WO1997029991A1 - PROCESS FOR PRODUCING BETA ZEOLITE CONTAINING Ti, AND WITHOUT Al - Google Patents

PROCESS FOR PRODUCING BETA ZEOLITE CONTAINING Ti, AND WITHOUT Al Download PDF

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Publication number
WO1997029991A1
WO1997029991A1 PCT/ES1997/000032 ES9700032W WO9729991A1 WO 1997029991 A1 WO1997029991 A1 WO 1997029991A1 ES 9700032 W ES9700032 W ES 9700032W WO 9729991 A1 WO9729991 A1 WO 9729991A1
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process according
solution
range
beta
impregnated
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PCT/ES1997/000032
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Spanish (es)
French (fr)
Inventor
Avelino Corma Canos
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Consejo Superior Investigaciones Cientificas
Universidad Politecnica Valencia
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
    • 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
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties

Definitions

  • the present invention relates to a crystalline material of a microporous nature to its preparation process, and its use as a catalyst for the selective oxidation of organic compounds
  • This material hereinafter referred to as Ti-Beta, contains Si and Ti in network positions
  • the material prepared by our procedure is also structurally and compositionally related to a Ti-Beta zeolite developed in patent ES-2037596, whose empirical formula in its calcined and anhydrous state can be represented by M 2 / nX0 2 bT ⁇ 0 2 aY0 2 (in where M is a vation cation n, Y corresponds to one or several elements with an oxidation state + 4, such as for example Si, Ge, V, X corresponds to one or several cations with a formal oxidation state of + 3, 10 ⁇ a ⁇ 100, and O b / a ⁇ 0 1
  • This material can be used as a catalyst for the selective oxidation of organic compounds using organic or inorganic peroxides and hydroperoxides as oxidizing agents
  • the preparation process for Beta-Ti disclosed in ES-2037596 involves the crystallization of a reaction mixture prepared by consecutive hydrolysis of a source of Ti and a source of Si, in a basic solution followed by the addition
  • the solid containing T ⁇ 0 S ⁇ 0 2 and 2 can be prepared by coprecipitation •? Or both as a cogel, followed by drying at a temperature adequate and atmospheric pressure or under vacuum conditions
  • a source of sili ⁇ cio hydrolyses in an acid solution (for example diluted HCL) and then, and in the same solution, a source of Ti is hydrolyzed in order to obtain a clear solution.
  • H 2 0 2 can be added to this solution.
  • the pH of the resulting solution is increased to a value such that coprecipitation of Ti0 2 -Si0 2 cogel (optionally including X 2 0 3 ) takes place.
  • the source of Ti may be halides of Ti, and organic derivatives of Ti such as, for example, alkyltitanates. Among the latter, tetareis or tetrabutyl titanate is preferred.
  • the source of Si is preferably selected from alkylsilicates among which tetraethyl is preferred.
  • the molar Ti0 2 / Si0 2 ratio in this cogel is greater than zero and preferably in the range from 0.2 to 0001, and more preferably in the range 0.1 -0025.
  • the reaction mixture After impregnation of the dried solid, with the solution containing the structure directing agent and the mineralizer (and optionally H 2 0 2 ), the reaction mixture crystallizes at the appropriate temperature, either under static conditions or with stirring Suitable temperatures are in the range 373-453K, and preferably in the range 393-443K, and more preferably at 400-420k.
  • the composition of the reaction mixture is characterized by its low H 2 0 content, with a molar ratio H 2 0 / SiO 2 preferably below 10, and more preferably in the range 4-6.
  • the molar ratio Q / Si0 2 (where Q represents the structure manager) is in the range 0.15-0.80, and preferably in the range 0.20-0.50, and more preferably 0.30-0.45.
  • Example 1 This example illustrates the preparation of a cogel T ⁇ 0 2 .S ⁇ 0 2 to be usa ⁇ do in crystallization of Ti-Beta zeolite
  • An acid solution is prepared by mixing 10 g of deionized H 2 0 and 10 g of a 0 1 N solution of HCI Then 24 90 g of tetraethylorthosilicate (TEOS) are hydrolyzed in this solution at room temperature, under a solution prepared by mixing 55g of Isopropanol and 1 36 g of tetrabutyl titanate (TBT) are added, stirring, to the previous solution, obtaining a clear solution. At this time, 1.88 g of 40% aqueous tetrapropylammonium hydroxide is added under stirring. The PH increases from ⁇ 2 to ⁇ 6 This causes the abrupt precipitation of a gel that is kept under stirring for 2.5 hours in a closed container. After this the container is moved to an oven and dried at 373K for 20 hours.
  • TEOS tetraethylorthosilicate
  • This example illustrates the preparation of Al-free Ti-Beta zeolite or other trivalent cation.
  • This example illustrates the catalytic activity of the free Ti-Beta of Al and with 2.8% of T00 2 by weight, in the oxidation of 1-hexene 14 2 g of 1-hexene (165 mmol), 4 0 g of H 2 0 2 35wt% (41 3 mmol), and 100 g of catalyst were placed in a glass reactor, using methanol (118g) as solvent The reaction temperature was 50 ° C After 2h of reaction the olefin conversion was 30% With an epoxide selectivity of 70%, and 30 of the methyl glycoleter
  • This example illustrates the catalytic activity of Ti-Beta, described in example 3, for the hydroxylation of phenol 47.2 g of phenol, 92 4 of water, 2 6 g of
  • H 2 0 2 (35% wt) and 2 25g of catalyst, were reacted at 80 ° C After 3 hours, the conversion of H 2 0 2 was 95%, the selectivity to catechol plus hydroquinone being 63% with a catechol / hydroquinone ratio of 1 1

Abstract

The invention relates to a process for the synthesis of beta zeolite with Si and Ti as unique lattice components. The preparation process involves the crystallization of a cogel of TiO2-SiO2 impregnated with a solution which contains an organic base. In its calcined and anhydrous form, the microporous material has a chemical composition corresponding to the empiric formula: a TiO2: SiO2. In this formula, a has a value higher than zero and smaller than 0.07. This material acts as a catalyst for the selective oxidation of organic compounds using hydrogen peroxide and organic hydroperoxides and peroxides as oxidants.

Description

TITULOTITLE
Procedimiento de preparación de Zeolita Beta conteniendo Ti, y sin AlPreparation procedure for Zeolite Beta containing Ti, and without Al
CAMPO DE LA TÉCNICAFIELD OF THE TECHNIQUE
Preparación de zeohta Ti-Beta como catalizador de oxidaciónPreparation of zeohta Ti-Beta as oxidation catalyst
ANTECEDENTES DE LA INVENCIÓNBACKGROUND OF THE INVENTION
La presente invención se refiere a un material cristalino de naturaleza mi- croporosa a su procedimiento de preparación, y a su uso como catalizador para la oxidación selectiva de compuestos orgánicos Este material, denominado a partir de ahora como Ti-Beta, contiene Si y Ti en posiciones de redThe present invention relates to a crystalline material of a microporous nature to its preparation process, and its use as a catalyst for the selective oxidation of organic compounds This material, hereinafter referred to as Ti-Beta, contains Si and Ti in network positions
Este material es isoestructural con una zeolita Beta descrita en USThis material is isostructural with a Beta zeolite described in US
3,308039, y US 28,341 , cuya formula empírica en su forma calcinada y anhidra se puede representar como M2/n AI02 a Sι02, en donde M es un catión de valencia n, y 5<a<1003,308039, and US 28,341, whose empirical formula in its calcined and anhydrous form can be represented as M 2 / n AI0 2 to Sι0 2 , where M is a cation of valence n, and 5 <a <100
El material preparado por nuestro procedimiento está también relacionado isoestructural y composicionalmente con una zeolita Ti-Beta desarrollada en la patente ES-2037596, cuya fórmula empírica en su estado calcinado y anhidro puede ser representada por M2/nX02 bTι02 aY02 (en donde M es un catión de valencia n, Y corresponde a uno o vanos elementos con estado de oxidación + 4, tales como por ejemplo Si, Ge, V, X corresponde a uno o vanos cationes con un estado formal de oxidación de + 3, 10<a<100, y O b/a<0 1 Este material puede ser utilizado como un catalizador para la oxidación selectiva de compuestos orgᬠnicos utilizando peróxidos e hidroperóxidos orgánicos o inorgánicos como agentes oxidantes El procedimiento de preparación de la Beta-Ti revelado en ES-2037596 conlleva la cristalización de una mezcla de reacción preparada por hidrólisis con¬ secutiva de una fuente de Ti y una fuente de Si, en una solución básica seguida por la adición de una solución básica conteniendo Al u otro elemento trivalente La relación H20/SιO2 en esta mezcla es 10-200, preferentemente 10-30, el cual determina que se obtenga un bajo rendimiento del producto cristalino Más aún, la relación Si/Al (o Si/x) del material no supera valores de 100The material prepared by our procedure is also structurally and compositionally related to a Ti-Beta zeolite developed in patent ES-2037596, whose empirical formula in its calcined and anhydrous state can be represented by M 2 / nX0 2 bTι0 2 aY0 2 (in where M is a vation cation n, Y corresponds to one or several elements with an oxidation state + 4, such as for example Si, Ge, V, X corresponds to one or several cations with a formal oxidation state of + 3, 10 <a <100, and O b / a <0 1 This material can be used as a catalyst for the selective oxidation of organic compounds using organic or inorganic peroxides and hydroperoxides as oxidizing agents The preparation process for Beta-Ti disclosed in ES-2037596 involves the crystallization of a reaction mixture prepared by consecutive hydrolysis of a source of Ti and a source of Si, in a basic solution followed by the addition of a solution basic containing Al or other trivalent element The H 2 0 / SιO 2 ratio in this mixture is 10-200, preferably 10-30, which determines that a low yield of the crystalline product is obtained. Moreover, the Si / Al (or Si / x) ratio of the material does not exceeds values of 100
5 Otros titanoaluminosilicatos isomorfos con la zeolita Beta y reivindicados en la literatura de patentes son indistinguibles del material y procedimiento reivin¬ dicados en ES-2037596, o son preparados por métodos de postsíntesis Por ejem¬ plo, una Ti-Beta con alto contenido en Al se reivindica en PCT/EP/93/01972, en donde tanto el procedimiento de síntesis como la composición química final caen5 Other isomorphic titanoaluminosilicates with the Beta zeolite and claimed in the patent literature are indistinguishable from the material and procedure claimed in ES-2037596, or are prepared by post-synthesis methods For example, a Ti-Beta with high Al content it is claimed in PCT / EP / 93/01972, where both the synthesis process and the final chemical composition fall
10 dentro del rango reivindicado por ES-2037596 Ejemplos de Ti-Betas preparadas por tratamientos de postsíntesis de un aluminosihcato del tipo Beta vienen descri¬ tos en las patentes Fr-2, 694549, US-5374747, US-5233097 Sin embargo, un método directo para la preparación de una zeolita Ti-Beta libre de Al utilizando reactivos no volátiles y no corrosivos tendría ventajas claras sobre los procedi-10 within the range claimed by ES-2037596 Examples of Ti-Betas prepared by post-synthesis treatments of an aluminosihcate of the Beta type are described in patents Fr-2, 694549, US-5374747, US-5233097 However, a method Directly for the preparation of an Al-free Ti-Beta zeolite using non-volatile and non-corrosive reagents would have clear advantages over the processes.
15 mientos de postsíntesis, por lo menos desde el punto de vista de la simplicidad de operación, y manejo de los reactivos15 hundred postsynthesis, at least from the point of view of simplicity of operation, and reagent handling
DESCRIPCIÓN DETALLADA DE LA INVENCIÓNDETAILED DESCRIPTION OF THE INVENTION
20 Recientemente, hemos descubierto un procedimiento nuevo y muy efi¬ ciente para la síntesis de Ti-Beta que se describe a continuación Este nuevo método permite la síntesis de Ti-Beta libre de Al En este procedimiento un sólido de Tι02-Sι02l se impregna con la solución adecuada y a continuación se calienta a la temperatura de cristalización La solución de impregnación contiene un com-20 Recently, we have discovered a new and very efficient procedure for the synthesis of Ti-Beta described below. This new method allows the synthesis of Al-free Ti-Beta. In this procedure a solid of Tι0 2 -Sι0 2l is impregnate with the appropriate solution and then heat to the crystallization temperature The impregnation solution contains a
25 puesto orgánico utilizado como agente director de estructura como por ejemplo (4,4'-trιmetιlenebιs (N-bencιl-N-metιlpιperιdιnιo)), y un agente mineralizante tal co¬ mo OH o F25 organic position used as the structure directing agent such as (4,4'-trιmetιlenebιs (N-benzl-N-metιlpιperιdιnιo)), and a mineralizing agent such as OH or F
El sólido conteniendo Tι02 y Sι02 puede ser preparado por coprecipitación •?o de ambos en forma de un cogel, seguido por secado a la temperatura adecuada y a presión atmosférica o en vacío En las condiciones preferidas, una fuente de sili¬ cio se hidroliza en una solución acida (por ejemplo HCL diluido) y a continuación, y en la misma solución, se hidroliza una fuente de Ti con el fin de obtener una so¬ lución clara Opcionalmente H202 puede ser añadido a esta solución. El PH de la solución resultante se aumenta hasta un valor tal que la coprecipitación de cogel de Ti02-Si02 (incluyendo opcionalmente X203) tiene lugar. La fuente de Ti puede ser haluros de Ti, y derivados orgánicos de Ti tales como por ejemplo alkyltitana- tos. Entre estos últimos se prefiere tetareis o tetrabutil titanato. La fuente de Si se selecciona preferentemente de alquilsilicatos entre los que el tetraetil es el preferi¬ do. La relación molar Ti02/Si02 en este cogel es mayor de cero y preferiblemente en el rango 0.2-0.001 , y más preferiblemente en el rango 0.1 -0.025.The solid containing Tι0 Sι0 2 and 2 can be prepared by coprecipitation •? Or both as a cogel, followed by drying at a temperature adequate and atmospheric pressure or under vacuum conditions In the preferred, a source of sili¬ cio hydrolyses in an acid solution (for example diluted HCL) and then, and in the same solution, a source of Ti is hydrolyzed in order to obtain a clear solution. Optionally H 2 0 2 can be added to this solution. The pH of the resulting solution is increased to a value such that coprecipitation of Ti0 2 -Si0 2 cogel (optionally including X 2 0 3 ) takes place. The source of Ti may be halides of Ti, and organic derivatives of Ti such as, for example, alkyltitanates. Among the latter, tetareis or tetrabutyl titanate is preferred. The source of Si is preferably selected from alkylsilicates among which tetraethyl is preferred. The molar Ti0 2 / Si0 2 ratio in this cogel is greater than zero and preferably in the range from 0.2 to 0001, and more preferably in the range 0.1 -0025.
Después de la impregnación del sólido secado, con la solución que con¬ tiene el agente director de estructura y el mineralizador (y opcionalmente H202), la mezcla de reacción se cristaliza a la temperatura adecuada, ya sea en condiciones estáticas o con agitación Las temperaturas adecuadas están comprendidas en el rango 373-453K, y preferiblemente en el rango 393-443K, y más preferiblemente a 400-420k. La composición de la mezcla de reacción, se caracteriza por su bajo contenido en H20, con una relación molar H20/SiO2 preferiblemente por debajo de 10, y más preferiblemente en el rango 4-6. La relación molar Q/Si02 (en donde Q representa el agente director de estructura) está en el rango 0.15-0.80, y preferi¬ blemente en el rango 0.20-0.50, y más preferiblemente 0.30-0.45.After impregnation of the dried solid, with the solution containing the structure directing agent and the mineralizer (and optionally H 2 0 2 ), the reaction mixture crystallizes at the appropriate temperature, either under static conditions or with stirring Suitable temperatures are in the range 373-453K, and preferably in the range 393-443K, and more preferably at 400-420k. The composition of the reaction mixture is characterized by its low H 2 0 content, with a molar ratio H 2 0 / SiO 2 preferably below 10, and more preferably in the range 4-6. The molar ratio Q / Si0 2 (where Q represents the structure manager) is in the range 0.15-0.80, and preferably in the range 0.20-0.50, and more preferably 0.30-0.45.
Este procedimiento de síntesis da lugar a zeolita Ti-Beta con una elevada cristalinidad. El espectro de infrarrojo del material obtenido por el presente proce- dimiento, en su forma calcinada y anhidra, se caracteriza por bandas con los si¬ guientes más representativos valores de longitud de onda y de sus intensidades relativas Longitud de Onda (cm 1) Intensidades relativasThis synthesis procedure gives rise to Ti-Beta zeolite with high crystallinity. The infrared spectrum of the material obtained by the present process, in its calcined and anhydrous form, is characterized by bands with the following most representative wavelength values and their relative intensities Wavelength (cm 1 ) Relative intensities
1200-1230 m1200-1230 m
1050-1110 s1050-1110 s
950-970 m 775-810 m950-970 m 775-810 m
625-640 w625-640 w
600-620 w600-620 w
560-580 m560-580 m
525-560 w 500-530 m525-560w 500-530m
455-470 m455-470 m
425-440 m425-440 m
En donde s significa fuerte, m = media, y w = débilWhere s means strong, m = medium, and w = weak
En el espectro i r , la presencia de una banda a 950-970 cm'1 es indicativa de la presencia de Ti en la redIn the ir spectrum, the presence of a band at 950-970 cm '1 is indicative of the presence of Ti in the network
Mediante el procedimiento de esta invención se obtiene Ti-Beta libre de Al u otro elemento trivalente, con un rendimiento de sólidos mayor de 25-30% (expresado como gramos de zeolita obtenida a partir de 100 gramos de mezcla de reacción) El efecto combinado de un bajo contenido en H20 y agente director de estructura, y del alto rendimiento en zeolita obtenido, resulta en una alta eficiencia del agente director de estructuraThrough the process of this invention, Ti-Beta free of Al or another trivalent element is obtained, with a solids yield greater than 25-30% (expressed as grams of zeolite obtained from 100 grams of reaction mixture) The combined effect of a low content in H 2 0 and structure managing agent, and of the high yield in zeolite obtained, results in a high efficiency of the structure managing agent
El procedimiento objeto de esta invención se describe con más detalles en los siguientes ejemplosThe process object of this invention is described in more detail in the following examples.
EJEMPLOSEXAMPLES
Ejemplo 1 Este ejemplo ilustra la preparación de un cogel de Tι02.Sι02 para ser usa¬ do en la cristalización de la zeolita Ti-BetaExample 1 This example illustrates the preparation of a cogel Tι0 2 .Sι0 2 to be usa¬ do in crystallization of Ti-Beta zeolite
Se prepara una solución acida mezclando 10 g de H20 desionizada y 10 g de una solución 0 1 N de HCI A continuación 24 90 g de tetraetilortosilicato (TEOS) se hidrolizan en esta solución a temperatura ambiente, bajo una solución preparada mezclando 55g de isopropanol y 1 36 g de tetrabutiltitanato (TBT) se añaden, agitando, a la solución anterior, obteniéndose una solución transparente En estos momentos, 1 88g de hidroxido de tetrapropilamonio acuoso al 40% se añade bajo agitación El PH aumenta desde ~ 2 hasta ~ 6 Esto causa la precipita¬ ción brusca de un gel que se mantiene bajo agitación durante 2 5 horas en un re¬ cipiente cerrado Después de esto el recipiente se traslada a una estufa y seca a 373K durante 20 horasAn acid solution is prepared by mixing 10 g of deionized H 2 0 and 10 g of a 0 1 N solution of HCI Then 24 90 g of tetraethylorthosilicate (TEOS) are hydrolyzed in this solution at room temperature, under a solution prepared by mixing 55g of Isopropanol and 1 36 g of tetrabutyl titanate (TBT) are added, stirring, to the previous solution, obtaining a clear solution. At this time, 1.88 g of 40% aqueous tetrapropylammonium hydroxide is added under stirring. The PH increases from ~ 2 to ~ 6 This causes the abrupt precipitation of a gel that is kept under stirring for 2.5 hours in a closed container. After this the container is moved to an oven and dried at 373K for 20 hours.
Como resultado de esto se obtiene un polvo fino y blanco que resulta ser amorfo a la difracción de Rayos X convencionalAs a result, a fine white powder is obtained that turns out to be amorphous to conventional X-ray diffraction
Ejemplo 2Example 2
Este ejemplo ilustra la preparación de zeolita Ti-Beta libre de Al u otro ca¬ tión trivalenteThis example illustrates the preparation of Al-free Ti-Beta zeolite or other trivalent cation.
1 80 g de cogel preparado en el ejemplo 1 , se impregnan con 6 0 g de una solución acuosa 1 M de 4,4'-tπmetιlen bis (N-benzyl-N metilpipeπdimo) La mezcla se lleva a una autoclave y se somete a 408K y bajo agitación suave (60 rpm) du¬ rante el período de cristalización Después de 172 horas el autoclave se enfría con H20, y el contenido se lava con agua y se centrifuga vanas veces hasta PH<10 El sólido se seca a 373K Después de ser calcinado a 813K durante 3 horas, el polvo blanco obtenido muestra un espectro de difracción de polvo característico de la zeolita Beta de alta cnstahnidad Su espectro de i r muestra una banda a ~ 960 cm"1 característica de zeohtas conteniendo Ti en la red El material final contiene 3 0% en peso de Tι02 Ejemplo 31 80 g of cogel prepared in Example 1, are impregnated with 6 0 g of a 1 M aqueous solution of 4,4'-tπmetιlen bis (N-benzyl-N methylpipeπdimo) The mixture is taken to an autoclave and subjected to 408K and under gentle agitation (60 rpm) during the crystallization period After 172 hours the autoclave is cooled with H 2 0, and the contents are washed with water and centrifuged several times until PH <10 The solid is dried at 373K After being calcined at 813K for 3 hours, the white powder obtained shows a characteristic powder diffraction spectrum of the high-density Beta zeolite. Its spectrum of ir shows a band at ~ 960 cm "1 characteristic of zeohtas containing Ti in the net The final material contains 3 0% by weight of Tι0 2 Example 3
Este ejemplo ilustra la actividad catalítica de la Ti-Beta libre de Al y con 2.8% de Tι02 en peso, en la oxidación de 1 -hexeno 14 2 g de 1 -hexeno (165 mmol), 4 0 g de H202 35wt% (41 3 mmol), y 100 g de catalizador se colocaron en un reactor de vidrio, utilizando metanol (118g) como disolvente La temperatura de reacción fue 50°C Después de 2h de reacción la conversión de olefina fue del 30% Con una selectividad a epóxido del 70%, y 30 del metilglicoleterThis example illustrates the catalytic activity of the free Ti-Beta of Al and with 2.8% of T00 2 by weight, in the oxidation of 1-hexene 14 2 g of 1-hexene (165 mmol), 4 0 g of H 2 0 2 35wt% (41 3 mmol), and 100 g of catalyst were placed in a glass reactor, using methanol (118g) as solvent The reaction temperature was 50 ° C After 2h of reaction the olefin conversion was 30% With an epoxide selectivity of 70%, and 30 of the methyl glycoleter
Ejemplo 4Example 4
Este ejemplo ilustra la actividad catalítica de la Ti-Beta, descrita en el ejemplo 3, para la hidroxilación de fenol 47.2 g de fenol, 92 4 de agua, 2 6 g deThis example illustrates the catalytic activity of Ti-Beta, described in example 3, for the hydroxylation of phenol 47.2 g of phenol, 92 4 of water, 2 6 g of
H202 (35% wt) y 2 25g de catalizador, se hicieron reaccionar a 80°C Después de 3 horas, la conversión de H202 fue del 95%, siendo la selectividad a catecol más hidroquinona del 63% con una relación catecol/hidroquinona de 1 1 H 2 0 2 (35% wt) and 2 25g of catalyst, were reacted at 80 ° C After 3 hours, the conversion of H 2 0 2 was 95%, the selectivity to catechol plus hydroquinone being 63% with a catechol / hydroquinone ratio of 1 1

Claims

REIVINDICACIONES
1 Proceso para la preparación de una zeolita Ti-Beta sin contener catio¬ nes trivalentes, en el que un sólido conteniendo Ti y Si se impregna con una solución conteniendo una base orgánica y, opcionalmente, hidroperóxido de hi¬ drógeno1 Process for the preparation of a Ti-Beta zeolite without containing trivalent cations, in which a solid containing Ti and Si is impregnated with a solution containing an organic base and, optionally, hydrogen peroxide
2 Proceso de acuerdo con la reivindicación 1 , en la que el sólido conte¬ niendo Ti y Si se prepara por precipitación de una solución modificando el pH de la solución2 Process according to claim 1, wherein the solid containing Ti and Si is prepared by precipitation of a solution by modifying the pH of the solution
3 Proceso de acuerdo con reivindicaciones 1 y 2 por el cual la solución se consigue hidrolizando una fuente de Ti y una fuente de Si, añadiendo, opcio- nalmente, H202 3 Process according to claims 1 and 2 whereby the solution is achieved by hydrolyzing a source of Ti and a source of Si, optionally adding H 2 0 2
4 Proceso según reivindicaciones 1-3 y caracterizado porque las fuentes de Ti y Si son sales de Ti como por ejemplo haluros de Ti y organodeπvados de Ti como por ejemplo alquiltitanatos, y la fuente de Si se selecciona, preferentemente, entre alquilsilicatosProcess according to claims 1-3 and characterized in that the sources of Ti and Si are salts of Ti such as for example halides of Ti and organodeπvados of Ti such as alkylthitanates, and the source of Si is preferably selected from alkylsilicates
5 Proceso de acuerdo con las reivindicaciones 1 -4 por el que se causa la precipitación de la solución añadiendo una base orgánica, preferentemente un hidróxido de amonio cuaternario, formando un cogel cuya relación molar Tι02/Sι02 es mayor de cero y preferiblemente en el rango 0 2-0 001Process according to claims 1 -4 whereby precipitation of the solution is caused by adding an organic base, preferably a quaternary ammonium hydroxide, forming a cogel whose molar ratio Tι0 2 / Sι0 2 is greater than zero and preferably in range 0 2-0 001
6 Proceso según reivindicaciones 1-5 por el que el precipitado secado se impregna con un agente director de estructura, entre los que se prefiere el 4-4'- tπmetilen bis N-benzil-Nmetilpipeπdimo, y un mineralizador tal como OH" o F* Op- cíonalmente se puede incluir H202 6 Process according to claims 1-5 whereby the dried precipitate is impregnated with a structure directing agent, among which 4-4'-t-methylene bis N-benzyl-N-methylpipeptide is preferred, and a mineralizer such as OH " or F * Optionally, H 2 0 2 can be included
7 Proceso según reivindicaciones 1 -6 por el que el sólido impregnado se cristaliza a temperaturas entre 373-453K y preferentemente entre 393-443K La composición de la mezcla reaccionante se caracteriza por contener una relación molar H20/SiO2 preferiblemente por debajo de 10 y más preferiblemente en el ran¬ go 4-6 La relación molar entre el agente director de estructura y S¡02 está en el rango 0 15-0.80, preferiblemente en el rango 0.20-0 50, y más preferiblemente en el rango 0 30-0 457 Process according to claims 1-6 whereby the impregnated solid crystallizes at temperatures between 373-453K and preferably between 393-443K. The composition of the reaction mixture is characterized by containing a molar ratio H 2 0 / SiO 2 preferably below 10 and more preferably in the range 4-6 The molar ratio between the structure directing agent and S0 2 is in the range 0 15-0.80, preferably in the range 0.20-0 50, and more preferably in the range 0 30-0 45
8 Proceso según reivindicaciones 1 -7 y caracterizado porque se obtiene una zeolita con estructura de Beta y conteniendo Ti y Si como únicos elementos de red8 Process according to claims 1-7 and characterized in that a zeolite with a Beta structure and containing Ti and Si as the only network elements is obtained
9 Proceso según reivindicaciones 1 -8, y caracterizado porque la zeolita Ti-Beta así obtenida es activa y selectiva para catalizar la oxidación de alcanos, cicloalcanos, alquilcicloalcanos, olefinas y cicloolefinas a los correspondientes alcoholes, cetonas, y epóxidos, así como de sulfuras a sulfóxidos y sulfonas, utili- zando H202 e hidroperóxidos orgánicos como disolventesProcess according to claims 1-8, and characterized in that the Ti-Beta zeolite thus obtained is active and selective to catalyze the oxidation of alkanes, cycloalkanes, alkylcycloalkanes, olefins and cycloolefins to the corresponding alcohols, ketones, and epoxides, as well as sulphides to sulfoxides and sulfones, using H 2 0 2 and organic hydroperoxides as solvents
10 Proceso según reivindicaciones 1-8 y caracterizado por al Tí-Beta así obtenida es activa y selectiva para la hidroxilación de aromáticos, alquiiaromáti- cos, fenoles y alquilfenoles, utilizando H202 e hidroperóxidos orgánicos como oxi- dantes Process according to claims 1-8 and characterized by the Ti-Beta thus obtained is active and selective for the hydroxylation of aromatics, alkyromatics, phenols and alkylphenols, using H 2 0 2 and organic hydroperoxides as oxidizers.
PCT/ES1997/000032 1996-02-16 1997-02-14 PROCESS FOR PRODUCING BETA ZEOLITE CONTAINING Ti, AND WITHOUT Al WO1997029991A1 (en)

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