WO2012049344A1 - Itq-45 material, method for obtaining same and use thereof - Google Patents

Itq-45 material, method for obtaining same and use thereof Download PDF

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WO2012049344A1
WO2012049344A1 PCT/ES2011/070650 ES2011070650W WO2012049344A1 WO 2012049344 A1 WO2012049344 A1 WO 2012049344A1 ES 2011070650 W ES2011070650 W ES 2011070650W WO 2012049344 A1 WO2012049344 A1 WO 2012049344A1
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material according
obtaining
value
crystalline material
microporous crystalline
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PCT/ES2011/070650
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Spanish (es)
French (fr)
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Avelino CORMA CANÓS
Fernando REY GARCÍA
María Teresa NAVARRO VILLALBA
Raquel Simancas Coloma
Noemí VELAMAZÁN CIRUJEDA
Ángel CANTÍN SANZ
José Luis JORDÁ MORET
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Consejo Superior De Investigaciones Científicas (Csic)
Universidad Politécnica De Valencia
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/005Silicates, i.e. so-called metallosilicalites or metallozeosilites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/047Germanosilicates; Aluminogermanosilicates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/86Borosilicates; Aluminoborosilicates
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02Crystalline 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
    • C01B39/04Crystalline 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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02Crystalline 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
    • C01B39/06Preparation 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
    • C01B39/12Preparation 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02Crystalline 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
    • C01B39/46Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G11/00Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04Oxides
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G3/00Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42Catalytic treatment
    • C10G3/44Catalytic treatment characterised by the catalyst used
    • C10G3/48Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58Refining 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
    • C10G45/68Aromatisation of hydrocarbon oil fractions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G47/00Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12Inorganic carriers
    • C10G47/16Crystalline alumino-silicate carriers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • This patent refers to a zeolitic material called ITQ-45 and its method of preparation.
  • Zeolites are porous crystalline aluminosilicates that have found important applications as catalysts, adsorbents and ion exchangers. These zeolitic materials have well-defined structures that form channels and cavities in their interior 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 pores This characteristic gives these materials molecular sieve properties. These molecular sieves may include in the network, in addition to Si, other elements of the NIA group of the periodic system, all of them tetrahedrally coordinated.
  • the negative charge generated by the elements of the MIA group tetrahedrally coordinated in network positions is compensated by the presence in the cation crystal, such as alkaline or alkaline earth cations.
  • cation crystal such as alkaline or alkaline earth cations.
  • These cations can be totally or partially exchanged for other types of cations by ion exchange techniques, thus being able to vary the properties of a given silicate by selecting the desired cations.
  • a synthetic microporous crystalline material called ITQ-45 is described.
  • the structure of this material has a microporous network consisting of channels with openings formed by 8 and 10 T0 4 tetrahedra that intersect each other giving rise to non-spherical cavities, which are accessed through two windows formed by 8 tetrahedra and others two of 10 tetrahedra, these cavities being accessible to molecules of interest in catalysis, in adsorption or separation processes.
  • the space not occupied by these cavities is completed with other smaller ones with a distorted dodecahedron shape, which are accessible only through windows formed by five tetrahedra, and therefore cannot be occupied by molecules of interest.
  • the structure of the ITQ-45 zeolite can be described by its unit cell, which is the smallest structural unit that contains all the structural elements of this material.
  • Table 1 shows the list of atomic positions of all atoms in tetrahedral coordination in a unit cell. All these atoms are connected to each other through bridge oxygen that bind contiguous tetrahedral atoms two to two. In total, each unit cell contains 92 atoms in tetrahedral coordination, called T1, T2, T3, T4 up to T92, other than oxygen, which are located in the crystallographic positions with Cartesian atomic coordinates x, yyz shown in Table 1.
  • Table 1 shows the list of atomic positions of all atoms in tetrahedral coordination in a unit cell. All these atoms are connected to each other through bridge oxygen that bind contiguous tetrahedral atoms two to two. In total, each unit cell contains 92 atoms in tetrahedral coordination
  • Each of the T atoms in Table 1 is surrounded by four oxygen atoms as first neighbors and four other T atoms as second neighbors, so that the T atoms are connected two by two through bridge oxygen forming TOT bonds .
  • the presence of cations or depending on the nature of the T atoms can modify the values presented in Table 1, so that each crystallographic coordinate can be modified up to 0.5 A of the value given in Table 1.
  • the ITQ-45 zeolite has in its uncalcrated form an X-ray diffraction diagram whose most important diffraction peaks are given in Table 2, and in Table 3 for its calcined form.
  • changes in the chemical composition can cause variations in the parameters of the unit cell and / or changes in the symmetry of the crystal, without a change in the structure.
  • 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.
  • the present invention relates to a microporous crystalline material called ITQ-45, which may have a chemical composition:
  • - 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 between Ti, Sn, Zr, or mixtures thereof;
  • - Z is a tetravalent element selected from Si, Ge or mixtures thereof, preferably Si;
  • z / y the value of z / y is between 10 and infinity, preferably between 15 and infinity.
  • the value of x can be equal to zero, so it can have a chemical composition:
  • the value of y is equal to zero, so it can have a chemical composition:
  • - Y is a tetravalent element selected from Ti, Sn, Zr, V or mixtures thereof, preferably between Ti, Sn, Zr, or mixtures thereof;
  • - Z is a tetravalent element selected from Si, Ge or mixtures thereof, preferably Si;
  • - P refers to phosphorus from the structure managing agent
  • z / y the value of z / y is between 10 and infinity, preferably between 15 and infinity.
  • ITQ-45 can be synthesized in the absence of added trivalent elements.
  • the X-ray diffractogram of the zeolite in its calcined form presents the diffraction peaks listed in Table 3.
  • x may be 0 and the ITQ-45 material may have a chemical composition:
  • the ITQ-45 material can have a chemical composition:
  • z / x the value of z / x is between 9 and infinity, preferably between 20 and infinity.
  • - t / (x + z) can be between 1 and 0.
  • the calcined crystalline material ITQ-45 can be subjected to one or several chemical extraction processes or washing in aqueous, alcoholic, organic or mixture thereof to eliminate P2O5 inorganic residues from the elimination of the structure directing agent.
  • This extraction or washing treatment can be performed in acid, neutral or alkaline medium.
  • the material of the present invention, ITQ-45 has a chemical composition:
  • - 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 between Ti, Sn, Zr, or mixtures thereof;
  • - Z is a tetravalent element selected from Si, Ge or mixtures thereof, preferably Si;
  • z / y the value of z / y is between 10 and infinity, preferably between 15 and infinity.
  • R is a structure directing agent, preferably said R contains P, more preferably R contains P-N bonds, and more preferably is selected from tert-butyl-imino-tris (di-methyl-amino) -phosphorane and its protonated derivative;
  • n / (x + y + z) is between 1 and 0.001.
  • the ITQ-45 crystalline material can be synthesized in the absence of added trivalent elements.
  • the n / z ratio may be between 1 and 0.001 in the ITQ-45 material as synthesized.
  • the X-ray diffractogram of the zeolite in its synthesized form presents the diffraction peaks listed in Table 2.
  • x may be 0 and the ITQ-45 material may have a chemical composition:
  • n / (y + z) is between 1 and 0.001.
  • ITQ-45 material can have a chemical composition
  • z / x the value of z / x is between 9 and infinity, preferably between 20 and infinity.
  • the calcined and / or calcined and washed ITQ-45 crystalline material may be subjected to one or more post-synthesis processes of incorporation or exchange of trivalent elements using solutions containing trivalent elements X that may be selected from Al, Ga, B, Cr , Fe, In and mixtures thereof in aqueous, alcoholic, organic or mixture thereof.
  • trivalent elements X may be selected from Al, Ga, B, Cr , Fe, In and mixtures thereof in aqueous, alcoholic, organic or mixture thereof.
  • inorganic P2O5 residues from the elimination of the structure directing agent and / or incorporating the trivalent elements of the solutions can be eliminated.
  • This treatment of incorporation of trivalent metals and / or washing can be carried out in acid, neutral or alkaline medium.
  • the crystalline material with trivalent metals incorporated by post-synthesis treatments has a molar composition in its anhydrous state that is given by the equation:
  • 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 + 4 .
  • 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 from the NA, MIA, IVA, Va, IB, NB, IIIB, IVB, VB, VIIB group of the periodic table of the elements.
  • the crystalline material of the present invention can be intimately combined with hydrogenating-dehydrogenating components such as platinum, palladium, nickel, rhenium, cobalt, tungsten, molybdenum, vanadium, chromium, manganese, iron and combinations thereof.
  • hydrogenating-dehydrogenating components such as platinum, palladium, nickel, rhenium, cobalt, tungsten, molybdenum, vanadium, chromium, manganese, iron and combinations thereof.
  • the introduction of these elements can be carried out in the crystallization stage, by exchange (if applicable), and / or by impregnation or by physical mixing.
  • These elements can be introduced in their cathonic 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 relates to the procedure for obtaining the ITQ-45 matenal described above.
  • the ITQ-45 material preparation process may comprise at least a first step of preparing a mixture containing H 2 0, an oxide or other source of the tetravalent material Z and 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:
  • Si0 2 / Ge0 2 greater than 2, preferably greater than 5
  • Z is Si.
  • the structure directing agent R can be a compound containing P, preferably R contains PN bonds, and more preferably is selected from tert-butyl-imino-tris (di-methyl-amino) -phosphorane and its derivative proton cationic.
  • the method of preparation of this material can be carried out in basic medium and absence of added fluoride ions.
  • This material can be prepared according to a particular embodiment, from a reaction mixture containing H 2 0, 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 Y, such as Si, a source of Ge, such as Ge02 and an organic structure directing agent (R ) generally an organic cation, which may contain atoms other than C, H and N in its composition.
  • compositions of the phosphazene base type characterized by the presence of PN bonds in its structure can be used as structure directing agents, and more preferably it is the tert-butyl-imino-tris (di-methyl-amino) -phosphorane compound or its cationic derivative protonated
  • composition of the reaction mixture has the following composition in terms of molar ratios of oxides:
  • the crystallization of the material can be carried out under stirring, in autoclaves at a temperature between 80 and 200 ° C, at times sufficient to achieve crystallization, for example between 12 hours and 30 days. At the end of the crystallization stage, the crystals of the material 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, crystals of the same material or of this calcined material can be added as seeds, in amounts of up to 15% by weight with respect to the total oxides, to the synthesis mixture. These can be added before or during crystallization.
  • said washing process or processes may comprise 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.
  • a solution is an aqueous, alcoholic, organic solution or mixture of both.
  • the washing process is carried out at a temperature preferably between 0 S C and 200-C.
  • the diffraction diagram of the resulting material presents the diffraction peaks listed in Table 3.
  • the calcined ITQ-45 material or the calcined and washed ITQ-45 material may be subjected to one or more post-synthesis treatments.
  • Such treatments may preferably consist of treating the ITQ-45 with aqueous, alcoholic, organic solutions or mixtures thereof containing trivalent elements X, preferably selected from Al, Ga, B, Cr, Fe In, and mixtures thereof in order to incorporate them into the zeolitic network.
  • This post-synthesis treatment can be carried out at alkaline, acidic or neutral pHs at temperatures preferably between 0 and 200 QC for a preferred time between 1 hour to 15 days.
  • the resulting material presents the diffraction peaks shown in Table 4 and contains elements from the treatment solution incorporated into the network.
  • the present invention also relates to the use of the ITQ-45 material obtained according to the procedure described above, as a component of catalytic cracking catalysts of hydrocarbons, catalytic hydro-cracking of hydrocarbons, aromatic alkylation processes with alcohols or olefins and in esterification, acylation, reaction of aniline with formaldehyde in its acid form and / or exchanged with suitable cations as well as to convert feeds formed by organic compounds to products of higher added value.
  • the produced ITQ-45 material can be pasted according to known techniques.
  • Example 1- Preparation of tert-butylimino-tris (dimethylamine »no) phosphorane.
  • 13.8 g of PCI5 are dissolved in 100 ml of anhydrous CH2CI2 under a nitrogen atmosphere.
  • a mixture consisting of 1.1 g of a 2M solution in dimethylamine tetrahydrofuran at -50 S C and 26.3 g of triethylamine.
  • the mixture is vigorously stirred at low temperature for 1 hour and the reaction is allowed to end at room temperature for 12 hours.
  • Example 3- Preparation of zeolite ITQ-45 in its calcined form.
  • the resulting solid presents an X-ray diffraction diagram that contains all the peaks indicated in Table 8.
  • Example 5- Post-synthesis treatment of a calcined ITQ-45 zeolite to obtain AI-ITQ-45 0.501 g of the solid prepared as described in example 3 are added to 25 ml of an 8% aluminum nitrate solution. The mixture is transferred to Teflon coated steel autoclaves and placed in a stove at 140 Q C for 3 days. The solid obtained is washed with 2000 ml of distilled water and dried at 100 9 C for 10 hours.
  • the resulting solid presents a characteristic X-ray diffraction diagram of the ITQ-45 zeolite.
  • Example 6- Post-synthesis treatment of a calcined ITQ-45 zeolite to obtain ITQ-45 without trivalent elements in its composition.
  • 0.42 g of the solid prepared as described in example 3 are added to 30 ml of a 0.01 N hydrochloric acid solution. The mixture is kept at room temperature for 24 h.
  • the solid obtained is washed with 2000 ml of distilled water and dried at 100 9 C for 10 hours.
  • the resulting solid presents a characteristic X-ray diffraction diagram of the ITQ-45 zeolite.
  • Example 7- Preparation of ITQ-45 zeolite At 2,554 g (0.01 1 mol) of tert-butylimino-tris (dimethylamino) phosphorane prepared as described in example 1, 4,281 g (0.238 mol) of H 2 O is added , keeping the mixture under stirring for fifteen minutes. To this mixture is added 6.378 g (0.031 mol) of tetraethylorthosilicate, 0.316 g (0.003 mol) of Ge0 2 and 0.079 g (0.0013 mol) of H 3 B0 3 . The mixture is kept under stirring at room temperature until the total evaporation of the ethanol formed during the hydrolysis of the tetraethylorthosilicate. Subsequently 2,792 g (0.155 mol) of H 2 0 are added until the ratio H 2 0 / Si + Ge of 10 is reached.
  • the resulting solid presents a characteristic X-ray diffraction diagram of the ITQ-45 zeolite.
  • Example 10- Preparation of the ITQ-45 zeolite
  • 7.529 g (0.418 mol) of H 2 0 are added, keeping the mixture under stirring for fifteen minutes.
  • To this mixture is added 9,480 g (0.0455 mol) of tetraethylorthosilicate, 0.474 g (0.0045 mol) of Ge0 2 and 0.126 g (0.002 mol) of H 3 B0 3 .
  • the mixture is kept under stirring at room temperature until the total evaporation of the ethanol formed during the hydrolysis of the tetraethylorthosilicate. Later they are added 0.136 g of ITQ-45 zeolite planting dispersed in 3,134 g (0.174 mol) of H 2 0 until reaching the ratio H 2 0 / Yes + Ge of 10.
  • the gel obtained is transferred to teflon coated steel autoclaves and placed in an oven at 160 9 C for 10 days.
  • the resulting solid presents a characteristic X-ray diffraction diagram of the ITQ-45 zeolite.
  • the structure of the ITQ-45 zeolite can be satisfactorily refined using the Rietveld method applied to an X-ray diffraction diagram obtained from a sample prepared as described in example 3.
  • the fit between the experimental and the simulated diagram is shown in Figure 1.
  • the spatial group, refinement parameters and atomic positions of the ITQ-45 zeolite are shown in Table 5.

Abstract

The invention relates to a microporous crystalline material and to the method for preparing same, which has the composition: x X203 : z Z02 : y Y02 where X is a trivalent element such as Al, B, Fe, In, Ga or Cr or mixtures thereof, wherein (y+z)/x can be between 9 and infinity; Z is a tetravalent element selected from Si and Ge or mixtures thereof; and Y is a tetravalent element such as Ti, Sn, Zr or V or mixtures thereof, wherein z/y is between 10 and infinity.

Description

Material ITQ-45, su procedimiento de obtención y su uso  ITQ-45 material, its procedure for obtaining and its use
Campo de la invención Field of the Invention
Esta patente se refiere a un material zeolítico denominado ITQ-45 y a su método de preparación. This patent refers to a zeolitic material called ITQ-45 and its method of preparation.
Estado de ia técnica anterior a ia invención State of the art prior to the invention
Las zeolitas son alumínosilicatos cristalinos porosos que han encontrado importantes aplicaciones como catalizadores, adsorbentes e intercambiadores iónicos. 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, además de Si, otros elementos del grupo NIA del sistema periódico, todos ellos tetraédricamente coordinados. La carga negativa generada por los elementos del grupo MIA tetraédricamente coordinados en posiciones de red está compensada por la presencia en el cristal de cationes, como por ejemplo cationes alcalinos o alcalinotérreos. Estos cationes pueden ser intercambiados 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. These zeolitic materials have well-defined structures that form channels and cavities in their interior 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 pores This characteristic gives these materials molecular sieve properties. These molecular sieves may include in the network, in addition to Si, other elements of the NIA group of the periodic system, all of them tetrahedrally coordinated. The negative charge generated by the elements of the MIA group tetrahedrally coordinated in network positions is compensated by the presence in the cation crystal, such as alkaline or alkaline earth cations. These cations can be totally or partially exchanged for other types 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) contienen generalmente nitrógeno en su composición, y pueden dar lugar a cationes orgánicos estables en el medio de reacción. Desde un punto de vista de sus posibles aplicaciones, las zeolitas que contienen sistemas de canales con distintas aperturas de poro son especialmente deseables ya que aportan selectividades en los procesos catalíticos que no pueden obtenerse con materiales con canales con aperturas idénticas en todos ellos. Es por ello, que se ha desarrollado una importante actividad científica en este sentido. 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) generally contain nitrogen in their composition, and can give rise to stable organic cations in the reaction medium. From a point of view of their possible applications, zeolites containing channel systems with different pore openings are especially desirable since they provide selectivities in catalytic processes that cannot be obtained with materials with channels with identical openings in all of them. That is why, an important scientific activity has been developed in this regard.
Descripción de la invención En ia presente invención, se describe un material cristalino microporoso sintético denominado ITQ-45. La estructura de este material presenta una red microporosa constituida por canales con aperturas formadas por 8 y 10 tetraedros T04 que se cruzan entre sí dando lugar a cavidades no esféricas, a las que se accede a través de dos ventanas formadas por 8 tetraedros y otras dos de 10 tetraedros, siendo estas cavidades accesibles a moléculas de interés en catálisis, en procesos de adsorción o de separación. El espacio no ocupado por estas cavidades se completa con otras de menor tamaño con forma de dodecaedro distorsionado, que son accesibles únicamente a través de ventanas formadas por cinco tetraedros, y por tanto no pueden ser ocupadas por moléculas de interés. Description of the invention In the present invention, a synthetic microporous crystalline material called ITQ-45 is described. The structure of this material has a microporous network consisting of channels with openings formed by 8 and 10 T0 4 tetrahedra that intersect each other giving rise to non-spherical cavities, which are accessed through two windows formed by 8 tetrahedra and others two of 10 tetrahedra, these cavities being accessible to molecules of interest in catalysis, in adsorption or separation processes. The space not occupied by these cavities is completed with other smaller ones with a distorted dodecahedron shape, which are accessible only through windows formed by five tetrahedra, and therefore cannot be occupied by molecules of interest.
La estructura de la zeolíta ITQ-45 puede describirse por su celda unidad, que es la unidad estructural más pequeña que contiene todos los elementos estructurales de este material. La tabla 1 muestra la lista de posiciones atómicas de todos los átomos en coordinación tetraédríca en una celda unidad. Todos estos átomos están conectados entre sí a través de oxígenos puente que unen átomos tetraédricos contiguos dos a dos. En total, cada celda unidad contiene 92 átomos en coordinación tetraédríca, denominados T1 , T2, T3, T4 hasta T92, distintos de oxígeno, que están localizados en las posiciones cristalográficas con coordenadas atómicas cartesianas x, y y z que se muestran en la Tabla 1 . Tabla 1 The structure of the ITQ-45 zeolite can be described by its unit cell, which is the smallest structural unit that contains all the structural elements of this material. Table 1 shows the list of atomic positions of all atoms in tetrahedral coordination in a unit cell. All these atoms are connected to each other through bridge oxygen that bind contiguous tetrahedral atoms two to two. In total, each unit cell contains 92 atoms in tetrahedral coordination, called T1, T2, T3, T4 up to T92, other than oxygen, which are located in the crystallographic positions with Cartesian atomic coordinates x, yyz shown in Table 1. Table 1
Coordenadas a (A) b(A) C(A) atómicas  Coordinates a (A) b (A) C (A) atomic
T1 7.1 2.2 5.0 T1 7.1 2.2 5.0
T2 8.5 4.6 12.3T2 8.5 4.6 12.3
T3 8.8 7.1 10.5T3 8.8 7.1 10.5
T4 10.6 2.1 2.3T4 10.6 2.1 2.3
T5 10.7 2.4 13.0T5 10.7 2.4 13.0
T6 7.0 5.1 1.1S6 7.0 5.1 1.1
T7 6.1 3.1 7.8T7 6.1 3.1 7.8
T8 7.2 2.2 10.7T8 7.2 2.2 10.7
T9 16.1 13.4 11.9S9 16.1 13.4 11.9
T10 17.5 15.8 5.4T10 17.5 15.8 5.4
T11 17.8 18.3 3.6T11 17.8 18.3 3.6
T12 1.6 13.3 9.2T12 1.6 13.3 9.2
T13 1.7 13.6 6.0T13 1.7 13.6 6.0
T14 15.9 16.3 8.1T14 15.9 16.3 8.1
T15 15.0 14.3 0.9T15 15.0 14.3 0.9
T16 16.2 13.4 3.7T16 16.2 13.4 3.7
T17 10.8 20.3 5.0T17 10.8 20.3 5.0
T18 9.3 17.9 12.3T18 9.3 17.9 12.3
T19 9.1 15.4 10.5T19 9.1 15.4 10.5
T20 7.3 20.3 2.3T20 7.3 20.3 2.3
T21 7.2 20.0 13.0T21 7.2 20.0 13.0
T22 10.9 17.4 1.1T22 10.9 17.4 1.1
T23 11.8 19.3 7.8T23 11.8 19.3 7.8
T24 10.7 20.2 10.7T24 10.7 20.2 10.7
T25 1.8 9.0 11.9T25 1.8 9.0 11.9
T26 0.4 6.6 5.4T26 0.4 6.6 5.4
T27 0.1 4.1 3.6T27 0.1 4.1 3.6
T28 16.2 9.1 9.2 T29 16.1 8.8 6.0T28 16.2 9.1 9.2 T29 16.1 8.8 6.0
T30 2.0 6.1 8.1T30 2.0 6.1 8.1
T31 2.9 8.1 0.9T31 2.9 8.1 0.9
T32 1.7 9.0 3.7T32 1.7 9.0 3.7
T33 16.1 20.3 5.0T33 16.1 20.3 5.0
T34 17.5 17.9 12.3T34 17.5 17.9 12.3
T35 17.8 15.4 10.5T35 17.8 15.4 10.5
T36 1.6 20.3 2.3T36 1.6 20.3 2.3
T37 1.7 20.0 13.0T37 1.7 20.0 13.0
T38 15.9 17.4 1.1T38 15.9 17.4 1.1
T39 15.0 19.3 7.8T39 15.0 19.3 7.8
T40 16.2 20.2 10.7T40 16.2 20.2 10.7
T41 7.1 9.0 11.9T41 7.1 9.0 11.9
T42 8.5 6.6 5.4T42 8.5 6.6 5.4
T43 8.8 4.1 3.6T43 8.8 4.1 3.6
T44 10.6 9.1 9.2T44 10.6 9.1 9.2
T45 10.7 8.8 6.0T45 10.7 8.8 6.0
T46 7.0 6.1 8.1T46 7.0 6.1 8.1
T47 6.1 8.1 0.9T47 6.1 8.1 0.9
T48 7.2 9.0 3.7T48 7.2 9.0 3.7
T49 1.8 2.2 5.0T49 1.8 2.2 5.0
T50 0.4 4.6 12.3T50 0.4 4.6 12.3
T51 0.1 7.1 10.5T51 0.1 7.1 10.5
T52 16.2 2.1 2.3T52 16.2 2.1 2.3
T53 16.1 2.4 13.0T53 16.1 2.4 13.0
T54 2.0 5.1 1.1T54 2.0 5.1 1.1
T55 2.9 3.1 7.8T55 2.9 3.1 7.8
T56 1.7 2.2 10.7T56 1.7 2.2 10.7
T57 10.8 13.4 11.9T57 10.8 13.4 11.9
T58 9.3 15.8 5.4T58 9.3 15.8 5.4
T59 9.1 18.3 3.6 T60 7.3 13.3 9.2T59 9.1 18.3 3.6 T60 7.3 13.3 9.2
T61 7.2 13.6 6.0T61 7.2 13.6 6.0
T62 10.9 16.3 8.1T62 10.9 16.3 8.1
T63 11.8 14.3 0.9T63 11.8 14.3 0.9
T64 10.7 13.4 3.7T64 10.7 13.4 3.7
T65 8.9 0.0 4.0T65 8.9 0.0 4.0
T66 8.9 0.0 1 1.8T66 8.9 0.0 1 1.8
T67 0.0 1 1.2 1 1.0T67 0.0 1 1.2 1 1.0
T68 0.0 1 1.2 4.9T68 0.0 1 1.2 4.9
T69 0.0 0.0 4.0T69 0.0 0.0 4.0
T70 0.0 0.0 1 1.8T70 0.0 0.0 1 1.8
T71 8.9 1 1.2 1 1.0T71 8.9 1 1.2 1 1.0
T72 8.9 1 1.2 4.9T72 8.9 1 1.2 4.9
T73 4.5 3.3 0.9T73 4.5 3.3 0.9
T74 4.5 1.9 3.6T74 4.5 1.9 3.6
T75 4.5 1.5 12.2T75 4.5 1.5 12.2
T76 13.4 14.5 7.8T76 13.4 14.5 7.8
T77 13.4 13.1 10.6T77 13.4 13.1 10.6
T78 13.4 12.7 5.2T78 13.4 12.7 5.2
T79 13.4 19.2 0.9T79 13.4 19.2 0.9
T80 13.4 20.6 3.6T80 13.4 20.6 3.6
T81 13.4 20.9 12.2T81 13.4 20.9 12.2
T82 4.5 7.9 7.8T82 4.5 7.9 7.8
T83 4.5 9.4 10.6T83 4.5 9.4 10.6
T84 4.5 9.7 5.2T84 4.5 9.7 5.2
T85 13.4 1.4 13.0T85 13.4 1.4 13.0
T86 13.4 1.1 2.4T86 13.4 1.1 2.4
T87 4.5 12.6 6.1T87 4.5 12.6 6.1
T88 4.5 12.3 9.3T88 4.5 12.3 9.3
T89 4.5 21.1 13.0T89 4.5 21.1 13.0
T90 4.5 21.3 2.4 T91 13.4 9.8 6.1 T90 4.5 21.3 2.4 T91 13.4 9.8 6.1
T92 13.4 10.1 9.3  T92 13.4 10.1 9.3
Cada uno de los átomos T de la Tabla 1 se encuentra rodeado por cuatro átomos de oxígeno como primeros vecinos y otros cuatro átomos T como segundos vecinos, de tal forma que los átomos T quedan conectados dos a dos a través de oxígenos puente formando enlaces T-O-T. La presencia de cationes o dependiendo de la naturaleza de los átomos T pueden modificar los valores presentados en la Tabla 1 , por lo que cada coordenada cristalográfica puede modificarse hasta 0.5 Á del valor dado en la Tabla 1 . Each of the T atoms in Table 1 is surrounded by four oxygen atoms as first neighbors and four other T atoms as second neighbors, so that the T atoms are connected two by two through bridge oxygen forming TOT bonds . The presence of cations or depending on the nature of the T atoms can modify the values presented in Table 1, so that each crystallographic coordinate can be modified up to 0.5 A of the value given in Table 1.
La zeolita ITQ-45 tiene en su forma sin calcinar un diagrama de difracción de rayos X cuyos picos de difracción más importantes vienen dados en la tabla 2, y en la tabla 3 para su forma calcinada. The ITQ-45 zeolite has in its uncalcrated form an X-ray diffraction diagram whose most important diffraction peaks are given in Table 2, and in Table 3 for its calcined form.
Tabla 2 Table 2
Intensidad  Intensity
26a 26 a
Relativa  Relative
6,3 m  6.3 m
7,5 f  7.5 f
7,9 md  7.9 md
9,9 md  9.9 md
1 1 ,3 md  1 1, 3 md
12,7 d  12.7 d
15,0 m  15.0 m
15,5 d  15.5 d
15,8 m  15.8 m
16,2 mf  16.2 mf
16,8 d  16.8 d
17,8 d  17.8 d
18,1 mf 18,7 md18.1 mf 18.7 md
19,1 d19.1 d
19,5 d19.5 d
20,4 md20.4 md
21,3 d21.3 d
22,6 md22.6 md
22,7 md22.7 md
23,0 d23.0 d
23,7 md23.7 md
24,2 md24.2 md
24,7 md24.7 md
25,6 m25.6 m
26,4 d26.4 d
28,1 md28.1 md
28,7 d28.7 d
28,9 d28.9 d
29,1 md29.1 md
29,4 md29.4 md
31,1 md31.1 md
31,9 md31.9 md
34,3 md a (± 0.4) 34.3 md a (± 0.4)
Tabla 3 Table 3
Intensidad Intensity
3 3
Relativa Relative
6,3 mf6.3 mf
7,5 f7.5 f
7,9 md7.9 md
9,9 md9.9 md
11,3 d 12,7 md11.3 d 12.7 md
12,8 md12.8 md
13,5 md13.5 md
14,3 md14.3 md
15,0 md15.0 md
15,4 md15.4 md
15,8 md15.8 md
16,2 md16.2 md
16,7 md16.7 md
17,8 md17.8 md
18,0 d18.0 d
18,1 md18.1 md
18,7 md18.7 md
19,0 md19.0 md
19,6 md19.6 md
20,0 md20.0 md
20,4 md20.4 md
21 ,3 md21.3 md
21 ,4 md21.4 md
22,7 md22.7 md
23,0 md23.0 md
23,7 md23.7 md
24,1 md24.1 md
24,7 md24.7 md
25,2 md25.2 md
25,5 md25.5 md
25,7 md25.7 md
25,8 md25.8 md
26,5 md26.5 md
27,7 md27.7 md
28,0 md 28,3 md 28.0 md 28.3 md
28,6 md  28.6 md
28,9 md  28.9 md
29,2 md  29.2 md
29,5 md  29.5 md
30,0 md  30.0 md
a (± 0.4)  a (± 0.4)
Estos difractogramas de Rayos X se obtuvieron con un difractómetro Panalytical X'Pert Pro equipado con una rendija de divergencia fija utilizando la radiación K« del cobre. La intensidad relativa de las líneas 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. Debe tenerse en cuenta que los datos de difracción listados para estas muestras como líneas sencillas o únicas, pueden estar formados por múltiples solapamíentos o superposición de reflexiones que, en ciertas condiciones, tales como diferencias en la composición química, pueden aparecer como líneas resueltas o parcialmente resueltas. Generalmente, los cambios en la composición química pueden originar 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. These X-ray diffractograms were obtained with a Panalytical X'Pert Pro diffractometer equipped with a fixed divergence slit using the K «radiation of copper. 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, average (m) = 40-60, weak ( d) = 20-40, and very weak (md) = 0-20. It should be borne in mind that the diffraction data listed for these samples as single or single lines, can be formed by multiple overlaps or overlapping reflections that, in certain conditions, such as differences in chemical composition, may appear as resolved or partially resolved lines. Generally, changes in the chemical composition can cause variations in the parameters of the unit cell and / or changes in the symmetry of the crystal, without a change in the 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.
La presente invención se refiere a un material cristalino microporoso denominado ITQ-45, que puede poseer una composición química: The present invention relates to a microporous crystalline material called ITQ-45, which may have a chemical composition:
x X203 : y Y02 : z Z02 x X 2 0 3 : y Y0 2 : z Z0 2
donde: - X es un elemento trivalente seleccionado entre Al, B, Fe, In, Ga, Cr, o mezclas de estos; where: - 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 between 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 10 e infinito, preferentemente entre 15 e infinito.  - the value of z / y is between 10 and infinity, preferably between 15 and infinity.
De los valores dados se deduce claramente que el material cristalino ITQ-45 se puede obtener en ausencia de elementos trivalentes añadidos. It is clear from the values given that the ITQ-45 crystalline material can be obtained in the absence of added trivalent elements.
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
Según otra realización particular, el valor de y es igual a cero por lo que puede poseer una composición química:  According to another particular embodiment, the value of y is 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, y más preferentemente entre 20 e infinito.  - the value of z / x is between 9 and infinity, and more preferably between 20 and infinity.
Según una realización preferente, el material de la presente invención, ITQ-45, posee una composición química:  According to a preferred embodiment, the material of the present invention, ITQ-45, has a chemical composition:
t P2O5 : x X2O3 : y Y02 : z Z02 t P2O5: x X2O3: 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; - Z es un elemento tetravalente seleccionado entre Si, Ge o mezclas de ellos, preferentemente Si; - Y is a tetravalent element selected from Ti, Sn, Zr, V or mixtures thereof, preferably between Ti, Sn, Zr, or mixtures thereof; - Z is a tetravalent element selected from Si, Ge or mixtures thereof, preferably Si;
- P se refiere a fósforo proveniente del agente director de estructura; - P refers to phosphorus from the structure managing agent;
- 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 10 e infinito, preferentemente entre 15 e infinito.  - the value of z / y is between 10 and infinity, preferably between 15 and infinity.
- el valor de t/(x+y+z) puede estar comprendido entre 1 y 0. De los valores dados se deduce claramente que el material cristalino - the value of t / (x + y + z) can be between 1 and 0. It is clear from the values given that the crystalline material
ITQ-45 se puede sintetizar en ausencia de elementos trivalentes añadidos. El difractograma de Rayos X de la zeolita en su forma calcinada presenta los picos de difracción que se listan en la Tabla 3. Según una realización particular, x puede ser 0 y el material ITQ-45 puede poseer una composición química: ITQ-45 can be synthesized in the absence of added trivalent elements. The X-ray diffractogram of the zeolite in its calcined form presents the diffraction peaks listed in Table 3. According to a particular embodiment, x may be 0 and the ITQ-45 material may have a chemical composition:
t P205 : y Y02 : z Z02 t P 2 0 5 : y Y0 2 : z Z0 2
donde: where:
- t/(y+z) puede estar comprendido entre 1 y 0.  - t / (y + z) can be between 1 and 0.
Según otra realización particular, y puede ser 0 y el material ITQ-45 puede poseer una composición química: According to another particular embodiment, and it can be 0 and the ITQ-45 material can have a chemical composition:
Figure imgf000012_0001
Figure imgf000012_0001
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.
- t/(x+z) puede estar comprendido entre 1 y 0.  - t / (x + z) can be between 1 and 0.
El material cristalino calcinado ITQ-45 puede ser sometido a uno o varios procesos de extracción química o lavado en medio acuoso, alcohólico, orgánico o mezcla de ellos para eliminar los residuos inorgánicos P2O5 provenientes de la eliminación del agente director de estructura. Este tratamiento de extracción o lavado puede ser realizado en medio ácido, neutro o alcalino. Según otra realización preferente, el material de la presente invención, ITQ-45, posee una composición química: The calcined crystalline material ITQ-45 can be subjected to one or several chemical extraction processes or washing in aqueous, alcoholic, organic or mixture thereof to eliminate P2O5 inorganic residues from the elimination of the structure directing agent. This extraction or washing treatment can be performed in acid, neutral or alkaline medium. According to another preferred embodiment, the material of the present invention, ITQ-45, has 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:
- 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 between 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 10 e infinito, preferentemente entre 15 e infinito.  - the value of z / y is between 10 and infinity, preferably between 15 and infinity.
- R es un agente director de estructura, preferentemente dicho R contiene P, más preferentemente R contiene enlaces P-N, y más preferentemente está seleccionado entre ter-butil-imino-trís(di-metíl- amino)-fosforano y su derivado protonado;  - R is a structure directing agent, preferably said R contains P, more preferably R contains P-N bonds, and more preferably is selected from tert-butyl-imino-tris (di-methyl-amino) -phosphorane and its protonated derivative;
- el valor de n/(x+y+z) está comprendido entre 1 y 0,001 .  - the value of n / (x + y + z) is between 1 and 0.001.
De los valores dados se deduce claramente que el material cristalino ITQ-45 se puede sintetizar en ausencia de elementos trivalentes añadidos. La relación n/z puede estar comprendida entre 1 y 0.001 en el material ITQ-45 según se sintetiza. El difractograma de Rayos X de la zeolita en su forma sintetizada presenta los picos de difracción que se listan en la Tabla 2. It is clear from the values given that the ITQ-45 crystalline material can be synthesized in the absence of added trivalent elements. The n / z ratio may be between 1 and 0.001 in the ITQ-45 material as synthesized. The X-ray diffractogram of the zeolite in its synthesized form presents the diffraction peaks listed in Table 2.
Según una realización particular, x puede ser 0 y el material ITQ-45 puede poseer una composición química: According to a particular embodiment, x may be 0 and the ITQ-45 material may have a chemical composition:
n R : y YO2 : z ZO2 n R: and YO 2 : z ZO 2
donde: where:
- el valor de n/(y+z) está comprendido entre 1 y 0,001 . Según otra realización particular, y puede ser 0 y el material ITQ-45 puedeposeer una composición química - the value of n / (y + z) is between 1 and 0.001. According to another particular embodiment, and it can be 0 and the ITQ-45 material can have 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, preferentemente entre 20 e infinito.  - the value of z / x is between 9 and infinity, preferably between 20 and infinity.
- el valor de n/(x+z) está comprendido entre 1 y 0,001 . El material cristalino ITQ-45 calcinado y/o calcinado y lavado pueden ser sometidos a uno o varios procesos post-síntesis de incorporación o intercambio de elementos trivalentes empleando disoluciones que contengan elementos trivalentes X que pueden estar seleccionados entre Al, Ga, B, Cr, Fe, In y mezclas de los mismos en medio acuoso, alcohólico, orgánico o mezcla de ellos. En este proceso se pueden eliminar los residuos inorgánicos P2O5 provenientes de la eliminación del agente director de estructura y/o incorporar los elementos trivalentes de las disoluciones. Este tratamiento de incorporación de metales trivalentes y/o lavado puede ser realizado en medio ácido, neutro o alcalino. El material cristalino con metales trivalentes incorporados mediante tratamientos post-síntesis tiene una composición molar en su estado anhidro que viene dado por la ecuación:  - the value of n / (x + z) is between 1 and 0.001. The calcined and / or calcined and washed ITQ-45 crystalline material may be subjected to one or more post-synthesis processes of incorporation or exchange of trivalent elements using solutions containing trivalent elements X that may be selected from Al, Ga, B, Cr , Fe, In and mixtures thereof in aqueous, alcoholic, organic or mixture thereof. In this process, inorganic P2O5 residues from the elimination of the structure directing agent and / or incorporating the trivalent elements of the solutions can be eliminated. This treatment of incorporation of trivalent metals and / or washing can be carried out in acid, neutral or alkaline medium. The crystalline material with trivalent metals incorporated by post-synthesis treatments has a molar composition in its 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
en la que X es un elemento trivalente tal como Al, B, Fe, In, Ga, Cr o mezclas de estos, Y es un elemento tetravalente tal como Ti, Sn, Zr, V o mezclas de ellos, y Z corresponde a un elemento seleccionado entre Si o Ge, o mezclas de ellos. El valor de (y+z)/x es al menos 9, y puede estar comprendido entre 20 e∞ y el valor z/y es de al menos 10. De los valores dados se deduce claramente que el material cristalino ITQ-45 se puede sintetizar en ausencia de elementos trivalentes añadidos. El difractograma de Rayos X de la zeolita tras el tratamiento post-síntesis para incorporar elementos trivalentes en su estructura presenta los picos de difracción que se listan en la Tabla 4. El componente orgánico presente en el material ITQ-45 según se sintetiza se puede eliminar, por ejemplo por extracción y/o por tratamiento térmico calentando a temperatura por encima de 200δ C durante un periodo de tiempo que puede estar comprendido entre 2 minutos y 25 horas. wherein X is a trivalent element such as Al, B, Fe, In, Ga, Cr or mixtures thereof, Y is a tetravalent element such as Ti, Sn, Zr, V or mixtures thereof, and Z corresponds to a element selected from Si or Ge, or mixtures of them. The value of (y + z) / x is at least 9, and can be between 20 e∞ and the value z / y is at least 10. From the given values it is clear that the ITQ-45 crystalline material is can synthesize in the absence of added trivalent elements. The X-ray diffractogram of the zeolite after post-synthesis treatment to incorporate trivalent elements in its structure presents the diffraction peaks listed in Table 4. The organic component present in the ITQ-45 material as synthesized can be removed, for example by extraction and / or by heat treatment by heating at a temperature above 200 δ C for a period of time that can be between 2 minutes and 25 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+ 4. 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 NA, MIA, IVA, Va, IB, NB, 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 + 4 . 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 from the NA, MIA, IVA, Va, IB, NB, IIIB, IVB, VB, VIIB group of the periodic table of the elements.
Asimismo, es posible introducir cationes en la red de la zeolita ITQ-45 mediante tratamientos post-síntesis. Estos tratamientos consisten en suspender la muestra de ITQ-45 calcinada o calcinada y lavada en una disolución acuosa, alcohólica, orgánica o mezclas de ambos que contiene el elemento trivalente que se desea incorporar a temperatura entre 0 y 2009C durante periodos comprendidos entre 1 hora y 15 días. It is also possible to introduce cations in the ITQ-45 zeolite network through post-synthesis treatments. These treatments consist in suspending the calcined or calcined ITQ-45 sample and washed in an aqueous, alcoholic, organic solution or mixtures of both containing the trivalent element that is to be incorporated at a temperature between 0 and 200 9 C for periods between 1 hour and 15 days
Con el fin de preparar catalizadores, el material cristalino de la presente invención puede combinarse íntimamente con componentes hidrogenantes- deshidrogenantes como 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 catíónica y/o a partir de sales u otros compuestos que por descomposición generen el componente metálico u óxido en su forma catalítica adecuada. Además, la presente invención se refiere al procedimiento de obtención del matenal ITQ-45 descrito anteriormente. In order to prepare catalysts, the crystalline material of the present invention can be intimately combined with hydrogenating-dehydrogenating components such as platinum, palladium, nickel, rhenium, cobalt, tungsten, molybdenum, vanadium, chromium, manganese, iron and combinations thereof. The introduction of these elements can be carried out in the crystallization stage, by exchange (if applicable), and / or by impregnation or by physical mixing. These elements can be introduced in their cathonic form and / or from salts or other compounds that by decomposition generate the metal component or oxide in its appropriate catalytic form. In addition, the present invention relates to the procedure for obtaining the ITQ-45 matenal described above.
Según la presente invención, el procedimiento de preparación del material ITQ-45 puede comprender al menos un primer paso de preparación de una mezcla que contiene H20, 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: According to the present invention, the ITQ-45 material preparation process may comprise at least a first step of preparing a mixture containing H 2 0, an oxide or other source of the tetravalent material Z and 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:
{Y02+Z02)/X203 mayor de 2, preferentemente mayor de 5 H20/(Y02+Z02) 1 -50, preferentemente 2-30. {Y0 2 + Z0 2 ) / X20 3 greater than 2, preferably greater than 5 H 2 0 / (Y0 2 + Z0 2 ) 1 -50, preferably 2-30.
R/(Y02 + Z02 ) 0.05-3.0, preferentemente entre 0.05-1 . R / (Y0 2 + Z0 2 ) 0.05-3.0, preferably between 0.05-1.
OH7(Y02 + Z02 ) 0.05-3.0, preferentemente entre 0.05-1 . OH7 (Y0 2 + Z0 2 ) 0.05-3.0, preferably between 0.05-1.
Z02/Y02 mayor de 5, preferentemente entre 8-25. Z0 2 / Y0 2 greater than 5, preferably between 8-25.
Si02/Ge02 mayor de 2, preferentemente mayor de 5 Si0 2 / Ge0 2 greater than 2, preferably greater than 5
Un segundo paso en el que se puede mantener la mezcla a una temperatura entre 80 y 200QC hasta que se formen los cristales del material y un paso posterior de recuperación del material cristalino. A second step in which the mixture can be maintained at a temperature between 80 and 200 Q C until crystals of the material and a subsequent step of recovering the crystalline material form.
Según una realización preferente de la presente invención, Z es Si. According to a preferred embodiment of the present invention, Z is Si.
Según otra realización preferente, el agente director de estructura R puede ser un compuesto que contiene P, preferentemente R contiene enlaces P-N, y más preferentemente está seleccionado entre ter-butíl-imino-tris(di-metil- amino)-fosforano y su derivado catiónico protonado.  According to another preferred embodiment, the structure directing agent R can be a compound containing P, preferably R contains PN bonds, and more preferably is selected from tert-butyl-imino-tris (di-methyl-amino) -phosphorane and its derivative proton cationic.
El método de preparación de este material se puede llevar a cabo en medio básico y ausencia de iones fluoruro añadidos. The method of preparation of this material can be carried out in basic medium and absence of added fluoride ions.
Este material se puede preparar según una realización particular, a partir de una mezcla de reacción que contiene H20, 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 Y, como por ejemplo Si, una fuente de Ge, como por ejemplo Ge02 y un agente orgánico director de estructura (R) generalmente un catión orgánico, que puede contener átomos distintos de C, H y N en su composición. Pueden utilizarse como agentes directores de estructura compuestos del tipo base de fosfaceno caracterizados por la presencia de enlaces P-N en su estructura, y más preferentemente es el compuesto ter-butil-imino-tris(di-metil-amino)-fosforano o su derivado catiónico protonado. This material can be prepared according to a particular embodiment, from a reaction mixture containing H 2 0, 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 Y, such as Si, a source of Ge, such as Ge02 and an organic structure directing agent (R ) generally an organic cation, which may contain atoms other than C, H and N in its composition. Compositions of the phosphazene base type characterized by the presence of PN bonds in its structure can be used as structure directing agents, and more preferably it is the tert-butyl-imino-tris (di-methyl-amino) -phosphorane compound or its cationic derivative protonated
La composición de la mezcla de reacción tiene la siguiente composición en términos de relaciones molares de óxidos: The composition of the reaction mixture has the following composition in terms of molar ratios of oxides:
Reactivos Útil Preferido Reagents Useful Preferred
(Y02+Z02)/X203 mayor de 2 mayor de 5(Y0 2 + Z0 2 ) / X 2 0 3 greater than 2 greater than 5
H20/(Y02+Z02) 1 -50 2-30 H 2 0 / (Y0 2 + Z0 2 ) 1 -50 2-30
R/(Y02 + Z02 ) 0.05-3.0 0.05-1.0R / (Y0 2 + Z0 2 ) 0.05-3.0 0.05-1.0
OH7{Y02 + Z02 ) 0.05-3.0 0.05-1.0OH7 {Y0 2 + Z0 2 ) 0.05-3.0 0.05-1.0
ZO2/YO2 mayor de 5 8-25 ZO 2 / YO 2 greater than 5 8-25
Si02/Ge02 mayor de 2 mayor de 5 Si0 2 / Ge0 2 greater than 2 greater than 5
La cristalización del material se puede llevar a cabo 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 30 días. Al finalizar la etapa de cristalización, se separan los cristales del material 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 del mismo material o de este material calcinado como semillas, en cantidades de hasta 15% en peso respecto del total de óxidos, a la mezcla de síntesis. Estas pueden ser adicionadas previamente o durante la cristalización. Según una realización particular, el procedimiento de preparación del material ITQ-45 puede comprender un paso de calcinación del material cristalino obtenido, calcinación que se puede llevar a cabo a vacío, en aire, nitrógeno, hidrógeno, argón, helio o cualquier otro gas y a una temperatura superior a 200eC e inferior a 1200SC, preferentemente entre 200 y 1000SC durante un tiempo que puede ser entre 2 minutos y 25 horas. El material ITQ- 45 tras la calcinación, posee un sistema de poros libre de materia orgánica, cuyo difractograma de Rayos X presenta los picos que se listan en la Tabla 2. Durante esta calcinación pueden quedar en el interior de los canales o sobre la superficie del material residuos inorgánicos provenientes del agente director de estructura. Estos residuos pueden ser eliminados mediante un tratamiento posterior de lavado con agua, cualquier alcohol con menos de seis carbonos o mezclas de ellos, así como por disoluciones acuosas o alcohólicas de sales inorgánicas. The crystallization of the material can be carried out under stirring, in autoclaves at a temperature between 80 and 200 ° C, at times sufficient to achieve crystallization, for example between 12 hours and 30 days. At the end of the crystallization stage, the crystals of the material 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, crystals of the same material or of this calcined material can be added as seeds, in amounts of up to 15% by weight with respect to the total oxides, to the synthesis mixture. These can be added before or during crystallization. According to a particular embodiment, the ITQ-45 material preparation process may comprise a step of calcining the crystalline material obtained, calcination that can be carried out under vacuum, in air, nitrogen, hydrogen, argon, helium or any other gas already a temperature greater than 200 e C and less than 1200 S C, preferably between 200 and 1000 S C for a time that can be between 2 minutes and 25 hours. The ITQ-45 material after calcination, has a pore system free of organic matter, whose X-ray diffractogram presents the peaks listed in Table 2. During this calcination they can remain inside the channels or on the surface of inorganic waste material from the structure director. These residues can be eliminated by a subsequent treatment of washing with water, any alcohol with less than six carbons or mixtures thereof, as well as by aqueous or alcoholic solutions of inorganic salts.
Según una realización particular, dicho proceso o procesos de lavado puede comprender 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. De manera preferente dicha disolución es una disolución acuosa, alcohólica, orgánica o mezcla de ambas. El proceso de lavado se lleva a cabo a una temperatura preferentemente comprendida entre 0SC y 200-C. El diagrama de difracción del material resultante presenta los picos de difracción que se listan en la Tabla 3. According to a particular embodiment, said washing process or processes may comprise 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. Preferably said solution is an aqueous, alcoholic, organic solution or mixture of both. The washing process is carried out at a temperature preferably between 0 S C and 200-C. The diffraction diagram of the resulting material presents the diffraction peaks listed in Table 3.
Además, el material ITQ-45 calcinado o el material ITQ-45 calcinado y lavado puede ser sometido a uno o más tratamientos post-síntesis. Dichos tratamientos pueden consistir de manera preferente en tratar la ITQ-45 con disoluciones acuosas, alcohólicas, orgánicas o mezclas de ellas que contenga elementos trivalentes X, seleccionados preferentemente entre Al, Ga, B, Cr, Fe In, y mezclas de ellos con el fin de incorporarlos a la red zeolítica. Este tratamiento post-síntesis se puede realizar a pHs alcalinos, ácidos o neutros a temperaturas comprendidas preferentemente entre 0 y 200QC durante un tiempo preferido entre 1 hora a 15 días. El material resultante presenta los picos de difracción que se muestran en la Tabla 4 y contiene elementos provenientes de la disolución de tratamiento incorporados a la red. In addition, the calcined ITQ-45 material or the calcined and washed ITQ-45 material may be subjected to one or more post-synthesis treatments. Such treatments may preferably consist of treating the ITQ-45 with aqueous, alcoholic, organic solutions or mixtures thereof containing trivalent elements X, preferably selected from Al, Ga, B, Cr, Fe In, and mixtures thereof in order to incorporate them into the zeolitic network. This post-synthesis treatment can be carried out at alkaline, acidic or neutral pHs at temperatures preferably between 0 and 200 QC for a preferred time between 1 hour to 15 days. The resulting material presents the diffraction peaks shown in Table 4 and contains elements from the treatment solution incorporated into the network.
Posteriormente se puede recuperar del sólido lavado mediante filtración, centrifugación o cualquier técnica de separación de sólidos de líquidos y puede ser posteriormente activado mediante calcinación a temperaturas superiores a 2009C. Subsequently, it can be recovered from the washed solid by filtration, centrifugation or any liquid solids separation technique and can subsequently be activated by calcination at temperatures above 200 9 C.
La presente invención se refiere, además, al uso del material ITQ-45 obtenido según el procedimiento descrito anteriormente, como componente de catalizadores de craqueo catalítico de hidrocarburos, hidro-craqueo catalítico de hidrocarburos, procesos de alquilación de aromáticos con alcoholes u olefinas y en procesos de esterificación, acílación, reacción de anilina con formaldehído en su forma ácida y/o intercambiado con cationes adecuados así como para convertir alimentaciones formadas por compuestos orgánicos a productos de mayor valor añadido. El material producido ITQ-45 puede ser pastillado de acuerdo con técnicas conocidas. The present invention also relates to the use of the ITQ-45 material obtained according to the procedure described above, as a component of catalytic cracking catalysts of hydrocarbons, catalytic hydro-cracking of hydrocarbons, aromatic alkylation processes with alcohols or olefins and in esterification, acylation, reaction of aniline with formaldehyde in its acid form and / or exchanged with suitable cations as well as to convert feeds formed by organic compounds to products of higher added value. The produced ITQ-45 material can be pasted according to known techniques.
Ejemplos Examples
Ejemplo 1- Preparación de tert-butilimino-trís(dimetílam»no)fosforano. 13.8 g de PCI5 se disuelven en 100 mi de CH2CI2 anhidro bajo atmósfera de nitrógeno. A esta disolución se le adiciona lentamente una mezcla compuesta por 1 1 .7 g de una disolución 2M en tetrahidrofurano de dimetilamína a -50SC y de 26.3 g de trietilamina. La mezcla se agita vigorosamente a baja temperatura durante 1 hora y se deja finalizar la reacción a temperatura ambiente durante 12 horas. Example 1- Preparation of tert-butylimino-tris (dimethylamine »no) phosphorane. 13.8 g of PCI5 are dissolved in 100 ml of anhydrous CH2CI2 under a nitrogen atmosphere. To this solution is slowly added a mixture consisting of 1.1 g of a 2M solution in dimethylamine tetrahydrofuran at -50 S C and 26.3 g of triethylamine. The mixture is vigorously stirred at low temperature for 1 hour and the reaction is allowed to end at room temperature for 12 hours.
Sobre esta mezcla se adicionan 33.0 g de tertbutilamina a -50eC. La mezcla resultante se filtra y se elimina el disolvente del filtrado a vacío. El producto sólido resultante se disuelve en agua y se precipita en forma de sal de tetrafluoroborato al adicionar un exceso de tetrafluoroborato sódico. Los cristales resultantes se recuperan mediante filtración, siendo recristalizados en acetato de etilo. Los cristales obtenidos son transformados en el tert-butilimíno- tris(dimetilamino)fosforano deseado mediante tratamiento con potasa metanólica, separando el residuo sólido no deseado del sobrenadante. La disolución resultante se lleva a sequedad medíante evacuación a alto vacío, y el sólido se trata con 0.5 g de óxido de bario, destilándose el tert-butilimino- tris(dimetilamino)fosforano a alto vacío. To this mixture 33.0 g of tertbutylamine are added and -50 C. The resulting mixture was filtered and the filtrate solvent removed under vacuum. The resulting solid product is dissolved in water and precipitated as a tetrafluoroborate salt by adding an excess of sodium tetrafluoroborate. The resulting crystals are recovered by filtration, being recrystallized from ethyl acetate. The crystals obtained are transformed into the desired tert-butylimino-tris (dimethylamino) phosphorane by treatment with methanolic potash, separating the unwanted solid residue from the supernatant. The resulting solution is brought to dryness by evacuation under high vacuum, and the solid is treated with 0.5 g of barium oxide, the tert-butyliminotris (dimethylamino) phosphorane distilled under high vacuum.
Ejemplo 2- Preparación de la zeolita ITQ-45 Example 2- Preparation of ITQ-45 Zeolite
A 7.063 g (0.030 mol) de tert-butílimino-tris(dimetilamino)fosforano preparados según se describe en el ejemplo 1 , se le añaden 7.875 g (0.4375 mol) de H20, manteniendo la mezcla bajo agitación durante quince minutos. A esta mezcla se le añade 13.084 g (0.063 mol) de tetraetilortosilicato, 1 .309 g (0.0125 mol) de Ge02 y 0.180 g (0.0029 mol) de H3B03. La mezcla se mantiene bajo agitación a temperatura ambiente hasta la total evaporación del etanol formado durante la hidrólisis del tetraetilortosilicato. Posteriormente se añaden 6.971 g (0.387 mol) de H20 hasta alcanzar la relación H20/Si+Ge de 10. To 7,063 g (0.030 mol) of tert-butylimino-tris (dimethylamino) phosphorane prepared as described in example 1, 7,875 g (0.4375 mol) of H 2 0 are added, keeping the mixture under stirring for fifteen minutes. To this mixture is added 13,084 g (0.063 mol) of tetraethylorthosilicate, 1,309 g (0.0125 mol) of Ge0 2 and 0.180 g (0.0029 mol) of H 3 B0 3 . The mixture is kept under stirring at room temperature until the total evaporation of the ethanol formed during the hydrolysis of the tetraethylorthosilicate. Subsequently, 6,971 g (0.387 mol) of H 2 0 are added until the ratio H 2 0 / Si + Ge of 10 is reached.
El gel obtenido es trasvasado a autoclaves de acero recubiertos de teflón y se introducen en una estufa a 160-C durante 10 días. Transcurrido el tiempo de síntesis, el sólido obtenido es lavado con 100 mi de una disolución acuosa de tert-butilímino-tris(dímetilamino)fosforano de pH = 1 1 .5. Posteriormente es lavado con 2000 mi de agua destilada y secado a 100 eC durante 10 horas. El sólido resultante presenta un diagrama de difracción de Rayos X que contiene todos los picos que se indican en la Tabla 6. The gel obtained is transferred to Teflon coated steel autoclaves and placed in an oven at 160-C for 10 days. After the synthesis time, the solid obtained is washed with 100 ml of an aqueous solution of tert-butylamino-tris (dimethylamino) phosphorane of pH = 1 1 .5. It is subsequently washed with 2000 ml of distilled water and dried at 100 e C for 10 hours. The resulting solid presents an X-ray diffraction diagram that contains all the peaks indicated in Table 6.
Tabla 6 Table 6
Intensidad  Intensity
 2Θ
Relativa  Relative
6,34 41  6.34 41
7,45 99  7.45 99
7,90 12  7.90 12
9,93 12  9.93 12
1 1 ,27 12  1 1, 27 12
12,70 22  12.70 22
14,97 43  14.97 43
15,45 28  15.45 28
15,82 46  15.82 46
16,15 97  16.15 97
16,75 28  16.75 28
17,78 36 18,10 100 17.78 36 18.10 100
18,70 15  18.70 15
19,10 21  19.10 21
19,50 29  19.50 29
20,35 10  20.35 10
21 ,32 34  21, 32 34
22,73 1 1  22.73 1 1
23,02 21  23.02 21
23,73 15  23.73 15
24,14 13  24.14 13
24,68 9  24.68 9
25,58 41  25.58 41
26,36 37  26.36 37
28,06 12  28.06 12
Ejemplo 3- Preparación de la zeolita ITQ-45 en su forma calcinada. Example 3- Preparation of zeolite ITQ-45 in its calcined form.
Un sólido preparado tal y como se describe en el ejemplo 2 se introduce en un horno de mufla y se calcina en aire a 700QC durante 5 horas para descomponer la materia orgánica retenida en su interior. A solid prepared as described in Example 2 is introduced into a muffle furnace and calcined in air at 700 Q C for 5 hours to decompose organic matter retained therein.
El sólido resultante presenta un diagrama de difracción de Rayos X que contiene todos los picos que se indican en la Tabla 7. The resulting solid presents an X-ray diffraction diagram that contains all the peaks indicated in Table 7.
Tabla 7 Table 7
Intensidad  Intensity
 2Θ
Relativa  Relative
6,34 100  6.34 100
7,52 75  7.52 75
7,90 10  7.90 10
9,90 13 1 1 ,31 349.90 13 1 1, 31 34
12,67 1212.67 12
12,79 1012.79 10
13,45 113.45 1
14,28 314.28 3
15,04 1515.04 15
15,39 315.39 3
15,82 915.82 9
16,19 2016.19 20
16,73 616.73 6
17,77 817.77 8
18,04 2118.04 21
18,14 1618.14 16
18,68 518.68 5
19,04 319.04 3
19,62 619.62 6
20,03 120.03 1
20,40 120.40 1
21 ,26 721, 26 7
21 ,37 621, 37 6
22,68 422.68 4
22,98 422.98 4
23,69 523.69 5
24,14 324.14 3
24,73 324.73 3
25,17 225.17 2
25,46 525.46 5
25,65 425.65 4
25,83 225.83 2
26,48 726.48 7
27,65 1 28,02 4 27.65 1 28.02 4
28,32 1  28.32 1
28,58 5  28.58 5
28,90 8  28.90 8
29,17 2  29.17 2
29,48 3  29.48 3
29,95 1  29.95 1
Ejemplo 4- Lavado de una zeolita ITQ-45 calcinada. Example 4- Washing of a calcined ITQ-45 zeolite.
0.25 g del sólido preparados tal y como se describe en el ejemplo 3 se tratan con 16 mi de una disolución de acetato amónico 3M a 75eC durante 1 hora, y 3 horas a 90SC. El sólido se recupera por filtración y se lava exhaustivamente con agua a ebullición. El sólido se seca a 100SC durante 10 horas. 0.25 g of the solid prepared as described in example 3 are treated with 16 ml of a solution of 3M ammonium acetate at 75 e C for 1 hour, and 3 hours at 90 S C. The solid is recovered by filtration and is Wash thoroughly with boiling water. The solid is dried at 100 S C for 10 hours.
El sólido resultante presenta un diagrama de difracción de Rayos X que contiene todos los picos que se indican en la Tabla 8. The resulting solid presents an X-ray diffraction diagram that contains all the peaks indicated in Table 8.
Tabla 8 Table 8
Intensidad  Intensity
29a 29 a
Relativa  Relative
6,34 79  6.34 79
7,51 100  7.51 100
7,9 9  7.9 9
9,92 12  9.92 12
11 ,3 32  11, 3 32
12,78 19  12.78 19
13,47 1  13.47 1
14,27 5  14.27 5
15,03 25 15,43 4 15.03 25 15.43 4
15,82 13  15.82 13
16,19 33  16.19 33
16,74 6  16.74 6
17,78 1 1  17.78 1 1
18,14 24  18.14 24
18,66 4  18.66 4
19,09 3  19.09 3
19,6 1 1  19.6 1 1
20,39 2  20.39 2
21 ,28 9  21, 28 9
22,68 4  22.68 4
23,06 6  23.06 6
23,71 8  23.71 8
24,13 5  24.13 5
24,77 4  24.77 4
25,68 10  25.68 10
26,48 18  26.48 18
26,93 2  26.93 2
28,08 5  28.08 5
28,84 12  28.84 12
29,53 4  29.53 4
30,07 2  30.07 2
38,14 4  38.14 4
Ejemplo 5- Tratamiento post-síntesis de una zeolita ITQ-45 calcinada para obtener AI-ITQ-45. 0.501 g del sólido preparados tal y como se describe en el ejemplo 3 se añaden a 25 mi de una disolución de nitrato de aluminio 8%. La mezcla se trasvasa a autoclaves de acero recubiertos de teflón y se introducen en una estufa a 140QC durante 3 días. El sólido obtenido es lavado con 2000 mi de agua destilada y secado a 100 9C durante 10 horas. Example 5- Post-synthesis treatment of a calcined ITQ-45 zeolite to obtain AI-ITQ-45. 0.501 g of the solid prepared as described in example 3 are added to 25 ml of an 8% aluminum nitrate solution. The mixture is transferred to Teflon coated steel autoclaves and placed in a stove at 140 Q C for 3 days. The solid obtained is washed with 2000 ml of distilled water and dried at 100 9 C for 10 hours.
El sólido resultante presenta un diagrama de difracción de Rayos X característico de la zeolita ITQ-45. The resulting solid presents a characteristic X-ray diffraction diagram of the ITQ-45 zeolite.
Ejemplo 6- Tratamiento post-síntesis de una zeolita ITQ-45 calcinada para obtener ITQ-45 sin elementos trivalentes en su composición. 0.42 g del sólido preparados tal y como se describe en el ejemplo 3 se añaden a 30 mi de una disolución de ácido clorhídrico 0.01 N. La mezcla se mantiene a temperatura ambiente durante 24 h. El sólido obtenido es lavado con 2000 mi de agua destilada y secado a 100 9C durante 10 horas. El sólido resultante presenta un diagrama de difracción de Rayos X característico de la zeolita ITQ-45. Example 6- Post-synthesis treatment of a calcined ITQ-45 zeolite to obtain ITQ-45 without trivalent elements in its composition. 0.42 g of the solid prepared as described in example 3 are added to 30 ml of a 0.01 N hydrochloric acid solution. The mixture is kept at room temperature for 24 h. The solid obtained is washed with 2000 ml of distilled water and dried at 100 9 C for 10 hours. The resulting solid presents a characteristic X-ray diffraction diagram of the ITQ-45 zeolite.
Ejemplo 7- Preparación de la zeolita ITQ-45 A 2.554 g (0.01 1 mol) de tert-butílimino-tris(dimetilamino)fosforano preparados según se describe en el ejemplo 1 , se le añaden 4.281 g (0.238 mol) de H2O, manteniendo la mezcla bajo agitación durante quince minutos. A esta mezcla se le añade 6.378 g (0.031 mol) de tetraetilortosilicato, 0.316 g (0.003 mol) de Ge02 y 0.079 g (0.0013 mol) de H3B03. La mezcla se mantiene bajo agitación a temperatura ambiente hasta la total evaporación del etanol formado durante la hidrólisis del tetraetilortosilicato. Posteriormente se añaden 2.792 g (0.155 mol) de H20 hasta alcanzar la relación H20/Si+Ge de 10. Example 7- Preparation of ITQ-45 zeolite At 2,554 g (0.01 1 mol) of tert-butylimino-tris (dimethylamino) phosphorane prepared as described in example 1, 4,281 g (0.238 mol) of H 2 O is added , keeping the mixture under stirring for fifteen minutes. To this mixture is added 6.378 g (0.031 mol) of tetraethylorthosilicate, 0.316 g (0.003 mol) of Ge0 2 and 0.079 g (0.0013 mol) of H 3 B0 3 . The mixture is kept under stirring at room temperature until the total evaporation of the ethanol formed during the hydrolysis of the tetraethylorthosilicate. Subsequently 2,792 g (0.155 mol) of H 2 0 are added until the ratio H 2 0 / Si + Ge of 10 is reached.
El gel obtenido es trasvasado a autoclaves de acero recubiertos de teflón y se introducen en una estufa a 160SC durante 18 días. Transcurrido el tiempo de síntesis, el sólido obtenido es lavado con 100 mi de una disolución acuosa de tert-butilímino-tris{dímetilamino)fosforano de pH = 1 1 .5. Posteriormente es lavado con 2000 mi de agua destilada y secado a 100 QC durante 10 horas. The gel obtained is transferred to Teflon coated steel autoclaves and placed in an oven at 160 S C for 18 days. After the synthesis time, the solid obtained is washed with 100 ml of an aqueous solution of tert-butylamino-tris {dimethylamino) phosphorane of pH = 1 1 .5. It is subsequently washed with 2000 ml of distilled water and dried at 100 QC for 10 hours.
El sólido resultante presenta un diagrama de difracción de Rayos X característico de la zeolita ITQ-45. The resulting solid presents a characteristic X-ray diffraction diagram of the ITQ-45 zeolite.
Ejemplo 8- Preparación de la zeolita ITQ-45 Example 8- Preparation of zeolite ITQ-45
A 2.932 g (0.013 mol) de tert-butílimino-tris(dimetilamino)fosforano preparados según se describe en el ejemplo 1 , se le añaden 3.254 g (0.181 mol) de H20, manteniendo la mezcla bajo agitación durante quince minutos. A esta mezcla se le añade 4.326 g (0.021 mol) de tetraetilortosilicato, 1 .100 g (0.01 1 mol) de Ge02 y 0.060 g (0.001 mol) de H3B03. La mezcla se mantiene bajo agitación a temperatura ambiente hasta la total evaporación del etanol formado durante la hidrólisis del tetraetilortosilicato. Posteriormente se añaden 2.376 g (0.132 mol) de H20 hasta alcanzar la relación H20/Si+Ge de 10. El gel obtenido es trasvasado a autoclaves de acero recubiertos de teflón y se introducen en una estufa a 160SC durante 25 días. To 2,932 g (0.013 mol) of tert-butylimino-tris (dimethylamino) phosphorane prepared as described in example 1, 3,254 g (0.181 mol) of H 2 0 are added, keeping the mixture under stirring for fifteen minutes. To this mixture is added 4,326 g (0.021 mol) of tetraethylorthosilicate, 1,100 g (0.01 1 mol) of Ge0 2 and 0.060 g (0.001 mol) of H 3 B0 3 . The mixture is kept under stirring at room temperature until the total evaporation of the ethanol formed during the hydrolysis of the tetraethylorthosilicate. Subsequently, 2,376 g (0.132 mol) of H 2 0 are added until the H 2 0 / Si + Ge ratio of 10 is reached. The gel obtained is transferred to Teflon coated steel autoclaves and placed in an oven at 160 S C during 25 days.
Transcurrido el tiempo de síntesis, el sólido obtenido es lavado con 100 mi de una disolución acuosa de tert-butilimino-tris(dimetilamino)fosforano de pH = 1 1 .5. Posteriormente es lavado con 2000 mi de agua destilada y secado a 100 QC durante 10 horas. After the synthesis time, the solid obtained is washed with 100 ml of an aqueous solution of tert-butylimino-tris (dimethylamino) phosphorane of pH = 1 1 .5. It is subsequently washed with 2000 ml of distilled water and dried at 100 QC for 10 hours.
El sólido resultante presenta un diagrama de difracción de Rayos X característico de la zeolita ITQ-45. Ejemplo 9- Preparación de la zeolita ITQ-45 The resulting solid presents a characteristic X-ray diffraction diagram of the ITQ-45 zeolite. Example 9- Preparation of ITQ-45 zeolite
A 2.578 g (0.01 1 mol) de tert-butil¡mino-tris(dimetilamino)fosforano preparados según se describe en el ejemplo 1 , se le añaden 3.971 g (0.221 mol) de H20, manteniendo la mezcla bajo agitación durante quince minutos. A esta mezcla se le añade 5.217 g (0.025 mol) de tetraetilortosilicato. La mezcla se mantiene bajo agitación a temperatura ambiente hasta la total evaporación del etanol formado durante la hidrólisis del tetraetilortosilicato. Posteriormente se añaden 0.075 g de siembra de zeolita ITQ-45 dispersa en 1 .068 g (0.059 mol) de H20 hasta alcanzar la relación H20/Si de 10. To 2,578 g (0.01 1 mol) of tert-butylamino-tris (dimethylamino) phosphorane prepared as described in Example 1, 3,971 g (0.221 mol) of H 2 0 is added, keeping the mixture under stirring for fifteen minutes To this mixture is added 5,217 g (0.025 mol) of tetraethylorthosilicate. The mixture is kept under stirring at room temperature until the total evaporation of the ethanol formed during the hydrolysis of the tetraethylorthosilicate. Subsequently, 0.075 g of ITQ-45 zeolite seed dispersed in 1.068 g (0.059 mol) of H 2 0 are added until reaching the H 2 0 / Si ratio of 10.
El gel obtenido es trasvasado a autoclaves de acero recubiertos de teflón y se introducen en una estufa a 160SC durante 30 días. Transcurrido el tiempo de síntesis, el sólido obtenido es lavado con 100 mi de una disolución acuosa de tert-butilimino-trís(dímetílamino)fosforano de pH = 1 1 .5. Posteriormente es lavado con 2000 mi de agua destilada y secado a 100 QC durante 10 horas. El sólido resultante presenta un diagrama de difracción de Rayos X que presenta líneas de difracción características de la zeolita ITQ-45. The gel obtained is transferred to teflon coated steel autoclaves and placed in an oven at 160 S C for 30 days. After the synthesis time, the solid obtained is washed with 100 ml of an aqueous solution of tert-butylimino-tris (dimethylamino) phosphorane of pH = 1 1 .5. It is subsequently washed with 2000 ml of distilled water and dried at 100 QC for 10 hours. The resulting solid presents an X-ray diffraction diagram that presents characteristic diffraction lines of the ITQ-45 zeolite.
Ejemplo 10- Preparación de la zeolita ITQ-45 A 4.690 g (0.020 mol) de tert-butílimino-tris(dimetilamíno)fosforano preparados según se describe en el ejemplo 1 , se le añaden 7.529 g (0.418 mol) de H20, manteniendo la mezcla bajo agitación durante quince minutos. A esta mezcla se le añade 9.480 g (0.0455 mol) de tetraetilortosilicato, 0.474 g (0.0045 mol) de Ge02 y 0.126 g (0.002 mol) de H3B03. La mezcla se mantiene bajo agitación a temperatura ambiente hasta la total evaporación del etanol formado durante la hidrólisis del tetraetilortosilicato. Posteriormente se añaden 0.136 g de siembra de zeolita ITQ-45 dispersa en 3.134 g (0.174 mol) de H20 hasta alcanzar la relación H20/Sí+Ge de 10. Example 10- Preparation of the ITQ-45 zeolite At 4,690 g (0.020 mol) of tert-butylimino-tris (dimethylamine) phosphorane prepared as described in example 1, 7.529 g (0.418 mol) of H 2 0 are added, keeping the mixture under stirring for fifteen minutes. To this mixture is added 9,480 g (0.0455 mol) of tetraethylorthosilicate, 0.474 g (0.0045 mol) of Ge0 2 and 0.126 g (0.002 mol) of H 3 B0 3 . The mixture is kept under stirring at room temperature until the total evaporation of the ethanol formed during the hydrolysis of the tetraethylorthosilicate. Later they are added 0.136 g of ITQ-45 zeolite planting dispersed in 3,134 g (0.174 mol) of H 2 0 until reaching the ratio H 2 0 / Yes + Ge of 10.
El gel obtenido es trasvasado a autoclaves de acero recubiertos de teflón y se introducen en una estufa a 1609C durante 10 días. The gel obtained is transferred to teflon coated steel autoclaves and placed in an oven at 160 9 C for 10 days.
Transcurrido el tiempo de síntesis, el sólido obtenido es lavado con 100 mi de una disolución acuosa de tert-butilimino-tris(dimetilamino)fosforano de pH = 1 1 .5. Posteriormente es lavado con 2000 mi de agua destilada y secado a 100 QC durante 10 horas. After the synthesis time, the solid obtained is washed with 100 ml of an aqueous solution of tert-butylimino-tris (dimethylamino) phosphorane of pH = 1 1 .5. It is subsequently washed with 2000 ml of distilled water and dried at 100 QC for 10 hours.
El sólido resultante presenta un diagrama de difracción de Rayos X característico de la zeolita ITQ-45. Ejemplo 11- Refinamiento de la estructura de ITQ-45 según el método de Rietveld. The resulting solid presents a characteristic X-ray diffraction diagram of the ITQ-45 zeolite. Example 11- Refinement of the ITQ-45 structure according to the Rietveld method.
La estructura de la zeolita ITQ-45 puede ser satisfactoriamente refinada empleando el método de Rietveld aplicado a un diagrama de difracción de Rayos X obtenido de una muestra preparada según se describe en el ejemplo 3. El ajuste entre el diagrama experimental y el simulado se muestra en la Figura 1 . El grupo espacial, los parámetros del refinamiento y las posiciones atómicas de la zeolita ITQ-45 se muestran en la Tabla 5. Tabla 5 The structure of the ITQ-45 zeolite can be satisfactorily refined using the Rietveld method applied to an X-ray diffraction diagram obtained from a sample prepared as described in example 3. The fit between the experimental and the simulated diagram is shown in Figure 1. The spatial group, refinement parameters and atomic positions of the ITQ-45 zeolite are shown in Table 5. Table 5
Grupo espacial:  Space Group:
i m a 2 i m to 2
Parámetros de celda unidad:  Unit cell parameters:
a= 17.8896(8) angstroms a = 17.8896 (8) angstroms
b= 22.4278(10) angstroms b = 22.4278 (10) angstroms
c= 13.8626(6) angstroms c = 13.8626 (6) angstroms
alpha=beta=gamma=90e Posiciones atómicas: alpha = beta = gamma = 90 e Atomic positions:
Sí1 0.3972(5) 0.0967(3) 0.3615(6) Yes1 0.3972 (5) 0.0967 (3) 0.3615 (6)
Si2 0.4774(5) 0.2036(4) 0.8896(5)Si2 0.4774 (5) 0.2036 (4) 0.8896 (5)
Si3 0.4941 (4) 0.3153(4) 0.7583(7)Si3 0.4941 (4) 0.3153 (4) 0.7583 (7)
Si4 0.5918(5) 0.0944(4) 0.1639(5)Si4 0.5918 (5) 0.0944 (4) 0.1639 (5)
S¡5 0.5974(4) 0.1065(4) 0.9352(6)S¡5 0.5974 (4) 0.1065 (4) 0.9352 (6)
Si6 0.3900(4) 0.2258(3) 0.0822(6)Si6 0.3900 (4) 0.2258 (3) 0.0822 (6)
Si7 0.3384(4) 0.1386(4) 0.5654(6)Si7 0.3384 (4) 0.1386 (4) 0.5654 (6)
Si8 0.4029(5) 0.0973(4) 0.7692(6)Si8 0.4029 (5) 0.0973 (4) 0.7692 (6)
Si9 0.5000 0.0000 0.2905(9)Si9 0.5000 0.0000 0.2905 (9)
SÍ10 0.5000 0.0000 0.8521 (8)YES10 0.5000 0.0000 0.8521 (8)
Si1 1 0.2500 0.1458(4) 0.0657(7)Si1 1 0.2500 0.1458 (4) 0.0657 (7)
SM 2 0.2500 0.0825(4) 0.2620(6)SM 2 0.2500 0.0825 (4) 0.2620 (6)
Si13 0.2500 0.0669(4) 0.8784(7)Si13 0.2500 0.0669 (4) 0.8784 (7)
SÍ14 0.7500 0.0613(4) 0.9408(6)YES14 0.7500 0.0613 (4) 0.9408 (6)
SÍ15 0.7500 0.0484(5) 0.1736(7)YES15 0.7500 0.0484 (5) 0.1736 (7)
01 0.552(3) 0.0478(13) 0.906(3)01 0.552 (3) 0.0478 (13) 0.906 (3)
02 0.4398(17) 0.0336(9) 0.3541 (19)02 0.4398 (17) 0.0336 (9) 0.3541 (19)
03 0.4204(9) 0.1558(1 1 ) 0.304(3)03 0.4204 (9) 0.1558 (1 1) 0.304 (3)
04 0.449(3) 0.9543(16) 0.231 (3)04 0.449 (3) 0.9543 (16) 0.231 (3)
05 0.6850(6) 0.1082(10) 0.920(3)05 0.6850 (6) 0.1082 (10) 0.920 (3)
06 0.5497(12) 0.1665(8) 0.923(3)06 0.5497 (12) 0.1665 (8) 0.923 (3)
07 0.5071 (14) 0.2515(12) 0.81 1 (3)07 0.5071 (14) 0.2515 (12) 0.81 1 (3)
08 0.3151 (9) 0.0761 (15) 0.3388(17)08 0.3151 (9) 0.0761 (15) 0.3388 (17)
09 0.5687(10) 0.3533(13) 0.734(2)09 0.5687 (10) 0.3533 (13) 0.734 (2)
010 0.5801 (13) 0.1023(13) 0.0480(5)010 0.5801 (13) 0.1023 (13) 0.0480 (5)
01 1 0.380(2) 0.1 13(2) 0.4714(12)01 1 0.380 (2) 0.1 13 (2) 0.4714 (12)
012 0.3296(7) 0.1767(8) 0.056(3)012 0.3296 (7) 0.1767 (8) 0.056 (3)
013 0.4499(12) 0.2192(19) 0.9967(12)013 0.4499 (12) 0.2192 (19) 0.9967 (12)
014 0.3552(12) 0.2083(5) 0.578(5)014 0.3552 (12) 0.2083 (5) 0.578 (5)
015 0.541 (2) 0.9595(13) 0.7744(13)015 0.541 (2) 0.9595 (13) 0.7744 (13)
016 0.4460(17) 0.1515(14) 0.823(3) 017 0.4341 (16) 0.291 (2) 0.6808(16)016 0.4460 (17) 0.1515 (14) 0.823 (3) 017 0.4341 (16) 0.291 (2) 0.6808 (16)
018 0.8205(8) 0.4078(13) 0.688(3)018 0.8205 (8) 0.4078 (13) 0.688 (3)
019 0.377(2) 0.390(2) 0.1600(12)019 0.377 (2) 0.390 (2) 0.1600 (12)
O20 0.3321 (10) 0.4259(15) 0.330(2) 021 0.2500 0.0929(9) 0.9870(1 1 )O20 0.3321 (10) 0.4259 (15) 0.330 (2) 021 0.2500 0.0929 (9) 0.9870 (1 1)
022 0.2500 0.1244(14) 0.572(7)022 0.2500 0.1244 (14) 0.572 (7)
023 0.2500 -0.0039(4) 0.8712(13)023 0.2500 -0.0039 (4) 0.8712 (13)
024 0.2500 0.0120(6) 0.2405(20)024 0.2500 0.0120 (6) 0.2405 (20)
025 0.2500 0.4059(8) 0.6470(8) 026 0.7500 0.0606(16) 0.0576(6) 025 0.2500 0.4059 (8) 0.6470 (8) 026 0.7500 0.0606 (16) 0.0576 (6)

Claims

REIVINDICACIONES
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 thereof;
- 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;  - the value of (y + z) / x is between 9 and infinity;
- el valor de z/y está comprendido entre 10 e infinito;  - the value of z / y is between 10 and infinity;
y porque tiene un patrón de difracción rayos X representado en la tabla 3. and because it has an X-ray diffraction pattern represented in table 3.
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;  - the value of (y + z) / x is between 20 and infinity;
- el valor de z/y está comprendido entre 15 e infinito;  - the value of z / y is between 15 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 and Y0 2 : z Z0 2
5.- Un material cristalino microporoso según cualquiera de las reivindicaciones 1 a 3, caracterizado porque y es igual a cero y posee una composición química: 5. A microporous crystalline material according to any of claims 1 to 3, characterized in that it is equal to zero and has a chemical composition:
x X2O3 : z Z02 donde: x X2O3: z Z0 2 where:
- el valor de z/x está comprendido entre 9 e infinito.  - the value of z / x is between 9 and infinity.
6. - Un material cristalino microporoso según la reivindicación 5, caracterizado porque el valor de z/x está comprendido entre 20 e infinito. 6. - A microporous crystalline material according to claim 5, characterized in that the value of z / x is between 20 and infinity.
7. - Un material cristalino microporoso según cualquiera de las reivindicaciones 1 a 3, caracterizado porque posee una composición química: 7. - A microporous crystalline material according to any of claims 1 to 3, characterized in that it has a chemical composition:
t P205 : x X2O3 : y Y02 : z Z02 t P 2 0 5 : x X2O3: y Y0 2 : z Z0 2
donde: where:
- el valor de t/(x+y+z) está comprendido entre 1 y 0.  - the value of t / (x + y + z) is between 1 and 0.
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.
8. - Un material cristalino microporoso según la reivindicación 7, caracterizado porque posee una composición química:8. - A microporous crystalline material according to claim 7, characterized in that it has a chemical composition:
Figure imgf000033_0001
Figure imgf000033_0001
donde: where:
- t/(y+z) puede estar comprendido entre 1 y 0.  - t / (y + z) can be between 1 and 0.
9. - Un material cristalino microporoso según la reivindicación 7, caracterizado porque posee una composición química: 9. - A microporous crystalline material according to claim 7, characterized in that it has a chemical composition:
t P205 : x X203 : z Z02 t P 2 0 5 : 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;
- t/(x+z) puede estar comprendido entre 1 y 0.  - t / (x + z) can be between 1 and 0.
10. - Un material cristalino microporoso según la reivindicación 9, caracterizado porque el valor de z/x está comprendido entre 20 e infinito. 10. - A microporous crystalline material according to claim 9, characterized in that the value of z / x is between 20 and infinity.
11.- Un material cristalino microporoso según una de las reivindicaciones 1 a 3, caracterizado porque posee una composición química: 11. A microporous crystalline material according to one of claims 1 to 3, characterized in that it has a chemical composition:
n R : x X203 : z Z02 : y Y02 donde: n R: x X 2 0 3 : z Z0 2 : y Y0 2 where:
- R es un agente director de estructura;  - R is a structure managing agent;
- el valor de n/(x+y+z) está comprendido entre 1 y 0,001 .  - the value of n / (x + y + z) is between 1 and 0.001.
y porque tiene un patrón de rayos X representado en la tabla 1 . and because it has an x-ray pattern represented in table 1.
12.- Un material cristalino microporoso según la reivindicación 1 1 , caracterizado porque el agente director de estructura R contiene P. 12. A microporous crystalline material according to claim 1, characterized in that the structure directing agent R contains P.
13.- Un material cristalino microporoso según la reivindicación 12, caracterizado porque R contiene enlaces P-N. 13. A microporous crystalline material according to claim 12, characterized in that R contains P-N bonds.
14. - Un material cristalino microporoso según la reivindicación 13, caracterizado porque R está seleccionado entre ter-butíl-imino-tris(di-metil-amíno)-fosforano y su derivado protonado. 14. - A microporous crystalline material according to claim 13, characterized in that R is selected from tert-butyl-imino-tris (di-methyl-amine) -phosphorane and its protonated derivative.
15. - Un material cristalino microporoso según cualquiera de las reivindicaciones 1 1 a 14, caracterizado por la siguiente composición química: 15. - A microporous crystalline material according to any of claims 1 to 14, characterized by 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 1 y 0,001 .  - the value of n / (y + z) is between 1 and 0.001.
16. - Un material cristalino microporoso según cualquiera de las reivindicaciones 1 1 a 14, caracterizado por la siguiente composición química: 16. - A microporous crystalline material according to any of claims 1 1 to 14, characterized by 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;  - the value of z / x is between 9 and infinity;
- el valor de n/(x+z) está comprendido entre 1 y 0,001 .  - the value of n / (x + z) is between 1 and 0.001.
17.- Un material cristalino microporoso según la reivindicación 16, caracterizado porque el valor de z/x está comprendido entre 20 e infinito. 17. A microporous crystalline material according to claim 16, characterized in that the value of z / x is between 20 and infinity.
18.- Un material cristalino microporoso isoestructural según cualquiera de las reivindicaciones anteriores, caracterizado porque posee átomos en coordinación tetraédrica unidos a través de átomos de oxígeno puente que conectan átomos en coordinación tetraédrica contiguos, conteniendo 92 átomos en coordinación tetraédrica en su celda unidad, denominados T1 , T2, T3, T4 hasta T92, que están localizados en las posiciones cristalográficas con coordenadas atómicas cartesianas x, y y z que se muestran en la Tabla 5. 18. An isostructural microporous crystalline material according to any one of the preceding claims, characterized in that it has tetrahedral coordination atoms linked through bridging oxygen atoms that connect contiguous tetrahedral coordination atoms, containing 92 tetrahedral coordination atoms in its unit cell, called T1, T2, T3, T4 through T92, which are located in the crystallographic positions with Cartesian atomic coordinates x, yyz, which are shown in Table 5.
19.- Un procedimiento de preparación del material descrito según cualquiera de las reivindicaciones 1 a 18, caracterizado porque comprende al menos los siguientes pasos: 19. A process for preparing the material described according to any of claims 1 to 18, characterized in that it comprises at least the following steps:
a) preparación de una mezcla que contiene H20, 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: a) preparation of a mixture containing H 2 0, an oxide or other source of the tetravalent material Z and 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:
(Y02+Z02)/X203 mayor de 2 (Y0 2 + Z0 2 ) / X 2 0 3 greater than 2
H20/(Y02+Z02) 1 -50 H 2 0 / (Y0 2 + Z0 2 ) 1 -50
R/(Y02 + Z02 ) 0.05-3.0 R / (Y0 2 + Z0 2 ) 0.05-3.0
OH7(Y02 + Z02 ) 0.05-3.0 OH7 (Y0 2 + Z0 2 ) 0.05-3.0
Z02/Y02 mayor de 5 Z0 2 / Y0 2 greater than 5
Sí02/Ge02 mayor de 2 Yes0 2 / Ge0 2 greater than 2
b) mantener la mezcla a una temperatura entre 80 y 2009C hasta que se formen los cristales del material; b) keep the mixture at a temperature between 80 and 200 9 C until the crystals of the material form;
c) recuperación del material cristalino.  c) recovery of the crystalline material.
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 un compuesto que contiene P. 21. Process for obtaining a material according to any of claims 19 and 20, characterized in that the structure directing agent R is a compound containing P.
22. - Procedimiento de obtención de un material según la reivindicación 21 , caracterizado porque R contiene enlaces P-N. 22. - Method of obtaining a material according to claim 21, characterized in that R contains P-N bonds.
23. - Procedimiento de obtención de un material según la reivindicación 22, caracterizado porque R está seleccionado entre ter-butil-imino-trís(dí-metíl- amino)-fosforano y su derivado catiónico protonado. 23. - Method of obtaining a material according to claim 22, characterized in that R is selected from tert-butyl-imino-tris (dí-methyl-amino) -phosphorane and its protonated cationic derivative.
24. - Procedimiento de obtención de un material según cualquiera de las reivindicaciones 19 a 23, caracterizado porque comprende, además, la calcinación del material cristalino obtenido. 24. - Method of obtaining a material according to any of claims 19 to 23, characterized in that it further comprises the calcination of the crystalline material obtained.
25. - Procedimiento de obtención de un material según la reivindicación 24, caracterizado porque la calcinación se lleva a cabo a una temperatura entre 200 y 10009C. 25. - Method of obtaining a material according to claim 24, characterized in that the calcination is carried out at a temperature between 200 and 1000 9 C.
26. - Procedimiento de obtención de un material según cualquiera de las reivindicaciones 24 y 25, caracterizado porque comprende, además, al menos un proceso de lavado del material calcinado. 26. - Method of obtaining a material according to any of claims 24 and 25, characterized in that it also comprises at least one process of washing the calcined material.
27.- Procedimiento de obtención de un material según la reivindicación 26, caracterizado porque dicho proceso o procesos de lavado comprende al menos la siguiente etapa: 27.- Procedure for obtaining a material according to claim 26, characterized in that said washing process or processes comprises at least the following stage:
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.  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.
28.- Procedimiento de obtención de un material según la reivindicación 27, caracterizado porque dicha disolución está seleccionada entre una disolución acuosa, alcohólica, orgánica o mezcla de ellas. 28.- Method of obtaining a material according to claim 27, characterized in that said solution is selected from an aqueous, alcoholic, organic solution or mixture thereof.
29.- Procedimiento de obtención de un material según cualquiera de las reivindicaciones 26 a 28, caracterizado porque dicho lavado se realiza a una temperatura entre 0 y 200eC. 29.- Procedure for obtaining a material according to any of claims 26 to 28, characterized in that said washing is carried out at a temperature between 0 and 200 e C.
30.- Procedimiento de obtención de un material según cualquiera de las reivindicaciones 19 a 29, caractenzado porque comprende, además uno o varios procesos post-síntesís. 30.- Procedure for obtaining a material according to any of claims 19 to 29, characterized in that it also comprises one or more post-synthesis processes.
31. - Procedimiento de obtención de un material según la reivindicación 30, caracterizado porque dicho tratamiento post-síntesis comprende al menos: 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; 31. - Method of obtaining a material according to claim 30, characterized in that said post-synthesis treatment comprises at least: a) suspending 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 liquid solids separation technique;
c) activación del material mediante calcinación a temperaturas superiores a 200QC. c) activation of the material by calcination at temperatures above 200 QC .
32. - Procedimiento de obtención de un material según la reivindicación 31 , caracterizado porque la disolución está seleccionada entre una disolución acuosa, alcohólica, orgánica o mezcla de ambas. 32. - Method of obtaining a material according to claim 31, characterized in that the solution is selected from an aqueous, alcoholic, organic solution or mixture of both.
33. - Procedimiento de obtención de un material según cualquiera de las la reivindicaciones 31 y 32, caracterizado porque el tratamiento post-síntesis se lleva a cabo a una temperatura entre 0 y 200QC. 33. - Procedure for obtaining a material according to any of claims 31 and 32, characterized in that the post-synthesis treatment is carried out at a temperature between 0 and 200 QC .
34. - Uso de un material descrito según las reivindicaciones 1 a 18, y obtenido según el procedimiento de obtención descrito en las reivindicaciones 19 a 33, para convertir alimentaciones formadas por compuestos orgánicos a productos de mayor valor añadido. 34. - Use of a material described according to claims 1 to 18, and obtained according to the method of obtaining described in claims 19 to 33, to convert feeds formed by organic compounds to products of greater added value.
35.- Uso de un material descrito según las reivindicaciones 1 a 18, y obtenido según el procedimiento de obtención descrito en las reivindicaciones 19 a 33, en procesos de craqueo catalítico de hidrocarburos. 35.- Use of a material described according to claims 1 to 18, and obtained according to the method of obtaining described in claims 19 to 33, in processes of catalytic cracking of hydrocarbons.
36.- Uso de un material descrito según las reivindicaciones 1 a 18, y obtenido según el procedimiento de obtención descrito en las reivindicaciones 19 a 33, en procesos de alquilación de compuestos aromáticos con alcoholes u olefinas. 36.- Use of a material described according to claims 1 to 18, and obtained according to the method of obtaining described in claims 19 to 33, in processes of alkylation of aromatic compounds with alcohols or olefins.
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