WO1998056780A1 - Process and catalysts for the production of epoxydes and hydroxylated derivatives of acids and esters of fatty acids - Google Patents
Process and catalysts for the production of epoxydes and hydroxylated derivatives of acids and esters of fatty acids Download PDFInfo
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- WO1998056780A1 WO1998056780A1 PCT/ES1997/000127 ES9700127W WO9856780A1 WO 1998056780 A1 WO1998056780 A1 WO 1998056780A1 ES 9700127 W ES9700127 W ES 9700127W WO 9856780 A1 WO9856780 A1 WO 9856780A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
Definitions
- the present invention describes the epoxidation of acids and derivatives of unsaturated fatty acids and the opening of epoxides by protic molecules catalyzed by molecular sieves with titanium in their structure using a peroxide as oxidizing agent.
- a peroxide as oxidizing agent.
- bifunctional solid catalysts containing an oxidizing function (Ti), and an acidic function which allows the formation of the epoxide and its opening in a single vessel and with a single catalyst to be carried out, is also claimed.
- the present invention relates to the use of molecular sieves with titanium incorporated in its structure, as well as titanium and acidic centers of the Brónsted type, as catalysts in the oxidation of acids and derivatives of unsaturated fatty acids for obtaining a single stage of epoxides, and / or products derived from their opening by protic molecules, using a peroxide as an oxidizing agent.
- the molecular sieves referred to in the present invention are:
- the zeolite T ⁇ -ZSM-5 containing or not (Tilo silica ta) aluminum in tetrahedral positions.
- the opening of the oxirane group by the addition of protic molecules is a reaction catalyzed by acids.
- Zeolite Ti-Beta can be synthesized by incorporating aluminum in its structure or not. The presence of aluminum gives this catalyst a bifunctional character with an oxidizing function associated with the Titanium atoms and an acid function associated with aluminum atoms
- the final products obtained in the oxidation of unsaturated compounds may be epoxides or hydroxylated derivative products or mixtures thereof.
- the mesoporous solid T ⁇ -MCM-41 has a strong hydrophilic character due to the large number of superficial SI-OH groups it contains.
- the treatment of T ⁇ -MCM-41 with a silanizing agent of the R3S ⁇ CI type allows to increase considerably the hydrophobicity of this material increasing its effectiveness as a catalyst in the oxidation of organic compounds by favoring the diffusion of reagents inside its channels
- Ti-Silicalite with a system of three-dimensional channels of 5.5 A of average diameter, imposes great restrictions on the diffusion of large molecules such as fatty acids and their derivatives
- this material is synthesized with sizes of very small glass, less than or equal to 50.5 ⁇ m, the increase in the external surface / internal surface ratio increases the number of active centers accessible to the substrate and decreases the diffusion problems of reactants and products increasing the effectiveness of the catalyst
- the fatty acids or their derivatives used as substrates in this process must have, at least, a carbon-carbon double bond that can be found in the terminal position or internal positions of the molecule. They can also incorporate any other type of group
- Non-restrictive examples are oleic, linoleic, iinolenic, palmitoleic, erucic, ricinoleic acid and its esters including mono-, di- and triglycerides.
- hydrogen peroxide is the preferred oxidant in this invention
- other peroxides can also be used.
- organic peroxides allows to obtain homogeneous reaction mixtures without the need to add solvents.
- the organic peroxides most commonly used in oxidation reactions are alkyl hydroperoxides, ROOH, such as tert-butyl hydroperoxides, eumene and ethylbenzene.
- the reaction can be carried out in the presence or absence of solvents.
- solvents As solvents, alcohols, ketones, ethers, nitriles and water can be used. Examples are methanol, ethanol, isopropanol, tert-butyl alcohol, acetone, methyl ethyl ketone, diethyl ether, tetrahydrofuran, acetonitrile and propionitrile.
- the opening of the oxirane groups is produced by the addition of nucleophiles, usually molecules of a practical nature such as water, alcohols such as methanol, ethanol, n-heptanol, n-octanol, ethylene glycol, of amines such as n-butylamine, methyl amine , ammonia, of carboxylic acids such as acetic acid and thiols.
- nucleophiles usually molecules of a practical nature such as water, alcohols such as methanol, ethanol, n-heptanol, n-octanol, ethylene glycol, of amines such as n-butylamine, methyl amine , ammonia, of carboxylic acids such as acetic acid and thiols.
- the reaction can take place in a continuous or discontinuous reactor.
- the optimal reaction temperature is influenced by the activity of the catalyst, the reactivity of the substrate, the concentration of reagents and the type of solvent among other factors but usually is between 25 and 150 ° C.
- the reaction time may vary between 1 min. and 48 hours depending on the factors mentioned.
- the amount of catalyst should be sufficient to achieve an acceptable conversion in a not too long time. Usually 0.001 to 10 g of catalyst are added per mole of substrate.
- the amount of oxidant is not critical. Since, theoretically, an equivalent of oxidant is required for each carbon-carbon double bond present in the substrate, it is convenient that the molar ratio between each unsaturation present in the substrate and the oxidant is between 10: 1 and 1:10.
- the solvent if any, can comprise from 1 to 99% by weight of the total reaction mixture.
- SUBSTITUTE SHEET (RULE 26) Similar to what happens with the oxidant, the amount of nucleophile chosen to open the epoxy ring will depend on the amount of oxirane groups that are formed. The appropriate mole ratio of nucleophile to theoretically formed oxirane group is between 1: 10 and 10: 1 although it is always convenient to use an excess.
- Example 2 Influence of the type of solvent.
- Example 3 Influence of the ion exchange of the zeolite Ti-Beta. Under the same conditions as in experiment 2 using as catalyst a Ti-Beta zeolite exchanged with sodium acetate at 80 ° C and subsequently calcined at 530 ° C, the epoxide is practically the only product obtained (99%). The conversion of H 2 0 2 is 95% with an efficiency of 60%.
- Example 4 Influence of the Si / Al ratio of the catalyst.
- This example shows how the activity and the epoxide selectivity of the Ti-Beta zeolite increases as the catalyst's aluminum content decreases.
- Example 5 Oxidation of methyl oleate with tert-butyl hydroperoxide (TBHP) using Ti-Beta as catalyst.
- Example 6 Oxidation of methyl oleate using Ti-MCM-41 as catalyst. Under the same experimental conditions as in Example 5 using Ti-MCM-41
- Example 7 Influence of surface silanization of the Ti-MCM-41.
- Example 8 Oxidation of methyl oleate with Ti-Silicalite as catalyst.
- Example 2 Under the same experimental conditions as in Example 2 at a temperature of 50 ° C using a Ti-Silicalite with a crystal size of less than 0.5 ⁇ m (average diameter of 0.10 ⁇ m) as catalyst, after 8 hours of reaction a conversion of H 2 0 2 of 90% is obtained with an epoxide selectivity of 100% and an efficiency of H 2 0 2 of 62%.
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Abstract
Description
TITULOTITLE
Procedimiento y catalizadores para la obtención de epóxidos y derivados hidroxilados de ácidos y esteres de ácidos grasos.Process and catalysts for obtaining epoxides and hydroxylated derivatives of fatty acids and esters of fatty acids.
CAMPO DE LA TÉCNICAFIELD OF THE TECHNIQUE
Preparación de epóxidos y derivados hidroxilados de ácidos y esteres de ácidos grasos por oxidación de ácidos grasos insaturados con peróxidos.Preparation of epoxides and hydroxylated derivatives of acids and esters of fatty acids by oxidation of unsaturated fatty acids with peroxides.
INTRODUCCIÓN El creciente interés en la producción de ácidos grasos epoxidados y en ios productos hidroxilados derivados de la apertura del epóxido se debe a las múltiples aplicaciones de estos compuestos en la industria. Entre otros, cabe destacar su uso como aditivos en la fabricación de polímeros, plásticos y lubricantes, como auxiliares en la industria textil y como producto base en la formulación de cosméticos.INTRODUCTION The growing interest in the production of epoxidized fatty acids and in hydroxylated products derived from the opening of the epoxide is due to the multiple applications of these compounds in the industry. Among others, its use as additives in the manufacture of polymers, plastics and lubricants, as auxiliaries in the textile industry and as a base product in the formulation of cosmetics.
BREVE DESCRIPCIÓN DE LA INVENCIÓNBRIEF DESCRIPTION OF THE INVENTION
En la presente invención se describe la epoxidación de ácidos y derivados de ácidos grasos insaturados y de la apertura de los epóxidos por moléculas próticas catalizadas por tamices moleculares con titanio en su estructura empleando un peróxido como agente oxidante. Por último, se reivindica también la utilización de catalizadores sólidos bifuncionales conteniendo una función oxidante (Ti), y una función acida, que permite llevar a cabo en un solo recipiente y con un único catalizador la formación del epóxido y su apertura.The present invention describes the epoxidation of acids and derivatives of unsaturated fatty acids and the opening of epoxides by protic molecules catalyzed by molecular sieves with titanium in their structure using a peroxide as oxidizing agent. Finally, the use of bifunctional solid catalysts containing an oxidizing function (Ti), and an acidic function, which allows the formation of the epoxide and its opening in a single vessel and with a single catalyst to be carried out, is also claimed.
DESCRIPCIÓN DETALLADA DE LA INVENCIÓN La presente invención se refiere a la utilización de tamices moleculares con titanio incorporado en su estructura, así como titanio y centros ácidos del tipo Brónsted, como catalizadores en la oxidación de ácidos y derivados de ácidos grasos insaturados para la obtención en una sola etapa de epóxidos, y/o productos derivados de la apertura de los mismos por moléculas próticas, empleando un peróxido como agente oxidante. Los tamices moleculares a los que hace referencia la presente invención son:DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the use of molecular sieves with titanium incorporated in its structure, as well as titanium and acidic centers of the Brónsted type, as catalysts in the oxidation of acids and derivatives of unsaturated fatty acids for obtaining a single stage of epoxides, and / or products derived from their opening by protic molecules, using a peroxide as an oxidizing agent. The molecular sieves referred to in the present invention are:
HOJA DE SUSTITUCIÓN (REGLA 26) - La zeolita Ti-Beta, conteniendo o no aluminio en posiciones tetraédπcasSUBSTITUTE SHEET (RULE 26) - Zeolite Ti-Beta, containing or not containing aluminum in tetrahedral positions
- Los sólidos mesoporosos Tι-MCM-41 (SP 9,301 ,327) y Ti-HMS (descrito en Nature, 368, pp 321 , 1994), conteniendo o no aluminio en posiciones tatraédπcas- Mesoporous solids Tι-MCM-41 (SP 9,301, 327) and Ti-HMS (described in Nature, 368, pp 321, 1994), containing or not containing aluminum in tattooed positions
- La zeolita Tι-ZSM-5, conteniendo o no (Tilo silica ta) aluminio en posiciones tetraédπcas.- The zeolite Tι-ZSM-5, containing or not (Tilo silica ta) aluminum in tetrahedral positions.
Así, la apertura del grupo oxirano por adición de moléculas próticas es una reacción catalizada por ácidos La zeolita Ti-Beta puede sintetizarse incorporando o no aluminio en su estructura La presencia de aluminio confiere a este catalizador un carácter bifuncional con una función oxidante asociada a los átomos de titanio y una función acida asociada a los átomos de aluminio Así pues, dependiendo de la relación molar Si/Al del catalizador los productos finales obtenidos en la oxidación de compuestos insaturados pueden ser epóxidos o productos derivados hidroxilados o mezclas de ellos Por otra parte, es posible obtener un catalizador altamente selectivo a epóxido realizando un intercambio iónico de una zeolita Ti- Beta con compuestos de metales alcalinos o alcalinotérreosThus, the opening of the oxirane group by the addition of protic molecules is a reaction catalyzed by acids. Zeolite Ti-Beta can be synthesized by incorporating aluminum in its structure or not. The presence of aluminum gives this catalyst a bifunctional character with an oxidizing function associated with the Titanium atoms and an acid function associated with aluminum atoms Thus, depending on the Si / Al molar ratio of the catalyst, the final products obtained in the oxidation of unsaturated compounds may be epoxides or hydroxylated derivative products or mixtures thereof. , it is possible to obtain a highly selective epoxide catalyst by performing an ion exchange of a T-Beta zeolite with alkali or alkaline earth metal compounds
El sólido mesoporoso Tι-MCM-41 tiene un fuerte carácter hidrófilo debido al gran número de grupos SI-OH superficiales que contiene El tratamiento de la Tι-MCM-41 con un agente silanizante del tipo R3S¡CI permite aumentar considerablemente la hidrofobicidad de este material aumentando su efectividad como catalizador en la oxidación de compuestos orgánicos al favorecer la difusión de los reactivos por el interior de sus canalesThe mesoporous solid Tι-MCM-41 has a strong hydrophilic character due to the large number of superficial SI-OH groups it contains. The treatment of Tι-MCM-41 with a silanizing agent of the R3S¡CI type allows to increase considerably the hydrophobicity of this material increasing its effectiveness as a catalyst in the oxidation of organic compounds by favoring the diffusion of reagents inside its channels
Las características estructurales de la Ti-Silicalita, con un sistema de canales tridimensional de 5,5 A de diámetro medio, impone grandes restricciones a la difusión de moléculas de gran tamaño como son los ácidos grasos y sus derivados Cuando este material se sintetiza con tamaños de cristal muy pequeños, menores o igual a 50.5 μm, el aumento de la relación superficie externa/superficie interna aumenta el número de centros activos accesibles al sustrato y disminuye los problemas difusionales de reactantes y productos aumentando la efectividad del catalizadorThe structural characteristics of Ti-Silicalite, with a system of three-dimensional channels of 5.5 A of average diameter, imposes great restrictions on the diffusion of large molecules such as fatty acids and their derivatives When this material is synthesized with sizes of very small glass, less than or equal to 50.5 μm, the increase in the external surface / internal surface ratio increases the number of active centers accessible to the substrate and decreases the diffusion problems of reactants and products increasing the effectiveness of the catalyst
Los ácidos grasos o sus derivados empleados como sustratos en este proceso deben tener, ai menos, un doble enlace carbono-carbono que puede encontrarse en posición terminal o posiciones internas de la molécula Además pueden incorporar cualquier otro tipo de grupoThe fatty acids or their derivatives used as substrates in this process must have, at least, a carbon-carbon double bond that can be found in the terminal position or internal positions of the molecule. They can also incorporate any other type of group
HOJA DE SUSTITUCIÓN (REGLA 26) funcional. Como ejemplos no restrictivos se consideran el ácido oleico, linoleico, iinolénico, palmitoleico, erúcico, ricinoleico y sus esteres incluyendo los mono-, di- y triglicéridos.SUBSTITUTE SHEET (RULE 26) functional. Non-restrictive examples are oleic, linoleic, iinolenic, palmitoleic, erucic, ricinoleic acid and its esters including mono-, di- and triglycerides.
Aunque el peróxido de hidrógeno es el oxidante preferente en esta invención también pueden emplearse otros peróxidos. El uso de peróxidos orgánicos permite obtener mezclas de reacción homogéneas sin necesidad de añadir disolventes. Los peróxidos orgánicos más comúnmente empleados en reacciones de oxidación son ios alquilhidroperóxidos, ROOH, como los hidroperóxidos de tert-butilo, eumeno y etilbenceno.Although hydrogen peroxide is the preferred oxidant in this invention, other peroxides can also be used. The use of organic peroxides allows to obtain homogeneous reaction mixtures without the need to add solvents. The organic peroxides most commonly used in oxidation reactions are alkyl hydroperoxides, ROOH, such as tert-butyl hydroperoxides, eumene and ethylbenzene.
La reacción puede llevarse a cabo en presencia o ausencia de disolventes. Cuando se emplea peróxido de hidrógeno como oxidante, el uso de disolventes favorece la miscibilidad entre los diferentes reactivos. Como disolventes pueden emplearse alcoholes, cetonas, éteres, nitrilos y agua. Ejemplos son el metanol, etanol, isopropanol, alcohol tert-butílico, acetona, metiletilcetona, éter dietílico, tetrahidrofurano, acetonitrilo y propionitrilo.The reaction can be carried out in the presence or absence of solvents. When hydrogen peroxide is used as an oxidant, the use of solvents favors miscibility between the different reagents. As solvents, alcohols, ketones, ethers, nitriles and water can be used. Examples are methanol, ethanol, isopropanol, tert-butyl alcohol, acetone, methyl ethyl ketone, diethyl ether, tetrahydrofuran, acetonitrile and propionitrile.
La apertura de los grupos oxirano se produce por la adición de nucleófilos, normalmente moléculas de carácter práctico del tipo de agua, alcoholes como metanol, etanol, n-heptanol, n-octanol, etilenglicol, de aminas como la n-butilamina, metil amina, amoníaco, de ácidos carboxílicos como el ácido acético y de tioles.The opening of the oxirane groups is produced by the addition of nucleophiles, usually molecules of a practical nature such as water, alcohols such as methanol, ethanol, n-heptanol, n-octanol, ethylene glycol, of amines such as n-butylamine, methyl amine , ammonia, of carboxylic acids such as acetic acid and thiols.
La reacción puede tener lugar en un reactor continuo o discontinuo. La temperatura óptima de reacción está influenciada por la actividad del catalizador, la reactividad del sustrato, la concentración de reactivos y el tipo de disolvente entre otros factores pero normalmente se encuentra entre 25 y 150°C. El tiempo de reacción puede variar entre 1 min. y 48 horas dependiendo de los factores mencionados.The reaction can take place in a continuous or discontinuous reactor. The optimal reaction temperature is influenced by the activity of the catalyst, the reactivity of the substrate, the concentration of reagents and the type of solvent among other factors but usually is between 25 and 150 ° C. The reaction time may vary between 1 min. and 48 hours depending on the factors mentioned.
La cantidad de catalizador deberá ser suficiente para alcanzar una conversión aceptable en un tiempo no excesivamente largo. Normalmente se adicionan de 0,001 a 10 g de catalizador por mol de sustrato. La cantidad de oxidante no es crítica. Puesto que, teóricamente, se requiere un equivalente de oxidante por cada doble enlace carbono-carbono presente en el sustrato, es conveniente que la relación molar entre cada insaturación presente en el sustrato y el oxidante se encuentre entre 10:1 y 1:10.The amount of catalyst should be sufficient to achieve an acceptable conversion in a not too long time. Usually 0.001 to 10 g of catalyst are added per mole of substrate. The amount of oxidant is not critical. Since, theoretically, an equivalent of oxidant is required for each carbon-carbon double bond present in the substrate, it is convenient that the molar ratio between each unsaturation present in the substrate and the oxidant is between 10: 1 and 1:10.
El disolvente, si lo hubiera, puede comprender desde el 1 al 99% en peso del total de la mezcla de reacción.The solvent, if any, can comprise from 1 to 99% by weight of the total reaction mixture.
HOJA DE SUSTITUCIÓN (REGLA 26) De modo similar a lo que ocurre con el oxidante, la cantidad del nucleófilo escogido para abrir el anillo del epóxido dependerá de la cantidad de grupos oxirano que se formen. La relación molar adecuada de nucleófilo por grupo oxirano teóricamente formado está entre 1 :10 y 10:1 aunque siempre es conveniente emplear un exceso.SUBSTITUTE SHEET (RULE 26) Similar to what happens with the oxidant, the amount of nucleophile chosen to open the epoxy ring will depend on the amount of oxirane groups that are formed. The appropriate mole ratio of nucleophile to theoretically formed oxirane group is between 1: 10 and 10: 1 although it is always convenient to use an excess.
Un procedimiento general de reacción y sin que sea restringido sería el que se describe en los siguientes ejemplos:A general reaction procedure and without being restricted would be the one described in the following examples:
EJEMPLOS Ejemplo 1 : Oxidación de oleato de metilo con H,0Z empleando Ti-Beta como catalizador.EXAMPLES Example 1: Oxidation of methyl oleate with H, 0 Z using Ti-Beta as catalyst.
En un matraz se introducen 296,5 mg (1 mmol) de oleato de metilo, 2ml de metanol,296.5 mg (1 mmol) of methyl oleate, 2 ml of methanol are introduced into a flask,
24,3 mg de H202 (disolución acuosa al 35% en peso) y 30 mg de Ti-Beta (Si/Al = 115,24.3 mg of H 2 0 2 (35% aqueous solution by weight) and 30 mg of Ti-Beta (Si / Al = 115,
2,2%TiO2). El sistema se calienta a reflujo a la temperatura de 70 °C con agitación magnética.2.2% TiO2). The system is heated to reflux at a temperature of 70 ° C with magnetic stirring.
Al cabo de 8 horas de reacción se filtra el catalizador y se analiza la mezcla. Los productos mayoritarios son los metilglicoléteres con una selectividad del 98% y una eficiencia del H202 delAfter 8 hours of reaction, the catalyst is filtered and the mixture is analyzed. The major products are methyl glycol ethers with a selectivity of 98% and an efficiency of H 2 0 2 of
80%. La conversión de H202 es del 90%.80% The conversion of H 2 0 2 is 90%.
Ejemplo 2 : Influencia del tipo de disolvente.Example 2: Influence of the type of solvent.
En las mismas condiciones experimentales que en el ejemplo 1 empleando acetonitrilo como disolvente, al cabo de 8 horas de reacción se obtiene una conversión de H202 del 96%. El epóxido es el producto mayoritaπo en estas condiciones con una selectividad del 93%. La eficiencia del H202 es del 60%.Under the same experimental conditions as in Example 1 using acetonitrile as solvent, after 8 hours of reaction a conversion of H 2 0 2 of 96% is obtained. Epoxide is the main product under these conditions with a selectivity of 93%. The efficiency of H 2 0 2 is 60%.
Ejemplo 3 : Influencia del intercambio iónico de la zeolita Ti-Beta. En las mismas condiciones que en el experimento 2 empleando como catalizador una zeolita Ti-Beta intercambiada con acetato sódico a 80 °C y calcinada posteriormente a 530°C el epóxido es, prácticamente, el único producto obtenido (99%). La conversión de H202 es del 95% con una eficiencia del 60%.Example 3: Influence of the ion exchange of the zeolite Ti-Beta. Under the same conditions as in experiment 2 using as catalyst a Ti-Beta zeolite exchanged with sodium acetate at 80 ° C and subsequently calcined at 530 ° C, the epoxide is practically the only product obtained (99%). The conversion of H 2 0 2 is 95% with an efficiency of 60%.
Ejemplo 4 : Influencia de la relación Si/Al del catalizador.Example 4: Influence of the Si / Al ratio of the catalyst.
HOJA DE SUSTITUCIÓN (REGLA 26) En las mismas condiciones que en el ejemplo 1 a la temperatura de 50°C se estudia la influencia de la relación Si/Al en la zeolita Ti-Beta. Los resultados obtenidos se muestran en la siguiente tabla 1:SUBSTITUTE SHEET (RULE 26) Under the same conditions as in example 1 at the temperature of 50 ° C, the influence of the Si / Al ratio on the Ti-Beta zeolite is studied. The results obtained are shown in the following table 1:
Composición Conversión Selectiva. Selectiv. química H202 epóxido H202(%)Composition Conversion Selective. Selectiv. Chemical H 2 0 2 Epoxide H 2 0 2 (%)
Cataliz. Si/Al %TiO2 (% molar)Cataliz Yes / Al% TiO 2 (% molar)
Ti-Beta(1) 151 4.0 88 11 75Ti-Beta (1) 151 4.0 88 11 75
Ti-Beta(2) 586 3.0 80 20 80Ti-Beta (2) 586 3.0 80 20 80
Ti-Beta(3) oo 2.4 90 35 88Ti-Beta (3) oo 2.4 90 35 88
Tabla 1Table 1
En este ejemplo se observa cómo la actividad y la selectividad a epóxido de la zeolita Ti-Beta aumenta al disminuir el contenido en aluminio del catalizador.This example shows how the activity and the epoxide selectivity of the Ti-Beta zeolite increases as the catalyst's aluminum content decreases.
Ejemplo 5 : Oxidación de oleato de metilo con hidroperóxido de tert-butilo (TBHP) empleando Ti-Beta como catalizador.Example 5: Oxidation of methyl oleate with tert-butyl hydroperoxide (TBHP) using Ti-Beta as catalyst.
En un matraz se introducen 593 mg (2mmol) de oleato de metilo, 225 mg de TBHP (disolución al 80% en peróxido de tert-butilo) y 60 mg de catalizador. El sistema se calienta a reflujo a 70°C y con agitación magnética durante 8 horas obteniéndose una conversión en TBHP del 19% con una selectividad a epóxido del 81% y una eficiencia de TBHP del 84%. Empleando como catalizador una Ti-Beta intercambiada con acetato sódico se obtiene una conversión de oxidante del 50%, una selectividad a epóxido del 93% y una eficiencia de TBHP del 75%.593 mg (2mmol) of methyl oleate, 225 mg of TBHP (80% solution in tert-butyl peroxide) and 60 mg of catalyst are introduced into a flask. The system is heated at reflux at 70 ° C and with magnetic stirring for 8 hours obtaining a conversion in TBHP of 19% with an epoxy selectivity of 81% and an efficiency of TBHP of 84%. Using a Ti-Beta exchanged with sodium acetate as catalyst, an oxidant conversion of 50%, an epoxide selectivity of 93% and a TBHP efficiency of 75% are obtained.
Ejemplo 6 : Oxidación de oleato de metilo empleando Ti-MCM-41 como catalizador. En las mismas condiciones experimentales que en el ejemplo 5 empleando Ti-MCM-41Example 6: Oxidation of methyl oleate using Ti-MCM-41 as catalyst. Under the same experimental conditions as in Example 5 using Ti-MCM-41
(2.4 %TiO2) como catalizador se obtiene una conversión de TBHP del 93% con una selectividad a epóxido del 93% y una eficiencia del TBHP del 90%.(2.4% TiO 2 ) as a catalyst a conversion of 93% TBHP is obtained with an epoxide selectivity of 93% and a TBHP efficiency of 90%.
Ejemplo 7 : Influencia de la silanización de la superficie de la Ti-MCM-41.Example 7: Influence of surface silanization of the Ti-MCM-41.
HOJA DE SUSTITUCIÓN (REGLA 26) En las mismas condiciones experimentales que en el ejemplo 5 se emplea una Ti-MCM-41 previamente tratada con una disolución de trimetilclorosílano, lavada con diclorometano y secada a 60°C como catalizador. Los resultados al cabo de 8 horas de reacción son: conversión de TBHP = 95%, selectividad a epóxido = 100% y eficiencia del TBHP = 96%. Como puede observarse, el aumento de hidrofobicidad en la Ti-MCM-41 se traduce en un aumento considerable tanto de su actividad como de su selectividad.SUBSTITUTE SHEET (RULE 26) Under the same experimental conditions as in Example 5, a Ti-MCM-41 previously treated with a solution of trimethylchlorosil, used with dichloromethane and dried at 60 ° C as a catalyst is used. The results after 8 hours of reaction are: conversion of TBHP = 95%, selectivity to epoxide = 100% and efficiency of TBHP = 96%. As can be seen, the increase in hydrophobicity in the Ti-MCM-41 translates into a considerable increase in both its activity and its selectivity.
Ejemplo 8 : Oxidación de oleato de metilo con Ti-Silicalita como catalizador.Example 8: Oxidation of methyl oleate with Ti-Silicalite as catalyst.
En las mismas condiciones experimentales que en el ejemplo 2 a una temperatura de 50°C empleando una Ti-Silicalita con un tamaño de cristal inferior a 0,5 μm (diámetro medio de 0.10 μm) como catalizador, al cabo de 8 horas de reacción se obtiene una conversión de H202 del 90% con una selectividad a epóxido del 100% y una eficiencia de H202 del 62%.Under the same experimental conditions as in Example 2 at a temperature of 50 ° C using a Ti-Silicalite with a crystal size of less than 0.5 μm (average diameter of 0.10 μm) as catalyst, after 8 hours of reaction a conversion of H 2 0 2 of 90% is obtained with an epoxide selectivity of 100% and an efficiency of H 2 0 2 of 62%.
HOJA DE SUSTITUCIÓN (REGLA 26) SUBSTITUTE SHEET (RULE 26)
Claims
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| Application Number | Priority Date | Filing Date | Title |
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| PCT/ES1997/000127 WO1998056780A1 (en) | 1997-06-10 | 1997-06-10 | Process and catalysts for the production of epoxydes and hydroxylated derivatives of acids and esters of fatty acids |
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| Application Number | Priority Date | Filing Date | Title |
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| PCT/ES1997/000127 WO1998056780A1 (en) | 1997-06-10 | 1997-06-10 | Process and catalysts for the production of epoxydes and hydroxylated derivatives of acids and esters of fatty acids |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103212437A (en) * | 2013-04-27 | 2013-07-24 | 大连理工大学 | Method for preparing titanium-based catalyst and synthesizing epoxypropane and dicumyl peroxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0568336A2 (en) * | 1992-04-30 | 1993-11-03 | ARCO Chemical Technology, L.P. | Epoxidation process using titanium-rich silicalite catalysts |
| EP0659479A1 (en) * | 1993-12-23 | 1995-06-28 | Uop | Epoxidation of olefins using a catalyst containing titania-supported titanosilicate |
| EP0659685A1 (en) * | 1993-12-23 | 1995-06-28 | ARCO Chemical Technology, L.P. | Epoxidation process and catalyst therefor |
-
1997
- 1997-06-10 WO PCT/ES1997/000127 patent/WO1998056780A1/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0568336A2 (en) * | 1992-04-30 | 1993-11-03 | ARCO Chemical Technology, L.P. | Epoxidation process using titanium-rich silicalite catalysts |
| EP0659479A1 (en) * | 1993-12-23 | 1995-06-28 | Uop | Epoxidation of olefins using a catalyst containing titania-supported titanosilicate |
| EP0659685A1 (en) * | 1993-12-23 | 1995-06-28 | ARCO Chemical Technology, L.P. | Epoxidation process and catalyst therefor |
Non-Patent Citations (1)
| Title |
|---|
| BLASCO T.Y. ET AL.: "Unseeded synthesis of A1-free Ti-beta zeolite in fluoride medium: a hydrophobic selective oxidation catalyst", CHEM. COMMUN.,, vol. 20, 1996, pages 2367 - 2368, XP002033134 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103212437A (en) * | 2013-04-27 | 2013-07-24 | 大连理工大学 | Method for preparing titanium-based catalyst and synthesizing epoxypropane and dicumyl peroxide |
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