kept under continuous stirring at room temperature for 7 days, forming a white precipitate. This solid is filtered under vacuum. Its characterization is done by elemental analysis and magnetic resonance.
  • R is ADE1.
  • the gel is heated for 14 days in steel autoclaves with an internal Teflon sheath at 175 ° C in static.
  • the solid obtained after filtering, washing with distilled water and drying at 100 ° C is ITQ-38.
  • the material is calcined at 540 ° C for 3 hours in air flow to remove organic matter.
  • the powder X-ray diffraction pattern of the solid contains the characteristic peaks of the ITQ-38 zeolite, shown in Table 1.
  • the gel is heated for 14 days in steel autoclaves with an internal Teflon sheath at 175 ° C in static.
  • the solid obtained after filtering, washing with distilled water and drying at 100 ° C shows the characteristic peaks of the ITQ-38 zeolite.
  • R is ADE1.
  • the gel is heated for 14 days in steel autoclaves with an internal Teflon sheath at 175 ° C in static.
  • the solid obtained after filtering, washing with distilled water and drying at 100 ° C shows the characteristic peaks of the ITQ-38 zeolite.
  • R is ADE1.
  • the gel is heated for 14 days in steel autoclaves with an internal Teflon sheath at 175 ° C in static.
  • the solid obtained after filtering, washing with distilled water and drying at 100 ° C shows the characteristic peaks of the ITQ-38 zeolite.
  • R is ADE1.
  • the gel is heated for 14 days in steel autoclaves with an internal Teflon sheath at 175 ° C in static.
  • the solid obtained after filtering, washing with distilled water and drying at 100 ° C shows the characteristic peaks of the ITQ-38 zeolite.

Abstract

ITQ-38 material, the method for the production thereof and the use thereof. The present invention relates to a crystalline material known as ITQ-38 that has a molar composition in the calcined and anhydrous state thereof that is given by the equation: x X2O3 : y YO2 : z ZO2, wherein:·X is a trivalent element selected from Al, B, Fe, In, Ga, Cr, or mixtures thereof; ·Y is a tetravalent element selected from Ti, Sn, Zr, V or mixtures thereof, preferably from Ti, Sn, Zr, or mixtures thereof; ·Z is a tetravalent element selected from Si, Ge or mixtures thereof, preferably Si; ·the value of (y+z)/x is between 9 and infinity, preferably between 20 and infinity; ·the value of z/y is between 5 and infinity, preferably between 10 and infinity, and more preferably between 10 and 150.

Description

MATERIAL ITQ-38, SU PROCEDIMIENTO DE OBTENCIÓN Y SU USO Campo de la técnica  ITQ-38 MATERIAL, ITS OBTAINING PROCEDURE AND ITS USE Field of technique
Esta patente se refiere a la síntesis de un nuevo material cristalino poroso, ITQ-38, a su método de preparación y a su uso en la conversión catalítica de compuestos orgánicos.  This patent refers to the synthesis of a new porous crystalline material, ITQ-38, its method of preparation and its use in the catalytic conversion of organic compounds.
Antecedentes Background
Las zeolitas son aluminosilicatos cristalinos porosos que han encontrado importantes aplicaciones como catalizadores, adsorbentes e intercambiadores iónicos. Muchos de estos materiales zeolíticos tienen estructuras bien definidas que forman canales y cavidades en su interior de tamaño y forma uniforme que permiten la adsorción de determinadas moléculas, mientras que impiden el paso al interior del cristal de otras moléculas de tamaño demasiado grande para difundir a través de los poros. Esta característica confiere a estos materiales propiedades de tamiz molecular. Estos tamices moleculares pueden incluir en la red Si y otros elementos del grupo IIIA del sistema periódico, todos ellos tetraédricamente coordinados, estando los tetraedros unidos por sus vértices a través de oxígenos formando una red tridimensional. La carga negativa generada por los elementos del grupo IIIA en posiciones de red está compensada por la presencia en el cristal de cationes, como por ejemplo alcalinos o alcalinotérreos . Un tipo de catión puede ser intercambiado total o parcialmente por otro tipo de cationes mediante técnicas de intercambio iónico, pudiendo variar así las propiedades de un silicato dado seleccionando los cationes deseados .  Zeolites are porous crystalline aluminosilicates that have found important applications as catalysts, adsorbents and ion exchangers. Many of these zeolitic materials have well-defined structures that form channels and cavities inside them of uniform size and shape that allow the adsorption of certain molecules, while preventing the passage into the glass of other molecules of size too large to diffuse through of the pores. This characteristic gives these materials molecular sieve properties. These molecular sieves can include in the Si network and other elements of group IIIA of the periodic system, all of them tetrahedrally coordinated, the tetrahedra being joined by their vertices through oxygen forming a three-dimensional network. The negative charge generated by the elements of group IIIA in network positions is compensated by the presence in the cation crystal, such as alkaline or alkaline earth. One type of cation can be totally or partially exchanged for another type of cations by ion exchange techniques, thus being able to vary the properties of a given silicate by selecting the desired cations.
Muchas zeolitas han sido sintetizadas en presencia de una molécula orgánica que actúa como agente director de estructura. Las moléculas orgánicas que actúan como agentes directores de estructura (ADE) pueden contener nitrógeno, fósforo o enlaces P-N en su composición, y pueden dar lugar a cationes orgánicos estables en el medio de reacción. La movilización de la sílice se puede llevar a cabo en presencia de grupos ΟΗ~ y medio básico, que puede introducirse como hidróxido del mismo ADE, como por ejemplo hidróxido de tetrapropilamonio en el caso de la zeolita ZSM- 5. Many zeolites have been synthesized in the presence of an organic molecule that acts as a structure directing agent. Organic molecules that act as structure directing agents (ADE) can contain nitrogen, phosphorus or PN bonds in their composition, and can lead to stable organic cations in the reaction medium. The mobilization of the silica can be carried out in the presence of groups y ~ and basic medium, which can be introduced as hydroxide of the same ADE, such as for example tetrapropylammonium hydroxide in the case of the zeolite ZSM-5.
Descripción de la invención  Description of the invention
En la presente invención se presenta un nuevo material cristalino poroso ITQ-38 que, tanto en su forma calcinada como sintetizada sin calcinar tiene un patrón de difracción de rayos X en polvo que es diferente al de otros materiales zeolíticos conocidos y cuyas líneas de difracción más importantes vienen dadas en la Tabla 1 para la forma calcinada y en la Tabla 2 para la forma sin calcinar. Tabla 1  In the present invention, a new ITQ-38 porous crystalline material is presented which, both in its calcined and synthesized form without calcining, has a powder X-ray diffraction pattern that is different from other known zeolitic materials and whose diffraction lines are more important are given in Table 1 for the calcined form and in Table 2 for the uncalcined form. Table 1
(d ± 0.4) Intensidad  (d ± 0.4) Intensity
(Á) Relativa  (Á) Relative
20,8 md  20.8 md
12,8 d  12.8 d
12,6 d  12.6 d
11,6 md  11.6 md
10,4 mf  10.4 mf
9,0 md Tabla 2  9.0 md Table 2
(d ± 0.4) Intensidad  (d ± 0.4) Intensity
(Á) Relativa  (Á) Relative
20,8 md  20.8 md
12,8 md  12.8 md
12,6 md  12.6 md
11,6 md  11.6 md
10,4 mf  10.4 mf
9,0 md  9.0 md
Estos difractogramas de rayos X se obtuvieron con un difractómetro Panalytical X'Pert Pro equipado con una rendija de divergencia fija utilizando la radiación Ka del cobre. Los datos de difracción se registraron mediante un paso de 2Θ de 0.01° en el que Θ es el ángulo de Bragg y un tiempo de cuenta de 10 segundos por paso. Los espaciados interplanares , d, se calcularon en Amgstrons, y la intensidad relativa de las lineas se calcula como el porcentaje respecto del pico más intenso, y se considera muy fuerte (mf)= 80-100, fuerte (f)=60-80, media (m) = 40-60, débil (d)=20-40, y muy débil (md)= 0-20. These X-ray diffractograms were obtained with a Panalytical X'Pert Pro diffractometer equipped with a fixed divergence slit using radiation K a of copper. The diffraction data was recorded by a 2Θ step of 0.01 ° in which Θ is the Bragg angle and a count time of 10 seconds per step. The inter-planar spacings, d, were calculated in Amgstrons, and the relative intensity of the lines is calculated as the percentage with respect to the most intense peak, and is considered very strong (mf) = 80-100, strong (f) = 60-80 , mean (m) = 40-60, weak (d) = 20-40, and very weak (md) = 0-20.
Otras lineas características del patrón de difracción de rayos X en polvo de la zeolita ITQ-38 en su forma calcinada y en su forma sin calcinar, se muestran tabuladas en las Tablas 3 y 4, respectivamente.  Other characteristic lines of the X-ray powder diffraction pattern of the ITQ-38 zeolite in its calcined form and in its uncalcined form, are shown tabulated in Tables 3 and 4, respectively.
Tabla 3 Table 3
(d ± 0.4) Intensidad  (d ± 0.4) Intensity
(Á) Relativa  (Á) Relative
20, 8 md  20.8 md
12, 8 d  12, 8 d
12, 6 d  12, 6 d
11, 6 md  11.6 md
10,4 mf  10.4 mf
9, 0 md  9.0 md
8, 6 d  8, 6 d
8,1 md  8.1 md
6, 4 md  6, 4 md
5,9 md  5.9 md
5, 6 md  5, 6 md
4,7 md  4.7 md
4,5 md  4.5 md
4,3 md  4.3 md
4,1 md  4.1 md
4,0 md  4.0 md
3,9 md  3.9 md
3, 8 md 3,5 md3, 8 md 3.5 md
3,3 md3.3 md
3,2 md3.2 md
3,2 md 3.2 md
Tabla 4Table 4
(d ± 0.4) Intensidad(d ± 0.4) Intensity
(Á) Relativa(Á) Relative
20, 8 md20.8 md
12, 8 md12.8 md
12, 6 md12.6 md
11, 6 md11.6 md
10,4 mf10.4 mf
9, 0 md9.0 md
8,5 d8.5 d
8, 0 md8.0 md
6, 4 md6, 4 md
5, 6 md5, 6 md
5, 4 md5, 4 md
4, 9 md4, 9 md
4,7 md4.7 md
4,5 md4.5 md
4,3 md4.3 md
4, 1 md4, 1 md
4, 0 d4, 0 d
3, 9 md3, 9 md
3, 8 md3, 8 md
3,7 md3.7 md
3,5 md3.5 md
3,4 md3.4 md
3,3 md3.3 md
3,2 md3.2 md
3,2 md Debe tenerse en cuenta que los datos de difracción listados para esta muestra como lineas sencillas o únicas, pueden estar formados por múltiples solapamientos o superposición de reflexiones que, en ciertas condiciones, tales como diferencias en cambios cristalográficos, pueden aparecer como lineas resueltas o parcialmente resueltas. Generalmente, los cambios cristalográficos pueden incluir pequeñas variaciones en los parámetros de la celda unidad y/o cambios en la simetría del cristal, sin que se produzca un cambio en la estructura. Estas modificaciones, que incluyen también cambios en intensidades relativas, pueden deberse también a diferencias en el tipo y cantidad de cationes de compensación, composición de red, tamaño de cristal y forma de los mismos, orientación preferente o al tipo de tratamientos térmicos o hidrotérmicos sufridos. 3.2 md It should be borne in mind that the diffraction data listed for this sample as single or single lines may be formed by multiple overlaps or overlapping reflections that, under certain conditions, such as differences in crystallographic changes, may appear as resolved or partially resolved lines. . Generally, crystallographic changes may include small variations in the parameters of the unit cell and / or changes in the symmetry of the crystal, without a change in structure. These modifications, which also include changes in relative intensities, may also be due to differences in the type and amount of compensation cations, network composition, crystal size and shape thereof, preferred orientation or the type of thermal or hydrothermal treatments suffered .
El material cristalino de esta invención denominado ITQ- 38 tiene una composición molar en su estado calcinado y anhidro que viene dado por la ecuación:  The crystalline material of this invention called ITQ-38 has a molar composition in its calcined and anhydrous state that is given by the equation:
x X203 : y Y02 : z Z02 x X 2 0 3 : y Y0 2 : z Z0 2
donde: where:
X es un elemento trivalente seleccionado entre Al, B, Fe, In, Ga, Cr, o mezclas de estos;  X is a trivalent element selected from Al, B, Fe, In, Ga, Cr, or mixtures thereof;
Y es un elemento tetravalente seleccionado entre Ti, Sn, Zr, V o mezclas de ellos, preferentemente entre Ti, Sn, Zr, o mezclas de los mismos;  Y is a tetravalent element selected from Ti, Sn, Zr, V or mixtures thereof, preferably from Ti, Sn, Zr, or mixtures thereof;
Z es un elemento tetravalente seleccionado entre Si, Ge o mezclas de ellos, preferentemente Si;  Z is a tetravalent element selected from Si, Ge or mixtures thereof, preferably Si;
el valor de (y+z)/x está comprendido entre 9 e infinito, preferentemente entre 20 e infinito;  the value of (y + z) / x is between 9 and infinity, preferably between 20 and infinity;
· el valor de z/y está comprendido entre 5 e infinito, preferentemente entre 10 e infinito, y más preferentemente entre 10 y 150.  · The value of z / y is between 5 and infinity, preferably between 10 and infinity, and more preferably between 10 and 150.
Según una realización particular de la presente invención, el valor de x puede ser igual a cero por lo que puede poseer una composición química:  According to a particular embodiment of the present invention, the value of x can be equal to zero, so it can have a chemical composition:
y Y02 : z Z02 and Y0 2 : z Z0 2
donde : el valor de z/y está entre 5 e infinito, preferentemente entre 10 e infinito, y más preferentemente entre 10 y 150. where : the value of z / y is between 5 and infinity, preferably between 10 and infinity, and more preferably between 10 and 150.
Según otra realización particular de la presente invención, el valor de y puede ser igual a cero por lo que puede poseer una composición química:  According to another particular embodiment of the present invention, the value of y can be equal to zero, so it can have a chemical composition:
x X203 : z Z02 x X 2 0 3 : z Z0 2
donde : where :
el valor de z/x está comprendido entre 9 e infinito, preferentemente entre 20 e infinito.  The value of z / x is between 9 and infinity, preferably between 20 and infinity.
Según otra realización particular, el material cristalino microporoso puede poseer una composición química:  According to another particular embodiment, the microporous crystalline material may have a chemical composition:
n R : x X203 : z Z02 : y Y02 n R: x X 2 0 3 : z Z0 2 : y Y0 2
donde : where :
R es un agente director de estructura, seleccionado preferentemente entre una amina, una sal de tetraalquilamonio, una molécula orgánica que contiene P, o una molécula orgánica que contiene enlaces P-N y combinaciones de los mismos;  R is a structure directing agent, preferably selected from an amine, a tetraalkylammonium salt, an organic molecule containing P, or an organic molecule containing P-N bonds and combinations thereof;
· el valor de n/(x+y+z) está comprendido entre 3 y 0.000, preferentemente entre 1 y 0.001, y más preferentemente entre 1 y 0.05,  · The value of n / (x + y + z) is between 3 and 0.000, preferably between 1 and 0.001, and more preferably between 1 and 0.05,
y porque tiene un patrón de rayos X representado en la tabla 2. and because it has an x-ray pattern represented in table 2.
Según una realización particular el agente director de estructura es una sal de tetraalquilamonio, y de manera preferente es hidróxido de 1 , l-dimetil-4- ( 1-metilpirrolidino- 1-il ) piperidino (ADE1) .  According to a particular embodiment, the structure directing agent is a tetraalkylammonium salt, and is preferably 1, l-dimethyl-4- (1-methylpyrrolidino-1-yl) piperidine hydroxide (ADE1).
Según una realización particular de la presente invención, el valor de x puede ser cero por lo que el material cristalino puede tener la siguiente composición química :  According to a particular embodiment of the present invention, the value of x can be zero whereby the crystalline material can have the following chemical composition:
n R : y Y02 : z Z02 n R: y Y0 2 : z Z0 2
donde : where :
· el valor de n/(y+z) está comprendido entre 3 y 0.000, preferentemente entre 1 y 0.001, y más preferentemente entre 1 y 0.05; el valor de z/y está entre 5 e infinito, preferentemente entre 10 e infinito, y más preferentemente entre 10 y 150. · The value of n / (y + z) is between 3 and 0.000, preferably between 1 and 0.001, and more preferably between 1 and 0.05; the value of z / y is between 5 and infinity, preferably between 10 and infinity, and more preferably between 10 and 150.
También puede ocurrir que el valor de y sea igual a cero. Según esta realización particular, el material cristalino podría tener la siguiente composición química:  It may also happen that the value of y is equal to zero. According to this particular embodiment, the crystalline material could have the following chemical composition:
n R : x X203 : z Z02 n R: x X 2 0 3 : z Z0 2
donde : where :
el valor de z/x está comprendido entre 9 e infinito, más preferentemente entre 20 e infinito;  the value of z / x is between 9 and infinity, more preferably between 20 and infinity;
el valor de n/(x+z) está comprendido entre 3 y 0.000, preferentemente entre 1 y 0.001, y más preferentemente entre 1 y 0.05.  the value of n / (x + z) is between 3 and 0.000, preferably between 1 and 0.001, and more preferably between 1 and 0.05.
Según una realización particular de la presente invención, el componente orgánico del Agente Director de Estructura, se puede eliminar, por ejemplo, por extracción o por tratamiento térmico calentando a temperatura por encima de 250°C durante un periodo de tiempo comprendido entre 2 minutos y 25 horas, preferentemente entre 1 hora y 8 horas.  According to a particular embodiment of the present invention, the organic component of the Structure Director Agent can be removed, for example, by extraction or by heat treatment by heating at a temperature above 250 ° C for a period of time between 2 minutes and 25 hours, preferably between 1 hour and 8 hours.
Los cationes de compensación en el material en su forma sin calcinar, o después de un tratamiento térmico, pueden intercambiarse, en el caso de estar presentes, por otros cationes tales como iones metálicos, H+ y precursores de H+ como por ejemplo NH+ . Entre los cationes que pueden introducirse por intercambio iónico se prefieren aquellos que pueden tener un papel positivo en la actividad del material como catalizador, y más específicamente se prefieren cationes tales como H+, cationes de tierras raras, y metales del grupo VIII, así como del grupo HA, IIIA, IVA, VA, IB, IIB, IIIB, IVB, VB, VIIB de la tabla periódica de los elementos. The compensation cations in the material in its uncalcined form, or after thermal treatment, can be exchanged in the case of being present, by other cations such as metal ions, H + and H + precursors such as NH + . Among the cations that can be introduced by ion exchange, those that can have a positive role in the activity of the material as a catalyst are preferred, and more specifically cations such as H + , rare earth cations, and group VIII metals are preferred, as well as of the group HA, IIIA, VAT, VA, IB, IIB, IIIB, IVB, VB, VIIB of the periodic table of the elements.
Según una realización particular de la presente invención, el material cristalino descrito puede, además, combinarse íntimamente con componentes hidrogenantes- deshidrogenantes seleccionados preferentemente entre platino, paladio, níquel, renio, cobalto, tungsteno, molibdeno, vanadio, cromo, manganeso, hierro y combinaciones de los mismos. La introducción de estos elementos se puede llevar a cabo en la etapa de cristalización, por intercambio (si ha lugar), y/o por impregnación o por mezcla física. Estos elementos pueden ser introducidos en su forma catiónica y/o a partir de sales u otros compuestos que por descomposición generen el componente metálico u óxido en su forma catalítica adecuada . According to a particular embodiment of the present invention, the described crystalline material can also be combined intimately with hydrogenating-dehydrogenating components preferably selected from platinum, palladium, nickel, rhenium, cobalt, tungsten, molybdenum, vanadium, chromium, manganese, iron and combinations thereof. The introduction of these elements can be carried out in the crystallization stage, by exchange (if place), 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.
La presente invención se refiere, también, al procedimiento de preparación del material cristalino ITQ-38 descrito anteriormente. Un procedimiento de preparación del material puede comprender, al menos, los siguientes pasos: a) preparación de una mezcla que contiene, al menos, ¾0, un óxido u otra fuente del material tetravalente Z, un agente director de estructura (R) ; una fuente del elemento trivalente X, un óxido u otra fuente del material tetravalente Y, donde la mezcla de síntesis tiene una composición molar de óxidos en los siguientes rangos:  The present invention also relates to the method of preparing the ITQ-38 crystalline material described above. A method of preparing the material may comprise at least the following steps: a) preparation of a mixture containing at least ¾0, an oxide or other source of the tetravalent material Z, a structure directing agent (R); a source of the trivalent element X, an oxide or other source of the tetravalent material Y, where the synthesis mixture has a molar composition of oxides in the following ranges:
Reactivos Útil Preferido Reagents Useful Preferred
( YO2+ Z O2 ) /X2O3 mayor de mayor de 9  (YO2 + Z O2) / X2O3 greater than greater than 9
H20/ ( YO2+ Z O2 ) 1-50 2-30 H 2 0 / (YO2 + Z O2) 1-50 2-30
R/ (Y02 + Z02 ) 0.000-3.0 0.05-1.0 R / (Y0 2 + Z0 2 ) 0.000-3.0 0.05-1.0
Z O2 / YO2 mayor de 10-150 b) mantener la mezcla a una temperatura entre 80 y 200°C hasta que se formen los cristales del material;  Z O2 / YO2 greater than 10-150 b) keep the mixture at a temperature between 80 and 200 ° C until the crystals of the material form;
c) recuperación del material cristalino,  c) recovery of the crystalline material,
donde : where :
X es un elemento trivalente seleccionado entre Al, B, Fe, In, Ga, Cr, o mezclas de estos;  X is a trivalent element selected from Al, B, Fe, In, Ga, Cr, or mixtures thereof;
Y es un elemento tetravalente seleccionado entre Ti, Sn, Zr, V o mezclas de ellos, preferentemente entre Ti, Sn, Y is a tetravalent element selected from Ti, Sn, Zr, V or mixtures thereof, preferably from Ti, Sn,
Zr, o mezclas de los mismos; Zr, or mixtures thereof;
Z es un elemento tetravalente seleccionado entre Si, Ge o mezclas de ellos, preferentemente Si;  Z is a tetravalent element selected from Si, Ge or mixtures thereof, preferably Si;
R es un agente director de estructura, seleccionado preferentemente entre una amina, una sal de tetraalquilamonio, una molécula orgánica que contiene P, o una molécula orgánica que contiene enlaces P-N y combinaciones de los mismos, preferentemente es una sal de tetraalquilamonio, y más preferentemente es hidróxido de 1 , l-dimetil-4- ( 1-metilpirrolidino-l-il ) piperidinoR is a structure directing agent, preferably selected from an amine, a tetraalkylammonium salt, an organic molecule containing P, or an organic molecule containing PN bonds and combinations thereof, preferably it is a salt of tetraalkylammonium, and more preferably it is 1, l-dimethyl-4- (1-methylpyrrolidino-l-yl) piperidine hydroxide
(ADE1) ; (ADE1);
el valor de (y+z)/x está comprendido entre 9 e infinito, preferentemente entre 20 e infinito;  the value of (y + z) / x is between 9 and infinity, preferably between 20 and infinity;
el valor de z/y está comprendido entre 5 e infinito, preferentemente entre 10 e infinito, y más preferentemente entre 10 y 150;  the value of z / y is between 5 and infinity, preferably between 10 and infinity, and more preferably between 10 and 150;
el valor de n/(x+y+z) está comprendido entre 3 y 0.000, preferentemente entre 1 y 0.001, y más preferentemente entre 1 y 0.05.  the value of n / (x + y + z) is between 3 and 0.000, preferably between 1 and 0.001, and more preferably between 1 and 0.05.
Según una realización particular en la que Z es una mezcla de Si y Ge, el rango Si02/GeC>2 seria mayor de 1, preferentemente mayor de 2.  According to a particular embodiment in which Z is a mixture of Si and Ge, the range Si02 / GeC> 2 would be greater than 1, preferably greater than 2.
Según una realización particular de la presente invención, el valor de x puede ser cero por lo que el material cristalino obtenido con el procedimiento de la presente invención puede tener la siguiente composición química :  According to a particular embodiment of the present invention, the value of x can be zero whereby the crystalline material obtained with the process of the present invention can have the following chemical composition:
n R : y Y02 : z Z02 n R: y Y0 2 : z Z0 2
donde : where :
el valor de n/(y+z) está comprendido entre 3 y 0.000, preferentemente entre 1 y 0.001, y más preferentemente entre 1 y 0.05;  the value of n / (y + z) is between 3 and 0.000, preferably between 1 and 0.001, and more preferably between 1 and 0.05;
· el valor de z/y está comprendido entre 5 e infinito, preferentemente entre 10 e infinito, y más preferentemente entre 10 y 150.  · The value of z / y is between 5 and infinity, preferably between 10 and infinity, and more preferably between 10 and 150.
También puede ocurrir que el valor de y sea igual a cero. Según esta realización particular, el material cristalino obtenido con el procedimiento de la presente invención podría tener la siguiente composición química:  It may also happen that the value of y is equal to zero. According to this particular embodiment, the crystalline material obtained with the process of the present invention could have the following chemical composition:
n R : x X203 : z Z02 n R: x X 2 0 3 : z Z0 2
donde : where :
el valor de z/x está comprendido entre 9 e infinito, más preferentemente entre 20 e infinito;  the value of z / x is between 9 and infinity, more preferably between 20 and infinity;
el valor de n/(x+z) está comprendido entre 3 y 0.000, preferentemente entre 1 y 0.001, y más preferentemente entre 1 y 0.05. Según una realización particular, el material cristalino ITQ-38, se puede preparar a partir de una mezcla de reacción que contiene ¾0, opcionalmente un óxido o una fuente del elemento trivalente X, como por ejemplo Al y/o B, un óxido o una fuente del elemento o elementos tetravalentes Z, como por ejemplo Si; una fuente de Ge, como por ejemplo GeC>2, y un agente orgánico director de estructura (R) generalmente una sal de amonio cuaternario, preferentemente el hidróxido . Agentes orgánicos directores de estructura (R) , que contengan P o enlaces P-N, también pueden ser introducidos en la mezcla reactiva . the value of n / (x + z) is between 3 and 0.000, preferably between 1 and 0.001, and more preferably between 1 and 0.05. According to a particular embodiment, the ITQ-38 crystalline material can be prepared from a reaction mixture containing ¾0, optionally an oxide or a source of the trivalent element X, such as Al and / or B, an oxide or a source of the tetravalent element or elements Z, such as Si; a source of Ge, such as GeC> 2, and an organic structure directing agent (R) generally a quaternary ammonium salt, preferably the hydroxide. Organic structure directing agents (R), containing P or PN bonds, can also be introduced into the reaction mixture.
La cristalización de ITQ-38 se puede llevar a cabo en estático o en agitación, en autoclaves a temperatura comprendida entre 80 y 200°C, a tiempos suficientes para conseguir la cristalización, por ejemplo entre 12 horas y 60 días .  The crystallization of ITQ-38 can be carried out in static or stirring, in autoclaves at a temperature between 80 and 200 ° C, at times sufficient to achieve crystallization, for example between 12 hours and 60 days.
Al finalizar la etapa de cristalización, se separan los cristales de ITQ-38 de las aguas madres, y se recuperan. Debe tenerse en cuenta que los componentes de la mezcla de síntesis pueden provenir de distintas fuentes, y dependiendo de estos pueden variar tiempos y condiciones de cristalización. Con el fin de facilitar la síntesis, se pueden añadir cristales de ITQ-38 como semillas, en cantidades de hasta 25% en peso respecto del total de óxidos, a la mezcla de síntesis. Estas pueden ser adicionadas previamente o durante la cristalización de ITQ-38.  At the end of the crystallization stage, the ITQ-38 crystals are separated from the mother liquors, and recovered. It should be taken into account that the components of the synthesis mixture can come from different sources, and depending on these, crystallization times and conditions may vary. In order to facilitate synthesis, ITQ-38 crystals can be added as seeds, in amounts of up to 25% by weight with respect to the total oxides, to the synthesis mixture. These can be added before or during the crystallization of ITQ-38.
Según una realización particular de la presente invención, el proceso de obtención del material cristalino puede comprender un paso de calcinación de dicho material cristalino que se puede llevar a cabo a una temperatura seleccionada entre 200 y 1000°C.  According to a particular embodiment of the present invention, the process of obtaining the crystalline material may comprise a step of calcining said crystalline material that can be carried out at a temperature selected between 200 and 1000 ° C.
Además, según una realización particular, el material cristalino calcinado puede sufrir un proceso de lavado que puede comprender al menos:  In addition, according to a particular embodiment, the calcined crystalline material may undergo a washing process that may comprise at least:
a) suspensión del material en una disolución de un compuesto seleccionado entre un ácido, una base, una sal amónica, una sal sódica, de cualquier metal alcalino, cualquier metal alcalino-terreo o mezclas de ellos. De manera preferente dicha disolución está seleccionada entre una disolución acuosa, alcohólica, orgánica o mezcla de ellas. Esta etapa de lavado se puede llevar a cabo de manera preferente a una temperatura entre 0 y 200°C. a) suspension of the material in a solution of a compound selected from an acid, a base, an ammonium salt, a sodium salt, of any alkali metal, any alkaline earth metal or mixtures thereof. By way of Preferably said solution is selected from an aqueous, alcoholic, organic solution or mixture thereof. This washing step can preferably be carried out at a temperature between 0 and 200 ° C.
Además, el material ITQ-38 calcinado o el material ITQ-38 calcinado y lavado puede ser sometido a uno o más tratamientos post-sintesis . Según una realización particular, dicho tratamiento post-sintesis puede comprender al menos: a) suspender en una disolución que contiene al menos un elemento trivalente X seleccionado entre Al, Ga, B, Cr, Fe, In addition, the calcined ITQ-38 material or the calcined and washed ITQ-38 material may be subjected to one or more post-synthesis treatments. According to a particular embodiment, said post-synthesis treatment may comprise at least: a) suspend in a solution containing at least one trivalent element X selected from Al, Ga, B, Cr, Fe,
In o mezclas de ellos; preferentemente dicha disolución está seleccionada entre una disolución acuosa, alcohólica, orgánica o mezcla de ambas. In or mixtures of them; preferably said solution is selected from an aqueous, alcoholic, organic solution or mixture of both.
b) recuperación del sólido mediante filtración, centrifugación o cualquier técnica de separación de sólidos de líquidos;  b) recovery of the solid by filtration, centrifugation or any liquid solids separation technique;
c) activación del material mediante calcinación a temperaturas seleccionadas entre 200°C y 1000°C.  c) activation of the material by calcination at selected temperatures between 200 ° C and 1000 ° C.
Según una realización particular, los pasos a y b del tratamiento post-sintesis se llevan a cabo a una temperatura entre 0 y 200°C.  According to a particular embodiment, steps a and b of the post-synthesis treatment are carried out at a temperature between 0 and 200 ° C.
La presente invención también se refiere al uso del material ITQ-38 para la convesrión de compuestos orgánicos.  The present invention also relates to the use of ITQ-38 material for the conversion of organic compounds.
Según una realización particular, el material descrito anteriormente y obtenido según el procedimiento de obtención descrito anteriormente puede ser utilizado para la transformación de compuestos orgánicos, preferentemente para convertir alimentaciones formadas por compuestos orgánicos en productos de mayor valor añadido.  According to a particular embodiment, the material described above and obtained according to the method of obtaining described above can be used for the transformation of organic compounds, preferably to convert feeds formed by organic compounds into products of greater added value.
Según otra realización particular, el material ITQ-38 puede ser utilizado en procesos de craqueo catalítico de hidrocarburos .  According to another particular embodiment, the ITQ-38 material can be used in hydrocarbon catalytic cracking processes.
Además, según otra realización particular, el material ITQ-38 puede ser utilizado en procesos de alquilación de compuestos aromáticos con alcoholes u olefinas.  In addition, according to another particular embodiment, the ITQ-38 material can be used in alkylation processes of aromatic compounds with alcohols or olefins.
El material descrito según la presente invención puede ser peletizado de acuerdo con técnicas conocidas, y puede ser utilizado como componente de catalizadores de craqueo catalítico de hidrocarburos, hidro-craqueo catalítico de hidrocarburos, alquilación de aromáticos con olefinas y en procesos de esterificación, acilación, reacción de anilina con formaldehído en su forma ácida y/o intercambiado con cationes adecuados. The material described according to the present invention can be pelletized according to known techniques, and can be used as a cracking catalyst component. hydrocarbon catalytic, hydrocarbon catalytic hydro-cracking, alkylation of aromatics with olefins and in processes of esterification, acylation, reaction of aniline with formaldehyde in its acidic form and / or exchanged with suitable cations.
EJEMPLOS EXAMPLES
Ejemplo 1: Síntesis del agente director de estructura: hidróxido de 1 , l-dimetil-4- (1-metilpirrolidino-l-il) piperidinio (ADE1)  Example 1: Synthesis of the structure directing agent: 1, l-dimethyl-4- (1-methylpyrrolidino-l-yl) piperidinium hydroxide (ADE1)
El catión orgánico se prepara de la siguiente manera: 10 g de pirrolidina se disuelven en 100 mi de metanol, y esta disolución se acidifica con HC1 (5 N en metanol) hasta alcanzar pH=7.5, enfriando la mezcla continuamente mediante un baño externo a 0°C. A continuación se adiciona 10 g de 1- metil-4-piperidona, seguidos de 3.5 g de NaBH3CN. La mezcla resultante se mantiene a temperatura ambiente y agitación continua durante 72 horas. The organic cation is prepared as follows: 10 g of pyrrolidine are dissolved in 100 ml of methanol, and this solution is acidified with HC1 (5 N in methanol) until pH = 7.5 is reached, cooling the mixture continuously by means of an external bath at 0 ° C Then 10 g of 1- methyl-4-piperidone is added, followed by 3.5 g of NaBH 3 CN. The resulting mixture is maintained at room temperature and continuous stirring for 72 hours.
Figure imgf000013_0001
Figure imgf000013_0001
Al crudo obtenido, se le adiciona lentamente HC1 hasta alcanzar un pH inferior a 2, siendo desplazado el HCN formado mediante una corriente de nitrógeno. La disolución resultante se concentra mediante rotavapor. Posteriormente, se adiciona una disolución de KOH (25% en peso) hasta alcanzar un pH superior a 12. En este paso, aparece un precipitado blanco. La mezcla resultante se satura con NaCl, y se vierte sobre agua. Finalmente, la diamina l-metil-4-pirrolidin-l-il- piperidina se extrae con éter dietílico y se seca con MgSC anhidro . To the crude obtained, HC1 is slowly added until a pH of less than 2 is reached, the formed HCN being displaced by a stream of nitrogen. The resulting solution is concentrated by rotary evaporator. Subsequently, a solution of KOH (25% by weight) is added until a pH greater than 12 is reached. In this step, a white precipitate appears. The resulting mixture is saturated with NaCl, and poured into water. Finally, the diamine l-methyl-4-pyrrolidin-l-yl-piperidine is extracted with diethyl ether and dried with anhydrous MgSC.
La cuaternización de la diamina se realiza de la siguiente manera: sobre una disolución de 10.4 g de diamina en 80 mi de MeOH se adicionan 42.2 g de ioduro de metilo. La mezcla se mantiene en agitación continua a temperatura ambiente durante 7 días, formándose un precipitado blanco. Este sólido se filtra a vacio. Su caracterización se realiza mediante análisis elemental y resonancia magnética. The quaternization of the diamine is carried out as follows: on a solution of 10.4 g of diamine in 80 ml of MeOH 42.2 g of methyl iodide are added. The mixture is kept under continuous stirring at room temperature for 7 days, forming a white precipitate. This solid is filtered under vacuum. Its characterization is done by elemental analysis and magnetic resonance.
Figure imgf000014_0001
Ejemplo 2: Síntesis de ITQ-38
Figure imgf000014_0001
Example 2: Synthesis of ITQ-38
Se disuelven 0.044 g de Ge02 y 0.003 g de A1203 en 2.177 g de una disolución de hidróxido de ADE1 (6.61% en peso) . Se añade 0.331 g de Ludox AS-40 en la disolución anterior, dejando la mezcla evaporar en agitación hasta alcanzar la composición final: 0.044 g of Ge0 2 and 0.003 g of A1 2 0 3 are dissolved in 2,177 g of a solution of ADE1 hydroxide (6.61% by weight). 0.331 g of Ludox AS-40 is added in the previous solution, allowing the mixture to evaporate with stirring until the final composition is reached:
0.84 Si02 : 0.16 Ge02 : 0.009 A1203 : 0.24 R(OH)2 : 14.20.84 Si0 2 : 0.16 Ge0 2 : 0.009 A1 2 0 3 : 0.24 R (OH) 2 : 14.2
H20 H 2 0
donde R es ADE1.  where R is ADE1.
El gel se calienta durante 14 días en autoclaves de acero con una funda interna de teflón a 175°C en estático. El sólido obtenido tras filtrar, lavar con agua destilada y secar a 100°C es ITQ-38.  The gel is heated for 14 days in steel autoclaves with an internal Teflon sheath at 175 ° C in static. The solid obtained after filtering, washing with distilled water and drying at 100 ° C is ITQ-38.
El material se calcina a 540°C durante 3 horas en flujo de aire para eliminar la materia orgánica. El patrón de difracción de rayos X de polvo del sólido contiene los picos característicos de la zeolita ITQ-38, mostrados en la Tabla 1.  The material is calcined at 540 ° C for 3 hours in air flow to remove organic matter. The powder X-ray diffraction pattern of the solid contains the characteristic peaks of the ITQ-38 zeolite, shown in Table 1.
Ejemplo 3: Síntesis de ITQ-38 Example 3: Synthesis of ITQ-38
Se disuelven 0.044 g de Ge02 en 2.194 g de una disolución de hidróxido de ADE1 (6.61% en peso) . A la disolución anterior, se añaden 0.071 g de una disolución de H3BO3 (5% en peso) y 0.323 g de Ludox AS-40, dejando la mezcla evaporar en agitación hasta alcanzar la composición final: 0.044 g of Ge0 2 are dissolved in 2,194 g of a solution of ADE1 hydroxide (6.61% by weight). To the above solution, 0.071 g of a solution of H 3 BO 3 (5% in weight) and 0.323 g of Ludox AS-40, allowing the mixture to evaporate under stirring until the final composition is reached:
0.84 Si02 : 0.16 Ge02 : 0.011 B203 : 0.24 R(OH)2 : 14.5 H20 donde R es ADE1. 0.84 Si0 2 : 0.16 Ge0 2 : 0.011 B 2 0 3 : 0.24 R (OH) 2 : 14.5 H 2 0 where R is ADE1.
El gel se calienta durante 14 días en autoclaves de acero con una funda interna de teflón a 175°C en estático. El sólido obtenido tras filtrar, lavar con agua destilada y secar a 100°C muestra los picos característicos de la zeolita ITQ-38.  The gel is heated for 14 days in steel autoclaves with an internal Teflon sheath at 175 ° C in static. The solid obtained after filtering, washing with distilled water and drying at 100 ° C shows the characteristic peaks of the ITQ-38 zeolite.
Ejemplo 4: Síntesis de ITQ-38 Example 4: Synthesis of ITQ-38
Se disuelven 0.044 g de Ge02 en 2.197 g de una disolución de hidróxido de ADE1 (6.61% en peso) . A la disolución anterior, se añaden 0.167 g de una disolución de H3BO3 (5% en peso) y 0.321 g de Ludox AS-40, dejando la mezcla evaporar en agitación hasta alcanzar la composición final: 0.044 g of Ge0 2 are dissolved in 2,197 g of a solution of ADE1 hydroxide (6.61% by weight). To the above solution, 0.167 g of a solution of H 3 BO 3 (5% by weight) and 0.321 g of Ludox AS-40 are added, allowing the mixture to evaporate under stirring until the final composition is reached:
0.835 Si02 : 0.165 Ge02 : 0.026 B203 : 0.24 R(OH)2 : 14.50.835 Si0 2 : 0.165 Ge0 2 : 0.026 B 2 0 3 : 0.24 R (OH) 2 : 14.5
H20 H 2 0
donde R es ADE1. where R is ADE1.
El gel se calienta durante 14 días en autoclaves de acero con una funda interna de teflón a 175°C en estático. El sólido obtenido tras filtrar, lavar con agua destilada y secar a 100°C muestra los picos característicos de la zeolita ITQ-38.  The gel is heated for 14 days in steel autoclaves with an internal Teflon sheath at 175 ° C in static. The solid obtained after filtering, washing with distilled water and drying at 100 ° C shows the characteristic peaks of the ITQ-38 zeolite.
Ejemplo 5: Síntesis de ITQ-38 Example 5: Synthesis of ITQ-38
Se disuelven 0.079 g de Ge02 en 3.077 g de una disolución de hidróxido de ADE1 (5.64% en peso) . A la disolución anterior, se añaden 0.075 g de una disolución de H3BO3 (5% en peso) y 0.358 g de Ludox AS-40, dejando la mezcla evaporar en agitación hasta alcanzar la composición final: 0.079 g of Ge0 2 are dissolved in 3.077 g of a solution of ADE1 hydroxide (5.64% by weight). To the above solution, 0.075 g of a solution of H 3 BO 3 (5% by weight) and 0.358 g of Ludox AS-40 are added, allowing the mixture to evaporate under stirring until the final composition is reached:
0.760 Si02 : 0.240 Ge02 : 0.01 B203 : 0.24 R(OH)2 : 19.10.760 Si0 2 : 0.240 Ge0 2 : 0.01 B 2 0 3 : 0.24 R (OH) 2 : 19.1
H20 H 2 0
donde R es ADE1. where R is ADE1.
El gel se calienta durante 14 días en autoclaves de acero con una funda interna de teflón a 175°C en estático. El sólido obtenido tras filtrar, lavar con agua destilada y secar a 100°C muestra los picos característicos de la zeolita ITQ-38. The gel is heated for 14 days in steel autoclaves with an internal Teflon sheath at 175 ° C in static. The solid obtained after filtering, washing with distilled water and drying at 100 ° C shows the characteristic peaks of the ITQ-38 zeolite.
Ejemplo 6: Síntesis de ITQ-38 utilizando como siembra cristales de ITQ-38 Example 6: Synthesis of ITQ-38 using ITQ-38 crystals as sowing
Se disuelven 0.078 g de Ge02 en 3.075 g de una disolución de hidróxido de ADE1 (5.64% en peso) . A la disolución anterior, se añaden 0.079 g de una disolución de H3BO3 (5% en peso) y 0.343 g de Ludox AS-40, dejando la mezcla evaporar en agitación hasta alcanzar la composición final: 0.078 g of Ge0 2 are dissolved in 3.075 g of a solution of ADE1 hydroxide (5.64% by weight). To the above solution, 0.079 g of a solution of H 3 BO 3 (5% by weight) and 0.343 g of Ludox AS-40 are added, allowing the mixture to evaporate under stirring until the final composition is reached:
0.754 Si02 : 0.246 Ge02 : 0.01 B203 : 0.25 R(OH)2 : 19.90.754 Si0 2 : 0.246 Ge0 2 : 0.01 B 2 0 3 : 0.25 R (OH) 2 : 19.9
H20 H 2 0
donde R es ADE1. where R is ADE1.
Una vez alcanzada la composición final deseada en el gel, se añaden 0.016 g de cristales de ITQ-38 como siembra.  Once the desired final composition in the gel is reached, 0.016 g of ITQ-38 crystals are added as sowing.
El gel se calienta durante 14 días en autoclaves de acero con una funda interna de teflón a 175°C en estático. El sólido obtenido tras filtrar, lavar con agua destilada y secar a 100°C muestra los picos característicos de la zeolita ITQ-38.  The gel is heated for 14 days in steel autoclaves with an internal Teflon sheath at 175 ° C in static. The solid obtained after filtering, washing with distilled water and drying at 100 ° C shows the characteristic peaks of the ITQ-38 zeolite.

Claims

RE IVI DICACIONES RE IVI DICATIONS
1. Un material cristalino microporoso, caracterizado porque posee una composición química: 1. A microporous crystalline material, characterized in that it has a chemical composition:
x X203 : y Y02 : z Z02 x X 2 0 3 : y Y0 2 : z Z0 2
donde : where :
X es un elemento trivalente seleccionado entre Al, B, Fe, In, Ga, Cr, o mezclas de estos; X is a trivalent element selected from Al, B, Fe, In, Ga, Cr, or mixtures of these;
Y es un elemento tetravalente seleccionado entre Ti, Sn, Zr, V, o mezclas de ellos; Y is a tetravalent element selected from Ti, Sn, Zr, V, or mixtures thereof;
Z es un elemento tetravalente seleccionado entre Si, Ge, o mezclas de ellos; Z is a tetravalent element selected from Si, Ge, or mixtures thereof;
el valor de (y+z)/x está comprendido entre 9 e infinito; el valor de z/y está comprendido entre 5 e infinito; the value of (y+z)/x is between 9 and infinity; the value of z/y is between 5 and infinity;
y porque sus líneas principales del patrón de difracción de rayos X en su forma sin calcinar se detallan en la Tabla 2, mientras que las líneas principales del patrón de difracción de rayos X en su forma calcinada se detallan en la Tabla 1: Tabla 1 and because its main lines of the X-ray diffraction pattern in its uncalcined form are detailed in Table 2, while the main lines of the X-ray diffraction pattern in its calcined form are detailed in Table 1: Table 1
(d ± 0.4) Intensidad (d ± 0.4) Intensity
(Á) Relativa (Á) Relative
20,8 md 20.8 million
12,8 d 12.8 d
12,6 d 12.6 d
11,6 md 11.6 million
10,4 mf 10.4mf
9,0 md Tabla 2 9.0 md Table 2
(d ± 0.4) Intensidad (d ± 0.4) Intensity
(Á) Relativa (Á) Relative
20,8 md 20.8 million
12,8 md 12.8 million
12,6 md 12.6 md
11,6 md 10,4 mf 11.6 million 10.4mf
9, 0 md 9.0 md
2. Un material cristalino microporoso según la reivindicación 1, caracterizado porque 2. A microporous crystalline material according to claim 1, characterized in that
Y está seleccionado entre Ti, Sn, Zr, o mezclas de los mismos; And it is selected from Ti, Sn, Zr, or mixtures thereof;
el valor de (y+z)/x está comprendido entre 20 e infinito; el valor de z/y está comprendido entre 10 e infinito. the value of (y+z)/x is between 20 and infinity; The value of z/y is between 10 and infinity.
3. Un material cristalino microporoso según cualquiera de las reivindicaciones 1 y 2, caracterizado porque Z es Si. 3. A microporous crystalline material according to any of claims 1 and 2, characterized in that Z is Si.
4. Un material cristalino microporoso según cualquiera de las reivindicaciones 1 a 3, caracterizado porque x es igual a cero y posee una composición química: 4. A microporous crystalline material according to any of claims 1 to 3, characterized in that x is equal to zero and has a chemical composition:
y Y02 : z Z02 y Y0 2 : z Z0 2
donde el valor de z/y está entre 5 e infinito. where the value of z/y is between 5 and infinity.
5 . Un material cristalino microporoso según la reivindicación 4, caracterizado porque z/y está entre 10 e infinito. 5 . A microporous crystalline material according to claim 4, characterized in that z/y is between 10 and infinity.
6 . Un material cristalino microporoso según cualquiera de las reivindicaciones 1 a 3, caracterizado porque y es igual a cero y posee una composición química: 6. A microporous crystalline material according to any of claims 1 to 3, characterized in that y is equal to zero and has a chemical composition:
x X203 : z Z02 x X 2 0 3 : z Z0 2
donde : where :
el valor de z/x está comprendido entre 9 e infinito. The value of z/x is between 9 and infinity.
7. Un material cristalino microporoso según la reivindicación 6, caracterizado porque el valor de z/x está comprendido entre 20 e infinito. 7. A microporous crystalline material according to claim 6, characterized in that the value of z/x is between 20 and infinity.
8 . Un material cristalino microporoso según una de las reivindicaciones 1 a 3, caracterizado porque posee una composición química: n R : x X203 : z Z02 : y Y02 8. A microporous crystalline material according to one of claims 1 to 3, characterized in that it has a chemical composition: n R : x X 2 0 3 : z Z0 2 : y Y0 2
donde : where :
R es un agente director de estructura; R is a structure directing agent;
el valor de n/(x+y+z) está comprendido entre 3 y 0.000; y porque tiene un patrón de rayos X representado en la tabla 4 : the value of n/(x+y+z) is between 3 and 0.000; and because it has an X-ray pattern represented in table 4:
Tabla 4 Table 4
(d ± 0.4) Intensidad (d ± 0.4) Intensity
(Á) Relativa (Á) Relative
20, 8 md 20.8 md
12, 8 md 12.8 md
12, 6 md 12.6 md
11, 6 md 11.6 md
10,4 mf 10.4mf
9, 0 md 9.0 md
8,5 d 8.5d
8, 0 md 8.0 md
6, 4 md 6.4 md
5, 6 md 5, 6 md
5, 4 md 5.4 md
4, 9 md 4.9 md
4,7 md 4.7 million
4,5 md 4.5 md
4,3 md 4.3 million
4, 1 md 4.1 md
4, 0 d 4.0d
3, 9 md 3.9 md
3, 8 md 3.8 md
3,7 md 3.7 million
3,5 md 3.5md
3,4 md 3.4 md
3,3 md 3.3 million
3,2 md 3.2 md
3,2 md 3.2 md
9 . Un material cristalino microporoso según la reivindicación 8, caracterizado porque el valor de n/(x+y+z) está comprendido entre 1 y 0.001. 9. A microporous crystalline material according to claim 8, characterized in that the value of n/(x+y+z) is between 1 and 0.001.
10 . Un material cristalino microporoso según la reivindicación 8, caracterizado porque el agente director de estructura R está seleccionado entre una amina, una sal de tetraalquilamonio, una molécula orgánica que contiene P, o una molécula orgánica que contiene enlaces P-N y combinaciones de los mismos. 10. A microporous crystalline material according to claim 8, characterized in that the structure directing agent R is selected from an amine, a tetraalkylammonium salt, an organic molecule containing P, or an organic molecule containing P-N bonds and combinations thereof.
11 . Un material cristalino microporoso según la reivindicación 10, caracterizado porque el agente director de estructura es una sal de tetraalquilamonio. eleven . A microporous crystalline material according to claim 10, characterized in that the structure directing agent is a tetraalkylammonium salt.
12 . Un material cristalino microporoso según la reivindicación 11, caracterizado porque R es hidróxido de 1 , l-dimetil-4- ( 1-metilpirrolidino-l-il ) piperidino (ADE1) . 12. A microporous crystalline material according to claim 11, characterized in that R is 1,l-dimethyl-4-(1-methylpyrrolidino-l-yl)piperidino hydroxide (ADE1).
13 . Un material cristalino microporoso según cualquiera de las reivindicaciones 8 a 12, caracterizado porque x es igual a cero y posee una composición química: 13. A microporous crystalline material according to any of claims 8 to 12, characterized in that x is equal to zero and has a chemical composition:
n R : y Y02 : z Z02 n R : y Y0 2 : z Z0 2
donde : where :
· el valor de n/(y+z) está comprendido entre 3 y 0.000, · the value of n/(y+z) is between 3 and 0.000,
el valor de z/y está entre 5 e infinito. the value of z/y is between 5 and infinity.
14 . Un material cristalino microporoso según la reivindicación 13, caracterizado porque el valor de n/(y+z) está entre 1 y 0.001 y el valor de z/y está entre 10 e infinito . 14. A microporous crystalline material according to claim 13, characterized in that the value of n/(y+z) is between 1 and 0.001 and the value of z/y is between 10 and infinity.
15 . Un material cristalino microporoso según cualquiera de las reivindicaciones 8 a 12, caracterizado porque y es igual a cero y posee una composición química: fifteen . A microporous crystalline material according to any of claims 8 to 12, characterized in that y is equal to zero and has a chemical composition:
n R : x X203 : z Z02 n R : x X 2 0 3 : z Z0 2
donde : where :
el valor de z/x está comprendido entre 9 e infinito; el valor de n/(x+z) está comprendido entre 3 y 0.000. the value of z/x is between 9 and infinity; the value of n/(x+z) is between 3 and 0.000.
16. Un material cristalino microporoso según la reivindicación 12, caracterizado porque el valor de n/(x+z) está comprendido entre 1 y 0.001 y el valor de z/x está comprendido entre 20 e infinito. 16. A microporous crystalline material according to claim 12, characterized in that the value of n/(x+z) is between 1 and 0.001 and the value of z/x is between 20 and infinity.
17. Un material cristalino microporoso según una de las reivindicaciones anteriores, caracterizado porque dicho material se combina con componentes hidrogenantes- deshidrogenantes . 17. A microporous crystalline material according to one of the preceding claims, characterized in that said material is combined with hydrogenating-dehydrogenating components.
18. Un material cristalino microporoso según la reivindicación 17, caracterizado porque dichos componentes hidrogenantes-deshidrogenantes están seleccionados entre platino, paladio, níquel, renio, cobalto, tungsteno, molibdeno, vanadio, cromo, manganeso, hierro y combinaciones de los mismos. 18. A microporous crystalline material according to claim 17, characterized in that said hydrogenating-dehydrogenating components are selected from platinum, palladium, nickel, rhenium, cobalt, tungsten, molybdenum, vanadium, chromium, manganese, iron and combinations thereof.
19. Un procedimiento de preparación del material descrito según cualquiera de las reivindicaciones anteriores, caracterizado porque comprende al menos los siguientes pasos: a) preparación de una mezcla que contiene, al menos, ¾0, un óxido u otra fuente del material tetravalente Z y un agente director de estructura (R) , una fuente del elemento trivalente X, un óxido u otra fuente del material tetravalente Y, donde la mezcla de síntesis tiene una composición molar de óxidos en los siguientes rangos : 19. A procedure for preparing the material described according to any of the preceding claims, characterized in that it comprises at least the following steps: a) preparation of a mixture that contains, at least, ¾0, an oxide or other source of the tetravalent material Z and a structure directing agent (R), a source of the trivalent element
( YO2+ Z O2 ) /X203 mayor de 2 ( YO2+ Z O2 ) /X 2 0 3 greater than 2
H20/ ( YO2+ Z O2 ) 1-50 H 2 0/ ( YO2+ Z O2 ) 1-50
R/ (Y02 + Z02 ) 0.00-3.0 R/ (Y0 2 + Z0 2 ) 0.00-3.0
Z O2 / YO2 mayor de 5 Z O2 / YO2 greater than 5
b) mantener la mezcla a una temperatura entre 80 y 200°C hasta que se formen los cristales del material; b) maintain the mixture at a temperature between 80 and 200°C until the material crystals form;
c) recuperación del material cristalino; c) recovery of crystalline material;
donde : X es un elemento trivalente seleccionado entre Al, B, Fe,where : X is a trivalent element selected from Al, B, Fe,
In, Ga, Cr, o mezclas de estos; In, Ga, Cr, or mixtures of these;
Y es un elemento tetravalente seleccionado entre Ti, Sn, Y is a tetravalent element selected from Ti, Sn,
Zr, V o mezclas de ellos; Zr, V or mixtures of them;
Z es un elemento tetravalente seleccionado entre Si, Ge o mezclas de ellos; Z is a tetravalent element selected from Si, Ge or mixtures of them;
R es un agente director de estructura. R is a structure directing agent.
20. Procedimiento de obtención de un material según la reivindicación 19, caracterizado porque Z es Si. 20. Procedure for obtaining a material according to claim 19, characterized in that Z is Si.
21. Procedimiento de obtención de un material según cualquiera de las reivindicaciones 19 y 20, caracterizado porque el agente director de estructura R es una amina, una sal de tetraalquilamonio, una molécula orgánica que contiene21. Procedure for obtaining a material according to any of claims 19 and 20, characterized in that the structure directing agent R is an amine, a tetraalkylammonium salt, an organic molecule containing
P, una molécula orgánica que contiene enlaces P-N o combinaciones de los mismos. P, an organic molecule containing P-N bonds or combinations thereof.
22. Procedimiento de obtención de un material según la reivindicación 21, caracterizado porque R una sal de tetraalquilamonio . 22. Procedure for obtaining a material according to claim 21, characterized in that R is a tetraalkylammonium salt.
23. Procedimiento de obtención de un material según la reivindicación 22, caracterizado porque R es hidróxido de 1 , l-dimetil-4- ( 1-metilpirrolidino-l-il ) piperidino (ADE1) . 23. Procedure for obtaining a material according to claim 22, characterized in that R is 1, l-dimethyl-4- (1-methylpyrrolidino-l-yl) piperidino hydroxide (ADE1).
2 . Procedimiento de obtención de un material según cualquiera de las reivindicaciones 19 a 23, caracterizado porque x es igual a cero y posee una composición química: 2 . Procedure for obtaining a material according to any of claims 19 to 23, characterized in that x is equal to zero and has a chemical composition:
n R : y Y02 : z Z02 n R : y Y0 2 : z Z0 2
donde : where :
el valor de n/(y+z) está comprendido entre 3 y 0.00; the value of n/(y+z) is between 3 and 0.00;
el valor de z/y está entre 5 e infinito. the value of z/y is between 5 and infinity.
25. Procedimiento de obtención de un material según la reivindicación 24, caracterizado porque el valor de n/(y+z) está entre 1 y 0.001 y el valor de z/y está entre 10 e infinito . 25. Procedure for obtaining a material according to claim 24, characterized in that the value of n/(y+z) is between 1 and 0.001 and the value of z/y is between 10 and infinity.
26. Procedimiento de obtención de un material según cualquiera de las reivindicaciones 19 a 23, caracterizado porque y es igual a cero y posee una composición química: 26. Procedure for obtaining a material according to any of claims 19 to 23, characterized in that y is equal to zero and has a chemical composition:
n R : x X203 : z Z02 n R : x X 2 0 3 : z Z0 2
donde : where :
el valor de z/x está comprendido entre 9 e infinito; the value of z/x is between 9 and infinity;
el valor de n/(x+z) está comprendido entre 3 y 0.000. the value of n/(x+z) is between 3 and 0.000.
27. Un material cristalino microporoso según la reivindicación 26, caracterizado porque el valor de z/x está comprendido entre 20 e infinito y el valor de n/(x+z) está comprendido entre 1 y 0.001. 27. A microporous crystalline material according to claim 26, characterized in that the value of z/x is between 20 and infinity and the value of n/(x+z) is between 1 and 0.001.
28. Procedimiento de obtención de un material según cualquiera de las reivindicaciones 19 a 27, caracterizado porque se añaden a la mezcla de síntesis cristales de zeolita ITQ-38 que actúan como siembra. 28. Procedure for obtaining a material according to any of claims 19 to 27, characterized in that ITQ-38 zeolite crystals that act as seeds are added to the synthesis mixture.
29. Procedimiento de obtención de un material según reivindicación 28, caracterizado porque dichos cristales de zeolita ITQ-38 que actúan como siembra se añaden en una proporción de hasta 25% en peso respecto al peso total de óxidos . 29. Procedure for obtaining a material according to claim 28, characterized in that said ITQ-38 zeolite crystals that act as seeds are added in a proportion of up to 25% by weight with respect to the total weight of oxides.
30. Procedimiento de obtención de un material según cualquiera de las reivindicaciones 19 a 29, caracterizado porque comprende, además, la calcinación del material cristalino obtenido. 30. Procedure for obtaining a material according to any of claims 19 to 29, characterized in that it also comprises the calcination of the crystalline material obtained.
31. Procedimiento de obtención de un material según la reivindicación 30, caracterizado porque la calcinación se lleva a cabo a una temperatura entre 200 y 1000°C. 31. Procedure for obtaining a material according to claim 30, characterized in that the calcination is carried out at a temperature between 200 and 1000°C.
32. Procedimiento de obtención de un material según cualquiera de las reivindicaciones 19 y 31, caracterizado porque comprende, además, al menos un proceso de lavado del material calcinado. 32. Procedure for obtaining a material according to any of claims 19 and 31, characterized in that it also comprises at least one process for washing the calcined material.
33. Procedimiento de obtención de un material según la reivindicación 32, caracterizado porque dicho proceso o procesos de lavado comprende al menos la siguiente etapa: a) suspensión del material en una disolución de un compuesto seleccionado entre un ácido, una base, una sal amónica, una sal sódica, de cualquier metal alcalino, cualquier metal alcalino-terreo o mezclas de ellos. 33. Procedure for obtaining a material according to claim 32, characterized in that said washing process or processes comprises at least the following stage: a) suspension of the material in a solution of a compound selected from an acid, a base, an ammonium salt , a sodium salt, of any alkali metal, any alkaline earth metal or mixtures thereof.
34. Procedimiento de obtención de un material según la reivindicación 33, caracterizado porque dicha disolución está seleccionada entre una disolución acuosa, alcohólica, orgánica o mezcla de ellas. 34. Procedure for obtaining a material according to claim 33, characterized in that said solution is selected from an aqueous, alcoholic, organic solution or a mixture thereof.
35. Procedimiento de obtención de un material según cualquiera de las reivindicaciones 32 a 34, caracterizado porque dicho lavado se realiza a una temperatura entre 0 y 200°C. 35. Procedure for obtaining a material according to any of claims 32 to 34, characterized in that said washing is carried out at a temperature between 0 and 200°C.
36. Procedimiento de obtención de un material según cualquiera de las reivindicaciones 19 a 35, caracterizado porque comprende, además uno o varios procesos post-sintesis . 36. Procedure for obtaining a material according to any of claims 19 to 35, characterized in that it also comprises one or more post-synthesis processes.
37. Procedimiento de obtención de un material según la reivindicación 36, caracterizado porque dicho tratamiento post-sintesis comprende al menos: 37. Procedure for obtaining a material according to claim 36, characterized in that said post-synthesis treatment comprises at least:
a) suspender en una disolución que contiene al menos un elemento trivalente X seleccionado entre Al, Ga, B, Cr, Fe, In o mezclas de ellos; a) suspend in a solution containing at least one trivalent element X selected from Al, Ga, B, Cr, Fe, In or mixtures thereof;
b) recuperación del sólido mediante filtración, centrifugación o cualquier técnica de separación de sólidos de líquidos; b) recovery of the solid by filtration, centrifugation or any technique for separating solids from liquids;
c) activación del material mediante calcinación a temperaturas superiores a 200°C. c) activation of the material by calcination at temperatures above 200°C.
38. Procedimiento de obtención de un material según la reivindicación 37, caracterizado porque la disolución está seleccionada entre una disolución acuosa, alcohólica, orgánica o mezcla de ambas. 38. Procedure for obtaining a material according to claim 37, characterized in that the solution is selected from an aqueous, alcoholic, organic solution or mixture of both.
39. Procedimiento de obtención de un material según la reivindicación 37, caracterizado porque el paso a y b del tratamiento post-sintesis se lleva a cabo a una temperatura entre 0 y 200°C. 39. Procedure for obtaining a material according to claim 37, characterized in that step a and b of the post-synthesis treatment is carried out at a temperature between 0 and 200°C.
40. Uso de un material descrito según las reivindicaciones 1 a 18, y obtenido según el procedimiento de obtención descrito en las reivindicaciones 19 a 39, para la transformación de compuestos orgánicos. 40. Use of a material described according to claims 1 to 18, and obtained according to the production procedure described in claims 19 to 39, for the transformation of organic compounds.
41. Uso de un material según la reivindicación 40, para convertir alimentaciones formadas por compuestos orgánicos en productos de mayor valor añadido. 41. Use of a material according to claim 40, to convert feeds formed by organic compounds into products with greater added value.
42. Uso de un material según la reivindicación 40, en procesos de craqueo catalítico de hidrocarburos. 42. Use of a material according to claim 40, in hydrocarbon catalytic cracking processes.
43. Uso de un material según la reivindicación 40, en procesos de alquilación de compuestos aromáticos con alcoholes u olefinas. 43. Use of a material according to claim 40, in alkylation processes of aromatic compounds with alcohols or olefins.
PCT/ES2013/070014 2012-01-25 2013-01-17 Itq-38 material, the method for the production thereof and the use thereof WO2013110838A1 (en)

Applications Claiming Priority (2)

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ES201230102A ES2421063B1 (en) 2012-01-25 2012-01-25 ITQ-38 material, its procedure for obtaining and its use
ESP201230102 2012-01-25

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006071871A1 (en) * 2004-12-27 2006-07-06 Saudi Basic Industries Corporation Process for making a germanium-zeolite
ES2303787A1 (en) * 2007-02-01 2008-08-16 Universidad Politecnica De Valencia Microporous crystalline material of zeolitic nature, zeolite itq-39, method of preparation and uses
EP2196437A1 (en) * 2008-10-29 2010-06-16 Ifp Method for preparing a FU-1 crystallised solid using a cation such as polymethylene alpha-psi diammonium as an organic structuring compound

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006071871A1 (en) * 2004-12-27 2006-07-06 Saudi Basic Industries Corporation Process for making a germanium-zeolite
ES2303787A1 (en) * 2007-02-01 2008-08-16 Universidad Politecnica De Valencia Microporous crystalline material of zeolitic nature, zeolite itq-39, method of preparation and uses
EP2196437A1 (en) * 2008-10-29 2010-06-16 Ifp Method for preparing a FU-1 crystallised solid using a cation such as polymethylene alpha-psi diammonium as an organic structuring compound

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ES2421063A1 (en) 2013-08-28

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