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WO2014122344A1 - Synthesis of itq-51 zeolite, method for the production thereof, and use of same - Google Patents

Synthesis of itq-51 zeolite, method for the production thereof, and use of same Download PDF

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Publication number
WO2014122344A1
WO2014122344A1 PCT/ES2014/070063 ES2014070063W WO2014122344A1 WO 2014122344 A1 WO2014122344 A1 WO 2014122344A1 ES 2014070063 W ES2014070063 W ES 2014070063W WO 2014122344 A1 WO2014122344 A1 WO 2014122344A1
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value
material according
crystalline material
microporous crystalline
obtaining
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French (fr)
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Avelino CORMA CANÓS
Manuel MOLINER MARÍN
Raquel MARTÍNEZ FRANCO
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Consejo Superior De Investigaciones Científicas (Csic)
Universitat Politécnica De Valéncia
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
    • 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
    • C01B37/04—Aluminophosphates [APO compounds]
    • 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
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/065—Aluminophosphates containing other elements, e.g. metals, boron the other elements being metals only
    • 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
    • C01B39/54—Phosphates, e.g. APO or SAPO compounds

Definitions

  • This patent refers to the synthesis of a new porous crystalline material, ITQ-51, its method of preparation and its use in the catalytic conversion of organic compounds.
  • the present patent also describes the novel use of "proton sponges" as organic structure directing agents in the synthesis of porous crystalline materials.
  • Zeolites are porous crystalline aluminosilicates that have found important applications as catalysts, adsorbents and ion exchangers. Many of these zeolitic materials have well-defined structures that form channels and cavities 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 of the pores. This characteristic gives these materials molecular sieve properties.
  • T Si or Al
  • heteroatoms have been incorporated into their structures, such as Ti, Sn, Ge, B, Fe, among others.
  • AlPOs aluminophosphates
  • SAPOs silicoaluminophosphates
  • MeAIPOs metalloaluminophosphates
  • ALPOs were first described in 1982 by UOP researchers (Wilson, S. T., et al. J. Am Chem. Soc. 1982, 104, 146).
  • the composition of said materials is formed by aluminum and phosphorus atoms in strict alternation in tetrahedral coordination, connected by oxygen atoms.
  • SAPOs are a particular case of AlPOs, where some of the atoms of the crystalline structure are partially substituted by silicon (Chen, J. S. et al. J. Phys.Chem., 1994, 98, 10216). When this happens, SAPOs show excellent cation exchange capacity. Possibly, the most common SAPOs are in their protonated form.
  • the protons associated with the Si atoms in the crystalline network introduce acidity to these materials, allowing their use as commercial catalysts in acid catalytic processes, such as the methanol-a-olefins process (SW Kaiser, US Patent 4,499,327; 1985).
  • MeAIPOs can be incorporated into the crystal structure of the AlPO, thus obtaining MeAIPOs, where Me can be any heteroatom other than silicon, aluminum and phosphorus.
  • MeAIPOs have been described in the literature. A long list of metals, including Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, have been introduced into the crystalline network of different zeotypes. These MeAIPOs are used as catalysts in different acid and redox catalytic processes (Hartmann et al., Res. Chem. Inter., 2002, 28, 625). Especially interesting is its use as redox catalysts, because the isolated metals in tetrahedral coordination in the crystalline network of the MeAIPOs present changes in their oxidation state.
  • zeolites and related zeotypes are synthesized in the presence of an organic molecule that acts as a structure directing agent.
  • Organic molecules that act as organic structure directing agents may contain nitrogen, phosphorus or PN bonds in their composition, and can result in stable organic cations in the reaction medium.
  • ADEOs organic structure directing agents
  • amines and ammonium cations are amines and ammonium cations.
  • "Proton sponges" are bulky aromatic diamines that have amino groups close to each other (Staab, et al. Angew. Chem. Int. Ed. 1988, 27, 865). The distance between these amino groups is between 2,553-2,654 A.
  • the present invention relates to a microporous crystalline material, which has a chemical composition:
  • - M is an element, or mixture of elements, other than Si, Al and P; preferably selected from Co, Zn, Mg, or mixtures thereof;
  • x is between 0 and 1.5, preferably between 0 and 0.8;
  • y is between 0.3 and 1 .6, preferably between
  • the value of z is between 0 and 1.5, preferably between 0 and 0.8;
  • This new porous crystalline material called ITQ-51 both in its calcined and synthesized form without calcining, has a powder X-ray diffraction pattern that is different from other known zeolitic materials and whose most important diffraction lines are given in the Table 1 for the calcined and anhydrous form and in Table 2 for the uncalcined form.
  • crystallographic changes may include small variations in the parameters of the unit cell and / or changes in the symmetry of the crystal, without a change in 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 .
  • the ITQ-51 microporous crystalline material can have "z" equal to zero, so it would have the following chemical composition:
  • x is between 0 and 1.5, preferably between 0 and 0.8.
  • y is between 0.3 and 1 .6, preferably between
  • the microporous crystalline material may have "x" equal to zero and may possess a chemical composition:
  • y is between 0.3 and 1 .6, preferably between 0.6 and 1 .3.
  • z is between 0 and 1.5, preferably between 0 and 0.8.
  • the microporous crystalline material may have "x" and "z" equal to zero and may have a chemical composition:
  • y is between 0.3 and 1 .6, preferably between 0.6 and 1 .3.
  • the microporous crystalline material may have a chemical composition:
  • - R is a structure directing agent preferably selected from an amine, a tetraalkylammonium salt, an organic molecule containing P, or an organic molecule containing P-N bonds and combinations thereof.
  • n / (1 + x + y + z) is between 0 and 8, preferably between 0.001 and 3, and more preferably between 0.05 and 2.
  • - M is an element, or mixture of elements, other than Si, Al and P.
  • x is between 0 and 1.5, preferably between 0 and 0.8.
  • y is between 0.3 and 1 .6, preferably between 0.6 and 1 .3.
  • z is between 0 and 1.5, preferably between 0 and 0.8.
  • the structure directing agent, R is a proton sponge, and preferably 1,8-bis (dimethylamine) naphthalene.
  • "z" may be zero and the microporous crystalline material called ITQ-51 may have a chemical composition:
  • n / (1 + x + y) is between 0 and 8, preferably between 0.001 and 3, and more preferably between 0.05 and 2.
  • x is between 0 and 1.5, preferably between 0 and 0.8.
  • y is between 0.3 and 1 .6, preferably between 0.6 and 1 .3.
  • microporous crystalline material may have the following chemical composition:
  • n R At 2 0 3 : and P 2 0 5
  • n / (1 + y) is between 0 and 8, preferably between 0.001 and 3, and more preferably between 0.05 and 2.
  • y is between 0.3 and 1 .6, preferably between 0.6 and 1 .3.
  • microporous crystalline material may have the following chemical composition:
  • n / (1 + and + z) is between 0 and 8, preferably between 0.001 and 3, and more preferably between 0.05 and 2.
  • y is between 0.3 and 1 .6, preferably between 0.6 and 1 .3.
  • the organic component of the ADE can be removed, for example, by extraction or by heat treatment by heating at a temperature above 250 ° C for a period of time between 2 minutes and 25 hours, preferably between 1 hour and 8 hours.
  • the compensation cations in the material in its uncalcined form, or after thermal treatment can be exchanged in the case of being present, by other cations such as metal ions, H + and precursors of H + such as NH4 + .
  • 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, IIB, IIIB, IVB, VB, VIIB group of the periodic table of the elements.
  • the crystalline material described can also be combined intimately with hydrogenating-dehydrogenating components preferably selected from platinum, palladium, nickel, rhenium, cobalt, tungsten, molybdenum, vanadium, chromium, manganese, iron and combinations thereof.
  • hydrogenating-dehydrogenating components preferably selected from platinum, palladium, nickel, rhenium, cobalt, tungsten, molybdenum, vanadium, chromium, manganese, iron and combinations thereof.
  • the introduction of these elements can be carried out in the crystallization stage, by exchange (if applicable), and / or by impregnation or by physical mixing.
  • These elements can be introduced in their cationic form and / or from salts or other compounds that by decomposition generate the metal component or oxide in its appropriate catalytic form.
  • a material preparation procedure may comprise at least the following steps: a) preparation of a mixture containing at least H 2 0; an oxide or other source of aluminum; an oxide or other source of phosphorus; an oxide or a source of silicon; an oxide or a source of one or more metal elements M, where M is at least one heteroatom other than Si, Al and P; a structure managing agent (R); where the synthesis mixture has a molar composition of oxides in the following ranges:
  • M may be selected from Zn, Mg, Co and mixtures thereof.
  • the structure directing agent R is an amine, a tetraalkylammonium salt, an organic molecule containing P, or an organic molecule containing P-N bonds.
  • R may be a "proton sponge", and more preferably it may be 1,8- bis (dimethylamine) naphthalene.
  • the crystallization of ITQ-51 can be carried out in static or stirring, in autoclaves at a temperature between 80 and 200 ° C, at times sufficient to achieve crystallization, for example between 12 hours and 60 days.
  • the ITQ-51 crystals are separated from the mother liquors, and recovered. It should be taken into account that the components of the synthesis mixture can come from different sources, and depending on these, crystallization times and conditions may vary.
  • ITQ-51 crystals can be added as seeds, in amounts of up to 25% by weight with respect to the total oxides, to the synthesis mixture. These can be added before or during the crystallization of ITQ-51.
  • the process of obtaining the crystalline material may further comprise a step of calcining said crystalline material that can be carried out at a temperature selected between 200 and 1000 ° C.
  • the ITQ-51 material described above and obtained according to the obtaining procedure described above can be used for the transformation of organic compounds, preferably to convert feeds formed by organic compounds into products of higher added value.
  • This gel is transferred to a steel autoclave with the Teflon protected inner walls, and heated at 135 ° C for five days. After this time, the resulting solid is recovered by filtration, washing it thoroughly with water, and subsequently drying it at 100 ° C for one hour. By means of X-ray diffraction it is observed that the solid obtained contains the characteristic peaks of ITQ-51, shown in Table 2.
  • the material is calcined at 550 ° C for 3 hours in air flow to remove organic matter.
  • the powder X-ray diffraction pattern of the solid contains the characteristic peaks of the ITQ-51 zeolite shown in Table 1.
  • the composition of the final gel is 0.4 S ⁇ 0 2/1 Al 2 0 3 / 0.9 P 2 0 5/1 1 DMAN / 38 H 2 0.
  • This gel is transferred to a steel autoclave with inner walls protected by Teflon , and heated at 150 ° C for five days. After this time, the resulting solid is recovered by filtration, washing it thoroughly with water, and subsequently drying it at 100 ° C for one hour.
  • X-ray diffraction it is observed that the solid obtained contains the characteristic peaks of ITQ-51, shown in Table 2.
  • the material is calcined at 550 ° C for 3 hours in air flow to remove organic matter.
  • the powder X-ray diffraction pattern of the solid contains the characteristic peaks of the ITQ-51 zeolite shown in Table 1.
  • the composition of the final gel is 1 Al 2 0 3/1 1 P2O5 / Mg 0.2 / 1 0.3 DMAN / 42 H 2 0.
  • This gel is transferred to a steel autoclave with inner walls protected by Teflon, and heated at 135 ° C for five days. After this time, the resulting solid is recovered by filtration, washing it thoroughly with water, and subsequently drying it at 100 ° C for one hour. By means of X-ray diffraction it is observed that the solid obtained contains the characteristic peaks of ITQ-51, shown in Table 2.
  • the material is calcined at 550 ° C for 3 hours in air flow to remove organic matter.
  • the powder X-ray diffraction pattern of the solid contains the characteristic peaks of the ITQ-51 zeolite shown in Table 1.
  • the composition of the final gel is 1 Al 2 0 3/1 2 P 2 0 5 / 0.2 Zn / 0.3 DMAN 1/42 H 2 0.
  • This gel is transferred to a steel autoclave with inner walls protected Teflon and heated at 135 ° C for five days. After this time, the resulting solid is recovered by filtration, washing it thoroughly with water, and subsequently drying it at 100 ° C for one hour. By means of X-ray diffraction it is observed that the solid obtained contains the characteristic peaks of ITQ-51, shown in Table 2.
  • the composition of the final gel is 1 Al 2 0 3/1 1 P2O5 / Co 0.2 / 1 0.3 DMAN / 42 H 2 0.
  • This gel is transferred to a steel autoclave with inner walls protected by Teflon, and heated at 135 ° C for five days. After this time, the resulting solid is recovered by filtration, washing it thoroughly with water, and subsequently drying it at 100 ° C for one hour. By means of X-ray diffraction it is observed that the solid obtained contains the characteristic peaks of ITQ-51, shown in Table 2.
  • the material is calcined at 550 ° C for 3 hours in air flow to remove organic matter.
  • the powder X-ray diffraction pattern of the solid contains the characteristic peaks of the ITQ-51 zeolite shown in Table 1.

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Abstract

The invention relates to a crystalline material called ITQ-51, having a molar composition in the calcined and anhydrous state thereof, corresponding to the following equation: x Si02 : AI2O3 : y P205 : z M wherein: M is an element or a mixture of elements different from Si, Al and P; the value of x is between 0 and 1.5, preferably between 0 and 0.8; the value of y is between 0.3 and 1.6, preferably between 0.6 and 1.3; and the value of z is between 0 and 1.5, preferably between 0 and 0.8.

Description

SÍNTESIS DE LA ZEOLITA ITQ-51, PROCEDIMIENTO DE OBTENCIÓN Y  SYNTHESIS OF THE ZEOLITE ITQ-51, PROCEDURE OF OBTAINING AND
USO  USE
DESCRIPCION DESCRIPTION
Campo de la Invención Field of the Invention
Esta patente se refiere a la síntesis de un nuevo material cristalino poroso, ITQ- 51 , a su método de preparación y a su uso en la conversión catalítica de compuestos orgánicos. La presente patente también describe el novedoso uso de las "esponjas de protones" como agentes directores de estructura orgánicos en la síntesis de materiales cristalinos porosos. This patent refers to the synthesis of a new porous crystalline material, ITQ-51, its method of preparation and its use in the catalytic conversion of organic compounds. The present patent also describes the novel use of "proton sponges" as organic structure directing agents in the synthesis of porous crystalline materials.
Antecedentes de la Invención Las zeolitas son aluminosilicatos cristalinos porosos que han encontrado importantes aplicaciones como catalizadores, adsorbentes e intercambiadores iónicos. Muchos de estos materiales zeolíticos tienen estructuras bien definidas que forman canales y cavidades en su interior de tamaño y forma uniforme que permiten la adsorción de determinadas moléculas, mientras que impiden el paso al interior del cristal de otras moléculas de tamaño demasiado grande para difundir a través de los poros. Esta característica confiere a estos materiales propiedades de tamiz molecular. Background of the Invention Zeolites are porous crystalline aluminosilicates that have found important applications as catalysts, adsorbents and ion exchangers. Many of these zeolitic materials have well-defined structures that form channels and cavities 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 of the pores. This characteristic gives these materials molecular sieve properties.
La estructura cristalina resultante proviene del acoplamiento de tetraedros T04 (T = Si ó Al), estando cada átomo de oxígeno compartido por dos tetraedros. A pesar que inicialmente la composición química de las zeolitas se limitaba a la presencia de átomos de silicio y aluminio, actualmente un gran número de heteroátomos han sido incorporados en sus estructuras, como Ti, Sn, Ge, B, Fe, entre otros. The resulting crystalline structure comes from the coupling of T0 4 tetrahedra (T = Si or Al), each oxygen atom being shared by two tetrahedra. Although initially the chemical composition of the zeolites was limited to the presence of silicon and aluminum atoms, currently a large number of heteroatoms have been incorporated into their structures, such as Ti, Sn, Ge, B, Fe, among others.
Junto a las zeolitas, existen otros materiales microporosos relacionados que no contienen silicio (o cuyo contenido es minoritario), los cuales se conocen como zeotipos. De entre ellos, destacan los aluminofosfatos (AlPOs), silicoaluminofosfatos (SAPOs), y metaloaluminofosfatos (MeAIPOs). Alongside zeolites, there are other related microporous materials that do not contain silicon (or whose content is minority), which are known as Zeotypes Among them, aluminophosphates (AlPOs), silicoaluminophosphates (SAPOs), and metalloaluminophosphates (MeAIPOs) stand out.
Los ALPOs se describieron por primera vez en 1982 por investigadores de UOP (Wilson, S. T. , et al. J. Am Chem. Soc. 1982, 104, 1 146). La composición de dichos materiales está formada por átomos de aluminio y fósforo en estricta alternancia en coordinación tetraédrica, conectados por átomos de oxígeno. Los SAPOs son un caso particular de los AlPOs, donde algunos de los átomos de la estructura cristalina son parcialmente sustituidos por silicio (Chen, J. S. et al. J. Phys.Chem. , 1994, 98, 10216). Cuando esto sucede, los SAPOs muestran una excelente capacidad de intercambio catiónico. Posiblemente, los SAPOs más comunes se encuentran en su forma protonada. De esta forma, los protones asociados a los átomos de Si en la red cristalina introducen acidez a estos materiales, permitiendo su uso como catalizadores comerciales en procesos catalíticos ácidos, tales como el proceso metanol-a-olefinas (S.W. Kaiser, U.S. Patent 4,499,327; 1985). ALPOs were first described in 1982 by UOP researchers (Wilson, S. T., et al. J. Am Chem. Soc. 1982, 104, 146). The composition of said materials is formed by aluminum and phosphorus atoms in strict alternation in tetrahedral coordination, connected by oxygen atoms. SAPOs are a particular case of AlPOs, where some of the atoms of the crystalline structure are partially substituted by silicon (Chen, J. S. et al. J. Phys.Chem., 1994, 98, 10216). When this happens, SAPOs show excellent cation exchange capacity. Possibly, the most common SAPOs are in their protonated form. In this way, the protons associated with the Si atoms in the crystalline network introduce acidity to these materials, allowing their use as commercial catalysts in acid catalytic processes, such as the methanol-a-olefins process (SW Kaiser, US Patent 4,499,327; 1985).
Otros heteroátomos metálicos se pueden incorporar a la estructura cristalina del AlPO, obteniéndose entonces MeAIPOs, donde Me puede ser cualquier heteroátomo diferente al silicio, aluminio y fósforo. Se han descrito muchos MeAIPOs en la literatura. Una larga lista de metales, incluyendo Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, se han introducido en la red cristalina de distintos zeotipos. Estos MeAIPOs se utilizan como catalizadores en distintos procesos catalíticos ácidos y redox (Hartmann et al. , Res. Chem. Inter. , 2002, 28, 625). Especialmente interesante es su uso como catalizadores redox, debido a que los metales aislados en coordinación tetraédrica en la red cristalina de los MeAIPOs presentan cambios en su estado de oxidación. Other metal heteroatoms can be incorporated into the crystal structure of the AlPO, thus obtaining MeAIPOs, where Me can be any heteroatom other than silicon, aluminum and phosphorus. Many MeAIPOs have been described in the literature. A long list of metals, including Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, have been introduced into the crystalline network of different zeotypes. These MeAIPOs are used as catalysts in different acid and redox catalytic processes (Hartmann et al., Res. Chem. Inter., 2002, 28, 625). Especially interesting is its use as redox catalysts, because the isolated metals in tetrahedral coordination in the crystalline network of the MeAIPOs present changes in their oxidation state.
Muchas zeolitas y zeotipos relacionados se sintetizan en presencia de una molécula orgánica que actúa como agente director de estructura. Las moléculas orgánicas que actúan como agentes directores de estructura orgánicos (ADEO) pueden contener nitrógeno, fósforo o enlaces P-N en su composición, y pueden dar lugar a cationes orgánicos estables en el medio de reacción. De entre los ADEOs más comúnmente utilizados se encuentran las aminas y los cationes amonio. Las "esponjas de protones" son diaminas aromáticas voluminosas que presentan los grupos amino próximos uno al otro (Staab, et al. Angew. Chem. Int. Ed. 1988, 27, 865). La distancia entre dichos grupos amino se encuentra entre 2.553-2.654 A. Este tipo de moléculas presentan una elevada basicidad, pKa>12.1 , debido a la repulsión de los pares de electrones desapareados próximos (Llamas-Saiz, J. Mol. Struct., 1994, 328, 297). Dicha elevada basicidad permite su protonación, incluso a los elevados pHs del medio de síntesis requeridos en la preparación de algunos tamices moleculares, favoreciendo las interacciones orgánicas-inorgánicas durante los procesos de nucleación/cristalización. Su elevada basicidad, junto a su relación C/N, y sus innumerables conformaciones estructurales (Llamas-Saiz, J. Mol. Struct., 1994, 328, 297), les confieren las características adecuadas para ser excelentes ADEOs en la síntesis de materiales microporosos. Many zeolites and related zeotypes are synthesized in the presence of an organic molecule that acts as a structure directing agent. Organic molecules that act as organic structure directing agents (ADEO) may contain nitrogen, phosphorus or PN bonds in their composition, and can result in stable organic cations in the reaction medium. Among the most commonly used ADEOs are amines and ammonium cations. "Proton sponges" are bulky aromatic diamines that have amino groups close to each other (Staab, et al. Angew. Chem. Int. Ed. 1988, 27, 865). The distance between these amino groups is between 2,553-2,654 A. These types of molecules have a high basicity, pKa> 12.1, due to the repulsion of the pairs of nearby missing electrons (Llamas-Saiz, J. Mol. Struct., 1994, 328, 297). This high basicity allows its protonation, even at the high pHs of the synthesis medium required in the preparation of some molecular sieves, favoring organic-inorganic interactions during nucleation / crystallization processes. Their high basicity, together with their C / N relationship, and their innumerable structural conformations (Llamas-Saiz, J. Mol. Struct., 1994, 328, 297), give them the appropriate characteristics to be excellent ADEOs in the synthesis of materials microporous
Descripción de la Invención Description of the Invention
La presente invención se refiere a un material cristalino microporoso, que posee una composición química: The present invention relates to a microporous crystalline material, which has a chemical composition:
x S¡O2 : AI2O3 : y P2O5 : z M x S¡O 2 : AI 2 O 3 : y P 2 O 5 : z M
donde: where:
- M es un elemento, o mezcla de elementos, diferentes a Si, Al y P; preferentemente seleccionado entre Co, Zn, Mg, o mezclas de los mismos;  - M is an element, or mixture of elements, other than Si, Al and P; preferably selected from Co, Zn, Mg, or mixtures thereof;
- El valor de x está comprendido entre 0 y 1 .5, preferentemente entre 0 Y 0.8;  - The value of x is between 0 and 1.5, preferably between 0 and 0.8;
- El valor de y está comprendido entre 0.3 y 1 .6, preferentemente entre - The value of y is between 0.3 and 1 .6, preferably between
0.6 y 1 .3; El valor de z está comprendido entre 0 y 1 .5, preferentemente entre 0 Y 0.8; 0.6 and 1 .3; The value of z is between 0 and 1.5, preferably between 0 and 0.8;
Este nuevo material cristalino poroso denominado ITQ-51 , tanto en su forma calcinada como sintetizada sin calcinar tiene un patrón de difracción de rayos X en polvo que es diferente al de otros materiales zeolíticos conocidos y cuyas líneas de difracción más importantes vienen dadas en la Tabla 1 para la forma calcinada y anhidra y en la Tabla 2 para la forma sin calcinar. This new porous crystalline material called ITQ-51, both in its calcined and synthesized form without calcining, has a powder X-ray diffraction pattern that is different from other known zeolitic materials and whose most important diffraction lines are given in the Table 1 for the calcined and anhydrous form and in Table 2 for the uncalcined form.
Tabla 1 Table 1
Intensidad  Intensity
(d ± 0.4) (A)  (d ± 0.4) (A)
Relativa  Relative
13,5 mf  13.5 mf
1 1 ,7 m  1 1, 7 m
5,4 md  5.4 md
4,5 md  4.5 md
4,3 md  4.3 md
4,2 md  4.2 md
4,0 md  4.0 md
3,9 md  3.9 md
Tabla 2 Table 2
Intensidad  Intensity
(d ± 0.4) (A)  (d ± 0.4) (A)
Relativa  Relative
13,4 mf  13.4 mf
12,0 f  12.0 f
7,2 md  7.2 md
4,3 md  4.3 md
4,2 m  4.2 m
4, 1 d  4, 1 d
4,0 d  4.0 d
3,8 d Estos difractogramas se obtuvieron con un difractómetro Philips X'Pert equipado con un monocromador de grafito y una rendija de divergencia automática utilizando la radiación x del cobre. Los datos de difracción se registraron mediante un paso de 2Θ de 0.01 ° en el que Θ es el ángulo de Bragg y un tiempo de cuenta de 10 segundos por paso. Los espaciados interplanares, d, se calcularon en Amgstrons, y la intensidad relativa de las 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. 3.8 d These diffractograms were obtained with a Philips X'Pert diffractometer equipped with a graphite monochromator and an automatic divergence slit using copper x radiation. The diffraction data was recorded by a 2Θ step of 0.01 ° in which Θ is the Bragg angle and a count time of 10 seconds per step. The inter-planar spacings, d, were calculated in Amgstrons, and the relative intensity of the lines is calculated as the percentage with respect to the most intense peak, and is considered very strong (mf) = 80-100, strong (f) = 60-80 , mean (m) = 40-60, weak (d) = 20-40, and very weak (md) = 0-20.
Otras líneas características del patrón de difracción de rayos X en polvo de la ITQ-51 en su forma calcinada y anhidra, y en su forma sin calcinar, se muestran tabuladas en las Tablas 3 y 4, respectivamente. Other characteristic lines of the X-ray powder diffraction pattern of the ITQ-51 in its calcined and anhydrous form, and in its uncalcined form, are shown tabulated in Tables 3 and 4, respectively.
Tabla 3 Table 3
Intensidad  Intensity
(d ± 0.4) (A)  (d ± 0.4) (A)
Relativa  Relative
13,5 mf  13.5 mf
1 1 ,7 m  1 1, 7 m
6,8 md  6.8 md
5,9 md  5.9 md
5,4 md  5.4 md
4,8 md  4.8 md
4,5 md  4.5 md
4,3 md  4.3 md
4,2 md  4.2 md
4,0 md  4.0 md
3,9 md  3.9 md
3,7 md  3.7 md
3,6 md  3.6 md
3,5 md  3.5 md
3,4 md Tabla 4 3.4 md Table 4
Intensidad  Intensity
(d ± 0.4) (A)  (d ± 0.4) (A)
Relativa  Relative
13,4 mf  13.4 mf
12,0 f  12.0 f
8, 1 md  8, 1 md
7,2 md  7.2 md
6,7 md  6.7 md
6,0 md  6.0 md
5,3 md  5.3 md
4,9 md  4.9 md
4,8 md  4.8 md
4,6 md  4.6 md
4,5 md  4.5 md
4,3 md  4.3 md
4,3 md  4.3 md
4,2 m  4.2 m
4, 1 d  4, 1 d
4,0 d  4.0 d
3,8 d  3.8 d
3,8 md  3.8 md
3,6 md  3.6 md
3,5 md  3.5 md
3,4 md  3.4 md
3,4 md  3.4 md
3,2 md  3.2 md
3,2 md  3.2 md
Debe tenerse en cuenta que los datos de difracción listados para esta muestra como líneas sencillas o únicas, pueden estar formados por múltiples solapam ientos o superposición de reflexiones que, en ciertas condiciones, tales como diferencias en cambios cristalográficos, pueden aparecer como líneas resueltas o parcialmente resueltas. Generalmente, los cambios cristalográficos pueden incluir pequeñas variaciones en los parámetros de la celda unidad y/o cambios en la simetría del cristal, sin que se produzca un cambio en la estructura. Estas modificaciones, que incluyen también cambios en intensidades relativas, pueden deberse también a diferencias en el tipo y cantidad de cationes de compensación, composición de red, tamaño de cristal y forma de los mismos, orientación preferente o al tipo de tratamientos térmicos o hidrotérmicos sufridos. It should be taken into account that the diffraction data listed for this sample as single or single lines, may be formed by multiple overlaps or overlapping reflections that, under certain conditions, such as differences in crystallographic changes, may appear as partially or resolved lines. resolved. Generally, crystallographic changes may include small variations in the parameters of the unit cell and / or changes in the symmetry of the crystal, without a change in 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 .
Según una realización particular de la presente invención, el material cristalino microporoso ITQ-51 , puede tener "z" igual a cero por lo que poseería la siguiente composición química: According to a particular embodiment of the present invention, the ITQ-51 microporous crystalline material can have "z" equal to zero, so it would have the following chemical composition:
x S¡02 : Al203 : y P205 x S¡0 2 : Al 2 0 3 : y P 2 0 5
donde: where:
- El valor de x está comprendido entre 0 y 1 .5, preferentemente entre 0 y 0.8.  - The value of x is between 0 and 1.5, preferably between 0 and 0.8.
- El valor de y está comprendido entre 0.3 y 1 .6, preferentemente entre - The value of y is between 0.3 and 1 .6, preferably between
0.6 y 1 .3. 0.6 and 1 .3.
Según otra realización particular de la presente invención, el material cristalino microporoso puede tener "x" igual a cero y puede poseer una composición química:According to another particular embodiment of the present invention, the microporous crystalline material may have "x" equal to zero and may possess a chemical composition:
Figure imgf000008_0001
Figure imgf000008_0001
donde: where:
- El valor de y está comprendido entre 0.3 y 1 .6, preferentemente entre 0.6 y 1 .3.  - The value of y is between 0.3 and 1 .6, preferably between 0.6 and 1 .3.
- El valor de z está comprendido entre 0 y 1 .5, preferentemente entre 0 y 0.8.  - The value of z is between 0 and 1.5, preferably between 0 and 0.8.
Según otra realización particular de la presente invención, el material cristalino microporoso puede tener "x" y "z" igual a cero y puede poseer una composición química:According to another particular embodiment of the present invention, the microporous crystalline material may have "x" and "z" equal to zero and may have a chemical composition:
Figure imgf000008_0002
Figure imgf000008_0002
donde: - El valor de y está comprendido entre 0.3 y 1 .6, preferentemente entre 0.6 y 1 .3. where: - The value of y is between 0.3 and 1 .6, preferably between 0.6 and 1 .3.
Según otra realización particular, el material cristalino microporoso puede poseer una composición química: According to another particular embodiment, the microporous crystalline material may have a chemical composition:
n R : x S¡02 : Al203 : y P205 : z M n R: x S¡0 2 : Al 2 0 3 : y P 2 0 5 : z M
donde: where:
- R es un agente director de estructura preferentemente seleccionado entre una amina, una sal de tetraalquilamonio, una molécula orgánica que contiene P, o una molécula orgánica que contiene enlaces P-N y combinaciones de los mismos.  - R is a structure directing agent preferably selected from an amine, a tetraalkylammonium salt, an organic molecule containing P, or an organic molecule containing P-N bonds and combinations thereof.
- El valor de n/(1 +x+y+z) está comprendido entre 0 y 8, preferentemente entre 0.001 y 3, y más preferentemente entre 0.05 y 2.  - The value of n / (1 + x + y + z) is between 0 and 8, preferably between 0.001 and 3, and more preferably between 0.05 and 2.
- M es un elemento, o mezcla de elementos, diferentes a Si, Al y P. - El valor de x está comprendido entre 0 y 1 .5, preferentemente entre 0 y 0.8.  - M is an element, or mixture of elements, other than Si, Al and P. - The value of x is between 0 and 1.5, preferably between 0 and 0.8.
- El valor de y está comprendido entre 0.3 y 1 .6, preferentemente entre 0.6 y 1 .3.  - The value of y is between 0.3 and 1 .6, preferably between 0.6 and 1 .3.
- El valor de z está comprendido entre 0 y 1 .5, preferentemente entre 0 y 0.8.  - The value of z is between 0 and 1.5, preferably between 0 and 0.8.
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.
En la presente invención también muestra la aplicación por primera vez de "esponjas de protones" como agentes directores de estructura orgánicos en la síntesis de materiales microporosos cristalinos. Las "esponjas de protones" son diaminas aromáticas voluminosas que presentan los grupos aromáticos próximos uno al otro. In the present invention it also shows for the first time the application of "proton sponges" as organic structure directing agents in the synthesis of crystalline microporous materials. "Proton sponges" are bulky aromatic diamines that present the aromatic groups close to each other.
Según una realización preferida, el agente director de estructura, R, es una esponja de protones, y de manera preferente 1 ,8-bis(dimet¡lam¡no)naftaleno. Según una realización particular, "z" puede ser cero y el material cristalino microporoso denominado ITQ-51 puede poseer composición química: According to a preferred embodiment, the structure directing agent, R, is a proton sponge, and preferably 1,8-bis (dimethylamine) naphthalene. According to a particular embodiment, "z" may be zero and the microporous crystalline material called ITQ-51 may have a chemical composition:
n R : x S¡02 : Al203 : y P205 n R: x S¡0 2 : Al 2 0 3 : y P 2 0 5
donde: where:
- El valor de n/(1 +x+y) está comprendido entre 0 y 8, preferentemente entre 0.001 y 3, y más preferentemente entre 0.05 y 2.  - The value of n / (1 + x + y) is between 0 and 8, preferably between 0.001 and 3, and more preferably between 0.05 and 2.
- El valor de x está comprendido entre 0 y 1 .5, preferentemente entre 0 y 0.8.  - The value of x is between 0 and 1.5, preferably between 0 and 0.8.
- El valor de y está comprendido entre 0.3 y 1 .6, preferentemente entre 0.6 y 1 .3.  - The value of y is between 0.3 and 1 .6, preferably between 0.6 and 1 .3.
Según otra realización particular, "x" y "z" pueden ser cero y el material cristalino microporoso puede tener siguiente composición química: According to another particular embodiment, "x" and "z" may be zero and the microporous crystalline material may have the following chemical composition:
n R : Al203 : y P205 n R: At 2 0 3 : and P 2 0 5
donde: where:
- El valor de n/(1 +y) está comprendido entre 0 y 8, preferentemente entre 0.001 y 3, y más preferentemente entre 0.05 y 2.  - The value of n / (1 + y) is between 0 and 8, preferably between 0.001 and 3, and more preferably between 0.05 and 2.
- El valor de y está comprendido entre 0.3 y 1 .6, preferentemente entre 0.6 y 1 .3.  - The value of y is between 0.3 and 1 .6, preferably between 0.6 and 1 .3.
Según otra realización particular, "x" puede ser cero y el material cristalino microporoso puede tener la siguiente composición química:According to another particular embodiment, "x" may be zero and the microporous crystalline material may have the following chemical composition:
Figure imgf000010_0001
Figure imgf000010_0001
donde: where:
- El valor de n/(1 +y+z) está comprendido entre 0 y 8, preferentemente entre 0.001 y 3, y más preferentemente entre 0.05 y 2.  - The value of n / (1 + and + z) is between 0 and 8, preferably between 0.001 and 3, and more preferably between 0.05 and 2.
- El valor de y está comprendido entre 0.3 y 1 .6, preferentemente entre 0.6 y 1 .3.  - The value of y is between 0.3 and 1 .6, preferably between 0.6 and 1 .3.
- El valor de z está comprendido entre 0 y 1 .5, preferentemente entre 0 y 0.8. Según una realización particular de la presente invención, el componente orgánico del ADE, se puede eliminar, por ejemplo, por extracción o por tratamiento térmico calentando a temperatura por encima de 250° C durante un periodo de tiempo comprendido entre 2 minutos y 25 horas, preferentemente entre 1 hora y 8 horas. - The value of z is between 0 and 1.5, preferably between 0 and 0.8. According to a particular embodiment of the present invention, the organic component of the ADE, can be removed, for example, by extraction or by heat treatment by heating at a temperature above 250 ° C for a period of time between 2 minutes and 25 hours, preferably between 1 hour and 8 hours.
Los cationes de compensación en el material en su forma sin calcinar, o después de un tratamiento térmico, pueden intercambiarse, en el caso de estar presentes, por otros cationes tales como iones metálicos, H+ y precursores de H+ como por ejemplo NH4 +. 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, IIB, IIIB, IVB, VB, VIIB de la tabla periódica de los elementos. The compensation cations in the material in its uncalcined form, or after thermal treatment, can be exchanged in the case of being present, by other cations such as metal ions, H + and precursors of H + such as NH4 + . 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, IIB, IIIB, IVB, VB, VIIB group of the periodic table of the elements.
Según una realización particular de la presente invención, el material cristalino descrito puede, además, combinarse íntimamente con componentes hidrogenantes-deshidrogenantes seleccionados preferentemente entre platino, paladio, níquel, renio, cobalto, tungsteno, molibdeno, vanadio, cromo, manganeso, hierro y combinaciones de los mismos. La introducción de estos elementos se puede llevar a cabo en la etapa de cristalización, por intercambio (si ha lugar), y/o por impregnación o por mezcla física. Estos elementos pueden ser introducidos en su forma catiónica y/o a partir de sales u otros compuestos que por descomposición generen el componente metálico u óxido en su forma catalítica adecuada. According to a particular embodiment of the present invention, the crystalline material described can also be combined intimately with hydrogenating-dehydrogenating components preferably selected from platinum, palladium, nickel, rhenium, cobalt, tungsten, molybdenum, vanadium, chromium, manganese, iron and combinations thereof. The introduction of these elements can be carried out in the crystallization stage, by exchange (if applicable), and / or by impregnation or by physical mixing. These elements can be introduced in their cationic form and / or from salts or other compounds that by decomposition generate the metal component or oxide in its appropriate catalytic form.
La presente invención se refiere, también, al procedimiento de preparación del material cristalino ITQ-51 descrito anteriormente. Un procedimiento de preparación del material puede comprender, al menos, los siguientes pasos: a) preparación de una mezcla que contiene, al menos, H20; un óxido u otra fuente de aluminio; un óxido u otra fuente de fósforo; un óxido o una fuente de silicio; un óxido o una fuente de uno o varios elementos metálicos M, donde M es, al menos, un heteroátomo diferente a Si, Al y P; un agente director de estructura (R); donde la mezcla de síntesis tiene una composición molar de óxidos en los siguientes rangos: The present invention also relates to the method of preparing the ITQ-51 crystalline material described above. A material preparation procedure may comprise at least the following steps: a) preparation of a mixture containing at least H 2 0; an oxide or other source of aluminum; an oxide or other source of phosphorus; an oxide or a source of silicon; an oxide or a source of one or more metal elements M, where M is at least one heteroatom other than Si, Al and P; a structure managing agent (R); where the synthesis mixture has a molar composition of oxides in the following ranges:
Si/(AI203+P205) 0.0-0.8 Yes / (AI 2 0 3 + P20 5 ) 0.0-0.8
Μ/(ΑΙ203+Ρ2θ5) 0.0-0.8 Μ / (ΑΙ 2 0 3 + Ρ2θ 5 ) 0.0-0.8
Η20/(ΑΙ2θ3+Ρ2θ5) 1 -400 Η 2 0 / (ΑΙ 2 θ3 + Ρ2θ5) 1 -400
R/(AI203+P205) 0.0-8.0R / (AI 2 0 3 + P20 5 ) 0.0-8.0
Figure imgf000012_0001
b) mantener la mezcla a una temperatura entre 80 y 200°C hasta que se formen los cristales del material;
Figure imgf000012_0001
b) keep the mixture at a temperature between 80 and 200 ° C until the crystals of the material form;
c) recuperación del material cristalino. c) recovery of the crystalline material.
Según una realización particular M puede estar seleccionado entre Zn, Mg, Co y mezclas de los mismos. According to a particular embodiment M may be selected from Zn, Mg, Co and mixtures thereof.
Según una realización particular, el agente director de estructura R es una amina, una sal de tetraalquilamonio, una molécula orgánica que contiene P, o una molécula orgánica que contiene enlaces P-N. Preferentemente R puede ser una "esponja de protones", y más preferentemente puede ser 1 ,8- bis(dimet¡lam¡no)naftaleno. According to a particular embodiment, the structure directing agent R is an amine, a tetraalkylammonium salt, an organic molecule containing P, or an organic molecule containing P-N bonds. Preferably R may be a "proton sponge", and more preferably it may be 1,8- bis (dimethylamine) naphthalene.
La cristalización de ITQ-51 se puede llevar a cabo en estático o en agitación, en autoclaves a temperatura comprendida entre 80 y 200°C, a tiempos suficientes para conseguir la cristalización, por ejemplo entre 12 horas y 60 días. Al finalizar la etapa de cristalización, se separan los cristales de ITQ-51 de las aguas madres, y se recuperan. Debe tenerse en cuenta que los componentes de la mezcla de síntesis pueden provenir de distintas fuentes, y dependiendo de estos pueden variar tiempos y condiciones de cristalización. Con el fin de facilitar la síntesis, se pueden añadir cristales de ITQ-51 como semillas, en cantidades de hasta 25% en peso respecto del total de óxidos, a la mezcla de síntesis. Éstas pueden ser adicionadas previamente o durante la cristalización de ITQ-51 . Según una realización particular de la presente invención, el proceso de obtención del material cristalino puede comprender, además, un paso de calcinación de dicho material cristalino que se puede llevar a cabo a una temperatura seleccionada entre 200 y 1000°C. Según una realización particular, el material ITQ-51 descrito anteriormente y obtenido según el procedimiento de obtención descrito anteriormente puede ser utilizado para la transformación de compuestos orgánicos, preferentemente para convertir alimentaciones formadas por compuestos orgánicos en productos de mayor valor añadido. The crystallization of ITQ-51 can be carried out in static or stirring, in autoclaves at a temperature between 80 and 200 ° C, at times sufficient to achieve crystallization, for example between 12 hours and 60 days. At the end of the crystallization stage, the ITQ-51 crystals are separated from the mother liquors, and recovered. It should be taken into account that the components of the synthesis mixture can come from different sources, and depending on these, crystallization times and conditions may vary. In order to facilitate synthesis, ITQ-51 crystals can be added as seeds, in amounts of up to 25% by weight with respect to the total oxides, to the synthesis mixture. These can be added before or during the crystallization of ITQ-51. According to a particular embodiment of the present invention, the process of obtaining the crystalline material may further comprise a step of calcining said crystalline material that can be carried out at a temperature selected between 200 and 1000 ° C. According to a particular embodiment, the ITQ-51 material described above and obtained according to the obtaining procedure described above can be used for the transformation of organic compounds, preferably to convert feeds formed by organic compounds into products of higher added value.
A lo largo de la descripción y las reivindicaciones la palabra "comprende" y sus variantes no pretenden excluir otras características técnicas, aditivos, componentes o pasos. Para los expertos en la materia, otros objetos, ventajas y características de la invención se desprenderán en parte de la descripción y en parte de la práctica de la invención. Los siguientes ejemplos se proporcionan a modo de ilustración, y no se pretende que sean limitativos de la presente invención. Throughout the description and the claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and features of the invention will be derived partly from the description and partly from the practice of the invention. The following examples are provided by way of illustration, and are not intended to be limiting of the present invention.
Ejemplos Examples
Ejemplo 1 : Síntesis de ITQ-51 en su forma aluminofosfato Example 1: Synthesis of ITQ-51 in its aluminophosphate form
257.1 mg de 1 ,8-bis(dimet¡lam¡no)naftaleno (DMAN, Sigma-Aldrich, 99% en peso) se mezclan con 237.9 mg de acido ortofosfórico (H3P04, Sigma- Aldrich, 85% en peso) y 676.1 mg de agua destilada. La mezcla se mantiene en agitación durante 2 horas hasta obtener una mezcla homogénea. Finalmente, 135.8 mg de alúmina (AI2O3, Condea, 75% en peso) se añaden a la disolución formándose un gel. La mezcla se mantiene en agitación hasta alcanzar la concentración deseada. La composición del gel final es 1 AI2O3 / 1 P2O5 / 1 .2 DMAN / 40 H20. Este gel se transfiere a un autoclave de acero con las paredes interiores protegidas de Teflon, y se calienta a 135 °C durante cinco días. Transcurrido este tiempo, el sólido resultante se recupera mediante filtración, lavándolo abundantemente con agua, y secándolo posteriormente a 100°C durante una hora. Por medio de difracción de rayos X se observa que el sólido obtenido contiene los picos característicos de ITQ-51 , mostrados en la Tabla 2. 257.1 mg of 1,8-bis (dimethylamine) naphthalene (DMAN, Sigma-Aldrich, 99% by weight) are mixed with 237.9 mg of orthophosphoric acid (H 3 P0 4 , Sigma- Aldrich, 85% by weight) and 676.1 mg of distilled water. The mixture is kept under stirring for 2 hours until a homogeneous mixture is obtained. Finally, 135.8 mg of alumina (AI2O3, Condea, 75% by weight) are added to the solution forming a gel. The mixture is kept under stirring until the desired concentration is reached. The final gel composition is 1 AI2O3 / 1 P2O5 / 1 .2 DMAN / 40 H 2 0. This gel is transferred to a steel autoclave with the Teflon protected inner walls, and heated at 135 ° C for five days. After this time, the resulting solid is recovered by filtration, washing it thoroughly with water, and subsequently drying it at 100 ° C for one hour. By means of X-ray diffraction it is observed that the solid obtained contains the characteristic peaks of ITQ-51, shown in Table 2.
El material se calcina a 550°C durante 3 horas en flujo de aire para eliminar la materia orgánica. El patrón de difracción de rayos X de polvo del sólido contiene los picos característicos de la zeolita ITQ-51 mostrados en la Tabla 1 .  The material is calcined at 550 ° C for 3 hours in air flow to remove organic matter. The powder X-ray diffraction pattern of the solid contains the characteristic peaks of the ITQ-51 zeolite shown in Table 1.
Ejemplo 2: Síntesis de ITQ-51 en su forma silicoaluminofosfato Example 2: Synthesis of ITQ-51 in its silicoaluminophosphate form
257.9 mg de 1 ,8-bis(dimet¡lam¡no)naftaleno (DMAN, Sigma-Aldrich, 99% en peso) se mezclan con 615 mg de agua destilada y 216.4 mg de acido ortofosfórico (H3PO4, Sigma-Aldrich, 85% en peso). La mezcla se mantiene en agitación durante 2 horas hasta obtener una mezcla homogénea. Posteriormente, se añaden 142.5 mg de alumina (AI2O3, Condea, 75% en peso) y 58.8 mg de sílice (Ludox AS40, Sigma-Aldrich, 40% en peso), dejando el gel resultante en agitación hasta alcanzar la concentración deseada. La composición del gel final es 0.4 S¡02 / 1 Al203 / 0.9 P205 / 1 .1 DMAN / 38 H20. Este gel se transfiere a un autoclave de acero con las paredes interiores protegidas de Teflon, y se calienta a 150 °C durante cinco días. Transcurrido este tiempo, el sólido resultante se recupera mediante filtración, lavándolo abundantemente con agua, y secándolo posteriormente a 100°C durante una hora. Por medio de difracción de rayos X se observa que el sólido obtenido contiene los picos característicos de ITQ-51 , mostrados en la Tabla 2. El material se calcina a 550°C durante 3 horas en flujo de aire para eliminar la materia orgánica. El patrón de difracción de rayos X de polvo del sólido contiene los picos característicos de la zeolita ITQ-51 mostrados en la Tabla 1 . 257.9 mg of 1,8-bis (dimethylamine) naphthalene (DMAN, Sigma-Aldrich, 99% by weight) are mixed with 615 mg of distilled water and 216.4 mg of orthophosphoric acid (H3PO4, Sigma-Aldrich, 85 % in weigh). The mixture is kept under stirring for 2 hours until a homogeneous mixture is obtained. Subsequently, 142.5 mg of alumina (AI2O3, Condea, 75% by weight) and 58.8 mg of silica (Ludox AS40, Sigma-Aldrich, 40% by weight) are added, leaving the resulting gel under stirring until reaching the desired concentration. The composition of the final gel is 0.4 S¡0 2/1 Al 2 0 3 / 0.9 P 2 0 5/1 1 DMAN / 38 H 2 0. This gel is transferred to a steel autoclave with inner walls protected by Teflon , and heated at 150 ° C for five days. After this time, the resulting solid is recovered by filtration, washing it thoroughly with water, and subsequently drying it at 100 ° C for one hour. By means of X-ray diffraction it is observed that the solid obtained contains the characteristic peaks of ITQ-51, shown in Table 2. The material is calcined at 550 ° C for 3 hours in air flow to remove organic matter. The powder X-ray diffraction pattern of the solid contains the characteristic peaks of the ITQ-51 zeolite shown in Table 1.
Ejemplo 3: Síntesis de Mg-ITQ-51 Example 3: Synthesis of Mg-ITQ-51
257.5 mg de 1 ,8-bis(dimetilamino)naftaleno (DMAN, Sigma-Aldrich, 99% en peso) se mezclan con 240 mg de acido ortofosfórico (H3P04, Sigma-Aldrich, 85% en peso) y 568 mg de agua destilada. La mezcla se mantiene en agitación durante 2 horas hasta obtener una mezcla homogénea. A continuación, se añaden 213.8 mg de una disolución al 20% en peso en agua de cloruro de magnesio hexahidratado (Aldnch, 99.95 % trazas de metales). Finalmente, se adicionan 128.9 mg de alúmina (AI2O3, Condea, 75% en peso) a la mezcla anterior, dejándola en agitación hasta alcanzar la concentración deseada. La composición del gel final es 1 Al203 / 1 .1 P2O5 / 0.2 Mg / 1 .3 DMAN / 42 H20. Este gel se transfiere a un autoclave de acero con las paredes interiores protegidas de Teflon, y se calienta a 135 °C durante cinco días. Transcurrido este tiempo, el sólido resultante se recupera mediante filtración, lavándolo abundantemente con agua, y secándolo posteriormente a 100°C durante una hora. Por medio de difracción de rayos X se observa que el sólido obtenido contiene los picos característicos de ITQ-51 , mostrados en la Tabla 2. 257.5 mg of 1,8-bis (dimethylamino) naphthalene (DMAN, Sigma-Aldrich, 99% by weight) are mixed with 240 mg of orthophosphoric acid (H 3 P0 4 , Sigma-Aldrich, 85% by weight) and 568 mg of distilled water. The mixture is kept under stirring for 2 hours until a homogeneous mixture is obtained. Next, 213.8 mg of a 20% by weight solution in water of magnesium chloride hexahydrate (Aldnch, 99.95% traces of metals) are added. Finally, 128.9 mg of alumina (AI2O3, Condea, 75% by weight) is added to the previous mixture, leaving it under stirring until reaching the desired concentration. The composition of the final gel is 1 Al 2 0 3/1 1 P2O5 / Mg 0.2 / 1 0.3 DMAN / 42 H 2 0. This gel is transferred to a steel autoclave with inner walls protected by Teflon, and heated at 135 ° C for five days. After this time, the resulting solid is recovered by filtration, washing it thoroughly with water, and subsequently drying it at 100 ° C for one hour. By means of X-ray diffraction it is observed that the solid obtained contains the characteristic peaks of ITQ-51, shown in Table 2.
El material se calcina a 550°C durante 3 horas en flujo de aire para eliminar la materia orgánica. El patrón de difracción de rayos X de polvo del sólido contiene los picos característicos de la zeolita ITQ-51 mostrados en la Tabla 1 .  The material is calcined at 550 ° C for 3 hours in air flow to remove organic matter. The powder X-ray diffraction pattern of the solid contains the characteristic peaks of the ITQ-51 zeolite shown in Table 1.
Ejemplo 4: Síntesis de Zn-ITQ-51 Example 4: Synthesis of Zn-ITQ-51
253.4 mg de 1 ,8-bis(dimet¡lam¡no)naftaleno (DMAN, Sigma-Aldrich, 99% en peso) se mezclan con 268.8 mg de acido ortofosfórico (H3P04, Sigma- Aldnch, 85% en peso) y 568 mg de agua destilada. La mezcla se mantiene en agitación durante 2 horas hasta obtener una mezcla homogénea. A continuación, se añaden 235.3 mg de una disolución al 20 % en peso en agua de acetato de zinc dihidratado (Aldnch, 99.999%). Finalmente, se adicionan 128.8 mg de alúmina (AI2O3, Condea, 75% en peso) a la mezcla anterior, dejándola en agitación hasta alcanzar la concentración deseada. La composición del gel final es 1 Al203 / 1 .2 P205 / 0.2 Zn / 1 .3 DMAN / 42 H20. Este gel se transfiere a un autoclave de acero con las paredes interiores protegidas de Teflon, y se calienta a 135 °C durante cinco días. Transcurrido este tiempo, el sólido resultante se recupera mediante filtración, lavándolo abundantemente con agua, y secándolo posteriormente a 100°C durante una hora. Por medio de difracción de rayos X se observa que el sólido obtenido contiene los picos característicos de ITQ-51 , mostrados en la Tabla 2. 253.4 mg of 1,8-bis (dimethylamine) naphthalene (DMAN, Sigma-Aldrich, 99% by weight) are mixed with 268.8 mg of orthophosphoric acid (H 3 P0 4 , Sigma-Aldnch, 85% by weight ) and 568 mg of distilled water. The mixture is kept under stirring for 2 hours until a homogeneous mixture is obtained. Then, 235.3 mg of a 20% solution by weight in water are added of zinc acetate dihydrate (Aldnch, 99.999%). Finally, 128.8 mg of alumina (AI2O3, Condea, 75% by weight) is added to the previous mixture, leaving it under stirring until reaching the desired concentration. The composition of the final gel is 1 Al 2 0 3/1 2 P 2 0 5 / 0.2 Zn / 0.3 DMAN 1/42 H 2 0. This gel is transferred to a steel autoclave with inner walls protected Teflon and heated at 135 ° C for five days. After this time, the resulting solid is recovered by filtration, washing it thoroughly with water, and subsequently drying it at 100 ° C for one hour. By means of X-ray diffraction it is observed that the solid obtained contains the characteristic peaks of ITQ-51, shown in Table 2.
Ejemplo 5: Síntesis de Co-ITQ-51 Example 5: Synthesis of Co-ITQ-51
257.9 mg de 1 ,8-bis(dimet¡lam¡no)naftaleno (DMAN, Sigma-Aldrich, 99% en peso) se mezclan con 235.8 mg de acido ortofosfórico (H3PO4, Sigma- Aldnch, 85% en peso) y 575 mg de agua destilada. La mezcla se mantiene en agitación durante 2 horas hasta obtener una mezcla homogénea. A continuación, se añaden 263 mg de una disolución al 20 % en peso en agua de acetato de cobalto (II) tetrahidratado (Aldrich, 99.99%). Finalmente, se adicionan 128.5 mg de alúmina (AI2O3, Condea, 75% en peso) a la mezcla anterior, dejándola en agitación hasta alcanzar la concentración deseada. La composición del gel final es 1 Al203 / 1 .1 P2O5 / 0.2 Co / 1 .3 DMAN / 42 H20. Este gel se transfiere a un autoclave de acero con las paredes interiores protegidas de Teflon, y se calienta a 135 °C durante cinco días. Transcurrido este tiempo, el sólido resultante se recupera mediante filtración, lavándolo abundantemente con agua, y secándolo posteriormente a 100°C durante una hora. Por medio de difracción de rayos X se observa que el sólido obtenido contiene los picos característicos de ITQ-51 , mostrados en la Tabla 2. 257.9 mg of 1,8-bis (dimethylamine) naphthalene (DMAN, Sigma-Aldrich, 99% by weight) are mixed with 235.8 mg of orthophosphoric acid (H3PO4, Sigma-Aldnch, 85% by weight) and 575 mg of distilled water The mixture is kept under stirring for 2 hours until a homogeneous mixture is obtained. Next, 263 mg of a 20% by weight solution in water of cobalt (II) acetate tetrahydrate (Aldrich, 99.99%) is added. Finally, 128.5 mg of alumina (AI2O3, Condea, 75% by weight) is added to the previous mixture, leaving it under stirring until reaching the desired concentration. The composition of the final gel is 1 Al 2 0 3/1 1 P2O5 / Co 0.2 / 1 0.3 DMAN / 42 H 2 0. This gel is transferred to a steel autoclave with inner walls protected by Teflon, and heated at 135 ° C for five days. After this time, the resulting solid is recovered by filtration, washing it thoroughly with water, and subsequently drying it at 100 ° C for one hour. By means of X-ray diffraction it is observed that the solid obtained contains the characteristic peaks of ITQ-51, shown in Table 2.
El material se calcina a 550°C durante 3 horas en flujo de aire para eliminar la materia orgánica. El patrón de difracción de rayos X de polvo del sólido contiene los picos característicos de la zeolita ITQ-51 mostrados en la Tabla 1 .  The material is calcined at 550 ° C for 3 hours in air flow to remove organic matter. The powder X-ray diffraction pattern of the solid contains the characteristic peaks of the ITQ-51 zeolite shown in Table 1.

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:
Figure imgf000017_0001
Figure imgf000017_0001
M es un elemento, o mezcla de elementos, diferentes a Si, Al y P; El valor de x está comprendido entre 0 y 1 .5; M is an element, or mixture of elements, different from Si, Al and P; The value of x is between 0 and 1 .5;
El valor de y está comprendido entre 0.3 y 1 .6;  The value of y is between 0.3 and 1 .6;
- El valor de z está comprendido entre 0 y 1 .5;  - The value of z is between 0 and 1 .5;
y porque sus líneas principales del patrón de difracción de rayos X en su forma sin calcinar se detallan en la Tabla 2, y las líneas principales del patrón de difracción de rayos X en su forma calcinada y anhidra se detallan en la Tabla 1 . and because its main lines of the X-ray diffraction pattern in its uncalcined form are detailed in Table 2, and the main lines of the X-ray diffraction pattern in its calcined and anhydrous form are detailed in Table 1.
2.- Un material cristalino microporoso según la reivindicación 1 , caracterizado porque 2. A microporous crystalline material according to claim 1, characterized in that
- M está seleccionado entre Co, Zn, Mg, o mezclas de los mismos; - M is selected from Co, Zn, Mg, or mixtures thereof;
- El valor de x está comprendido entre 0 y 0.8; - The value of x is between 0 and 0.8;
- El valor de y está comprendido entre 0.6 y 1 .3;  - The value of y is between 0.6 and 1.3.
- El valor de z está comprendido entre 0 y 0.8.  - The value of z is between 0 and 0.8.
3. - Un material cristalino microporoso según cualquiera de las reivindicaciones 1 a 2, caracterizado porque "z" es igual a cero y posee una composición química: 3. - A microporous crystalline material according to any of claims 1 to 2, characterized in that "z" is equal to zero and has a chemical composition:
x S¡02 : Al203 : y P205 x S¡0 2 : Al 2 0 3 : y P 2 0 5
donde: where:
- El valor de x está comprendido entre 0 y 1 .5,  - The value of x is between 0 and 1 .5,
- El valor de y está comprendido entre 0.3 y 1 .6.  - The value of y is between 0.3 and 1 .6.
4. - Un material cristalino microporoso según la reivindicación 3, caracterizado porque: 4. - A microporous crystalline material according to claim 3, characterized in that:
- El valor de x está comprendido entre 0 y 0.8.  - The value of x is between 0 and 0.8.
- El valor de y está comprendido entre 0.6 y 1 .3. - The value of y is between 0.6 and 1 .3.
5. - Un material cristalino microporoso según cualquiera de las reivindicaciones 1 a 2, caracterizado porque "x" es igual a cero y posee una composición química:5. - A microporous crystalline material according to any of claims 1 to 2, characterized in that "x" is equal to zero and has a chemical composition:
Figure imgf000018_0001
Figure imgf000018_0001
donde: where:
- El valor de y está comprendido entre 0.3 y 1 .6,  - The value of y is between 0.3 and 1 .6,
- El valor de z está comprendido entre 0 y 1 .5.  - The value of z is between 0 and 1 .5.
6. - Un material cristalino microporoso según la reivindicación 5, caracterizado porque: 6. - A microporous crystalline material according to claim 5, characterized in that:
- El valor de y está comprendido entre 0.6 y 1 .3.  - The value of y is between 0.6 and 1 .3.
- El valor de z está comprendido entre 0 y 0.8.  - The value of z is between 0 and 0.8.
7. - Un material cristalino microporoso según cualquiera de las reivindicaciones 1 a 2, caracterizado porque "x" y "z" son igual a cero y posee una composición química:7. - A microporous crystalline material according to any one of claims 1 to 2, characterized in that "x" and "z" are equal to zero and have a chemical composition:
Figure imgf000018_0002
Figure imgf000018_0002
donde: where:
- El valor de y está comprendido entre 0.3 y 1 .6,  - The value of y is between 0.3 and 1 .6,
8.- Un material cristalino microporoso según la reivindicación 7, caracterizado porque: 8. A microporous crystalline material according to claim 7, characterized in that:
- El valor de y está comprendido entre 0.6 y 1 .3.  - The value of y is between 0.6 and 1 .3.
9.- Un material cristalino microporoso según una de las reivindicaciones 1 a 2, caracterizado porque posee una composición química: 9. A microporous crystalline material according to one of claims 1 to 2, characterized in that it has a chemical composition:
n R : x S¡02 : Al203 : y P2O5 : z M n R: x S¡0 2 : Al 2 0 3 : y P2O5: z M
donde: where:
- R es un agente director de estructura,  - R is a structure managing agent,
- El valor de n/(1 +x+y+z) está comprendido entre 0 y 8;  - The value of n / (1 + x + y + z) is between 0 and 8;
- M es un elemento, o mezcla de elementos, diferentes a Si, Al y P; - M is an element, or mixture of elements, other than Si, Al and P;
- El valor de x está comprendido entre 0 y 1 .5; - The value of x is between 0 and 1 .5;
- El valor de y está comprendido entre 0.3 y 1 .6; - El valor de z está comprendido entre 0 y 1 .5; y porque tiene un patrón de rayos X representado en la Tabla 2. - The value of y is between 0.3 and 1 .6; - The value of z is between 0 and 1 .5; and because it has an x-ray pattern represented in Table 2.
10.- Un material cristalino microporoso según la reivindicación 9, caracterizado porque: 10. A microporous crystalline material according to claim 9, characterized in that:
El valor de n/(1 +x+y+z) está comprendido entre 0.001 y 3, The value of n / (1 + x + y + z) is between 0.001 and 3,
- El valor de x está comprendido entre 0 y 0.8. - The value of x is between 0 and 0.8.
- El valor de y está comprendido entre 0.6 y 1 .3.  - The value of y is between 0.6 and 1 .3.
- El valor de z está comprendido entre 0 y 0.8.  - The value of z is between 0 and 0.8.
11. - Un material cristalino microporoso según la reivindicación 9, caracterizado porque el agente director de estructura R está seleccionado entre una amina, una sal de tetraalquilamonio, una molécula orgánica que contiene P, una molécula orgánica que contiene enlaces P-N y mezclas de los mismos. 11. - A microporous crystalline material according to claim 9, characterized in that the structure directing agent R is selected from an amine, a tetraalkylammonium salt, an organic molecule containing P, an organic molecule containing PN bonds and mixtures thereof .
12. - Un material cristalino microporoso según la reivindicación 1 1 , caracterizado porque el agente director de estructura es una "esponja de protones". 12. - A microporous crystalline material according to claim 1, characterized in that the structure directing agent is a "proton sponge".
13.- Un material cristalino microporoso según la reivindicación 12, caracterizado porque la "esponja de protones" es 1 ,8-bis(dimet¡lam¡no)naftaleno. 13. A microporous crystalline material according to claim 12, characterized in that the "proton sponge" is 1,8-bis (dimethylamine) naphthalene.
14.- Un matenal cristalino microporoso según cualquiera de las reivindicaciones 9 a 13, caracterizado porque "z" es igual a cero y posee la siguiente composición química: 14. A microporous crystalline matten according to any of claims 9 to 13, characterized in that "z" is equal to zero and has the following chemical composition:
n R : x S¡02 : Al203 : y P205 n R: x S¡0 2 : Al 2 0 3 : y P 2 0 5
donde: where:
- El valor de n/(1 +x+y) está comprendido entre 0 y 8;  - The value of n / (1 + x + y) is between 0 and 8;
- El valor de x está comprendido entre 0 y 1 .5;  - The value of x is between 0 and 1 .5;
- El valor de y está comprendido entre 0.3 y 1 .6. - The value of y is between 0.3 and 1 .6.
15. - Un material cristalino microporoso según la reivindicación 14, caracterizado porque: 15. - A microporous crystalline material according to claim 14, characterized in that:
El valor de n/(1 +x+y) está comprendido entre 0.001 y 3; The value of n / (1 + x + y) is between 0.001 and 3;
- El valor de x está comprendido entre 0 y 0.8; - The value of x is between 0 and 0.8;
- El valor de y está comprendido entre 0.6 y 1 .3.  - The value of y is between 0.6 and 1 .3.
16. - Un material cristalino microporoso según cualquiera de las reivindicaciones 9 a 13, caracterizado porque "x" y "z" son igual a cero y posee la siguiente composición química: 16. - A microporous crystalline material according to any of claims 9 to 13, characterized in that "x" and "z" are equal to zero and have the following chemical composition:
n R : Al203 : y P205 n R: At 2 0 3 : and P 2 0 5
donde: where:
- El valor de n/(1 +y) está comprendido entre 0 y 8;  - The value of n / (1 + y) is between 0 and 8;
- El valor de y está comprendido entre 0.3 y 1 .6.  - The value of y is between 0.3 and 1 .6.
17.- Un material cristalino microporoso según la reivindicación 16, caracterizado porque: 17. A microporous crystalline material according to claim 16, characterized in that:
- El valor de n/(1 +y) está comprendido entre 0.001 y 3;  - The value of n / (1 + y) is between 0.001 and 3;
- El valor de y está comprendido entre 0.6 y 1 .3.  - The value of y is between 0.6 and 1 .3.
18.- Un material cristalino microporoso según cualquiera de las reivindicaciones 9 a 13, caracterizado porque "x" es igual a cero y posee la siguiente composición química:18. A microporous crystalline material according to any of claims 9 to 13, characterized in that "x" is equal to zero and has the following chemical composition:
Figure imgf000020_0001
Figure imgf000020_0001
donde: where:
- El valor de n/(1 +y+z) está comprendido entre 0 y 8;  - The value of n / (1 + and + z) is between 0 and 8;
- El valor de y está comprendido entre 0.3 y 1 .6;  - The value of y is between 0.3 and 1 .6;
- El valor de z está comprendido entre 0 y 1 .5.  - The value of z is between 0 and 1 .5.
19.- Un material cristalino microporoso según la reivindicación 18, caracterizado porque: 19. A microporous crystalline material according to claim 18, characterized in that:
- El valor de n/(1 +y+z) está comprendido entre 0.001 y 3;  - The value of n / (1 + and + z) is between 0.001 and 3;
- El valor de y está comprendido entre 0.6 y 1 .3; - El valor de z está comprendido entre 0 y 0.8. - The value of y is between 0.6 and 1.3. - The value of z is between 0 and 0.8.
20.- Un procedimiento de preparación del material descrito según las reivindicaciones 1 a 19, caracterizado porque comprende, al menos, los siguientes pasos: 20. A process for preparing the material described according to claims 1 to 19, characterized in that it comprises at least the following steps:
d) preparación de una mezcla que contiene, al menos, H20; un óxido u otra fuente de aluminio; un óxido u otra fuente de fósforo; un óxido o una fuente de silicio; un óxido o una fuente de uno o varios elementos metálicos M donde M es, al menos, un heteroátomo diferente a Si, Al y P; un agente director de estructura (R); donde la mezcla de síntesis tiene una composición molar de óxidos en los siguientes rangos: d) preparation of a mixture containing at least H 2 0; an oxide or other source of aluminum; an oxide or other source of phosphorus; an oxide or a source of silicon; an oxide or a source of one or more metal elements M where M is at least one heteroatom other than Si, Al and P; a structure managing agent (R); where the synthesis mixture has a molar composition of oxides in the following ranges:
Si/(AI203+P205) 0.0-0.8 Yes / (AI 2 0 3 + P20 5 ) 0.0-0.8
Μ/(ΑΙ203+Ρ2θ5) 0.0-0.8 Μ / (ΑΙ 2 0 3 + Ρ2θ 5 ) 0.0-0.8
Η20/(ΑΙ2θ3+Ρ2θ5) 1 -400 Η 2 0 / (ΑΙ 2 θ3 + Ρ2θ5) 1 -400
R/(AI203+P205) 0.0-8.0R / (AI 2 0 3 + P20 5 ) 0.0-8.0
Figure imgf000021_0001
e) mantener la mezcla a una temperatura entre 80 y 200°C hasta que se formen los cristales del material;
Figure imgf000021_0001
e) keep the mixture at a temperature between 80 and 200 ° C until the crystals of the material form;
f) recuperación del material cristalino. f) recovery of the crystalline material.
21. - Procedimiento de obtención de un material según la reivindicación 20, caracterizado porque M está seleccionado entre Zn, Mg, Co y mezclas de los mismos. 21. - Method of obtaining a material according to claim 20, characterized in that M is selected from Zn, Mg, Co and mixtures thereof.
22. - Procedimiento de obtención de un material según la reivindicación 20, caracterizado porque el agente director de estructura R es una amina, una sal de tetraalquilamonio, una molécula orgánica que contiene P, o una molécula orgánica que contiene enlaces P-N. 22. - Method of obtaining a material according to claim 20, characterized in that the structure directing agent R is an amine, a tetraalkylammonium salt, an organic molecule containing P, or an organic molecule containing P-N bonds.
23. - Procedimiento de obtención de un material según la reivindicación 22, caracterizado porque R una "esponja de protones". 23. - Method of obtaining a material according to claim 22, characterized in that R is a "proton sponge".
24. - Procedimiento de obtención de un material según la reivindicación 23, caracterizado porque la "esponja de protones" es 1 ,8- bis(dimet¡lam¡no)naftaleno. 24. - Method of obtaining a material according to claim 23, characterized in that the "proton sponge" is 1, 8-bis (dimethylamine) naphthalene.
25. - Procedimiento de obtención de un material según cualquiera de las reivindicaciones 20 a 24, caracterizado porque se añaden a la mezcla de síntesis cristales de ITQ-51 . 25. - Method of obtaining a material according to any of claims 20 to 24, characterized in that crystals of ITQ-51 are added to the synthesis mixture.
26.- Procedimiento de obtención de un material según reivindicación 25, caracterizado porque dichos cristales de ITQ-51 se añaden en una proporción de hasta 25% en peso respecto al peso total de óxidos. 26.- Procedure for obtaining a material according to claim 25, characterized in that said ITQ-51 crystals are added in a proportion of up to 25% by weight with respect to the total weight of oxides.
27. - Procedimiento de obtención de un material según cualquiera de las reivindicaciones 20 a 26, caracterizado porque comprende, además, la calcinación del material cristalino obtenido. 27. - Method of obtaining a material according to any of claims 20 to 26, characterized in that it further comprises the calcination of the crystalline material obtained.
28. - Procedimiento de obtención de un material según la reivindicación 27, caracterizado porque la calcinación se lleva a cabo a una temperatura entre 200 y 1000°C. 28. - Method of obtaining a material according to claim 27, characterized in that the calcination is carried out at a temperature between 200 and 1000 ° C.
29. - Uso de un material descrito según las reivindicaciones 1 a 19, y obtenido según el procedimiento de obtención descrito en las reivindicaciones 20 a 28, para convertir alimentaciones formadas por compuestos orgánicos a productos de mayor valor añadido. 29. - Use of a material described according to claims 1 to 19, and obtained according to the method of obtaining described in claims 20 to 28, to convert feeds formed by organic compounds to products of greater added value.
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WO2015196023A1 (en) * 2014-06-20 2015-12-23 Exxonmobil Research And Engineering Company Separation, storage, and catalytic conversion of fluids using itq-55
WO2015196026A1 (en) * 2014-06-20 2015-12-23 Exxonmobil Research And Engineering Company Separation and storage of fluids using itq-55
WO2015196049A1 (en) * 2014-06-20 2015-12-23 Exxonmobil Research And Engineering Company Separation and storage of fluids using itq-55
WO2015196018A1 (en) * 2014-06-20 2015-12-23 Higher Council Of Scientific Research (Csic) Material itq-55, method for preparation and use
WO2015196043A1 (en) * 2014-06-20 2015-12-23 Exxonmobil Research And Engineering Company Separation and storage of fluids using itq-55
KR20170021314A (en) * 2014-06-20 2017-02-27 엑손모빌 리서치 앤드 엔지니어링 컴퍼니 Separation and storage of fluids using itq-55
US9617164B2 (en) 2014-06-20 2017-04-11 Exxonmobil Research And Engineering Company Separation, storage, and catalytic conversion of fluids using ITQ-55
US9688542B2 (en) 2014-06-20 2017-06-27 Exxonmobil Research And Engineering Company Separation and storage of fluids using ITQ-55
US9695056B2 (en) 2014-06-20 2017-07-04 Exxonmobil Research And Engineering Company Separation and storage of fluids using ITQ-55
US9738539B2 (en) 2014-06-20 2017-08-22 Exxonmobil Research And Engineering Company Separation and storage of fluids using ITQ-55
US9856145B2 (en) 2014-06-20 2018-01-02 Exxonmobil Research And Engineering Company Material ITQ-55, method for preparation and use
RU2682600C2 (en) * 2014-06-20 2019-03-19 Хайер Каунсил Оф Сайентифик Рисерч (Ксис) Itq-55 material, method for obtaining and application thereof
KR102360244B1 (en) 2014-06-20 2022-02-09 엑손모빌 리서치 앤드 엔지니어링 컴퍼니 Separation and storage of fluids using itq-55

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