WO1994021378A1 - Process for the preparation of catalysts based on zeolites treated with phosphoric acid, useful for catalytic cracking units - Google Patents
Process for the preparation of catalysts based on zeolites treated with phosphoric acid, useful for catalytic cracking units Download PDFInfo
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- WO1994021378A1 WO1994021378A1 PCT/ES1994/000028 ES9400028W WO9421378A1 WO 1994021378 A1 WO1994021378 A1 WO 1994021378A1 ES 9400028 W ES9400028 W ES 9400028W WO 9421378 A1 WO9421378 A1 WO 9421378A1
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/28—Phosphorising
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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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
Definitions
- Catalytic cracking units are used to produce medium distillates, as well as C 3 and C 4 olefins and ibutane from vacuum diesel, and even waste.
- Zeolite Y is used as catalyst in its different forms: completely exchanged with rare earths (KING), without rare earths (USY), or intermediate (REUSY). These zeolites are dispersed in a matrix of kaolin and silica and / or A1 2 0 3 , forming particles of spherical shape and with sizes in the range 20-200 microns in diameter.
- a phosphoric acid treatment in the appropriate amount increases the activity of the zeolite, decreasing the formation of dry gas and coke, and increasing the yield in gasoline.
- the process of the present invention includes pretreatment and modification of the zeolite with an aqueous solution of phosphoric acid in amounts of 0.5 to 4% by weight of phosphorus relative to the zeolite.
- This process is useful in the treatment of large and medium-sized pore zeolites, including: Y, Beta, ZSM-20, MCM, offering, omega,
- SUBSTITUTED SHEET ZSM-5 ' ZSM-11, ZSM-22, ZSM-23, ZSM-4, ZSM-35, and mixtures thereof.
- Y, Beta, ZSM-20, MCM, offer and ZSM-5 are preferred.
- the phosphoric acid treatment allows to increase their conversion while reducing the formation of dry gas and coke by increasing the yield in medium distillates.
- the zeolite is well dispersed in the aqueous solution, which is achieved by vigorous stirring or by treatment in a ball mill, of the zeolite suspension, or even with the introduction of dispersants in order to facilitate the contact of Al extrarred with phosphoric acid.
- the treatment is preferably carried out at temperatures between 20 and 100 ° C, and for times between 1 and 16 hours.
- the zeolite used must be previously partially de-illuminated by a previous calcination at 500 D -650 C C in the presence of water vapor.
- phosphoric solution USY zeolites with unit cell size between 24.54 A and 24-40 A are treated.
- the zeolite thus treated can be exchanged with rare earths in order to obtain a final zeolite of the REUSY type.
- a slurry of the treated zeolite is combined with a suspension of the matrix precursor, which may or may not be treated with phosphoric acid.
- the new suspension formed by the zeolite and the matrix after homogenization is atomized (spray driying) forming particles in the appropriate range for FCC processes (20-200 microns).
- NMR-MAS that both in the treated zeolite, and in the final catalyst, containing the treated zeolite, Al phosphate is formed, with Al extrared, when subjected to a hydrothermal treatment that simulates catalyst deactivation in the regenerator of an FCC unit. This zeolite-phosphorus interaction decreases the Lewis acidity of
- SUBSTITUTED SHEET catalyst At the same time the number of acidic centers of high acid strength decreases, and the number of medium-weak strength ones increases as observed during the programmed thermal desorption of NH3. This variation in acid distribution, as well as the formation of Al phosphate, would be responsible for the lower yield in dry gas and coke, and the greater selectivity to medium distillates of the catalysts treated with H 3 P0, during the catalytic cracking of Vacuum diesel and heavier feeds.
- This example describes the preparation of the zeolite that is used as a reference to demonstrate the positive effect of treatment with H 3 P0 4 .
- the unit cell size of the resulting material USY00
- This zeolite was exchanged and calcined, in order to reduce the Na 2 0 content, between 0.01 and 4% in
- SUBSTITUTED SHEET weight preferably below 0.1%.
- a suspension was formed in kaolin, (this may or may not be previously treated with H 3 P0 4 ), sodium silicate and water.
- the suspension was neutralized with H 2 S0 4 and Al sulfate.
- the zeolite was added in a percentage that can range between 15 and 40% by weight.
- the resulting suspension was atomized (spray driying) to the size distribution mentioned above.
- Example 1 This example describes the zeolite modification treatment of Example 1.
- a solution of phosphoric acid is prepared, dissolving 0.446g of H 3 P0 4 (85%) in 120g of H 2 0, the final pH of the solution being 1.8.
- To this solution was added 12 g. of the zeolite described in example 1.
- the resulting suspension was heated at 100 ° C for 2 h.
- the characteristics of the resulting zeolite are given in Table 1.
- This example describes the preparation of zeolites with different amounts of phosphorus.
- Zeolite samples were prepared following the same procedure as in example 1 and 2, but with amounts of H 3 P0 4 (85%) in H 2 0 of: 0.22, 1.78, 2.67 gr., Maintaining the amounts of H 2 0 4 and zeolite identical to those of example 2.
- the characteristics of the final zeolites are given in Table 1.
- two samples of zeolite were prepared according to example 1 with two NaY zeolites of Si / Al ratio (2.4) and 2-8, and of these the corresponding two samples of zeolites following example 2.
- This example demonstrates the catalytic effect of phosphoric treatments during the catalytic cracking of diesel oil, comparing the activity and selectivity of the catalysts prepared in Examples 1-7 in a MAT reactor using a vacuum diesel oil whose characteristics are given in the Table 4.
- the experimental conditions were:
- This example describes the preparation and catalytic activity of a catalyst in which the zeolite is an NHUSY, impregnated with P0H.
- SUBSTITUTED SHEET is a d i mpregnó aqueous isolución H 3 P0 4 (0.446 g. d e P0 4 H 3,
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Abstract
The invention relates to a process for preparing a catalyst which contains a zeolite, and which improves the activity and selectivity in distilled media, reducing the production of dry gas and coke. The catalyst is prepared by modifying the zeolite with an aqua solution of phosphoric acid. A prefered zeolite is a zeolite USY which has been partially dealuminized by a prior calcination-vapor treatment, and wherein the treatment with H3PO4 is carried out in an aqueous solution containing between 0.5 and 4 % by weight of H3PO4 with respect to the zeolite. The modified zeolite is combined with the precursor of the matrix and is atomized to give the zeolite the appropriate shape and size in order to use it in FCC units. The catalyst is useful for the cracking of gas oil, and heavier supplies.
Description
MEMORIA DESCRIPTIVA Titulo DESCRIPTIVE MEMORY Title
Procedimiento de preparación de catalizadores a base de zeolitas tratadas con ácido fosfórico, útiles para su aplicación en unidades de craqueo catalítico Estado del arteProcess for preparing phosphoric acid treated zeolite catalysts, useful for application in catalytic cracking units State of the art
Las unidades de craqueo catalítico se utilizan para producir destilados medios, así como olefinas C3 y C4 e ibutano a partir de gasoil de vacío, e incluso residuos. Como catalizador se utiliza zeolita Y en sus diferentes formas: completamente intercambiadas con tierras raras (REY), sin tierras raras (USY), o intermedias (REUSY). Estas zeolitas se dispersan en una matriz de caolín y sílice y/o A1203, formando partículas de forma esférica y con tamaños en el rango 20-200 micrones de diámetro.Catalytic cracking units are used to produce medium distillates, as well as C 3 and C 4 olefins and ibutane from vacuum diesel, and even waste. Zeolite Y is used as catalyst in its different forms: completely exchanged with rare earths (KING), without rare earths (USY), or intermediate (REUSY). These zeolites are dispersed in a matrix of kaolin and silica and / or A1 2 0 3 , forming particles of spherical shape and with sizes in the range 20-200 microns in diameter.
En este catalizador, aun cuando parte de la conversión puede ser obtenida sobre la matriz, la mayor parte de los productos se forman en reacciones primarias y secundarias sobre el componente zeolítico. Así pues las propiedades catalíticas del componente zeolítico son vitales para el comportamiento final del catalizador. Debido a esto, se han desarrollado numerosos métodos de activación de la zeolita que conducen a catalizadores de FCC con distinta actividad y selectividad. Recientemente (A.Corma, V. Fornés, A. Martínez, F. Meló, and 0. Pallota, in P.J. Grobet, W.J. Mortier, E.F. Vansant and G. Schulz-Ekloff (Editors), Studies in Surface Science, Vol.37, Elsevier, Amsterdam, 1988, p.495.), (A. Corma, V, Fornés, A. Martínez, and A. V. Orchilles, "Parameters in Addition to the Unit Cell That Determine the Cracking Activity and Selectivity of Dealuminated HY Zeolites", Perspective in Molecular Sieve Science ACS Symposium Series, 368 Edited by William H. Flank and Thaddens E. Whyte, Jr ) se ha visto que además de la composición de red, la composición de extrarred de la zeolita tiene un claro impacto sobre la distribución de productos de craqueo. Todo parece indicar que el Al extrarred formado durante los procesosIn this catalyst, although part of the conversion can be obtained on the matrix, most of the products are formed in primary and secondary reactions on the zeolitic component. Thus the catalytic properties of the zeolitic component are vital for the final behavior of the catalyst. Because of this, numerous zeolite activation methods have been developed that lead to FCC catalysts with different activity and selectivity. Recently (A.Corma, V. Fornés, A. Martínez, F. Meló, and 0. Pallota, in PJ Grobet, WJ Mortier, EF Vansant and G. Schulz-Ekloff (Editors), Studies in Surface Science, Vol. 37 , Elsevier, Amsterdam, 1988, p.495.), (A. Corma, V, Fornés, A. Martínez, and AV Orchilles, "Parameters in Addition to the Unit Cell That Determine the Cracking Activity and Selectivity of Dealuminated HY Zeolites" , Perspective in Molecular Sieve Science ACS Symposium Series, 368 Edited by William H. Flank and Thaddens E. Whyte, Jr) it has been seen that in addition to the network composition, the extra-network composition of the zeolite has a clear impact on the distribution of cracking products. Everything seems to indicate that the Al extrarred formed during the processes
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de activación de la zeolita, así como durante el proceso de regeneración de la zeolita en el proceso de FCC, aun cuando puede convertir fondo, produce coque y gas seco que limitan las posibilidades del catalizador. Con el fin de disminuir los efectos nocivos de este Al extrarred se han desarrollado procedimientos químicos de activación de la zeolita que eliminan el Al extrarred durante el mismo procedimiento de desaluminización (D. W. Breck, H. Blass, and G. . Skeels, U.S. Pat 4 502 023, 1985), o con posterioridad a este (A. Corma, V. Fornes and F. Rey, "Extraction of Extraframework aluminium in Ultrastable Y Zeolites by *(NH4)2SiF6 Treatments", Applied Catalysis, 59, 1990), (A. Corma, J. Nieman, in AKZO FCC Symposium Meeting 1991, Holand). Existe otra posibilidad de eliminar los efectos nocivos del Al extrarred y que consiste en provocar su reacción, especialmente durante la etapa de regeneración, con sílice altamente reactiva depositada en el catalizador (A. Corma, M. Grande and V. Fornes, "Interaction of zeolite alumina wilh matrix silica in catalytic cracking catalysts", Applied Catalysis, 66, 1990). Postratamientos con sales de fosfato amónico (Chitnis y Herbst, U.S. -Pat. 5110776, 1992) aumentan la resistencia a la atrición, y el número de octanos de la gasolina sin producir variaciones en el gas seco y coque.SUBSTITUTED SHEET of activation of the zeolite, as well as during the regeneration process of the zeolite in the FCC process, even when it can convert bottom, it produces coke and dry gas that limit the possibilities of the catalyst. In order to reduce the harmful effects of this Al extrarred, chemical zeolite activation procedures have been developed that eliminate Al extrarred during the same desaluminization procedure (DW Breck, H. Blass, and G. Skeels, US Pat 4 502 023, 1985), or after this (A. Corma, V. Fornes and F. Rey, "Extraction of Extraframework aluminum in Ultrastable Y Zeolites by * (NH 4 ) 2 SiF 6 Treatments", Applied Catalysis, 59, 1990), (A. Corma, J. Nieman, in AKZO FCC Symposium Meeting 1991, Holand). There is another possibility to eliminate the harmful effects of Al extrarred and that is to cause its reaction, especially during the regeneration stage, with highly reactive silica deposited in the catalyst (A. Corma, M. Grande and V. Fornes, "Interaction of Zeolite alumina wilh matrix silica in catalytic cracking catalysts ", Applied Catalysis, 66, 1990). Post-treatments with ammonium phosphate salts (Chitnis and Herbst, US Pat. 5110776, 1992) increase the resistance to attrition, and the octane number of gasoline without producing variations in dry gas and coke.
En la presente invención se presenta que un tratamiento con ácido fosfórico en la cantidad adecuada aumenta la actividad de la zeolita, disminuyendo la formación de gas seco y coque, y aumentando el rendimiento en gasolina.In the present invention it is presented that a phosphoric acid treatment in the appropriate amount increases the activity of the zeolite, decreasing the formation of dry gas and coke, and increasing the yield in gasoline.
Descripción detallada de la invención El proceso de la presente invención incluye el pretratamiento y la modificación de la zeolita con una disolución acuosa de ácido fosfórico en cantidades de 0,5 a 4% en peso de fósforo en relación a la zeolita. Este proceso es útil en el tratamiento de zeolitas de poro grande y medio entre las que se incluyen: Y, Beta, ZSM-20, MCM, ofretita, omega,DETAILED DESCRIPTION OF THE INVENTION The process of the present invention includes pretreatment and modification of the zeolite with an aqueous solution of phosphoric acid in amounts of 0.5 to 4% by weight of phosphorus relative to the zeolite. This process is useful in the treatment of large and medium-sized pore zeolites, including: Y, Beta, ZSM-20, MCM, offering, omega,
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ZSM-5', ZSM-11, ZSM-22, ZSM-23, ZSM-4, ZSM-35, y mezclas de ellas. De entre ellas, y desde el punto de vista de catalizadores de FCC, se prefieren la Y, Beta, ZSM-20, MCM, ofretita y ZSM-5. Utilizando las zeolitas Y y Beta como ejemplo, el tratamiento con ácido fosfórico permite aumentar su conversión al mismo tiempo que reduce la formación de gas seco y coque aumentando el rendimiento en destilados medios. Se obtienen mejores resultados durante el tratamiento si la zeolita está bien dispersa en la solución acuosa, lo que se consigue por vigorosa agitación o por tratamiento en un molino de bolas, de la suspensión de zeolita, o incluso con la introducción de dispersantes con el fin de facilitar el contacto de Al extrarred con el ácido fosfórico. El tratamiento se lleva a cabo preferentemente a temperaturas entre 20 y 100°C, y durante tiempos comprendidos entre 1 y 16 horas. En esta invención la zeolita utilizada debe ser previamente desaluminizada parcialmente por una calcinación previa a 500D-650CC en presencia de vapor de agua. De esta manera se tratan con la disolución de fosfórico zeolitas USY con tamaño de celda unidad comprendido entre 24.54 A y 24-40 A. La zeolita así tratada puede ser intercambiada con tierras raras con el fin de obtener una zeolita final del tipo REUSY.SUBSTITUTED SHEET ZSM-5 ' , ZSM-11, ZSM-22, ZSM-23, ZSM-4, ZSM-35, and mixtures thereof. Among them, and from the point of view of FCC catalysts, Y, Beta, ZSM-20, MCM, offer and ZSM-5 are preferred. Using the Y and Beta zeolites as an example, the phosphoric acid treatment allows to increase their conversion while reducing the formation of dry gas and coke by increasing the yield in medium distillates. Better results are obtained during treatment if the zeolite is well dispersed in the aqueous solution, which is achieved by vigorous stirring or by treatment in a ball mill, of the zeolite suspension, or even with the introduction of dispersants in order to facilitate the contact of Al extrarred with phosphoric acid. The treatment is preferably carried out at temperatures between 20 and 100 ° C, and for times between 1 and 16 hours. In this invention, the zeolite used must be previously partially de-illuminated by a previous calcination at 500 D -650 C C in the presence of water vapor. In this way, phosphoric solution USY zeolites with unit cell size between 24.54 A and 24-40 A are treated. The zeolite thus treated can be exchanged with rare earths in order to obtain a final zeolite of the REUSY type.
Una vez que la zeolita ha sido tratada con la disolución conteniendo el ácido fosfórico, una suspensión (slurry) de la zeolita tratada se combina con una suspensión del precursor de la matriz, que puede ser tratada o no con ácido fosfófico. La nueva suspensión formada por la zeolita y la matriz después de homogeneizarse se atomiza (spray driying) formando partículas en el rango adecuado para procesos de FCC (20-200 micrones). Hemos visto por RMN-MAS que tanto en la zeolita tratada, como en el catalizador final, conteniendo la zeolita tratada, se forma fosfato de Al, con el Al extrarred, cuando se someten a un tratamiento hidrotérmico que simule desactivación del catalizador en el regenerador de una unidad de FCC. Esta interacción zeolita-fósforo disminuye la acidez Lewis delOnce the zeolite has been treated with the solution containing phosphoric acid, a slurry of the treated zeolite is combined with a suspension of the matrix precursor, which may or may not be treated with phosphoric acid. The new suspension formed by the zeolite and the matrix after homogenization is atomized (spray driying) forming particles in the appropriate range for FCC processes (20-200 microns). We have seen by NMR-MAS that both in the treated zeolite, and in the final catalyst, containing the treated zeolite, Al phosphate is formed, with Al extrared, when subjected to a hydrothermal treatment that simulates catalyst deactivation in the regenerator of an FCC unit. This zeolite-phosphorus interaction decreases the Lewis acidity of
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catalizador. Al mismo tiempo disminuye el número de centros ácidos de elevada fuerza acida, y aumenta el número de los de fuerza media-débil tal y como se observa durante la desorción térmica programada de NH3. Esta variación en la distribución de acideces, así como la formación del fosfato de Al, sería la responsable del menor rendimiento en gas seco y coque, y la mayor selectividad a destilados medios de los catalizadores tratados con H3P0 , durante el craqueo catalítico de gasoil de vacío y alimentaciones más pesadas. Se ha encontrado también que la impregnación de una solución de ácido fosfórico con un PH entre 1-8-3, sobre una zeolita NH4 USY, con celda unidad comprendida en el rango 24- 30-24-50 Aδ y siguiendo el método descrito anteriormente produce catalizadores con un menor rendimiento a gas seco y coque y una mayor selectividad a destilados medios. Además, aumente la conversión de fondo.SUBSTITUTED SHEET catalyst. At the same time the number of acidic centers of high acid strength decreases, and the number of medium-weak strength ones increases as observed during the programmed thermal desorption of NH3. This variation in acid distribution, as well as the formation of Al phosphate, would be responsible for the lower yield in dry gas and coke, and the greater selectivity to medium distillates of the catalysts treated with H 3 P0, during the catalytic cracking of Vacuum diesel and heavier feeds. It has also been found that the impregnation of a phosphoric acid solution with a PH between 1-8-3, on an NH 4 USY zeolite, with a unit cell in the range 24-30-24-50 Aδ and following the described method Previously it produces catalysts with a lower yield of dry gas and coke and greater selectivity to medium distillates. Also, increase the background conversion.
El efecto positivo del P se observa también cuando se trata una zeolita Y crecida "in situ" sobre Metacaolín, y se estabiliza por tratamiento con vapor de la forma amónica entre 500 y 650°C.The positive effect of P is also observed when a zeolite Y grown "in situ" on Metacaolin is treated, and is stabilized by steam treatment of the ammonium form between 500 and 650 ° C.
EJEMPLOS Ejemplo 1EXAMPLES Example 1
En este ejemplo se describe la preparación de la zeolita que se utiliza como referencia para demostrar el efecto positivo del tratamiento con H3P04.This example describes the preparation of the zeolite that is used as a reference to demonstrate the positive effect of treatment with H 3 P0 4 .
Una zeolita NaY (LZY-52) con una relación Si/Al de partida de 2.7, se intercambia con una disolución acuosa de NH4 *, a 80βC, con una relación líquido solido de 10, hasta que el - 70% del Na inicial ha sido intercambiado con NH4 *. Una vez secada, se calcina en presencia de 90% vapor en aire a 550βC durante 5 horas. En la zeolita resultante parte del Al de red ha sido extraído y el tamaño de la celda unidad del material resultante (USY00) es de 24.48 A. Esta zeolita se intercambió y calcinó, con el fin de reducir el contenido de Na20, entre 0,01 y 4% enA NaY zeolite (LZY-52) with an initial Si / Al ratio of 2.7, is exchanged with an aqueous solution of NH 4 * , at 80 β C, with a solid liquid ratio of 10, until - 70% of the Initial Na has been exchanged with NH 4 * . Once dried, it is calcined in the presence of 90% steam in air at 550 β C for 5 hours. In the resulting zeolite part of the network Al has been extracted and the unit cell size of the resulting material (USY00) is 24.48 A. This zeolite was exchanged and calcined, in order to reduce the Na 2 0 content, between 0.01 and 4% in
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peso, preferentemente por debajo del 0,1%. Cuando se desea incorporar la zeolita a la matriz, esta se lleva a cabo de la forma siguiente:SUBSTITUTED SHEET weight, preferably below 0.1%. When it is desired to incorporate the zeolite into the matrix, it is carried out as follows:
Esta zeolita se dispersó en H20 (relación L/S = 2 en peso), aumentándose con posterioridad la relación L/S a cuatro. En una vasija aparte se formó una suspensión en caolín, (pudiendo este ser tratado o no previamente con H3P04), silicato sódico y agua. La suspensión se neutralizó con H2S04 y sulfato de Al. A esta suspensión, se añadió la zeolita en un porcentaje que puede oscilar entre 15 y 40% en peso. En una etapa previa y tras ajustar el contenido de agua- solidos con el fin de optimizar la etapa de atomizado, la suspensión resultante se atomizó (spray driying) a la distribución de tamaños antes dicho.This zeolite was dispersed in H 2 0 (L / S ratio = 2 by weight), subsequently increasing the L / S ratio to four. In a separate vessel a suspension was formed in kaolin, (this may or may not be previously treated with H 3 P0 4 ), sodium silicate and water. The suspension was neutralized with H 2 S0 4 and Al sulfate. To this suspension, the zeolite was added in a percentage that can range between 15 and 40% by weight. At a previous stage and after adjusting the water-solids content in order to optimize the atomizing stage, the resulting suspension was atomized (spray driying) to the size distribution mentioned above.
Ejemplo 2Example 2
En este ejemplo se describe el tratamiento de modificación de la zeolita del Ejemplo 1.This example describes the zeolite modification treatment of Example 1.
Se prepara una solución de ácido fosfórico, disolviendo 0.446g de H3P04 (85%) en 120g de H20, siendo el PH final de la disolución de 1.8. A esta disolución se añadieron 12 g. de la zeolita descrita en el ejemplo 1. La suspensión resultante se calentó a 100°C durante 2 h. Las características de la zeolita resultante se dan en la Tabla 1.A solution of phosphoric acid is prepared, dissolving 0.446g of H 3 P0 4 (85%) in 120g of H 2 0, the final pH of the solution being 1.8. To this solution was added 12 g. of the zeolite described in example 1. The resulting suspension was heated at 100 ° C for 2 h. The characteristics of the resulting zeolite are given in Table 1.
Ejemplo 3:Example 3:
En este ejemplo se describe la preparación de zeolitas con distinta cantidad de fósforo.This example describes the preparation of zeolites with different amounts of phosphorus.
Se prepararon muestras de zeolita siguiendo el mismo procedimiento que en el ejemplo 1 y 2, pero con cantidades de H3P04 (85%) en H20 de: 0.22, 1.78, 2.67 gr., manteniendo las cantidades de H204 y zeolita idénticas a las del ejemplo 2. Las características de las zeolitas finales se dan en la Tabla 1.Zeolite samples were prepared following the same procedure as in example 1 and 2, but with amounts of H 3 P0 4 (85%) in H 2 0 of: 0.22, 1.78, 2.67 gr., Maintaining the amounts of H 2 0 4 and zeolite identical to those of example 2. The characteristics of the final zeolites are given in Table 1.
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SUBSTITUTED SHEET
Tabla 1Table 1
Nueatraa Descripción Si/Al CU. Criat rea 8 meao 8 microNueatraa Description Yes / Al CU. Criat rea 8 meao 8 micro
(A) (%) «7gr m2/gr «7gr(A) (%) «7gr m 2 / gr« 7gr
2.7 24.48 95% 676 103 5662.7 24.48 95% 676 103 566
EjemAhem
Con se pr
pero 600° trat
finalWith se pr but 600 ° trat final
UX81P0 1% PUX81P0 1% P
Ejemplo 6Example 6
Influencia de la naturaleza del reactivo de fósforo. Para demostrar el efecto del reactivo de fósforo, se prepararon a partir de una zeolita NaY de relación Si/Al = 2.5 dos muestras siguiendo los ejemplos 1 y 2, pero utilizando durante el tratamiento con el reactivo de fósforo, ácido fosfórico o fosforoso, cuyas características se dan en la Tabla 3.Influence of the nature of the phosphorus reagent. To demonstrate the effect of the phosphorus reagent, two samples were prepared from a NaY zeolite of Si / Al ratio = 2.5 two samples following examples 1 and 2, but using during the treatment with the phosphorus reagent, phosphoric or phosphorous acid, whose characteristics are given in Table 3.
Tabla 3Table 3
MUESTRA DESCRIPCIÓN Si/Al CU. CRISTSAMPLE DESCRIPTION Yes / Al CU. CRIST
(A) (*)(TO) (*)
USYOOA 550βC-5h 24.49 101 vapor de aguaUSYOOA 550 β C-5h 24.49 101 water vapor
UYA1P0 1% P (H3P04)UYA1P0 1% P (H 3 P0 4 )
Y1PP0A 1% P (H3PO3)Y1PP0A 1% P (H 3 PO 3 )
USYOAS USYOOA
vapor 750βC-5hUSYOAS USYOOA steam 750 β C-5h
UYA1PS USA1P0 24.29 68 vapor 750°C-5hUYA1PS USA1P0 24.29 68 steam 750 ° C-5h
Y1PPAS Y1PP0A 24.27 51 vapor 750βC-5hY1PPAS Y1PP0A 24.27 51 steam 750 β C-5h
Ejemplo 7Example 7
En este ejemplo se presenta el efecto del tratamiento descrito en el ejemplo 2 utilizando una Beta con relación Si/Al=13 como zeolita de partida, tratada con vapor a 750°C durante 5 horas.In this example, the treatment effect described in Example 2 is presented using a Beta with Si / Al ratio = 13 as the starting zeolite, treated with steam at 750 ° C for 5 hours.
HOJA SUSTITUIDA
Ejemplo 8SUBSTITUTED SHEET Example 8
En este ejemplo se demuestra el efecto catalítico de los tratamientos con fosfórico durante el craqueo catalítico de gasoil, comparando la actividad y selectividad de los catalizadores preparados en los ejemplos 1-7 en un reactor MAT utilizando un gasoil de vacío cuyas características se dan en la tabla 4. Las condiciones experimentales fueron:This example demonstrates the catalytic effect of phosphoric treatments during the catalytic cracking of diesel oil, comparing the activity and selectivity of the catalysts prepared in Examples 1-7 in a MAT reactor using a vacuum diesel oil whose characteristics are given in the Table 4. The experimental conditions were:
Desactivación con vapor 750°C, 90% vapor en aire durante 5 horas.Deactivation with steam 750 ° C, 90% steam in air for 5 hours.
Temperatura de Reacción: 482°C.Reaction Temperature: 482 ° C.
Relación Catalizador (referido a zeolita)/alimentación = 0.7-2.0 g.g"1 Catalyst Ratio (referred to zeolite) / feed = 0.7-2.0 gg "1
Tiempo de reacción = 75 segundosReaction time = 75 seconds
Tabla 4Table 4
Características del gasoilDiesel characteristics
NITRÓGENO 125 ppm AZUFRE 1,7%NITROGEN 125 ppm SULFUR 1.7%
PUNTO DE ANILINA 76,5%ANILINA POINT 76.5%
DENSIDAD 60βC 0,859 g/ccDENSITY 60 β C 0.859 g / cc
DENSIDAD 15βC 0,888 g/ccDENSITY 15 β C 0.888 g / cc
PESO MOLECULAR MEDIO 383 383 ÍNDICE DE REFRACCIÓN A 60° 1.48254MIDDLE MOLECULAR WEIGHT 383 383 60 ° REFRACTION INDEX 1,485,254
VOP K = 11.90VOP K = 11.90
% CARBONO AROMÁTICO 19,22%% AROMATIC CARBON 19.22%
% CARBONO EN NAFTENOS 16.30%% CARBON IN NAFTENS 16.30%
CARBONO EN PARAFINAS 64,48%CARBON IN PARFINES 64.48%
HOJA SUSTITUIDA
SUBSTITUTED SHEET
Los resultados de conversión en las mismas condiciones experimentales, para diferentes catalizadores, y los rendimientos a los distintos productos obtenidos al mismo nivel de conversión se comparan en Tabla 5, 6 y 7. De éstas se deduce que el tratamiento con fosfórico produce un aumento en la actividad y selectividad del catalizador, produciendo menosgas seco y coque. Un óptimo de actividad se obtiene con la muestra conteniendo entre 1-4% en peso de P sobre la Zeolita. Además se observa también como se obtienen mejores resultados partiendo de una zeolita activada a T > 500°C. Finalmente el ácido fosfórico es más adecuado que el fosforoso para producir el efecto deseado, y además el efecto positivo se observa independientemente de la relación Si/Al de la zeolita NaY de partida.The conversion results in the same experimental conditions, for different catalysts, and the yields to the different products obtained at the same conversion level are compared in Table 5, 6 and 7. From these it follows that phosphoric treatment produces an increase in the activity and selectivity of the catalyst, producing dry and coke losses. An optimal activity is obtained with the sample containing between 1-4% by weight of P on the Zeolite. In addition, it is also observed how better results are obtained from an activated zeolite at T> 500 ° C. Finally, phosphoric acid is more suitable than phosphorous to produce the desired effect, and in addition the positive effect is observed independently of the Si / Al ratio of the starting NaY zeolite.
HOJA SUSTITUIDA
ω ω J tπ o en o HSUBSTITUTED SHEET ω ω J tπ or in or H
<j\ O m<j \ O m
Tabla 5Table 5
* Conversión se define como la suma de gasolina + diesel + coque + gases ** Relación Si/Al de la zeolita NaY de partida = 2.8. *** Relación Si/Al de la zeolita NaY de partida = 2.4.* Conversion is defined as the sum of gasoline + diesel + coke + gases ** Si / Al ratio of the starting NaY zeolite = 2.8. *** Si / Al ratio of the starting NaY zeolite = 2.4.
Tabla 6Table 6
CATALIZADORESCATALYSTS
USY50S US51PSUSY50S US51PS
Conversión* 84.20 84.11 (cat/oil - 2.0 g/g"1 Conversion * 84.20 84.11 (cat / oil - 2.0 g / g " 1
Rendimientoperformance
(a 85 % conversión)(at 85% conversion)
USYX8S* UX81PSUSYX8S * UX81PS
Conversión 84.94 82.13Conversion 84.94 82.13
(cat/oil - 2.0 g/g'1)(cat / oil - 2.0 g / g ' 1 )
Rendimientoperformance
(a 85% conversión)(at 85% conversion)
Diesel 14.82 15.70Diesel 14.82 15.70
Gasolina 48.85 49.58Gasoline 48.85 49.58
Gases 17.00 16.00Gases 17.00 16.00
Coke 4.36 3.86Coke 4.36 3.86
Cl + C2 1.13 0.97Cl + C2 1.13 0.97
HOJA SUSTITUIDA
* Conversión se define como la suma de gasolina + diesel + coque + gases ** Relación Si/Al de la zeolita NaY de partida = 2.4SUBSTITUTED SHEET * Conversion is defined as the sum of gasoline + diese l + coke + gases ** Si / Al ratio of the starting NaY zeolite = 2.4
Tabla 7Table 7
CATALIZADORCATALYST
Conversión se define como la suma de gas + gasolina + diesel + coqueConversion is defined as the sum of gas + gasoline + diesel + coke
Ejemplo 9Example 9
En este ejemplo se describe la preparación y actividad catalítica de un catalizador en el que la zeolita es una NHUSY, impregnada con P0H. Para ello, se preparó la zeolita USYOO tal y como se describe en el ejemplo 1. A continuación, ésta se intercambió con una disolución acuosa 2-5M de NH4C1, con una relación en peso líquido/sólido = 10, a 802C durante 30 una hora. Después se filtró y lavó con agua desionizada, y se secó a 1000C. Una parte de la muestra resultante (12 g. de zeolita) This example describes the preparation and catalytic activity of a catalyst in which the zeolite is an NHUSY, impregnated with P0H. For this, the USYOO zeolite was prepared as described in example 1. Next, it was exchanged with a 2-5M aqueous solution of NH4C1, with a liquid / solid weight ratio = 10, at 802C for 30 years. time. It was then filtered and washed with deionized water, and dried at 100 ° C. A part of the resulting sample (12 g. Of zeolite )
HOJA SUSTITUIDA
se impregnó con una disolución acuosa de P04H3 (0,446 g. de P0 4 H 3,SUBSTITUTED SHEET is a d i mpregnó aqueous isolución H 3 P0 4 (0.446 g. d e P0 4 H 3,
85%, en 120 g. de H20). 8 5%, in 120 g. of H 2 0).
El catalizador final conteniendo la zeolita preparada de la forma descrita se equilibró por tratamiento 75SQC durante 5 horas, y su actividad para gasoil, y las condiciones descritas en el 5 resultados obtenidos se dan en la tabla 8. The c to rt l hoisted d or inal f containing the prepared zeolite d o f f orm d written equilibrated by treating 75 SQC d uring 5 hours, and its activity for oil, and the conditions described in the five results they are given in table 8.
Tabla 8 CATALIZADORTable 8 CATALYST
UYI1PSUYI1PS
Conversión *Conversion *
(cat5/oil*=2.0 g.g*1) 90.05(cat5 / oil * = 2.0 gg * 1 ) 90.05
Rendimientoperformance
(a 85% conversión)(at 85% conversion)
Diesel 13.5Diesel 13.5
Gasolina 54.0Gasoline 54.0
Gases 13.8 Coque 3.2
Gases 13.8 Coke 3.2
* Conversión se define como la suma de gas + gasolina + diesel + coque* Conversion is defined as the sum of gas + gasoline + diesel + coke
HOJA SUSTITUIDA
SUBSTITUTED SHEET
Claims
1.- PROCEDIMIENTO DE PREPARACIÓN DE CATALIZADORES A BASE DE ZEOLITAS TRATADAS CON ACIDO FOSFÓRICO, ÚTILES PARA SU APLICACIÓN EN UNIDADES DE CRAQUEO CATALÍTICO, que son más activos y producen menos gas seco y coque, que otros que parten de zeolitas que no han sido sometidas a dicho tratamiento con fosfórico, caracterizado porque la zeolita se dispersa en una solución de ácido fosfórico en agua, con contenido en P/zeolita en el rango 0,5-6% en peso, preferentemente entre 0,5 y 4%, a una temperatura de tratamiento comprendida entre 20 y 100°C y con un tiempo de tratamiento oscilando entre 1 y 16 horas.1.- PROCEDURE FOR PREPARATION OF CATALYZERS BASED ON ZEOLITES TREATED WITH PHOSPHORIC ACID, USEFUL FOR APPLICATION IN CATALYTIC DRIVING UNITS, which are more active and produce less dry gas and coke, than others that start from zeolites that have not been subjected to said phosphoric treatment, characterized in that the zeolite is dispersed in a solution of phosphoric acid in water, containing P / zeolite in the range 0.5-6% by weight, preferably between 0.5 and 4%, at a treatment temperature between 20 and 100 ° C and with a treatment time ranging from 1 to 16 hours.
2.- Procedimiento según reivindicación 1, caracterizado porque el contenido en Na20 de la zeolita, antes de impregnar con fosfórico, está comprendido entre 0,01 y 4,00 % en peso.2. Method according to claim 1, characterized in that the Na 2 0 content of the zeolite, before impregnating with phosphoric, is comprised between 0.01 and 4.00% by weight.
3.- Procedimiento según reivindicaciones 1 y 2, caracterizado porque las zeolitas pueden estar en su forma acida o amónica cuando se lleva a cabo la impregnación con P04H3.3. Method according to claims 1 and 2, characterized in that the zeolites can be in their acid or ammonium form when the impregnation with P0 4 H 3 is carried out .
4.- Procedimiento según reivindicaciones 1, 2 y 3, caracterizado porque se parte de una zeolita del tipo Y, Beta, ZSM-20, Ofretita, Omega, MCM, ZSM-5.4. Method according to claims 1, 2 and 3, characterized in that it is based on a zeolite of type Y, Beta, ZSM-20, Ofretita, Omega, MCM, ZSM-5.
5.- Procedimiento según reivindicaciones 1, 2, 3 y 4, caracterizado porque en el caso de la zeolita Y, obtenida "in situ" sobre un metacaolín, se desaluminiza previamente por calcinación en presencia de vapor, a temperaturas en el rango 500-700°C, y preferentemente entre 550 y 650βC.5. Method according to claims 1, 2, 3 and 4, characterized in that in the case of zeolite Y, obtained "in situ" on a metacaolin, it is previously de-illuminated by calcination in the presence of steam, at temperatures in the range 500- 700 ° C, and preferably between 550 and 650 β C.
6.- Procedimiento según reivindicaciones anteriores, caracterizado porque durante y/o en una etapa posterior al tratamiento con H3P04 se puede introducir tierras raras en la zeolita modificada.6. Method according to previous claims, characterized in that during and / or at a stage subsequent to treatment with H 3 P0 4 , rare earths can be introduced into the modified zeolite.
HOJA SUSTITUIDA SUBSTITUTED SHEET
7.-Procedimiento según reivindicaciones anteriores, caracterizado porque la zeolita modificada con H3P04 en suspensión acuosa se incorpora a un precursor de una matriz, del tipo caolín, sílice y/o A1203 , que en una etapa posterior es atomizada (spray drying) obteniéndose el catalizador final en tamaño y formas adecuadas para uso en unidades de craqueo catalítico de gasoil de vacío o fracciones más pesadas.7. Method according to previous claims, characterized in that the zeolite modified with H 3 P0 4 in aqueous suspension is incorporated into a precursor of a matrix, of the type kaolin, silica and / or A1 2 0 3 , which at a later stage is atomized (spray drying) obtaining the final catalyst in size and shapes suitable for use in catalytic cracking units of vacuum diesel or heavier fractions.
HOJA SUSTITUIDA SUBSTITUTED SHEET
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ESP9300560 | 1993-03-17 | ||
| ES9300560A ES2076068B1 (en) | 1993-03-17 | 1993-03-17 | PROCEDURE FOR PREPARING CATALYZERS BASED ON ZEOLITES TREATED WITH PHOSPHORIC ACID, USEFUL FOR APPLICATION IN CATALYTIC CRACHING UNITS. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1994021378A1 true WO1994021378A1 (en) | 1994-09-29 |
Family
ID=8281163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/ES1994/000028 WO1994021378A1 (en) | 1993-03-17 | 1994-03-17 | Process for the preparation of catalysts based on zeolites treated with phosphoric acid, useful for catalytic cracking units |
Country Status (2)
| Country | Link |
|---|---|
| ES (1) | ES2076068B1 (en) |
| WO (1) | WO1994021378A1 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0741608A1 (en) * | 1994-02-02 | 1996-11-13 | Mobil Oil Corporation | Improved mcm-22 catalyst composition |
| WO2007043742A1 (en) * | 2005-10-07 | 2007-04-19 | Sk Energy Co., Ltd. | Hydrothermally stable microporous molecular sieve catalyst and preparation method thereof |
| EP1797951A1 (en) * | 2005-12-15 | 2007-06-20 | Total Petrochemicals Research Feluy | Catalytic cracking catalyst additive |
| EP1892040A1 (en) * | 2005-05-31 | 2008-02-27 | China Petroleum & Chemical Corporation | Modifed zeolites beta |
| CN100406416C (en) * | 2006-07-03 | 2008-07-30 | 中国石油化工集团公司 | Method of preparing ethylene and propylene and catalyst used in said method |
| EP2527035A1 (en) * | 2010-01-20 | 2012-11-28 | JX Nippon Oil & Energy Corporation | Catalyst for production of hydrocarbons and process for production of hydrocarbons |
| CN104556122A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Molecular sieve supported nanocrystal Y-type molecular sieve and synthesis method thereof |
| US9441167B2 (en) | 2013-12-19 | 2016-09-13 | Basf Corporation | Boron oxide in FCC processes |
| US9796932B2 (en) | 2013-12-19 | 2017-10-24 | Basf Corporation | FCC catalyst compositions containing boron oxide and phosphorus |
| US9895680B2 (en) | 2013-12-19 | 2018-02-20 | Basf Corporation | FCC catalyst compositions containing boron oxide |
| US10086367B2 (en) | 2013-12-19 | 2018-10-02 | Basf Corporation | Phosphorus-containing FCC catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2285176A1 (en) * | 1974-09-23 | 1976-04-16 | Mobil Oil | CATALYST CONTAINING PHOSPHORUS, ITS METHOD OF PREPARATION AND ITS USE |
| EP0095364A2 (en) * | 1982-05-24 | 1983-11-30 | Exxon Research And Engineering Company | Phosphorus-containing catalyst and catalytic cracking process utilizing the same |
| EP0252761A2 (en) * | 1986-07-11 | 1988-01-13 | Exxon Research And Engineering Company | Hydrocarbon cracking catalysts and processes utilizing the same |
| EP0397183A1 (en) * | 1989-05-12 | 1990-11-14 | W.R. Grace & Co.-Conn. | Catalytic compositions |
-
1993
- 1993-03-17 ES ES9300560A patent/ES2076068B1/en not_active Expired - Lifetime
-
1994
- 1994-03-17 WO PCT/ES1994/000028 patent/WO1994021378A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2285176A1 (en) * | 1974-09-23 | 1976-04-16 | Mobil Oil | CATALYST CONTAINING PHOSPHORUS, ITS METHOD OF PREPARATION AND ITS USE |
| EP0095364A2 (en) * | 1982-05-24 | 1983-11-30 | Exxon Research And Engineering Company | Phosphorus-containing catalyst and catalytic cracking process utilizing the same |
| EP0252761A2 (en) * | 1986-07-11 | 1988-01-13 | Exxon Research And Engineering Company | Hydrocarbon cracking catalysts and processes utilizing the same |
| EP0397183A1 (en) * | 1989-05-12 | 1990-11-14 | W.R. Grace & Co.-Conn. | Catalytic compositions |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0741608A1 (en) * | 1994-02-02 | 1996-11-13 | Mobil Oil Corporation | Improved mcm-22 catalyst composition |
| EP0741608A4 (en) * | 1994-02-02 | 1998-01-07 | Mobil Oil Corp | Improved mcm-22 catalyst composition |
| EP1892040A1 (en) * | 2005-05-31 | 2008-02-27 | China Petroleum & Chemical Corporation | Modifed zeolites beta |
| EP1892040A4 (en) * | 2005-05-31 | 2008-12-24 | China Petroleum & Chemical | Modifed zeolites beta |
| WO2007043742A1 (en) * | 2005-10-07 | 2007-04-19 | Sk Energy Co., Ltd. | Hydrothermally stable microporous molecular sieve catalyst and preparation method thereof |
| EP1797951A1 (en) * | 2005-12-15 | 2007-06-20 | Total Petrochemicals Research Feluy | Catalytic cracking catalyst additive |
| WO2007068734A1 (en) * | 2005-12-15 | 2007-06-21 | Total Petrochemicals Research Feluy | Catalytic cracking |
| CN100406416C (en) * | 2006-07-03 | 2008-07-30 | 中国石油化工集团公司 | Method of preparing ethylene and propylene and catalyst used in said method |
| EP2527035A1 (en) * | 2010-01-20 | 2012-11-28 | JX Nippon Oil & Energy Corporation | Catalyst for production of hydrocarbons and process for production of hydrocarbons |
| EP2527035A4 (en) * | 2010-01-20 | 2014-02-26 | Jx Nippon Oil & Energy Corp | Catalyst for production of hydrocarbons and process for production of hydrocarbons |
| US9827558B2 (en) | 2010-01-20 | 2017-11-28 | Jx Nippon Oil & Energy Corporation | Catalyst for production of hydrocarbons and method of producing hydrocarbons |
| CN104556122A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Molecular sieve supported nanocrystal Y-type molecular sieve and synthesis method thereof |
| US9441167B2 (en) | 2013-12-19 | 2016-09-13 | Basf Corporation | Boron oxide in FCC processes |
| US9796932B2 (en) | 2013-12-19 | 2017-10-24 | Basf Corporation | FCC catalyst compositions containing boron oxide and phosphorus |
| US9895680B2 (en) | 2013-12-19 | 2018-02-20 | Basf Corporation | FCC catalyst compositions containing boron oxide |
| US10086367B2 (en) | 2013-12-19 | 2018-10-02 | Basf Corporation | Phosphorus-containing FCC catalyst |
| US10525451B2 (en) | 2013-12-19 | 2020-01-07 | Basf Corporation | FCC catalyst compositions containing boron oxide |
| US10683458B2 (en) | 2013-12-19 | 2020-06-16 | Basf Corporation | FCC catalyst compositions containing boron oxide and phosphorus |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2076068A1 (en) | 1995-10-16 |
| ES2076068B1 (en) | 1996-06-16 |
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