WO2005040041A1 - Process for the synthesis of zeolite itq-13 in a basic medium and in the absence of fluoride ions - Google Patents

Process for the synthesis of zeolite itq-13 in a basic medium and in the absence of fluoride ions Download PDF

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WO2005040041A1
WO2005040041A1 PCT/EP2004/011531 EP2004011531W WO2005040041A1 WO 2005040041 A1 WO2005040041 A1 WO 2005040041A1 EP 2004011531 W EP2004011531 W EP 2004011531W WO 2005040041 A1 WO2005040041 A1 WO 2005040041A1
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process according
crystalline material
cations
mixture
itq
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PCT/EP2004/011531
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French (fr)
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Avelino Corma Canos
Fernando Rey Garcia
Vicente Fornes Segui
Rafael Castaneda Sanchez
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Consejo Superior De Investigaciones Cientificas
Universidad Politecnica De Valencia
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/86—Borosilicates; Aluminoborosilicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/12—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the replacing atoms being at least boron atoms
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent

Definitions

  • TECHNICAL FIELD This invention refers to the obtainment of the microporous crystalline material ITQ-13 in a basic medium and in the absence of fluoride atoms .
  • Zeolites are porous crystalline materials that have important uses as catalysts, adsorbents and ionic exchangers. These zeolitic materials have well defined structures that form channels and cavities in the inside thereof, of a uniform size and shape, that permit adsorption of certain molecules while they prevent other molecules - that are too big to be diffused through the pores - from passing inside the crystal. This characteristic gives these materials properties of a molecular sieve.
  • These molecular sieves may generally include silicon in the lattice, but aside from Si, they may include other group IIIA elements of the periodic table, all of them tetrahedrally coordinated.
  • the negative charge generated by the group IIIA elements tetrahedrally coordinated in positions of the lattice is compensated for by the presence of the cation crystal, such as for example, alkaline or alkaline ones.
  • These cations may be totally or partially exchanged with another type of cations by means of ionic exchange techniques.
  • 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 (SDA) generally contain nitrogen in their composition and may give rise to organic cations that are stable in the reaction medium. It is known that for the obtainment of the zeolite ITQ-13, the silica is mobilized by using fluoride ions (T. Boix, M. Puche, M.A. Camblor, A. Corma, US-6,471,941 Bl (2000) and A. Corma, M. Puche, F. Rey, G. Sanker, S.J. Teat, Angew. Chem. , Inter. Ed., 42, 1156-1159 (2003) and the synthesis is carried out at a low pH.
  • fluoride ions T. Boix, M. Puche, M.A. Camblor, A. Corma, US-6,471,941 Bl (2000) and A. Corma, M. Puche, F. Rey, G. Sanker, S.J. Teat, Angew. Chem. , Inter. Ed., 42
  • fluoride ions in synthesis is generally a method less desired from an industrial point of view, than the use of OH " , given that the presence of fluoride ions requires the use of special materials in the synthesis equipment, as well as special treatment of the waste waters and gases in order to minimize the risk of environmental pollution.
  • the present invention refers to a process for the synthesis of a microporous crystalline material called zeolite ITQ-13 or of a precursor of ITQ-13, said ITQ-13 having a three-dimensional system of channels, that comprises two groups of channels, each one of them defined by ten-member rings of tetrahedrally coordinated atoms, that intersect with each other, and a third group of channels, defined by nine-member rings of tetrahedrally coordinated atoms, and that intersect with the two previous groups of channels, said process being characterized in that it comprises: a) preparing a mixture that comprises at least water, a source of at least one tetravalent element Y, and a structure directing agent R, without any source of fluoride ions being present in the synthesis medium; b) keeping the synthesis mixture at a temperature between 80 and 200°C until crystals of the material are formed, obtaining a crystalline material; and c) recovering the crystalline material.
  • the process may
  • said process comprises the following steps: a) preparing a mixture that comprises water, a source of at least one tetravalent element Y, a source of at least one trivalent element X and a structure directing agent (R) , without any source of fluoride ions being present in the synthesis medium; b) keeping the synthesis structure at a temperature between 80° and 200° until crystals of the material are formed, obtaining a crystalline material; c) recovering the crystalline material and, optionally, d) eliminating the organic material occluded inside the crystalline material by means of a steps selected from among: - extraction, - thermal treatment at temperatures higher than
  • a second preferred embodiment of the process it comprises the following steps : a) preparing a mixture that comprises water, a source of at least one tetravalent element Y, a source of a tetravalent element Z different from Y, a source of at least one trivalent element X, and a structure directing agent R, the synthesis mixture having a composition, in terms of molar ratios of oxides, in the following ranges (Y0 2 +Z0 2 ) /X 2 0 3 higher than 5 H 2 0/ (Y0 2 +Z0 2 ) 1-50 R/ (Y0 2 + Z0 2 ) 0.05-3.0 OH " /(Y0 2 + Z0 2 ) 0.1-6.0 Y0 2 /Z0 2 higher than 1 without any source of fluoride ions being present b) keeping the synthesis mixture at a temperature between 80 and 200°C until crystals of the material are formed, obtaining a crystalline material
  • the source of tetravalent element Y is preferably an oxide, hydroxide, oxyhydroxide, hydrolyzable alkoxide, a salt of element Y or a mixture thereof .
  • the source of the tetravalent element Z is preferably an oxide, hydroxide, oxyhydroxide, hydrolyzable alkoxide, a salt of element Z, or a mixture thereof.
  • Z is Ge
  • a preferred source of Ge is Ge0 2 .
  • the source of the trivalent element X is preferably selected from among an oxide, hydroxide, oxyhydroxide, a hydrolyzable alkoxide, a salt of the element X and a mixture thereof .
  • the structure directing agent is a salt of the cation hexamethylene-bis (trimethylammonium) , and even more preferably it is a hexamethylene-bis (trimethylammonium) cation hydroxide.
  • the synthesis mixture preferably has a composition in terms of oxide molar ratios, in the following range: (Y0 2 +Z0 2 ) /X 2 0 3 higher than 200 H 2 0/ (Y0 2 +Z0 2 ) 2-30 R/(Y0 2 +Z0 2 ) 0.05-1.0 OH " /(Y0 2 +Z0 2 ) 0.1-2.0 Y0 2 /Z0 2 8-25
  • X is one or more trivalent elements selected from the group formed by Al, B, In, Ga, Cr and Fe
  • Y is one or more tetravalent elements selected among Si, Sn, Ti, V and Z is Ge.
  • Crystallization of the material is carried out in autoclaves with stirring comprised between 80 and 200°C and at sufficient times to achieve crystallization, for example, between 10 hours and 30 days.
  • the crystals of the material are separated from the mother liquors and are recovered.
  • the components of the synthesis mixture may come from different sources and depending thereon, times and crystallization conditions may change.
  • crystals of the same material or of this material in calcined form may be added to the synthesis mixture as seeds in amounts up to 15% by weight with respect to the total oxides. These seeds may be added before or during crystallization.
  • the step of eliminating the organic material is carried out by roasting at a temperature above 250°C.
  • a step of ionic exchange of the compensation cations may also be carried out with one or more cations.
  • the exchange of the compensation cations may be carried out in the material ITQ-13 in its uncalcined form, or after thermal treatment .
  • said cations for the exchange are selected among cations such as metallic ions, H + and H + precursors such as for example NH + 4 .
  • cations for the exchange monovalent cations, divalent cations, trivalent cations and mixtures thereof may be used for example .
  • cations that may be introduced by ionic exchange those that may 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 metals of group VIII, as well as group IIA, IIIA, IVA, VA, IB, IIB, IIIB, IVB, VB, VIIB of the periodic table of elements, and mixtures thereof are preferred.
  • a second object of the present invention is a microporous crystalline material, ITQ-13 precursor, characterized by an X-ray diffraction pattern that comprises at least the following lines, in the synthesized uncalcined form:
  • vs means an intensity between 80-100 %
  • s means between 60-80 %
  • m medium means 40-60 %
  • w means 20-40 %
  • vw means between 0-20 %
  • R is a Structure Directing Agent (SDA)
  • X is one or more trivalent elements
  • Y is one or more tetravalent elements
  • Z corresponds to a tetravalent element other than Y
  • the value of (y+z)/x is comprised between 5 and oo and the y/z value is at least 1 and z may be 0.
  • the ITQ-13 precursor defined may have an X-ray diffraction pattern that comprises aside from the above- mentioned listed lines, the following lines in the synthesized uncalcined form thereof
  • the structure directing agent is preferably a salt of the hexamethylene-bis (trimethylammonium) cation, and even more preferably the structure directing agent is the hydroxide of the hexamethylene-bis (trimethylammonium) cation.
  • X, Y and Z preferably have the following meaning in said microporous crystalline ITQ-13 precursor material: - X is one or more trivalent materials selected from the group formed by Al, B, In, Ga, Cr and Fe; - Y is one or more tetravalent elements selected from among Si, Sn, Ti, V and - Ze is Ge.
  • An additional object of the present invention is the crystalline ITQ-13 precursor material defined that is prepared by a process that comprises the steps (a) to (c) of the process defined for the synthesis of ITQ-13: a) preparing a mixture that comprises water, a source of at least one tetravalent element Y, and a structure directing agent R, without any source of fluoride ions being present in the synthesis medium; b) keeping the synthesis mixture at a temperature between 80 and 200°C until crystals of the material are formed, obtaining a crystalline material; and c) recovering the crystalline material.
  • the crystalline material is prepared by means of a process that comprises the following steps (a) to (c) : a) preparing a mixture that comprises water, a source of at least one tetravalent element Y, a source of at least one trivalent element X, and a structure directing agent R, without any source of fluoride ions being present, b) keeping the synthesis mixture at a temperature between 80 and 200°C until crystals of the material are formed; and c) recovering the crystalline material.
  • the crystalline material is prepared by a process that comprises the following steps (a) to (c) : a) preparing a mixture that comprises water, a source of at least one tetravalent element Y, a source of a tetravalent element Z different from Y, a source of at least one trivalent element X, and a structure directing agent R, the synthesis mixture having a composition, in terms of molar ratios of oxides, in the following ranges:
  • ITQ-13 has for a particular embodiment, in its calcined form as well as in its synthesized uncalcined form, an X-ray diffraction pattern whose most important diffraction lines are given in table 1 for the calcined form and in table 2 for the uncalcined form.
  • Table 1 Relative 2 ⁇ a Intensity 7.065 vs 8.015 m 8.765 w a ( ⁇ 0.2) These diffractograms were obtained with a Philips X'Pert diffractometer equipped with a graphite monochromator and an automatic divergence slit, using K « radiation of the copper. The diffraction data were recorded by means of a 2 ⁇ interval of 0.01°, wherein ⁇ is the Bragg angle, and a measuring time of 10 seconds per interval.
  • the relative intensity of the lines is calculated as the percentage with respect to the most intense peak and very strong "vs” means 80-100 %, strong “s” means 60-80 %, medium “m” means 40-60 %, weak "w” means 20-40 % and very weak "vw” means 0-20 % .
  • the diffraction data listed for this sample as simple lines or single lines may be formed by multiple overlapping or superposition of reflections that in certain conditions, such as differences in the chemical composition, may appear as distinguishable lines or partially distinguishable lines.
  • changes in the chemical composition may give rise to small variations in the parameters of each unit cell and/or changes in the symmetry of the crystal, without producing a change in the structure.
  • modifications, that include changes in the relative intensities may also be due to differences in the type and amount of compensation cations, composition of the lattice, size of the crystal and shape thereof, preferable orientation or to the type of thermal or hydrothermal treatments the material can have undergone .
  • the crystalline material ITQ-13 has a molar composition in its calcined and anhydrous state that is represented by the equation: x X 2 0 3 : y Y0 2 : z Z0 2 wherein X is one or more trivalent elements, Y is one or more tetravalent elements, and Z corresponds to a tetravalent element different from Y, the value of (y+z)/x being comprised between 5 and ⁇ , the value of y/z being at least 1 and z may be 0. From the values given, it is clearly inferred that the crystalline material ITQ-13 can by synthesized in the absence of added trivalent elements .
  • the crystalline material, ITQ-13, of the present invention can be closely combined with hydrogenating- dehydrogenating components such as platinum, palladium, nickel, rhenium, cobalt, tungsten, molybdenum, vanadium, chrome, manganese, iron.
  • hydrogenating- dehydrogenating components such as platinum, palladium, nickel, rhenium, cobalt, tungsten, molybdenum, vanadium, chrome, manganese, iron.
  • hydrogenating- dehydrogenating components such as platinum, palladium, nickel, rhenium, cobalt, tungsten, molybdenum, vanadium, chrome, manganese, iron.
  • These elements may be introduced during the crystallization step, by exchange (if appropriate) , and/or by impregnation or by physical mixing.
  • These elements may be introduced in their cationic form and/or from salts or other compounds that by decomposition produce the metallic component or oxide in its suitable catalytic form.
  • the resulting materials can be
  • the process consists of dissolving 9 g of hexamethonium dibromide obtained according to example 1 in 250 g of Milli Q water (Millipore) .
  • the resulting solution is passed through a washed Amberlite IRN-78 resin column adjusting the flow rate in order to reach an exchange level higher than 95%.

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Abstract

The present invention refers to a process for the synthesis of a microporous crystalline material called ITQ-13 or a precursor of ITQ-13, said ITQ-13 having a three-dimensional system of channels, which comprises two groups of channels, each one of them defined by tenmember rings of tetrahedrally coordinated atoms, that intersect with each other, and a third group of channels, defined by nine-member rings of tetrahedrally coordinated atoms, and that intersect with the two previous groups of channels, said process being characterized in that it comprises: a) preparing a synthesis mixture without any source of fluoride ions being present in the synthesis medium; b) keeping the synthesis mixture at a temperature between 80 and 200° C until crystals of the material are formed, obtaining a crystalline material; c) recovering the crystalline material and, optionally, d) eliminating the organic material occluded inside the crystalline material.

Description

TITLE PROCESS FOR THE SYNTHESIS OF ZEOLITE ITQ-13 IN A BASIC MEDIUM AND IN THE ABSENCE OF FLUORIDE IONS
TECHNICAL FIELD This invention refers to the obtainment of the microporous crystalline material ITQ-13 in a basic medium and in the absence of fluoride atoms . BACKGROUND OF THE INVENTION Zeolites are porous crystalline materials that have important uses as catalysts, adsorbents and ionic exchangers. These zeolitic materials have well defined structures that form channels and cavities in the inside thereof, of a uniform size and shape, that permit adsorption of certain molecules while they prevent other molecules - that are too big to be diffused through the pores - from passing inside the crystal. This characteristic gives these materials properties of a molecular sieve. These molecular sieves may generally include silicon in the lattice, but aside from Si, they may include other group IIIA elements of the periodic table, all of them tetrahedrally coordinated. The negative charge generated by the group IIIA elements tetrahedrally coordinated in positions of the lattice is compensated for by the presence of the cation crystal, such as for example, alkaline or alkaline ones. These cations may be totally or partially exchanged with another type of cations by means of ionic exchange techniques. Thus, it is possible to vary the properties of a given zeolite by selecting the desired cations. 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 (SDA) generally contain nitrogen in their composition and may give rise to organic cations that are stable in the reaction medium. It is known that for the obtainment of the zeolite ITQ-13, the silica is mobilized by using fluoride ions (T. Boix, M. Puche, M.A. Camblor, A. Corma, US-6,471,941 Bl (2000) and A. Corma, M. Puche, F. Rey, G. Sanker, S.J. Teat, Angew. Chem. , Inter. Ed., 42, 1156-1159 (2003) and the synthesis is carried out at a low pH. Nonetheless, the use of fluoride ions in synthesis is generally a method less desired from an industrial point of view, than the use of OH", given that the presence of fluoride ions requires the use of special materials in the synthesis equipment, as well as special treatment of the waste waters and gases in order to minimize the risk of environmental pollution. DESCRIPTION OF THE INVENTION The present invention refers to a process for the synthesis of a microporous crystalline material called zeolite ITQ-13 or of a precursor of ITQ-13, said ITQ-13 having a three-dimensional system of channels, that comprises two groups of channels, each one of them defined by ten-member rings of tetrahedrally coordinated atoms, that intersect with each other, and a third group of channels, defined by nine-member rings of tetrahedrally coordinated atoms, and that intersect with the two previous groups of channels, said process being characterized in that it comprises: a) preparing a mixture that comprises at least water, a source of at least one tetravalent element Y, and a structure directing agent R, without any source of fluoride ions being present in the synthesis medium; b) keeping the synthesis mixture at a temperature between 80 and 200°C until crystals of the material are formed, obtaining a crystalline material; and c) recovering the crystalline material. The process may also further comprise the step of d) eliminating the organic material occluded inside the crystalline material by means of a step selected from among : - extraction, - thermal treatment at temperatures higher than
250°, and mixture of both the extraction and thermal treatment steps . According to a preferred embodiment of the process, said process comprises the following steps: a) preparing a mixture that comprises water, a source of at least one tetravalent element Y, a source of at least one trivalent element X and a structure directing agent (R) , without any source of fluoride ions being present in the synthesis medium; b) keeping the synthesis structure at a temperature between 80° and 200° until crystals of the material are formed, obtaining a crystalline material; c) recovering the crystalline material and, optionally, d) eliminating the organic material occluded inside the crystalline material by means of a steps selected from among: - extraction, - thermal treatment at temperatures higher than
250°, and mixture of both the extraction and thermal treatment steps. According to a second preferred embodiment of the process it comprises the following steps : a) preparing a mixture that comprises water, a source of at least one tetravalent element Y, a source of a tetravalent element Z different from Y, a source of at least one trivalent element X, and a structure directing agent R, the synthesis mixture having a composition, in terms of molar ratios of oxides, in the following ranges (Y02+Z02) /X203 higher than 5 H20/ (Y02+Z02) 1-50 R/ (Y02 + Z02) 0.05-3.0 OH"/(Y02 + Z02) 0.1-6.0 Y02/Z02 higher than 1 without any source of fluoride ions being present b) keeping the synthesis mixture at a temperature between 80 and 200°C until crystals of the material are formed, obtaining a crystalline material; c) recovering the crystalline material and, optionally, d) eliminating the organic material occluded inside the crystalline material by means of a step selected from among : - extraction, - thermal treatment at temperatures higher than 250°, and mixture of both the extraction and thermal treatment steps . According to the process defined above, the source of tetravalent element Y is preferably an oxide, hydroxide, oxyhydroxide, hydrolyzable alkoxide, a salt of element Y or a mixture thereof . Moreover, the source of the tetravalent element Z is preferably an oxide, hydroxide, oxyhydroxide, hydrolyzable alkoxide, a salt of element Z, or a mixture thereof. In the event that Z is Ge, a preferred source of Ge is Ge02. The source of the trivalent element X is preferably selected from among an oxide, hydroxide, oxyhydroxide, a hydrolyzable alkoxide, a salt of the element X and a mixture thereof . Preferably, the structure directing agent is a salt of the cation hexamethylene-bis (trimethylammonium) , and even more preferably it is a hexamethylene-bis (trimethylammonium) cation hydroxide. According to the process of the present invention, the synthesis mixture preferably has a composition in terms of oxide molar ratios, in the following range: (Y02+Z02) /X203 higher than 200 H20/ (Y02+Z02) 2-30 R/(Y02+Z02) 0.05-1.0 OH"/(Y02+Z02) 0.1-2.0 Y02/Z02 8-25 In a preferred embodiment of the process, X is one or more trivalent elements selected from the group formed by Al, B, In, Ga, Cr and Fe; and Y is one or more tetravalent elements selected among Si, Sn, Ti, V and Z is Ge. Crystallization of the material is carried out in autoclaves with stirring comprised between 80 and 200°C and at sufficient times to achieve crystallization, for example, between 10 hours and 30 days. When the crystallization step ends, the crystals of the material are separated from the mother liquors and are recovered. It should be taken into account that the components of the synthesis mixture may come from different sources and depending thereon, times and crystallization conditions may change. For the purpose of facilitating the synthesis, crystals of the same material or of this material in calcined form may be added to the synthesis mixture as seeds in amounts up to 15% by weight with respect to the total oxides. These seeds may be added before or during crystallization. Preferably the step of eliminating the organic material is carried out by roasting at a temperature above 250°C. Preferably, at a temperature between 350°C and 700°C. When said step is carried out by roasting, it is preferably carried out for a period of time between 2 minutes and 25 hours. The organic component used in the synthesis of ITQ- 13 can be alternatively eliminated by extraction. According to the process of the present invention, a step of ionic exchange of the compensation cations may also be carried out with one or more cations. The exchange of the compensation cations may be carried out in the material ITQ-13 in its uncalcined form, or after thermal treatment . In a preferred manner, said cations for the exchange are selected among cations such as metallic ions, H+ and H+ precursors such as for example NH+ 4. Among the cations for the exchange, monovalent cations, divalent cations, trivalent cations and mixtures thereof may be used for example . Among the cations that may be introduced by ionic exchange, those that may 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 metals of group VIII, as well as group IIA, IIIA, IVA, VA, IB, IIB, IIIB, IVB, VB, VIIB of the periodic table of elements, and mixtures thereof are preferred. The acid materials generated by activation and ionic exchange may be used a catalysts in reactions that take place through carbocations such as for example: cracking reactions, isomerization and alkylation of organic compounds . A second object of the present invention is a microporous crystalline material, ITQ-13 precursor, characterized by an X-ray diffraction pattern that comprises at least the following lines, in the synthesized uncalcined form:
Figure imgf000008_0001
wherein the relative intensity is calculated as the percentage with respect to the most intense peak, and "vs" means an intensity between 80-100 %, s means between 60-80 %, m medium means 40-60 %, w means 20-40 % and vw means between 0-20 %, and wherein its chemical composition is : n R : X X203 : y Y02 : Z Z02 wherein R is a Structure Directing Agent (SDA) , X is one or more trivalent elements, Y is one or more tetravalent elements, Z corresponds to a tetravalent element other than Y, the value of (y+z)/x is comprised between 5 and oo and the y/z value is at least 1 and z may be 0. From the values given, it is clearly inferred that the zeolitic material can by synthesized in the absence of added trivalent elements. The ITQ-13 precursor defined may have an X-ray diffraction pattern that comprises aside from the above- mentioned listed lines, the following lines in the synthesized uncalcined form thereof
Figure imgf000009_0001
wherein the relative intensity is calculated as the percentage with respect to the most intense peak, "w" means between 20-40 % and "vw" means between 0-20 %. In said ITQ-13 precursor material the structure directing agent is preferably a salt of the hexamethylene-bis (trimethylammonium) cation, and even more preferably the structure directing agent is the hydroxide of the hexamethylene-bis (trimethylammonium) cation. X, Y and Z preferably have the following meaning in said microporous crystalline ITQ-13 precursor material: - X is one or more trivalent materials selected from the group formed by Al, B, In, Ga, Cr and Fe; - Y is one or more tetravalent elements selected from among Si, Sn, Ti, V and - Ze is Ge. An additional object of the present invention is the crystalline ITQ-13 precursor material defined that is prepared by a process that comprises the steps (a) to (c) of the process defined for the synthesis of ITQ-13: a) preparing a mixture that comprises water, a source of at least one tetravalent element Y, and a structure directing agent R, without any source of fluoride ions being present in the synthesis medium; b) keeping the synthesis mixture at a temperature between 80 and 200°C until crystals of the material are formed, obtaining a crystalline material; and c) recovering the crystalline material. In a preferred embodiment the crystalline material is prepared by means of a process that comprises the following steps (a) to (c) : a) preparing a mixture that comprises water, a source of at least one tetravalent element Y, a source of at least one trivalent element X, and a structure directing agent R, without any source of fluoride ions being present, b) keeping the synthesis mixture at a temperature between 80 and 200°C until crystals of the material are formed; and c) recovering the crystalline material. In a second preferred embodiment the crystalline material is prepared by a process that comprises the following steps (a) to (c) : a) preparing a mixture that comprises water, a source of at least one tetravalent element Y, a source of a tetravalent element Z different from Y, a source of at least one trivalent element X, and a structure directing agent R, the synthesis mixture having a composition, in terms of molar ratios of oxides, in the following ranges:
(Y02+Z02)/X203 higher than 5 H20/(Y02+Z02) 1-50 R/(Y02 + Z02) 0.05-3.0 OH"/ (Y02 + Z02) 0.1-6.0 Y02/Z02 higher than 1 without any source of fluoride ions being present b) keeping the synthesis mixture at a temperature between 80 and 200°C until crystals of the material are formed; and c) recovering the crystalline material. The present invention thus achieves synthesizing in a basic medium, and in the absence of fluoride ions, the microporous crystalline material called ITQ-13. ITQ-13 has for a particular embodiment, in its calcined form as well as in its synthesized uncalcined form, an X-ray diffraction pattern whose most important diffraction lines are given in table 1 for the calcined form and in table 2 for the uncalcined form.
Table 1 Relative 2θa Intensity 7.065 vs 8.015 m 8.765 w
Figure imgf000012_0001
a (± 0.2) These diffractograms were obtained with a Philips X'Pert diffractometer equipped with a graphite monochromator and an automatic divergence slit, using K« radiation of the copper. The diffraction data were recorded by means of a 2θ interval of 0.01°, wherein θ is the Bragg angle, and a measuring time of 10 seconds per interval. The relative intensity of the lines is calculated as the percentage with respect to the most intense peak and very strong "vs" means 80-100 %, strong "s" means 60-80 %, medium "m" means 40-60 %, weak "w" means 20-40 % and very weak "vw" means 0-20 % .
Table 2
Figure imgf000012_0002
Figure imgf000013_0001
a (± 0.2) It should be taken into account that the diffraction data listed for this sample as simple lines or single lines, may be formed by multiple overlapping or superposition of reflections that in certain conditions, such as differences in the chemical composition, may appear as distinguishable lines or partially distinguishable lines. Generally, changes in the chemical composition may give rise to small variations in the parameters of each unit cell and/or changes in the symmetry of the crystal, without producing a change in the structure. These modifications, that include changes in the relative intensities, may also be due to differences in the type and amount of compensation cations, composition of the lattice, size of the crystal and shape thereof, preferable orientation or to the type of thermal or hydrothermal treatments the material can have undergone . The crystalline material ITQ-13 has a molar composition in its calcined and anhydrous state that is represented by the equation: x X203 : y Y02 : z Z02 wherein X is one or more trivalent elements, Y is one or more tetravalent elements, and Z corresponds to a tetravalent element different from Y, the value of (y+z)/x being comprised between 5 and ∞, the value of y/z being at least 1 and z may be 0. From the values given, it is clearly inferred that the crystalline material ITQ-13 can by synthesized in the absence of added trivalent elements . For the purpose of preparing catalysts, the crystalline material, ITQ-13, of the present invention can be closely combined with hydrogenating- dehydrogenating components such as platinum, palladium, nickel, rhenium, cobalt, tungsten, molybdenum, vanadium, chrome, manganese, iron. These elements may be introduced during the crystallization step, by exchange (if appropriate) , and/or by impregnation or by physical mixing. These elements may be introduced in their cationic form and/or from salts or other compounds that by decomposition produce the metallic component or oxide in its suitable catalytic form. The resulting materials can be used as catalysts in bifunctional acid- hydrogenating/dehydrogenating processes . The crystalline material ITQ-13 including Ti, Sn, Fe, V and mixtures thereof in the lattice can be used as an oxidation catalyst of organic molecules. The material produced by means of this invention can be tableted according to known techniques, and can be used as a component of catalytic cracking catalysts of hydrocarbons, catalytic hydrocracking of hydrocarbons, alkylation of aromatics with olefins and in esterification, acylation processes, aniline reaction with formaldehyde in its acid form and/or exchanged with suitable cations. EXAMPLES Example 1 - Preparation of hexamethyelene-bis (trimethylammonium) bromide 37.38 g of 1, 6-dibromohexane (purity = 96%), 82,35 g of a trimethylamine solution (31-35% by weight in ethanol) are added to a 500 ml flask. The ethanol needed to obtain a suitable mixture of the different products added is immediately added, while they are homogenized by magnetic stirring. The resulting mixture is kept at room temperature with constant stirring for 48 hours, then the solid formed is recovered by filtration and washed thoroughly with ethyl acetate and diethyl ether. The white solid obtained is dried at room temperature for 12 hours . Example 2 - Preparation of hexamethyelene-bis (trimethylammonium) dihydroxide Hexamethonium dihydroxide is prepared by direct anionic exchange, using a resin, Amberlite IRN-78 (Supelco) , as a source of hydroxide anions, having previously washed the resin with water distilled to pH=7. The process consists of dissolving 9 g of hexamethonium dibromide obtained according to example 1 in 250 g of Milli Q water (Millipore) . The resulting solution is passed through a washed Amberlite IRN-78 resin column adjusting the flow rate in order to reach an exchange level higher than 95%. The resulting solution of mexamethylene-bis (trimethylammonium) dihydroxide is collected in a precipitate vessel. This solution is concentrated at 50°C and in a vacuum until a concentration of hexamethylene-bis (trimethylammonium) dihydroxide of approximately 0.5 mol/kg is obtained. Example 3 - Preparation of the material containing exclusively Silica/Germanium 0.785 g of Ge02 are dissolved in 161 g of a solution of hexamethylenebis (trimethylammonium) dihydroxide with a concentration of 0.256 mols/1,000 g. Once dissolved, 15.621 g of tetraethylorthosilicate are hydrolyzed in said solution, with stirring until the ethanol formed in the hydrolysis evaporates the reaction mixture obtaining a final composition: 10 Siθ2 : 1 Ge02 : 2.75 R(OH)2 : 55 H20 wherein R(0H)2 is hexamethyelene-bis (trimethylammonium) dihydroxide . This gel is put into steel autoclaves with an inside Teflon cover which, in turn, is put inside ovens at 175°C for 22 days. The solid obtained, is filtered, washed and dried at 60°C Example 4 Preparation of the material Silica/germanium, including boron, and seeding with 5% of ITQ-13 0.655 g of Ge02 are dissolved in 65.166 g of a hexamethelene-bis (trimethylammonium) dihydroxide solution with a concentration of 0.5265 moles/lOOOg. Once dissolved, 0.217 g of recently synthesized ITQ-13 crystals are added and dissolved, and then 12.329 g of tetraethylothosilicate are hydrolyzed in said solution, with stirring until the ethanol formed in the hydrolysis evaporates, the reaction mixture obtaining a final composition: 10 Siθ2 : 1 Ge02 : 2.75 R(OH)2 : 55 H20 : 0.00045 B203 wherein R(OH)2 is hexamethylene-bis (trimethylammonium) dihydroxide . This gel is put in steel autoclaves with an inside Teflon cover which, in turn, is put inside ovens at 175°C for 22 days. The solid obtained, is filtered, washed and dried at 60°C.

Claims

1.- A process for the synthesis of a microporous crystalline material called ITQ-13 or of a precursor of ITQ-13, said ITQ-13 having a three-dimensional system of channels, that comprises two groups of channels, each one of which is defined by ten-member rings of tetrahedrally coordinated atoms, that intersect with each other, and a third group of channels, defined by nine-member rings of tetrahedrally coordinated atoms, and that intersect with the two previous groups of channels, said process being characterized in that it comprises: a) preparing a mixture that comprises at least water, a source of at least one tetravalent element Y, and a structure directing agent R, without any source of fluoride ions being present in the synthesis medium; b) keeping the synthesis mixture at a temperature between 80 and 200°C until crystals of the material are formed, obtaining a crystalline material; and c) recovering the crystalline material.
2.- The process according to claim 1, characterized in that it further comprises the step of d) eliminating the organic material occluded inside the crystalline material by means of a step selected from among : - extraction, thermal treatment at temperatures higher than 250°, and - mixture of both the extraction and thermal treatment steps .
3.- A process according to claim 1 or claim 2, characterized in that the mixture prepared in step a) further comprises a source of at least one trivalent element X.
4.- A process according to any of the preceding claims, characterized in that the mixture prepared in step a) further comprises a source of a tetravalent element Z different from Y.
5.- A process according to claim 4, wherein the mixture prepared in step a) has a composition, in terms of molar ratios of oxides, in the following ranges (Y02+Z02) /X203 higher than 5 H20/ (Y02+Z02) 1-50 R/ (Y02 + Z02) 0.05-3.0 OH"/ (Y02 + Z02) 0.1-6.0 YO2/ZO2 higher than 1
6.- A process according to claim 5, characterized in that the mixture prepared in step a) has a composition, in terms of molar ratios of oxides, in the following ranges : (Y02+Z02) /X203 higher than 200
Figure imgf000019_0001
R/(Y02+Z02) 0.05-1.0 OH"/ (YO2+ZO2) 0.1-2.0 Y02/Z02 8-25
7. - A process according to any one of the preceding claims, characterized in that the source of the tetravalent element Y is selected from among an oxide, hydroxide, oxyhydroxide, hydrolyzable alkoxide, a salt of element Y and a mixture thereof .
8.- A process according to any one of claim 3 to 7, characterized in that the sources of the trivalent element X is selected from among an oxide, hydroxide, oxyhydroxide, hydrolyzable ' alkoxide, a salt of the element X and a mixture thereof .
9.- A process according any one of claims 4 to 8, characterized in that the source of the tetravalent element Z is selected from among an oxide, hydroxide, oxyhydroxide, hydrolyzable alkoxide, a salt of element Z and a mixture thereof .
10. - A process according to any one of the preceding claims, characterized in that the structure directing agent is a salt of the hexamethylene-bis (trimethyl ammonium) cation.
11.- A process according to claim 10, wherein the salt of the hexamethylene-bis (trimethylammonium) cation is the hydroxide .
12. - A process, according to any one of the preceding claims, characterized in that Y is one or more tetravalent elements selected among Si, Sn, Ti and V.
13. - A process according to any one of claims 3 to 12, characterized in that X is one or more trivalent elements selected from the group formed by Al, B, In, Ga, Cr and Fe.
14.- A process according to any one of claims 4 to 13, characterized in that Z is Ge.
15. - A process according to any one of claims 2 to 14, characterized in that the step of eliminating the occluded organic material is carried out by calcining at a temperature between 350°C and 700°C.
16.- A process according to any one of hte preceding claims, characterized in that it further comprises the step of carrying out an ionic exchange step with one or more cations selected between metallic cations and H+ precursor.
17.- A process according to claim 16, characterized in that said cations are selected from among monovalent cations, divalent cations, trivalent cations and mixtures thereof .
18.- A process, according to any one of claims 16 or 17, characterized in that said cations are selected from among rare earth cations, group VIII metal cations, group IIA, IIIA, IVA, VA, IB, IIB, IIIB, IVB, VB, VIIB metal cations and mixtures thereof.
19.- A microporous crystalline material, precursor of ITQ-13, characterized in that the material possesses an X-ray diffraction pattern that comprises at least the following lines, in its as-synthesized uncalcined form:
Figure imgf000021_0001
Figure imgf000022_0001
wherein the relative intensity is calculated as the percentage with respect to the most intense peak and "vs" means an intensity between 80-100 % and s means between 60-80 %, and in that its chemical composition is: n R : x X03 : y Y02 : z Z02 wherein R is a Structure Directing Agent (SDA) , X is one or more trivalent elements, Y is one or more tetravalent elements, Z corresponds to Ge, the value of (y+z)/x is comprised between 5 and ∞, the value y/z is at least 1 and z may be 0.
20.- A crystalline material, according to claim 19, characterized in that the material possesses an X-ray diffraction pattern further comprising at least the following lines, in its as-synthesized uncalcined form:
Figure imgf000022_0002
Figure imgf000023_0001
wherein the relative intensity is calculated as the percentage with respect to the most intense peak, "w" means between 20-40 % and "vw" means between 0-20 %.
21.- A microporous crystalline material, according to any one of claims 19 or 20, characterized in that the structure directing agent is a salt of the hexamethylenebis (trimethylammmonium) cation.
22.- A microporous crystalline material according to claim 21, characterized in that the salt of the hexamethylene-bis (trimethylammmonium) cation is the hydroxide .
23.- A microporous crystalline material, according to any one of claims 19 to 22, characterized in that - X is one or more trivalent elements selected from the group formed by Al, B, In, Ga, Cr and Fe; - Y is one or more tetravalent elements selected among Si, Sn, Ti, V and - Z is Ge.
24. - A microporous crystalline material according to any one of claims 19 to 23, characterized in that it is prepared by a process comprising at least steps a) , b) and c) of the process of any one of claims 3 to 6.
PCT/EP2004/011531 2003-10-14 2004-10-14 Process for the synthesis of zeolite itq-13 in a basic medium and in the absence of fluoride ions WO2005040041A1 (en)

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