Abstract:
A surface-inactive shape selective metallosilicate catalyst, useful for the conversion of lower molecular weight olefins to liquid hydrocarbons such as gasoline, distillate, and high viscosity lube oils, is prepared by forming a silica shell on a medium pore metallosilicate core by crystallizing silica in the presence of fluoride ion onto the surface of the core. 
     A novel catalyst composition is provided comprising an inner core portion and an outer portion disposed as a porous shell around the inner portion, wherein the inner portion consists essentially of metallosilicate zeolite having a medium pore structure, such as ZSM-5 or ZSM-23, and the outer portion comprising a fluoride-containing crystalline shell consisting essentially of silica substantially free of acid sites and having substantially the same crystalline structure as the inner core portion.

Description:
REFERENCE TO COPENDING APPLICATION 
     This application is a continuation-in-part of U.S. patent application Ser. No. 137,223, filed 23 Dec 1987, now U.S. Pat. No. 4,488,374, incorporated herein by reference. 
    
    
     FIELD OF THE INVENTION 
     This invention relates to a zeolitic composition having an acidic metallosilicate core an outer silica-rich portion. It also relates to a process for preparing an essentially surface-inactive medium pore shape selective crystalline metallosilicate material. The novel zeolite can be employed in catalytic hydrocarbon conversion reactions, such as oligomerization of olefins. 
     BACKGROUND OF THE INVENTION 
     In the past, various methods have been employed for preparing surface-inactive catalysts. Several techniques may be used to increase the relative ratio of intra-crystalline acid sites to surface active sites. This ratio increases with crystal size due to geometric relationship between volume and superficial surface area. Deposition of carbonaceous materials by coke formation can also shift the effective ratio. Enhanced effectiveness is observed where the surface acid sites of small crystal zeolites are reacted with a chemisorbed organic base or the like. 
     Catalysts of low surface activity can be obtained by using medium pore zeolites of small crystal size that have been selectively deactivated by basic compounds, such as bulky amines and/or phosphines having an effective critical dimension or cross section diameter of about 6-7 Angstrom or greater. Another surface modification technique is deactivation by treating with metal compounds. 
     Zeolite catalysts having active pore acidic sites and inactive surfaces are of particular interest in shape selective catalysis, such as oligomerization of olefins. Recent work in the field of olefin upgrading has resulted in catalytic processes for converting lower olefins to heavier hydrocarbons. Heavy distillate and lubricant range hydrocarbons can be synthesized over ZSM-5 type catalysts at elevated temperature and pressure to provide a product having substantially linear molecular conformations due to the ellipsoidal shape selectivity of certain medium pore catalysts. 
     Conversion of olefins to gasoline and/or distillate products is disclosed in U.S. Pat. Nos. 3,960,978 and 4,021,502 (Givens, Plank and Rosinski) wherein gaseous olefins in the range of ethylene to pentene, either alone or in admixture with paraffins are converted into an olefinic gasoline blending stock by contacting the olefins with a catalyst bed made up of medium pore zeolites having the structure of ZSM-5, In U.S. Pat. Nos. 4,150,062, 4,211,640, 4,227,992 and 4,547,613 (Garwood et al) disclose the operating conditions for various process techniques for selective conversion of C 3   +  olefins to mainly aliphatic hydrocarbons. 
     The final molecular conformation product of shape selective oligomerization is influenced by the pore structure of the catalyst. For the higher carbon numbers, the structure is primarily a methyl-branched straight olefinic chain, with the maximum cross section of the chain limited by the 5.4×5.6 Angstrom dimension of the largest ZSM-5 pore. Although emphasis is placed on the normal 1-alkenes as feedstocks, other lower olefins such as 2-butene or isobutylene, are readily employed as starting materials due to rapid isomerization over the acidic zeolite catalyst. At conditions chosen to maximize heavy distillate and lubricant range products (C 20   + ) the raw aliphatic product is essentially mono-olefinic. Overall branching is not extensive, with most branches being methyl at about one branch per eight or more atoms. 
     Useful oligomerization catalysts may be made by treatment with organic silicon compounds, as described in U.S. Pat. Nos. 4,100,215 and 4,002,697 (Chen) to impart the desired degree of surface deactivation while being essentially free of carbonaceous deposits. Such treatment involves contacting the catalyst with a silane surface modifying agent capable of deactivating catalytic (acidic) sites located on the external surface of the zeolite by chemisorption. Other disclosures relating to shape selective oligomerization catalysts include U.S. Pat. Nos. 4,520,221, 4,568,768 and 4,658,079 (Chen et al). 
     It is a main object of this invention to provide an improved process for upgrading olefins to valuable lubricant quality product. Significantly improved linearity can be achieved by employing a catalyst comprising a medium pore shape selective siliceous metallosilicate with a substantially inactive surface. 
     SUMMARY OF THE INVENTION 
     A process for preparing a unique shape selective porous silica shell catalyst has been discovered. An epitaxial silica shell, essentially free of acid sites, is grown on a crystalline medium pore shape selective metallosilicate core containing tetrahedrally coordinated metal acid sites. By this procedure, a novel composition of matter has been produced comprising an active catalytic inner portion and an outer portion disposed as an inactive porous shell around the inner portion. The preferred crystalline metallosilicate inner portion has a silica:metal oxide molar ratio of about 10:1 to about 300:1 and a Constraint Index of about 1 to 12; for instance, having the crystalline metallosilicate structure of ZSM-5 zeolite having an average core crystal size of about 0.02 to about 0.5 microns. 
     The novel catalyst composition may be used advantageously for conversion of lower molecular weight olefins to gasoline, distillate range hydrocarbons and/or high viscosity lubricant oils. Olefin conversion reactions taking place at the acid sites inside the channels or pores of the catalyst particles produce essentially linear aliphatic hydrocarbons with minimal branching. Since the outer surface of the treated catalyst is essentially free of acid sites, undesirable reactions are essentially eliminated and highly branched hydrocarbons are not generated as molecular rearrangement products. 
     DETAILED DESCRIPTION OF THE INVENTION 
     In this description, metric units and parts by weight are employed unless otherwise stated. The catalyst prepared according to the process of the present invention comprises an inner portion and an outer portion disposed as a porous shell around the inner portion wherein the inner portion comprises a medium pore metallosilicate and the outer portion comprises crystalline silica substantially free of acid sites, the outer portion being crystallized from an alkaline silicate solution containing fluoride ion. 
     The inner portion which defines the interior of the catalyst is a crystalline metallosilicate material which can be selected from aluminosilicates, gallosilicates, ferrosilicates, borosilicates and mixtures thereof. This inner portion is a medium pore crystalline metallosilicate with a silica:metal oxide molar ratio of about 10:1 to about 300:1. The pore size of the core material is in the intermediate range of about 5 to 7 Angstroms. The average crystal size of the metallosilicate core material is about 0.02 to about 5.0 microns. The acid cracking activity (alpha-value) of the metallosilicate is at least about 40. 
     Developments in zeolite technology have provided a group of medium pore siliceous materials having similar pore geometry. Most prominent among these intermediate pore size zeolites is ZSM-5, which is usually synthesized with acid active sites by incorporating a tetrahedrally coordinated metal, such as Al, Ga, or Fe, within the zeolytic framework. These medium pore zeolites are favored for acid catalysis; however, the advantages of ZSM-5 structures may be utilized by employing highly siliceous materials or crystalline metallosilicate having one or more tetrahedral species having varying degrees of acidity. ZSM-5 crystalline structure is readily recognized by its X-ray diffraction pattern, which is described in U.S. Pat. No. 3,702,866 (Argauer, et al.), incorporated by reference. 
     The metallosilicate catalysts useful in the process of this invention include siliceous zeolites generally known as medium pore, shape-selective catalysts. Recent developments in zeolite technology have provided a group of medium pore siliceous materials having similar pore geometry. Most prominent among these intermediate pore size zeolites is ZSM-5, which is usually synthesized with active acid sites by incorporating a tetrahedrally coordinated metal, such as Al, Ga, B, or Fe, within the zeolitic framework. While suitable zeolites having a coordinated metal oxide to silica molar ratio of 20:1 to 200:1 or higher may be used, it is advantageous to employ a standard aluminosilicate ZSM-5 having a silica:alumina molar ratio of about 25:1 to70:1, suitably modified to provide an inactive surface. The members of the class of zeolites useful for such catalysts have an effective pore size of generally from about 5 to about 8 Angstroms such as to freely sorb normal hexane. In addition, the structure must provide constrained access to larger molecules. It is sometimes possible to judge from a known crystal structure whether such constrained access exists. For example, if the only pore windows in a crystal are formed by 8-membered rings of silicon and aluminum atoms, then access by molecules of larger cross-section than normal hexane is excluded and the zeolite is not of the desired type. Windows of 10-membered rings are preferred, although, in some instances, excessive puckering of the rings or pore blockage may render these zeolites ineffective. 
     A convenient measure of the extent to which a zeolite provides control to molecules of varying sizes to its internal structure is the Constraint Index of the zeolite. Zeolites which provide a highly restricted access to and egress from its internal structure have a high value for the Constraint Index, and zeolites of this kind usually have pores of small size, e.g. less than 5 Angstroms. On the other hand, zeolites which provide relatively free access to the internal zeolite structure have a low value for the Constraint Index, and usually have pores of large size, e.g. greater than 8 Angstroms. The method by which Constraint Index is described fully in U.S. Pat. No. 4,016,218 (Haag et al), incorporated herein by reference for details of the method. It is noted that the Constraint Index is determined with the hydrogen form of the zeolite, but that the property is believed to be an atttribute of the crystal structure. 
     Constraint Index (CI) values for some typical materials are shown in Table 1. 
     
                       TABLE 1______________________________________Zeolite        CI        (at test temperature)______________________________________ZSM-5          6-8.3     (371° C.-316° C.)ZSM-11         5-8.7     (371° C.-316° C.)ZSM-12         2.3       (316° C.)ZSM-20         0.5       (371° C.)ZSM-22         7.3       (427° C.)ZSM-23         9.1       (427° C.)ZSM-35         4.5       (454° C.)ZSM-48         3.5       (538° C.)ZSM-50         2.1       (427° C.)TMA Offretite  3.7       (316° C.)Zeolite Beta   0.6-2.0   (316° C.-399° C.)______________________________________ 
    
     The above-described Constraint Index is an important definition of those medium pore zeolites which are useful in the instant invention. Zeolites having a CI of about 1 to 12 are preferred. The very nature of this parameter and the recited technique by which it is determined, however, admit of the possibility that a given zeolite can be tested under somewhat different conditions and thereby exhibit different Constraint Indices. Constraint Index seems to vary somewhat with severity of operations (conversion) and the presence or absence of binders. Likewise, other variables, such as crystal size of the zeolite, the presence of occluded contaminants, etc., may affect the Constraint Index. Therefore, it will be appreciated that it may be possible to so select test conditions, e.g. temperature, as to establish more than one value for the Constraint Index of a particular zeolite. This explains the range of Constraint Indices for some zeolites, such as ZSM-5, ZSM-11 and Beta. 
     The class of highly siliceous zeolites defined herein is exemplified by ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, and other similar materials. ZSM-5 is described in U.S. patent No. 4,702,886 (Argauer et al); ZSM-11 in U.S. Pat. No. 3,709,979 (Chu); ZSM-12 in U.S. Pat. No. 3,832,449 (Rosinski et al); ZSM-22 in U.S. Pat. No. 4,046,859 (Plank et al); ZSM-23 in U.S. Pat. No. 4,076,842 (Plank et al); ZSM-35 in U.S. Pat. No. 4,016,245 (Plank et al); and ZSM-48 in U.S. Pat. No. 4,397,827 (Chu); incorporated herein by reference. Similar layered zeolites are disclosed in U.S. Pat. 4,088,605 (Rollman). In a preferred example the catalyst of the present invention comprises aluminosilicate H-ZSM-5 zeolite free of hydrogenation-dehydrogenation components. 
     It is desirable in this invention to employ variants to the zeolite that have at least a moderate amount of acid activity. A zeolite having a lower silica-to-alumina ratio (e.g. 20:1 to 100:1) is usually preferred since the acid cracking activity, as measured by alpha value, is higher, typically about 100 to 500. The alpha test, which provides a measure of the relative rate constant of the zeolite for cracking normal hexane (i.e. the alpha value), is described by Miale et al. in Journal of Catalysis, Volume 6, No. 2, October 1966, incorporated by reference. 
     The zeolitic components of the catalyst may be the only components, and may be shaped into pellets using known methods, and in such shaped form it can serve as an effective catalyst in the process of this invention. The shell-type zeolite may be composited with a binder, such as alumina, to form catalyst particles by extrusion or other methods known in the art. Extrudate particles containing about 65 wt. % zeolite and 35 wt. % alumina binder exemplify a catalyst suitable for use in oligomerization. 
     The outer portion of the zeolitic catalyst is a crystalline silica material disposed as a porous shell around the core, as by epitaxial growth. The silica shell, crystallized from an alkaline silicate solution containing fluoride ion, is substantially free of acid sites such as tetrahedrally coordinated metal oxides, for example, aluminum oxide, gallium oxide, iron (II) or iron (III) oxide, and boron oxide. Although not wishing to be bound by theory, it is believed that the crystalline silica shell outer portion of the catalyst may contain a substantial amount of fluoride-silicon bonds in place of hydroxide-silicon bonds. At any account, the crystalline silica shell outer portion prepared by the preferred method contains a substantial amount of fluoride. This feature further reduces the acid activity of the porous outer shell. The amount of fluoride incorporated within the outer portion of the catalyst is typically in the range of about 0.01 to 1% by weight based on total crystal weight, preferably about 0.05 to 0.5% by weight. 
     The outer portion of the catalyst is in the range of about 10 to 50% by weight of the total product, preferably about 20 to 30% by weight. 
     A process for preparing the catalyst, which is a siliceous zeolite particle, is a series of steps comprising preparing an aqueous alkaline solution comprising a source of silicate ions, optionally an organic directing agent, and a source of hydroxide ions; mixing the aqueous solution with an aqueous dispersion of crystalline metallosilicate to form a homogenous mixture which is subsequently heated; and adding an aqueous solution of a fluoride compound to the homogeneous mixture and heating the resulting composition at a temperature to effectively form a particle comprising a crystalline silica outer shell substantially free of acid sites on a metallosilicate core. The particle is withdrawn from the composition and treated by a series of washing, drying and calcining steps to yield an active catalyst having internal acid sites. 
     The aqueous alkaline silica solution is prepared by mixing an alkali metal or alkaline earth metal base such as sodium hydroxide, optionally an organic directing agent such as tetrapropylammonium bromide, and a source of silicate ions such as colloidal silica (Ludox LS, 30% silica). The organic directing agent serves to promote the contact between reactive species. Other suitable organic directing agents are disclosed in U.S. Pat. Nos. 4,139,600 and 4,151,189, incorporated by reference. 
     An alternative process for preparing the catalyst comprises reacting a source of metal oxide and a source of silica under crystallization conditions to obtain an intermediate metallosilicate product which is about 50% to 75% crystallized, adding a source of fluoride ions, and completing the crystallization procedure with heating. 
     The source of silicate ions can be the oxide, silicic acid, or salts of the acid such as sodium silicate. There must be present in the reaction mixture an amount of silicate ions to effectively form a porous shell covering the metallosilicate core. 
     The aqueous solution containing the fluoride compound is prepared by mixing a compound which generates fluoride ions in situ with water. The compound is present in an amount sufficient to complex any dissolved aluminum ion. In a preferred embodiment, the fluoride compound is ammonium fluoride. When a gaseous species such as hydrogen fluoride or fluorine gas is employed, the reactive fluoride compound can be injected directly into the previously prepared homogeneous mixture containing a source of silicate ions and metallosilicate particles by known methods such as bubbling the gas through the mixture. 
     The effective temperature for forming the crystalline silica outer shell is about 80° C. to 200° C., preferably about 100° C. The reaction is conducted in an autoclave at autogenous or higher pressures. 
     The process dramatically increases the relative ratio of intra-crystalline acid sites to surface active sites. Acid activity on the surface of a porous crystalline acidic zeolite catalyst having a silica:alumina molar ratio greater than about 10 is reduced by a novel method. A method comprises contacting the acidic zeolite catalyst with a hot alkaline solution comprising silicate ions, an organic directing agent, and a source of hydroxide ions to form a homogenous colloidal suspension; adding a source of fluoride ions to the suspension to form a chemically reactive aqueous composition; and heating the composition at a temperature to effectively deposit an outer porous shell comprising silica on the acid zeolite catalyst, thereby reducing the acid activity on the surface of the catalyst. The acidic zeolite catalyst having a deposited porous outer shell comprising silica and fluoride is separated from the chemically reactive aqueous composition, washed, dried and calcined to form a zeolite catalyst having internal acid sites and a substantially acid-free surface. 
     The surface-inactive metallosilicate catalyst of the present invention can be employed in a variety of acid-catalyzed hydrocarbon conversion processes that depend upon a shape-selective catalyst. Such conversion processes include aromatics alkylation, xylenes isomerization, selective hydrocracking, dewaxing, aliphatics (e.g., olefin) isomerization and the like. 
    
    
     EXAMPLE 1 
     A surface-inactive small crystal acid ZSM-5 zeolite is prepared as follows.Preparation of a first solution is conducted by adding sequentially 12 g ofsodium hydroxide, 30 g. of tetrapropylammonium bromide directing agent, and383 g. of colloidal silica (Ludox LS, 30% silica) to200 g of water. A second mixture is prepared by dispersing 115 g of small crystal (0.02-0.05micron) acid ZSM-5 having a silica:alumina molar ratio of 40:1 in 300 g of water. 
     The first solution is added to the second mixture and blended into a homogeneous mixture, which mixture is charged to an autoclave and heated at 99° C. for a period of 3 hours with stirring. Then a third solution containing 23 g. of ammonium fluoride in 50 g of water is added to the autoclave which is heated for another 16 hours. The solid product is then collected on a filter, washed with water, and dried in air. The product is precalcined in an inert nitrogen atmosphere, cation exchanged with ammonium nitrate, and finally calcined in air. 
     EXAMPLE 2 
     To demonstrate utility of the novel zeolitic material, propylene is converted to liquid hydrocarbons at oligomerization conditions over a surface-deactivated catalyst prepared according to Example 1. The zeolite is sized to about 14-25 mesh. About 5 g. of the catalyst is placed in a stainless steel tubular isothermal reactor having an inside diameter of 3/8 inch. The reactor is purged with hydrogen at 482° C. and at atmospheric pressure for one hour. Propylene is directed over the catalystat a weight hourly space velocity (WHSV) of 0.5 hr -1 , an average temperature of 211° C., and a pressure of about 10,300 kPa for a period of 24 hours. The liquid recovery after 24 hours is 78% by weight. 
     To continue the conversion, the temperature is then raised to 234° C. and propylene is directed over the catalyst for a period of 36 hours. The second liquid recovery is 99% by weight. 
     Again the temperature is raised, this time to 261° C. A stream of propylene is passed over the catalyst for 24 hours to give a third liquid recovery of 90% by weight. 
     A mixture of the liquid products is distilled to achieve a bottoms lubricant range fraction of 13% by weight (based on propylene feed). The lube oil fraction has the following properties: 
     
         ______________________________________Gravity (API)    41.6Gravity (Specific)            0.8174Pour point (°C.)            -18KV @ 40° C., cs            7.56KV @ 100° C., cs            2.27Viscosity Index  111.9______________________________________ 
    
     EXAMPLE 3 
     As a comparative experiment, a conventional crystalline acidic ZSM-5 catalyst having a silica:alumina molar ratio of 70:1 is employed for the conversion of propylene. The procedure of Example 2 is followed, except asnoted. The reactor is purged with hydrogen at 482° C. and at atmospheric pressure for one hour. 
     Propylene is then directed over the catalyst at a weight hourly space velocity (WHSV) of 0.5, an average temperature of 205° C., and a pressure of 10,300 kPA for a period of 48 hours. The first liquid recoveryafter 48 hours is 985 by weight. 
     The temperature is then raised to 238° C. and propylene is directed over the catalyst for 24 hours to give a liquid recovery of 97% by weight. 
     A mixture of the liquid products is distilled to achieve a bottoms lube fraction of 10% by weight (based on propylene feed). The lube oil fractionhas the following properties: 
     
         ______________________________________Gravity (API)    33.3Gravity (Specific)            0.8587Pour Point (°C.)            -34KV @ 40° C., cs            56.35KV @ 100° C., cs            6.93Viscosity Index  70______________________________________ 
    
     EXAMPLE 4 
     Surface activity of the prepared catalysts is measured by acid cracking of a sterically hindered hydrocarbon. A feed of 1,3,5-triethylbenzene (TEB) is passed over a catalyst sample at a liquid hourly space velocity (LHSV) of 20 and at a temperature of 260° C. A molecule of 1,3,5-TEB is too bulky to enter the internal pores of a zeolite having a Constraint Index of 1-12. Therefore the equilibrium conversion reaction of 1,3,5-TEB occurs at the acid sites on the surface of such medium pore zeolites. The results of the test are as follows: 
     
         ______________________________________Method of                    % TEBZSM-5 preparation           SiO.sub.2 Al.sub.2 O.sub.3 (bulk)                        converted______________________________________Conventional    70           77Example 1       64           6______________________________________ 
    
     The results of this test confirm that a catalyst prepared according to the present invention process has low surface acid activity, ie- less than 10%of the inner portion. 
     EXAMPLE 5 
     A further medium pore aluminosilicate zeolitic catalyst is prepared using ZSM-23. A caustic solution is prepared by dissolving 1.1 parts of aluminumsulfate, 2.54 parts of 50% NaOH and 9.45 parts of pyrrolidine in 171 parts of de-ionized water. One part of ZSM-23 (100% solid basis) and 28.8 parts of Hi Sil 233 are then added to form a thick slurry. The crystallization is carried out at 320° F. and 80 rpm agitation, and is complete in about 20 hours. The filtered, water-washed and dried solid product is found to be pure ZSM-23 by X-ray diffraction method. The core crystals areneedle shaped, having average crystallite length about 0.5 micron and average diameter of about 0.05 micron. 
     EXAMPLE 6 
     Surface-inactivate crystals having the structure of ZSM-23 are prepared as follows. A caustic solution is prepared by dissolving 0.51 g of NaOH and 11.7 g of pyrrolidine in 156 g of water. To this solution 83 g of Ludox AS-40,3 g of NH 4  F and ZSM-23 (product from Example 5) core crystal seed slurry (33g seed in 60 g of water) are added sequentially to form a silica gel. The mixture is heated at 150° C. in an autoclave for about 46 hours. The solids are filtered, water washed, dried and found to have the structure of ZSM-23 by X-ray diffraction method. The sample contains 0.24% fluorine and .65% sodium. The sample is then converted to acid form by precalcination in nitrogen at 537° C., ammonium exchange to remove sodium and activation in air at 537° C. for 3 hours. The final product contains 0.02% residual sodium. 
     EXAMPLE 7 
     The surface-inactivate ZSM-23 sample prepared in Example 5 is tested by theTEB test described in Example 4. The results are as follows: 
     
         ______________________________________Method of                    % Conv.ZSM-23 preparation           SiO.sub.2 /Al.sub.2 O.sub.3 (bulk)                        of TEB______________________________________No Silica Shell 120          11(Exam. 5)With Silica Shell           130          0.8(Exam. 6)______________________________________The results confirm that the ZSM-23 prepared by the method in Example 6 haslow surface activity, less than 10% of that of pure ZSM-23. 
    
     While the invention has been described by reference to certain embodiments,there is no intent to limit the inventive concept except as set forth in the following claims.