CATALYSTS COMPRISING SILICA SUPPORTED ON A BOEHMITE-LIKE SURFACE, THEIR PREPARATION AND USE

Abstract: Useful cracking catalysts and catalyst supports compris­ ing silica supported on a boehmite-like surface are prepared by compositing particles of silica or hydrated silica with particles of porous boehmite and subjecting the resulting composite to high temperature steaming at a temperature of at least about 600°C for a time sufficient to disperse at least a portion of the silica over the boehmite surface as the boehmite converts to γ-­ Al₂O₃. The silica wets, spreads out and reacts with the sur­ face hydroxyl groups of the transforming boehmite.

Description: This invention relates to catalysts and catalyst supports comprising silica supported on a boehmite like surface, their preparation and use. More particularly, this invention relates to cracking catalysts and catalyst supports comprising silica supported on a boehmite like surface which are prepared by compositing particles of silica or hydrated silica with particles of boehmite or pseudo-boehmite and subjecting said composite to high temperature steaming at a temperature of at least 500 o C for a time sufficient for at least a portion of said silica to disperse over and react with the surface of the boehmite as it converts to gamma alumina. The use of silica-alumina composites as catalysts and as catalyst support materials is well known to those skilled in the art. These catalysts are prepared in many different ways such as co-precipitation, various co-gel techniques, by contacting alumina with various silica precursor salts such as organo-silanes, including alkoxy silanes followed by calcination of the so-formed composite to produce the desired silica-alumina material. Representative of these various preparative techniques are the following US patent specifications: U.S-A-4,440,872; U.S-A-3,671,432; U.S-A-3,668,151; U.S-A-3,182,012; U.S-A-2,830,960; U.S-A-2,640,802; U.S-A-3,151,091; U.S-A-2,394,796; U.S-A-2,493,896; U.S-A-4,172,809; U.S-A-2,579,123; U.S-A-3,502,595; U.S-A-4,038,337; and U.S-A-4,013,589. US-A-4305810 describes and claims a process for reforming a naphtha fraction which comprises contacting the naphtha fraction under reforming conditions and in the presence of hydrogen with a reforming catalyst comprising a modified alumina support, derived from an alumina precursor, having distributed thereon from about 0.3 to about 1.0 weight percent platinum, from about 0.3 to about 1.0 weight percent rhenium, and from about 0.5 to about 2.0 weight percent chloride, wherein the modified alumina support precursor comprises at least about 75 (preferably at least 80) weight percent boehmite, having an average crystallite diameter no greater than about 60 Angstroms (6 nm), and the modified alumina support additionally comprises from about 0.25 to about 5.0 weight percent silica, the silica having been added to the boehmite-containing alumina as an aqueous colloidal dispersion. The said modified alumina support is made, in some embodiments, by mulling a thick paste of water and a boehmite-containing alumina support material with a low-sodium colloidal silica dispersion. The mulled mixture is extruded, dried and calcined in dry air for 3 hours or thereabouts at a temperature of 950°F (510°C). This document provides test data on surface area stability of the thus-made modified alumina support. The test data are obtained by maintaining samples of the modified alumina support, or reforming catalyst compositions made therefrom, at 1100°F (593.3°C) in flowing air containing 1.4 to 1.5 psia (9.65 to 10.34 kPa) water to accelerate surface area losses. The present invention provides a composition comprising silica and gamma-alumina and including an amorphous disordered alumina phase (which is an intermediate of boehmite and gamma-alumina) supported on the external surface of the gamma-alumina and silica supported on said amorphous disordered alumina phase, said composition being obtained by a method comprising the steps of: (a) mixing particles of silica or of an insoluble silica precursor convertible to silica upon steaming at an elevated temperature in an inert atmosphere with particles of boehmite, and (b) subjecting the resulting uncalcined mixture to a temperature of at least 600°C in an inert atmosphere and in the presence of steam to form the said composition, the amount of silica or silica precursor being sufficient to provide from 1 to 50 w % silica (eg. 1-25 w %) based on the total weight of the composition. The silica may be in the form of discrete particles of bulk silica. Preferably, the silica is non-crystalline and is supported in discrete areas on said amorphous disordered alumina phase. The said boehmite may be porous. The invention also provides a process for cracking a hydrocarbon feed which comprises contacting said feed and a catalyst at elevated temperature to crack at least a portion of said feed, wherein the catalyst comprises a composition as described. The invention further provides a process for cracking a hydrocarbon feed which comprises contacting said feed and a catalyst at elevated temperature to crack at least a portion of said feed, wherein the catalyst comprises either the novel composition as herein described or a composition made by the method as herein described. In most embodiments of the composition of this invention, the silica spreads out, wets and disperses over at least a portion of the boehmite surface. In a preferred embodiment, the boehmite will be porous possessing both external and internal surfaces so that the silica will spread out, wet and disperse over at least a portion of the combined external and internal surface of the porous boehmite particles. As the composite of boehmite and silica is steamed, the boehmite converts to a transitional alumina phase. At the same time the silica reacts with the surface hydroxyls of the converting boehmite thereby stabilizing or "freezing" the surface of the converting boehmite in a transitional state, while the bulk of the boehmite converts to gamma alumina. This transitional state is a boehmite-like surface phase (hereinafter referred to as a boehmite-like phase) having an amorphous, disordered structure which is different from both boehmite and gamma alumina. Thus the compositions produced by the method of this invention comprise silica supported on a boehmite like surface phase which, in turn, is supported on bulk alumina. These compositions are different from similar types of compositions formed by (a) compositing particles of silica with particles of alumina and steaming the composite at high temperatures or (b) calcining composites of silica and boehmite. A number of different compositions comprising silica supported on the surface of a boehmite like surface phase may be prepared employing the process of this invention, some of which are believed to be novel. The resulting composition will be a function of (i) the time, temperature and water content of the steaming treatment; (ii) the relative particle sizes of the silica and boehmite; (iii) the amount of silica employed or composited with the boehmite; (iv) the porosity of the boehmite, and (v) the nature of the silica or silica precursor. The different types of composition which can be prepared employing the process of this invention are set forth below. (a) A composition comprising discrete islands or areas of silica in a non-crystalline form supported on a boehmite like phase present on the external surface of the alumina which compositions exhibits properties substantially different from those of bulk crystalline or non-crystalline silica, boehmite, and alumina. (b) Discrete particles of silica supported on a boehmite like phase present on the external surface of the alumina which particles exhibit properties of bulk silica, so that the resulting composite exhibits, in part, properties of both bulk crystalline or non-crystalline silica and bulk alumina. (c) A composition wherein the surface of the (so-formed) alumina is covered completely or in part with silica in a non-crystalline form supported on a boehmite like surface phase on alumina which exhibits properties different from either bulk crystalline or non-crystalline silica, bulk alumina, or silica reacted with a transition alumina phase formed from calcined boehmite. (d) Compositions wherein discrete islands or areas of silica exhibiting properties of bulk crystalline or non-crystalline silica are supported on a layer of silica in non-crystalline form which is supported on and reacted with boehmite-like surface phase which, in turn, is supported on the bulk alumina, so that the composite exhibits properties of both bulk crystalline or non-crystalline silica and that of non-crystalline silica supported on a boehmite like surface phase supported on alumina. Thus, it will be appreciated that the compositions that can be prepared by the process of this invention will range from alumina whose surface is partially covered with and which supports discrete areas or islands of silica in a non-crystalline form supported on a transitional, boehmite like surface phase, so that the composition exhibits properties of both alumina and a non-crystalline silica, to alumina whose surface is partly or completely covered with silica in a non-crystalline form supported on a boehmite-like surface phase, in turn, supported on the alumina, to silica in crystalline or non-crystalline bulk form supported on surface silica in a non-crystalline form supported on a boehmite like surface phase which, in turn, is supported on alumina, so that the composition exhibits the properties of bulk silica and the non-crystalline silica surface phase reacted with the boehmite-like surface phase.Further, the compositions of this invention will generally have considerably higher surface areas than prior art compositions. The compositions of this invention are useful as cracking catalysts for processes such as gas oil cat cracking, heavy ends cat cracking, resid cat cracking, acid hydrocracking, etc. as well as being useful as catalyst support materials. Further, because the compositions of this invention are resistant to steam under conditions of high temperature, one may, if desired, have steam present in a reaction or cracking zone employing these compositions. DETAILED DESCRIPTION Those skilled in the art know that boehmite is a form of hydrated alumina described as aluminum oxide monohydroxide which can be represented by the simple formula A100H. Boehmites also have relatively high surface areas. Commercially available boehmites generally have surface areas of about 300-500 m²/g (BET). These materials are generally relatively porous and, consequently, their measured surface areas include both the exterior surface and the internal pore surface. When boehmite is steamed at temperatures in excess of about 500 o C, it undergoes a phase change first to a pseudo-boehmite and then to gamma alumina which results in a reduction of the surface area of from about 300-500 m²/g to about 200-300 m²/g. If the temperature is greater than 800 o C the formation of ϑ-Al₂O₃ or a mixture of γ-Al₂O₃ and γ-Al₂O₃ occurs with a concommitant surface area reduction to from about 1-100 m²/g. In marked contrast, in the process of this invention the surface area of the final, silica-containing composition will generally range from about 180-220 m²/g when the surface area of the starting boehmite material is about 300-500 m²/g. In the process and compositions of this invention, boehmite refers to the bulk structure and is meant to include pseudo-boehmite and mixture of boehmite with pseudo-boehmite. In the process of this invention, the silica reacts with the surface of the boehmite as it is undergoing phase transition, thereby "freezing" the changing surface in the form of a boehmite-like phase reacted with silica which, in turn, is supported on alumina. The so-formed boehmite-like surface phase has an amorphous, disordered structure unlike either boehmite, pseudo boehmite or alumina. Consequently, even though the bulk boehmite converts to alumina during the high temperature steaming treatment, the surface of the so-formed alumina or, more precisely, those portions of the surface of the so-formed alumina underlying and supporting the silica, will be a boehmite like phase stabilized or "frozen" in that transitional state due to the reaction of the silica with the surface of the boehmite as the boehmite phase changes through a transitional alumina to gamma alumina. It is the formation of this silica-locked, boehmite-like surface phase that prevents the boehmite from desurfacing down to about 100 or even 1 m²/g, which will occur without the presence of the silica in a high temperature steaming environment. As will be shown in the Examples below, the compositions of this invention are different from compositions formed by high temperature steaming a composite of particulate silica and a conventional alumina, such as gamma alumina. The amount of steam employed in forming the compositions of this invention may vary over a wide range, i.e., from less than about 1% to more than 90% of the non-reducing environment. Compositions of this invention have been made employing as little as 3% steam to as much as 90% steam. In general, the more steam that is employed the faster will be the reaction of the silica with the boehmite surface. While not wishing to be held to any particular theory, those skilled in the art know that boehmite is a particular form of hydrated alumina which loses water of hydration at elevated temperatures. Boehmite has a relatively large amount of surface hydroxyl groups. It is believed that these surface hydroxyls on the boehmite react with the silica with the formation of oxygen-silicon bonds. Thus, during the process of this invention, the silica reacts with the surface of the transforming boehmite to form a surface phase complex. This surface phase complex is non-crystalline in form and exhibits properties substantially different from either bulk silica, bulk tungsten oxide, bulk boehmite or the bulk alumina formed from high temperature steaming on the boehmite. In general, the loading level of the silica wil be such that the amount of silica will range from about 1-50 wt.% of the total composition and more generally from about 1-25 wt.% of the total composition. Preferably the amount of silica will be present in an amount of from about 1 to 20 wt.% of the total composition, more preferably from about 2-10 wt.% and most preferably from about 4-6 wt.%. As previously stated, boehmites are generally porous materials. That is, there are a multitude of pores and channels from the exterior of a discrete, macroscopic particle to the interior of the particle. Consequently, the surface of a boehmite particle includes all the pores and channels of said boehmite and their surface area as measured by nitrogen gas adsorption according to BET theory. There is much more surface in the interior of such a discrete, macroscopic particle of boehmite than on its exterior surface. In many cases, the external surface is less than 2% of the total surface area. In this application, "surface" is used in such an art-recognized fashion and, unless expressly stated otherwise, is not to be restricted to the physical exterior surface of macroscopic particles to boehmite. By way of example, Davison Chemical Automotive grade of boehmite has an average particle size, expressed as the diameter, of about 44 microns (44µm). The average diameter of the channels or pores after calcining this alumina at 600 o C in air is from about 70-75 Å (7.0-7.5nm). The average diameter of the channels or pores of the boehmite are about 40 Å (4.0nm) diameter. The average particle size of, for example, colloidal silica is about 200 Å (20.0nm). Colloidal silica comprises colloidal size particles of silica in the form of an aqueous slurry. These materials are available, for example, from DuPont as "Ludox"® slurries. Thus, if one mixes a colloidal slurry of silica with an aqueous slurry of Davison boehmite with sufficient water present to completely wet the pores of the boehmite, one will obtain, on drying, a composite which one can ideally represent as large spheres of boehmite having holes and channels dispersed there through of a diameter of less than 70-75 Å (7 to 7.5 nm), with spheres of silica on the external surface of said large particle of boehmite, wherein the silica spheres or hydrated silica spheres have an average diameter of about 200Å (20 nm). Thus, in this particular type of situation, the particle size of the silica is too large to fit into the pores and channels of the boehmite. Therefore, the silica particles are present on the exterior surface of the boehmite. The amount of silica present can be such that each particle of silica is ideally considerably separated from the next nearest particle of silica or so much silica can be present that the particles of silica completely cover the surface of the boehmite, or even form multilayers on the exterior surface of the boehmite particles. In this composite which is merely dried, but not steamed, the silica has not reacted with the surface hydroxyls of the boehmite in the vicinity of the particles. One can readily envision that when such a composite is steamed, what will initially happen will be that the silica will react with the surface hydroxyls present on the exterior surface of the boehmite in the vicinity of contact between each particle of silica and the boehmite surface at the same time that the boehmite is phase changing to, for example, γ-Al₂O₃. Thus, one can, under the right conditions of loading and particle size difference, obtain a composite comprising discrete particles of silica a portion of which has reacted with the surface hydroxyls of the boehmite and is bound therefore to the boehmite like phase formed on the exterior surface of the so-formed alumina. Such a composite will exhibit properties of both bulk alumina and bulk crystalline or non-crystalline silica. At this point, if the steaming treatment continues the silica will start to spread out over the surface of the phase-changing, desurfacing boehmite essentially in the form of a monolayer or surface phase complex, including penetration into the internal pores and channels of the alumina. One can envision that in the initial phases of this wetting, dispersing and reacting of the silica with the surface hydroxyls of the boehmite, that one will reach a point where particles of bulk silica rest or are supported on an island of silica on the alumina formed from the boehmite in the form of a surface phase complex such that if the steaming treatment were to be stopped at this point one would have a composition exhibiting the properties of bulk alumina, boehmite or pseudo-boehmite, bulk crystalline or non-crystalline silica and a surface phase silica complex which has properties different from bulk crystalline or non-crystalline silica, boehmite and bulk alumina. If the steaming treatment is continued, then all of the silica will ultimately spread out, wet and disperse over both the exterior and interior surface of the boehmite. If the initial silica loading is sufficiently low, then one will obtain a composite comprising discrete areas of the surface phase complex silica which has reacted with the boehmite hydroxyls interspersed with areas of alumina which have not been wet by and reacted with the silica due to an insufficient amount of silica on the boehmite when the process started. In such a case, one will have a composite which exhibits properties of both bulk alumina and the surface phase silica-boehmite like complex which has properties different from either bulk alumina or bulk crystalline or non-crystalline silica or bulk boehmite. On the other hand, if the silica loading is sufficient, then one can obtain a composite wherein all of the so-formed alumina surface is covered by and supports the surface phase silica-boehmite complex so that the resulting composite exhibits properties different from bulk crystalline or non-crystalline silica, bulk boehmite and bulk alumina. By way of example, if the boehmite has a total BET surface area of about 350 m²/g, the amount of silica required to get what one may term to be essentially a saturation monolayer coverage of silica on the ultimately formed alumina support would be about 10 wt.% silica. By 10 wt.% silica is meant that the 10 wt.% silica of the total silica-alumina composite. To carry this progression further, if the silica loading is above that required to achieve saturation monolayer coverage, then it becomes immediately obvious that one will have alumina whose surface is covered with a saturation monolayer surface phase silica-boehmite like, surface complex on an alumina support which, in turn, supports discrete areas of bulk silica. In this case the composite would exhibit properties of the surface phase complex and those of bulk silica at the same time. Finally, to arrive at the final and logical conclusion of the process of this invention, if the initial silica loading is sufficiently high then one will ultimately achieve a composite wherein the silica has completely spread out and wet the surface of the silica but wherein sufficient silica is present that the monolayer silica-boehmite like phase is partially covered by islands or particles of silica. Thus, one can readily understand from the above discussion, that the final composition will be a function of the many variables including (i) the time, temperature and steam content of the steaming treatment; (ii) the relative particle sizes of the silica and boehmite; (iii) the silica loading or amount of silica relative to the amount of boehmite employed; (iv) the porosity of the boehmite, and (v) the nature of the silica or silica precursor. With regard to the relative particle sizes of the silica or silica precursor and the boehmite, the above discussion relating to the use of, for instance, Davison Chemical Automotive Grade boehmite having an average diameter of about 44 microns (44 µm) which corresponds to a mesh size of 325 (Tyler) results in the various compositions that can be made employing the process of this invention. On the other hand, when a reforming grade of boehmite was employed in the process of this invention having a mesh size of 60 (Tyler) which corresponds to an average particle diameter of 250 microns (250 µm), ESCA analysis found that when this was slurried with silica with sufficient water to wet the pores of the alumina, the silica did not diffuse significantly into the pores of the 60 mesh (250 µm average particle size) boehmite material following steam treatment. Thus, even after a 32 hours steam treatment at 870°C employing 90% steam in N₂, the atomic percent of silica as measured by ESCA was only 17. It has been found that this value is similar to that expected for a composition employing boehmite and silica in the form of a "Ludox" slurry wherein the silica has been found to be entirely on the exterior surface of the boehmite particle. Thus, this gives rise to the conclusion that the silica surface diffusion or dispersion is relatively sluggish when diffusion or dispersion over significant geometric distances is required. Thus, where it is desired to make relatively large mesh size particles or extrudates employing the process of this invention, the silica particles must be composited with the boehmite before the large particles or extrudates are formed. In order to confirm the fact that if these relatively large mesh size extrudates when slurried with a "Ludox" slurry and then steamed in order to disperse the silica into the extrudate would not occur, an experiment was performed by preparing an alumina extrudate that was slurried with sufficient "Ludox" slurry to completely coat the extrudate with silica. This material was made and comprised a thin outer coating of silica from the "Ludox" slurry. This thin outer coating was removed by gentle abrasion with a sharp metal blade and then analyzed by ESCA. No silica could be detected by the ESCA on the external surface of this extrudate with the silica coating removed. An identical result would be expected if the extrudate were boehmite instead of alumina. In general, boehmite particle sizes of about 80 microns (80 µm), or smaller are suitable for the process of this invention. Compositions made by the method of this invention in the form of larger particles or extrudates may be formed by spray drying, tableting or extruding composites which contain a mixture of the alumina and silica which have not yet been steamed. Once these larger particles are formed, the silica is then dispersed to form a composition by the method of this invention via the high temperature steaming in a non-reducing environment or atmosphere. It is to be noted that the method of this invention of dispersing the silica onto the surface of boehmite by the high temperature steam treatment in a non-reducing atmosphere will not work with oxides or oxide salt precursors of, for example, titanium, zirconium, hafnium, vanadium, niobium, tantalum and chromium. That is, none of these oxides will disperse onto the surface of boehmite via the high temperature steam treatment process of this invention. In the method of this invention, the silica source may be hydrated silica in the form of an aqueous slurry of colloidal silica or very fine particles of silicic acid which is also a form of hydrated silica. Alternatively, if convenient, the silica source may also be in the form of an insoluble silica precursor material such as silicon tetraacetate, silicon oxylate, etc. By insoluble silica precursor material is meant a silicon compound which is insoluble both in water and polar and non-polar solvents ranging from acetone, ethanol, or methanol, ketones, aldehydes, cyclic ketones, hydrocarbons, etc. The important requirement is that the precursor material be one which when subjected to the steam treatment in the non-reducing atmosphere fairly readily converts to silica under the conditions of the steaming treatment. The invention will be more readily understood by reference to the Examples below: EXAMPLES A number of catalysts of this invention were evaluated for gas oil cracking activity in a micro activity test unit (MAT) modified to allow for water (steam) addition along with the feed. The MAT unit is recognized in the industry as a standard diagnostic test unit for cat cracking catalysts (see Ciapetta, F. G. and D. J. Henderson, Oil and Gas J 65 (72), 88, (1967) and Gustofson, W. R., Div. of Pet. Chem, ACS, Preprints 14 , B46 (1969). The oil feed was an East Texas Light Gas Oil having a boiling range of from 450-700 o F (204.4 - 371.1 o C). The operating conditions for the test were: H₂O to Oil mole ratio = 3/1 Temp. (catalyst) 900 o F (482 o C) Pressure 1 atmosphere (WHSV) oil 8hr-¹ (weight hourly space velocity) A number of acid catalysts were prepared employing boehmite (A100H) obtained as a 325-400 mesh (Tyler) (44 - 37 µm) powder from the American Cyanamid Company as the support and either a "Ludox" slurry or silica acid (H₂SiO₃) as the silica. During the preparation of each sample by treatment in steam at high temperature to produce a catalyst (or catalyst support), the boehmite phase converted essentially to γ-Al₂O₃, (or ϑ-Al ₂ O ₃) and the silica dispersed on the alumina surface to introduce strong acid sites. In the process of steaming these materials, high cracking activity and high surface area were introduced in the final composition. The unexpected activity and high surface area of the catalysts is a result of starting with boehmite and dispersing the silica over the surface. Each sample was steamed at 870 o C in 90 % H₂O-10 % N₂. Example 1 The preparation of a 6 wt.% SiO₂ on alumina sample was carried out by contacting the boehmite (powder, 325 mesh (44 µm)), A100H (Cyanamid, reforming grade BET surface area to 698 m²/g) with a colloidal SiO₂ ("Ludox" AS-40, DuPont Trade name) in sufficient water to fill the pore volume of the support. To 50g of Cyanamid A100H, which will decrease to about 40g weight following a high temperature steaming treatment, was added 6.38g of "Ludox" AS-40 (containing 2.55g SiO₂) in a total aqueous suspension of 37.5 ml. The impregnated sample was dried at 120 o C for 16 hrs., and then steamed at 870 o C for 16 hrs. in 90% H₂O-10% N₂ in a vertical tube furnace. The BET surface area of this steamed sample was 174 m²/g. This result is set forth in Table 1. The surface area of an analogously steam-treated alumina, as a reference point, was 115 m²/g. This example demonstrates that steam treatment of a boehmite alumina contacted with colloidal silica retains a very high surface area following a high temperature treatment in a steam rich atmosphere. Example 2 The preparation of a 6.2 wt.% SiO₂ on alumina sample was carried by contacting 28.5g boehmite (powder, 325 mesh (44 µm)), A100H (Cyanamid, reforming grade, BET surface area 698 m²/g) with 1.95g silica acid, SiO₂-H₂O (containing 1.5g SiO₂) and ball-milling the dry sample for 15 minutes. The sample was then steamed at 870 o C for 16 hours in 90% H₂O-10% N₂ in a vertical tube furnace. The BET surface area of the steam sample was 151 m²/g. This example demonstrates that silicic acid as a precursor serves to retain a quite high surface area following a high temperature treatment in a steam rich atmosphere. A portion of this steam-treated 6.2wt.% SiO₂ on alumina material was used to establish the catalytic cracking activity. The catalytic cracking activity tests were performed on a modified MAT unit described in the Experimental Section. The MAT activity (volume percent conversion to 400- o F (204.4 o C-) liquids) was 22 with a conversion to liquids of 5.4 wt.% based on feed. These results are listed in Table 1.This example will be useful for comparison to other examples of instant invention. A second portion of the 6.2 wt. of SiO₂ on alumina sample following the ball-milling step was steamed at 760 o C for 1 hr. in 90% H₂O-10% N₂ in a vertical tube furnace. The MAT activity of this sample was 21 with a conversion to liquids of 1.8 wt.% based on feed. This example shows that a steam treatment of 760 o C for 1 hr. produces a less effective 6% SiO₂ on alumina solid acid catalyst than a steaming treatment of 870 o C for 16 hrs. For reference purposes, the MAT activity of γ-Al₂O₃ steam-treated at 870 o C for 16 hrs. in 90% H₂O-10% N₂ was 17 with a conversion to liquids of 1.8 wt.% based on feed. Example 3 The preparation of a 12 wt.% SiO₂ on alumina sample was carried out as described in Example 1. To 27g of Cyanamid A100H was added 7.5g of "Ludox" AS-40 (containing 3.0g SiO₂) in a total aqueous suspension of 18 ml. The impregnated sample was dried at 120 o C for 16 hrs., and then steamed at 870 o C for 1 hr. in 90% H₂O-10% N₂ in a vertical tube furnace. The BET surface area of this steamed sample was 214 m²/g. This example further serves to demonstrate that steam treatment of a boehmite alumina contacted with colloidal silica retains a very high surface area for a high temperature treatment in a steam rich atmosphere. A portion of this steam-treated 12 wt.% SiO₂ on alumina material was used to establish the catalytic cracking activity as described in Example 2. The MAT activity was 28 with a conversion to liquids of 9.5 wt.% based on feed. These results are set forth in Table 1. This sample has both a higher MAT activity and a higher conversion to liquid products than the 6 wt.% SiO₂ on alumina samples of Example 2. This example demonstrates that quite active cracking catalysts can be prepared by contacting colloidal SiO₂ with a boehmite alumina followed by a one hour steaming treatment at 870 o C. Example 4 By way of comparison, ten and 15 wt.% SiO₂ on alumina samples were prepared on a reforming grade gamma-alumina according to the procedure described in Example 3. Both samples were steamed at 870 o C for 1 hr. in 90% H₂O-10% N₂ in a vertical tube furnace. The BET surface areas of these samples were 157 and 153 m²/g, respectively. Therefore, it is clear that the 12% SiO₂ on alumina sample prepared employing A100H as the starting phase has a higher surface (214 m²/g) than either of the samples prepared on gamma-alumina by the procedure of the instant invention. Example 5 In order to demonstrate the unique stability of the SiO₂ on alumina catalysts prepared using boehmite as the precursor alumina the surface area stability of different samples was investigated after impregnation of 3 wt.% V (as the metal). For example, to 14.92g Cyanamid boehmite described in Example 1 was added 1.44g VO(OC₃H₇)₃ (containing 0.3g V) in 12 ml methanol by the incipient wetness impregnation technique. The sample was dried for 16 hrs. at 120 o C and heated for 1 hr. at 500 o C for 16 hrs. in air. The final sample weight was 10.1g so the vanadium loading was 3 wt.%. The sample was then calcined at 890 o C for 16 hrs. in air. The BET surface area of the calcined catalyst was 5 m²/g. Example 6 A portion of the 6% SiO₂ on alumina sample of Example 1 was impregnated with VO(OC₃H₅)₃ as described for the A100H sample of this example. Following an analogous drying and calcination procedure as for the 3 wt.% V on boehmite the BET surface area was 57 m²/g following calcination at 890 o C for 16 hrs. in air. This example serves to demonstrate the unique surface area stability of SiO₂ on alumina catalysts of the instant invention. Example 7 The 12 wt.% SiO₂ on alumina sample of 214 m²/g surface area of Example 3 was impregnated with 3 wt.% V as described in Example 5. The sample was then steam-treated at 927 o C for 16 hrs. in 90% H₂O-10% N₂ in a vertical tube furnace. The BET surface area of this sample was 121 m²/g. This example serves to demonstrate the unique stability of SiO₂ on alumina materials prepared by the procedure of the instant invention. Example 8 A 3 wt.% V on γ-Al₂O₃ sample was prepared as described in Example 5. The sample was steam-treated at 927 o C for 16 hrs. in 90% H₂O-10% N₂ in a vertical tube furnace. The BET surface area of this sample was 3 m²/g. A 25 wt.% SiO₂ on gamma-alumina sample was prepared as described in Example 1. To a portion of this sample 3 wt.% V was added as described in Example 4. Following a steam-treatment at 927 o C for 16 hrs. in 90% H₂O-10% N₂ in a vertical tube furnace the BET surface area was found to be 30 m²/g. A commercial silica-alumina containing 10 wt.% SiO₂ and prepared by a co-gelation procedure was impregnated with 3 wt.% V as described in this Example. Following a steaming treatment as described in this Example at 927 o C the sample had completely converted to α-Al₂O₃ as determined by x-ray diffraction. A 2 wt.% SiO₂ content silica-alumina co-gel was prepared by precipitation of the metal alkoxides by well-known precipitation procedures. The 2% SiO₂ content sample was calcined at 500 o C and impregnated with 3 wt.% V as described in this Example. Following a steaming treatment as described in this Example, the BET surface area was found to be 10 m²/g. These samples demonstrate that stability to vanadium in high temperature steam environments is completely unique to the silica on alumina catalysts prepared using boehmite as the precursor alumina source of this instant invention. Finally, two samples of SiO₂ on boehmite were prepared containing 3.5 and 6 wt.% SiO₂. These two samples were then impregnated with 3% V as described in this. Each sample was then steamed at 927 o C for sixteen hours. The results are set forth in Table 2.

Claims: A composition comprising silica and gamma-alumina and including an amorphous disordered alumina phase (which is an intermediate of boehmite and gamma-alumina) supported on the external surface of the gamma-alumina and silica supported on said amorphous disordered alumina phase, said composition being obtained by a method comprising the steps of: (a) mixing particles of silica or of an insoluble silica precursor convertible to silica upon steaming at an elevated temperature in an inert atmosphere with particles of boehmite, and (b) subjecting the resulting uncalcined mixture to a temperature of at least 600°C in an inert atmosphere and in the presence of steam to form the said composition, the amount of silica or silica precursor being sufficient to provide from 1 to 50 w% silica (e.g. 1-25 w%) based on the total weight of the composition. The composition of claim 1 wherein said silica is in the form of discrete particles of bulk silica. The composition of claim 1 or claim 2 wherein said silica is non-crystalline and is supported in discrete areas on said amorphous disordered alumina phase. The composition of any one of claims 1 to 3 wherein the said boehmite is porous. A process for cracking a hydrocarbon feed which comprises contacting said feed and a catalyst at elevated temperature to crack at least a portion of said feed, wherein the catalyst comprises a composition according to any one of claims 1 to 4.

Inventors: DISPENZIERE, NICHOLAS CHARLES, JR., MURRELL, LAWRENCE LEE
Applicants: EXXON RESEARCH AND ENGINEERING COMPANY
Application year: 1986
Main classification: B01J37
IPC codes: B01J37, B01J21, C10G11, C10G47