NZ234403A

NZ234403A - Zeolite having a mole ratio of silicon and/or germanium oxide to boron, gallium and/or iron oxide of between 20:1 and 100:1; preparation thereof and modification of hydrocarbons using such material

Info

Publication number: NZ234403A
Application number: NZ234403A
Authority: NZ
Inventors: Stacey I Zones; Dennis L Holtermann; Robert A Innes; Donald S Santilli; Teh Yuen Lun; James N Ziemer
Original assignee: Chevron Res & Tech
Priority date: 1989-07-07
Filing date: 1990-07-06
Publication date: 1992-08-26
Also published as: EP0483222A1; KR920703444A; AU5965490A; EP0483222A4; CA2062799A1; BR9007513A; ZA905368B; WO1991000844A1; JPH05500352A

Description

<div id="description" class="application article clearfix"> New Zealand Paient Spedficaiion for Paient Number £34403 f 1 234 40 Priority Datecs/: Coraptetp S;-.i!>c;;;cc-iion Fi'sJ: Class: £ IS&k:.C /£.$> k-R.h.X .... Pubficatiori vzts P.O. JoUkP.s-, ~ NO DRAMS / No.: Date: NEW ZEALAND PATENTS ACT, 1953 COMPLETE SPECIFICATION ZEOLITE (B)SSZ-24 patent office ~6JUU990 - j Xl We. CHEVRON RESEARCH AND TECHNOLOGY COMPANY, a corporation duly organised under the laws of the State of Delaware, of 100 West Tenth Street, Wilmington, Delaware, USA and having a place of business at 555 Market Street, san Fransico, CA, USA hereby declare the invention, for which jSj we pray that a patent may be granted to rp^fus, and the method by which it is to be performed, to be particularly described in and by the following statement: - - 1 - (followed by page la) 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 23 4 4 03 BACKGROUND OF THE INVENTION Natural and synthetic zeolitic crystalline aluminosilicates are useful as catalysts and adsorbents. These aluminosilicates have distinct crystal structures which are demonstrated by X-ray diffraction. The crystal structure defines cavities and pores which are characteristic of the different species. The adsorptive and catalytic properties of each crystalline aluminosilicate are determined in part by the dimensions of its pores and cavities. Thus, the utility of a particular zeolite in a particular application depends at least partly on its crystal structure. Because of their unique molecular sieving characteristics, as well as their catalytic properties, crystalline aluminosilicates are especially useful in such applications as gas drying and separation and hydrocarbon conversion. Although many different crystalline aluminosilicates and silicates have been disclosed, there is a continuing need for new zeolites and silicates with desirable properties for gas separation and drying, hydrocarbon and chemical conversions, and other applications. Crystalline aluminosilicates are usually prepared from aqueous reaction mixtures containing alkali or alkaline earth metal oxides, silica, and alumina. "Nitrogenous zeolites" have been prepared from reaction mixtures containing an organic templating agent, usually a nitrogen-containing organic cation. By varying the synthesis conditions and the composition of the reaction mixture, different zeolites can be formed using the same templating agent. Use of N,N,N-trimethy1 cyclopentylammonium iodide in -lc\~ 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 234403 the preparation of Zeolite SSZ-15 molecular sieve is disclosed in U.S. Patent No. 4,610,854; use of 1-azoniaspiro [4.4] nonyl bromide and N,N,N-trimethyl neopentylammonium iodide in the preparation of a molecular sieve termed "Losod" is disclosed in Helv. Chim. Acta (1974); Vol. 57, p. 1533 (W. Sieber and W. M. Meier); use of quinuclidinium compounds to prepare a zeolite termed "NU-3n is disclosed in European Patent Publication No. 40016; use of l,4-di(l-azoniabicyclo[2.2.2.]octane) lower alkyl compounds in the preparation of Zeolite SSZ-16 molecular sieve is disclosed in U.S. Patent No. 4,508,837; use of N, N,N—trialkyl-1-adamantamine in the preparation of Zeolite SSZ-13 molecular sieve is disclosed in U.S. Patent No. 4,544,538, and for SSZ-24 in U.S. Patent No. 4,665,110. Synthetic zeolitic crystalline borosilicates are useful as catalysts. Methods for preparing high silica content zeolites that contain framework boron are known and disclosed in U.S. Patent No. 4,269,813. The amount of boron contained in the zeolite may be made to vary by incorporating different amounts of borate ion in the zeolite-forming solution. The use of a quaternary ammonium compound in the preparation of a boron-containing zeolite is disclosed in European Patent Application No. 188,913. A method for treating a zeolite containing aluminum and boron with a silicon substitution treatment is disclosed in U.S. Patent No. 4,701,313. The present invention relates to a novel family of stable synthetic crystalline materials characterized as borosilicates identified as SSZ-24 and having a specified X-ray diffraction pattern, and also to the preparation and use of such materials. -2- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 234 4 03 SUMMARY OF INVENTION We have prepared crystalline borosilicate molecular sieves with unique properties, referred to herein as "zeolite (B)SSZ-24" or simply "(B)SSZ-24" and have found highly effective methods for preparing this zeolite. The boron in the crystalline network may be replaced by other metals. Advantageous uses for (B)SSZ-24 have also been discovered. Thus, according to the present invention, a zeolite composition, (B)SSZ-24, is provided. (B)SSZ-24 has a mole ratio of an oxide selected from silicon oxide, germanium oxide, and mixtures thereof to an oxide selected from boron oxide or mixtures of boron oxide with aluminum oxide, gallium oxide or iron oxide between 20:1 and 100:1, and having the X—ray diffraction lines of Table I below. This zeolite further has a composition, as synthesized and in the anhydrous state, in terms of mole ratios of oxides as follows: (1.0 to 5)Q2O:(0.1 to 1.0)M20:W203:(20 to 100)Y02 wherein M is an alkali metal cation, W is selected from boron, gallium oxide or iron oxide, Y is selected from silicon, germanium and mixtures thereof, and Q is an adamantammonium quaternary ammonium ion. (B)SSZ-24 zeolites can have a Y02:W20j mole ratio between 20:1 to 100:1 and can be made essentially alumina free. As prepared, the silica:boron ratio is typically in the range of 20:1 to about 100:1. Higher mole ratios can be obtained by treating the zeolite with chelating agents or acids to extract boron from the zeolite lattice. The silicarboron mole ratio can also be increased by using silicon and carbon halides and other similar compounds. -3- • 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 23 4 4 03 A portion of the boron in the crystalline network may be replaced by aluminum. For example, aluminum insertion may occur by thermal treatment of the zeolite in combination with an aluminum binder or dissolved source of aluminum. Such procedures are described in U.S. Patent Nos. 4,559,315 and 4,550,092. According to one embodiment of the present invention, a method is provided for making (B)SSZ-24 zeolites, comprising preparing an aqueous mixture containing sources of an adamantane quaternary ammonium ion, an alkali oxide, an oxide selected from boron as a borosilicate, not simply a boron oxide, and an oxide selected from silicon oxide, germanium oxide, and mixtures thereof, and having a composition, in terms of mole ratios of oxides, falling within the following ranges: YO2/W2O3, 20:1 to 100; wherein Y is selected from silicon, germanium, and mixtures thereof, W is selected from boron, and Q is an adamantane quaternary ammonium ion; maintaining the mixture at a temperature of at least 100°C until the crystals of said zeolite are formed; and recovering said crystals. A zeolite having the same X-ray diffraction pattern as the (B)SSZ—24 zeolite is described in our U.S. Patent No. 4,834,958 entitled "New Zeolite SSZ-24". As synthesized using the method described therein, this zeolite contains a mole ratio of YC^/^O^ greater than 100:1. The method for preparing SSZ-24 described in this application cannot be used to make (B)SSZ-24. The mole ratio of YO2/W2O2 cannot be reduced by using large quantities of aluminum, gallium, iron, or boron. -4- ? 3 4 4 0 3 23 24 01 A preferred borosilicate source is boron beta zeolite 02 described in commonly assigned co-pending New Zealand Patent 03 Application No. 234405 filed concurrently 04 herewith, and entitled "Low-Aluminum Boron Beta Zeolite". 05 06 We now find that by using a suitable borosilicate source, 07 the Y02/W2°3 mole ratio can be decreased to 20:1 where W is 08 boron. Aluminum, gallium, iron and other metals can replace 09 boron in the (B)SSZ-24 framework by post-synthetic treatment 10 as described herein. This type of framework substitution extends the range of catalytic applications for (B)SSZ-24. 12 13 Among other factors, the present invention is based on our 14 finding that (B)SSZ-24 with a mole ratio between 15 20:1 and 100:1 can be synthesized using a new borosilicate 15 source. Surprisingly, we have found that the mole ratio of 17 YO2/W2O3 can be decreased below 100:1 by using certain 18 borosilicate sources. We have found that the (B)SSZ-24 ig zeolite has unexpectedly outstanding hydrocarbon conversion 20 properties, particularly including hydrocracking, chemicals 21 production, and oxygenate conversion properties. 22 DETAILED DESCRIPTION OF THE INVENTION 25 SSZ-24 zeolites, as synthesized, have a crystalline struc-2g ture whose X-ray powder diffraction pattern shows the 27 following characteristic lines: 28 29 30 31 32 33 34 ** // 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 23 4 4 ( TABLE I 2 9 d/n i/i hkl (hexagonal) 7.50 ± 0.05 11.79 13.00 ± 0.05 6.81 15.03 ± 0.05 5.89 19.9 ± 0.10 4.45 21.5 ± 0.10 4.13 22.75 ± 0.10 3.91 25.25 ± 0.05 3.53 26.3 ± 0.05 3.39 29.51 ± 0.05 3.03 30.43 + 0.05 2.94 45 6 32 75 64 100 7 35 16 21 100 110 200 210 002 211 112 220 212,311 400 Typical SSZ—24 borosilicate and aluminosilicate zeolites have the X-ray diffraction patterns and lattice constants of Tables 2, 4, and 6 below. Lattice constants are shown in Table 6 and demonstrate framework substitution. The X-ray powder diffraction patterns were determined by standard techniques. The radiation was the K-alpha/doublet of copper and a scintillation counter spectrometer with a strip chart pen recorder was used. The peak heights I and the positions, as a function of 2 9 where 0 is the Bragg angle, were read from the spectrometer chart. From these measured values, the relative intensities, 100I/I , where I o o is the intensity of the strongest line or peak, and d, the interplanar spacing in Angstroms corresponding to the recorded lines, can be calculated. The X-ray diffraction pattern of Table I is characteristic of SSZ-24 zeolites. The zeolite produced by exchanging the metal or other cations present in the zeolite with various other cations yields substantially the same diffraction pattern although -6- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 234 4 0 there can be minor shifts in interplanar spacing and minor variations in relative intensity. Minor variations in the diffraction pattern can also result from variations in the organic compound used in the preparation and from variations in the silica-to-alumina mole ratio from sample to sample. Calcination can also cause minor shifts in the X-ray diffraction pattern. Notwithstanding these minor perturbations, the basic crystal lattice structure remains unchanged. (B)SSZ-24 zeolites can be suitably prepared from an aqueous solution containing sources of an alkali metal oxide, a tricyclo[3.3.1.1]decane quaternary ammonium ion, borosilicate, and an oxide of silicon or germanium, or mixture of the two. The reaction mixture should have a composition in terms of mole ratios falling within the following ranges: Broad Preferred y02/^w2°3 20-100 30-100 oh/yo2 0 .10-1.0 0.15-0.25 Q/yo2 0 .05-0.50 0.10-0.25 m+/yo2 0 .05-0.30 0.05-0.15 h2o/yo2 15-300 25-60 q/q+m+ 0 .30-0.70 0.40-0.60 wherein Q is an adamantane (or tricyclo[3.3.1.1]decane) quaternary ammonium ion, Y is silicon, germanium or both, and W is boron. M is an alkali metal, preferably potassium. The organic compound which acts as a source of the quaternary ammonium ion employed can provide hydroxide ion. W is shown as boron, but is provided to the reaction as borosilicate. -7- 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 23440. When using the quaternary ammonium hydroxide compound as a template, it has also been found that purer forms of (B)SSZ-24 are prepared when there is an excess of compound present relative to the amount of alkali metal hydroxide. The tricyclodecane quaternary ammonium ion component Q, of the crystallization mixture, is derived from the quaternary ammonium compound. Preferably, the tricyclo[3.3.1.1]decane quaternary ammonium ion is derived from a compound of the formula: wherein each of Y^, Y2, and Y- independently is lower alkyl and most preferably methyl; A is an anion which is not detrimental to the formation of the zeolite; and each of R^, R2, and R^ independently is hydrogen, or lower alkyl and most preferably hydrogen; and (b) n°,(y1,y2,y3)a 9 wherein each of R^, R^, and Rg independently is hydrogen or lower alkyl; and most preferably hydrogen; each of Y^, Y2, -8- 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 234403 and Y3 independently is lower alkyl and most preferably 9 methyl; and A is an anion which is not detrimental to th formation of the zeolite. The quaternary ammonium compounds are prepared by methods known in the art. A0 is an anion which is not detrimental to the formation of the zeolite. Representative of the anions include halogen, e.g., fluoride, chloride, bromide and iodide, hydroxide, acetate, sulfate, carboxylate, etc. Hydroxide is the most preferred anion. It may be beneficial to ion exchange, for example, the halide for hydroxide ion, thereby reducing or eliminating the alkali metal hydroxide quantity required. The reaction mixture is prepared using standard zeolitic preparation techniques. Sources of borosilicates for the reaction mixture include borosilicate glasses and most particularly, other reactive borosilicate molecular sieves-One very reactive source is boron beta zeolite described in commonly assigned copending New Zealand Patent Application No. 234405 filed concurrently herewith, and entitled "Low-Aluminum Boron Beta Zeolite". Typical sources of silicon oxide include silicates, silica hydrogel, silicic acid, colloidal silica, fumed silica, tetra-alkyl orthosilicates, and silica hydroxides. The reaction mixture is maintained at an elevated temperature until the crystals of the zeolite are formed. The temperatures during the hydrothermal crystallization step are typically maintained from about 120°C to about By "lower alkyl" is meant alkyl of from atoms. 1 to 3 carbon -9- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 234 4 1 200°C, preferably from about 130°C to about 170°C and most preferably from about 135°C to about 165°C. The crystallization period is typically greater than one day and preferably from about three days to about seven days. The hydrothermal crystallization is conducted under pressure and usually in an autoclave so that the reaction mixture is subject to autogenous pressure. The reaction mixture can be stirred during crystallization. Once the zeolite crystals have formed, the solid product is separated from the reaction mixture by standard mechanical separation techniques such as filtration. The crystals are water-washed and then dried, e.g., at 90°C to 150°C from 8 to 24 hours, to obtain the as synthesized, (B)SSZ-24 zeolite crystals. The drying step can be performed at atmospheric or subatmospheric pressures. During the hydrothermal crystallization step, the (B)SSZ-24 crystals can be allowed to nucleate spontaneously from the reaction mixture. The reaction mixture can also be seeded with (B)SSZ-24 crystals both to direct, and accelerate the crystallization, as well as to minimize the formation of undesired borosilicate contaminants. The synthetic (B)SSZ-24 zeolites can be used as synthesized or can be thermally treated (calcined). Usually, it is desirable to remove the alkali metal cation by ion exchange and replace it with hydrogen, ammonium, or any desired metal ion. The zeolite can be leached with chelating agents, e.g., EDTA or dilute acid solutions, to increase the silica:boron mole ratio. The zeolite can also be steamed; steaming helps stabilize the crystalline lattice to attack from acids. The zeolite can be used in intimate combination -10- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 23 4 4 0 with hydrogenating components, such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal, such as palladium or platinum, for those applications in which a hydrogenation-dehydrogenation function is desired. Typical replacing cations can include metal cations, e.g., rare earth, Group IIA and Group VIII metals, as well as their mixtures. Of the replacing metallic cations, cations of metals such as rare earth, Mn, Ca, Mg, Zn, Cd, Pt, Pd, Ni, Co, Ti, Al, Sn, Fe, and Co are particularly preferred. The hydrogen, ammonium, and metal components can be exchanged into the zeolite. The zeolite can also be impregnated with the metals, or, the metals can be physically intimately admixed with the zeolite using standard methods known to the art. And, some metals can be occluded in the crystal lattice by having the desired metals present as ions in the reaction mixture from which the (B)SSZ-24 zeolite is prepared. Typical ion exchange techniques involve contacting the synthetic zeolite with a solution containing a salt of the desired replacing cation or cations. Although a wide variety of salts can be employed, chlorides and other halides, nitrates, and sulfates are particularly preferred. Representative ion exchange techniques are disclosed in a wide variety of patents including U.S. Nos. 3,140,249; 3,140,251; and 3,140,253. Following contact with the salt solution of the desired replacing cation, the zeolite is typically washed with water and dried at temperatures ranging from 65°C to about 315°C. After washing, the zeolite can be calcined in air or inert gas at temperatures ranging from about 200°C to 820°C for -11- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 2 3 4 4 0 3 periods of time ranging from 1 to 48 hours, or more, to produce a catalytically active product especially useful in hydrocarbon conversion processes. Regardless of the cations present in the synthesized form of the zeolite, the spatial arrangement of the atoms which form the basic crystal lattice of the zeolite remains essentially unchanged. The exchange of cations has little, if any, effect on the zeolite lattice structures. The (B)SSZ-24 borosilicate and aluminosilicate can be formed into a wide variety of physical shapes. Generally speaking, the zeolite can be in the form of a powder, a granule, or a molded product, such as extrudate having particle size sufficient to pass through a 2-mesh (Tyler) screen and be retained on a 400-mesh (Tyler) screen. In cases where the catalyst is molded, such as by extrusion with an organic binder, the aluminosilicate can be extruded before drying, or, dried or partially dried and then extruded. The zeolite can be composited with other materials resistant to the temperatures and other conditions employed in organic conversion processes. Such matrix materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and metal oxides. The latter may occur naturally or may be in the form of gelatinous precipitates, sols, or gels, including mixtures of silica and metal oxides. Use of an active material in conjunction with the synthetic zeolite, i.e., combined with it, tends to improve the conversion and selectivity of the catalyst in certain organic conversion processes. Inactive materials can suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained economically without using other means for controlling the rate of reaction. -12- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 23 4 4 0 , Frequently, zeolite materials have been incorporated into naturally occurring clays, e.g., bentonite and kaolin. These materials, i.e., clays, oxides, etc., function, in part, as binders for the catalyst. It is desirable to provide a catalyst having good crush strength, because in petroleum refining the catalyst is often subjected to rough handling. This tends to break the catalyst down into powders which cause problems in processing. Naturally occurring clays which can be composited with the synthetic zeolites of this invention include the montmorillonite and kaolin families, which families include the sub-bentonites and the kaolins commonly known as Dixie, McNamee, Georgia, and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or anauxite. Fibrous clays such as sepiolite and attapulgite can also be used as supports. Such clays can be used in the raw state as originally mined or can be initially subjected to calcination, acid treatment or chemical modification. In addition to the foregoing materials, the SSZ-24 zeolites can be composited with porous matrix materials and mixtures of matrix materials such as silica, alumina, titania, magnesia, silica:alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, and silica-magnesia-zirconia. The matrix can be in the form of a cogel. The (B)SSZ-24 zeolites can also be composited with other zeolites such as synthetic and natural faujasites (e.g., X and Y), erionites, and mordenites. They can also be -13- • 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 2 3 4 4 0c composited with purely synthetic zeolites such as those of the ZSM series. The combination of zeolites can also be composited in a porous inorganic matrix. (B)SSZ-24 zeolites are useful in hydrocarbon conversion reactions. Hydrocarbon conversion reactions are chemical and catalytic processes in which carbon-containing compounds are changed to different carbon-containing compounds. Examples of hydrocarbon conversion reactions include catalytic cracking, hydrocracking, and olefin and aromatics formation reactions. The catalysts are useful in other petroleum refining and hydrocarbon conversion reactions such as isomerizing n-paraffins and naphthenes, polymerizing and oligomerizing olefinic or acetylenic compounds such as isobutylene and butene-1, reforming, alkylating, isomerizing polyalkyl substituted aromatics (e.g., ortho xylene), and disproportionating aromatics (e.g., toluene) to provide mixtures of benzene, xylenes, and higher methylbenzenes. The (B)SSZ-24 catalysts have high selectivity, and under hydrocarbon conversion conditions can provide a high percentage of desired products relative to total products. (B)SSZ-24 zeolites can be used in processing hydrocarbonaceous feedstocks. Hydrocarbonaceous feedstocks contain carbon compounds and can be from many different sources, such as virgin petroleum fractions, recycle petroleum fractions, shale oil, liquefied coal, tar sand oil, and in general, can be any carbon containing fluid susceptible to zeolitic catalytic reactions. Depending on the type of processing the hydrocarbonaceous feed is to undergo, the feed can contain metal or be free of metals, it can also have high or low nitrogen or sulfur impurities. It can be appreciated, however, that processing will generally -14- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 ?34 403 be more efficient (and the catalyst more active) if the metal, nitrogen, and sulfur content of the feedstock is lower. Using the (B)SSZ-24 catalyst which contains aluminum framework substitution and a hydrogenation promoter, heavy petroleum residual feedstocks, cyclic stocks, and other hydrocracking charge stocks can be hydrocracked at hydrocracking conditions including a temperature in the range of from 175°C to 485°C, molar ratios of hydrogen to hydrocarbon charge from 1 to 100, a pressure in the range of from 0.5 to 350 bar, and a liquid hourly space velocity (LHSV) in the range of from 0.1 to 30. The hydrocracking is most preferably conducted in the absence of added hydrogen. Hydrocracking catalysts comprising (B)SSZ-24 contain an effective amount of at least one hydrogenation catalyst (component) of the type commonly employed in hydrocracking catalysts. The hydrogenation component is generally selected from the group of hydrogenation catalysts consisting of one or more metals of Group VIB and Group VIII, including the salts, complexes, and solutions containing such. The hydrogenation catalyst is preferably selected from the group of metals, salts, and complexes thereof of the group consisting of at least one of platinum, palladium, rhodium, iridium, and mixtures thereof or the group consisting of at least one of nickel, molybdenum, cobalt, tungsten, titanium, chromium, and mixtures thereof. Reference to the catalytically active metal or metals is intended to encompass such metal or metals in the elemental state or in some form such as an oxide, sulfide, halide, carboxylate, and the like. -15- 234403 ^01 A hydrogenation component is present in the hydrocracking 02 catalyst in an effective amount to provide the hydrogenation 03 function of the hydrocracking catalyst and preferably in the 04 range of from 0.05% to 25% by weight. 05 05 The (B)SSZ-24 catalyst may be employed in conjunction with 07 traditional hydrocracking catalysts, e.g., any 03 aluminosilicate heretofore employed as a component in 0g hydrocracking catalysts. Representative of the zeolitic 10 aluminosilicates disclosed heretofore as employable as 12 component parts of hydrocracking catalysts are Zeolite Y 12 (including steam stabilized, e.g., ultra-stable Y), Zeolite 13 X, Zeolite beta (U.S. Patent No. 3,308,069), Zeolite ZK-20 14 (U.S. Patent No. 3,445,727), Zeolite ZSM-3 (U.S. Patent No. 15 3,415,736), faujasite, LZ-10 (U.K. Patent 2,014,970, June 9, 15 1982), ZSM-5-type zeolites, e.g., ZSM-5, ZSM-11, ZSM-12, 17 ZSM-23, ZSM-35, ZSM-38, ZSM-48, crystalline silicates such 10 as silicalite (U.S. Patent No. 4,061,724), erionite, 19 mordenite, offretite, chabazite, FU-l-type zeolite, NU-type 20 zeolites, LZ-210-type zeolite, and mixtures thereof. 21 Traditional hydrocracking catalysts containing amounts of 22 Na2° less than about one percent by weight are generally preferred. The traditional hydrocracking catalyst is also preferably a large pore size crystalline aluminosilicate cracking catalyst. The relative amounts of the (B)SSZ-24 component 24 and traditional hydrocracking component, if any, will depend 25 at least in part, on the selected hydrocarbon feedstock and 25 on the desired product distribution to be obtained 27 therefrom, but in all instances an effective amount of 2q (B)SSZ-24 is employed. 29 3Q The hydrocracking catalysts are typically employed with an 3^ inorganic oxide matrix component which may be any of the 22 inorganic oxide matrix components which have been employed 22 heretofore in the formulation of hydrocracking catalysts 24 including: amorphous catalytic inorganic oxides, e.g., -16- O ■••v \ x ' A s 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 254403 catalytically active silica-aluminas, clays, silicas, aluminas, silica-aluminas, silica-zirconias, silica-magnesias, alumina-borias, alumina-titanias, and the like and mixtures thereof. The traditional hydrocracking catalyst and (B)SSZ-24 may be mixed separately with the matrix component and then mixed or the THC component and (B)SSZ-24 may be mixed and then formed with the matrix component. A physical mixture of the THC component and (B)SSZ-24 can also be used as the catalyst composition. (B)SSZ-24 can be used to dewax hydrocarbonaceous feeds by selectively removing straight chain paraffins. The catalytic dewaxing conditions are dependent in large measure on the feed used and upon the desired pour point. Generally, the temperature will be between about 200°C and about 475°C, preferably between about 250°C and about 450°C. The pressure is typically between about 15 psig and about 3000 psig, preferably between about 200 psig and 3000 psig. The LHSV preferably will be from 0.1 to 20, preferably between about 0.2 and about 10. Hydrogen is preferably present in the reaction zone during the catalytic dewaxing process. The hydrogen to feed ratio is typically between about 500 and about 30,000 SCF/bbl (standard cubic feet per barrel), preferably about 1,000 to about 20,000 SCF/bbl. Generally, hydrogen will be separated from the product and recycled to the reaction zone. Typical feedstocks include light gas-oil, heavy gas-oils, and reduced crudes boiling about 350°F. The (B)SSZ-24 hydrodewaxing catalyst may optionally contain a hydrogenation component of the type commonly employed in dewaxing catalysts. The hydrogenation component mayiJbe // cr\ -17- ^ ^ %t "C <• 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 23 4 4 0 3 selected from the group of hydrogenation catalysts consisting of one or more metals of Group VIB and Group VIII, including the salts, complexes and solutions containing such metals. The preferred hydrogenation catalyst is at least one of the group of metals, salts, and complexes selected from the group consisting of at least one of platinum, palladium, rhodium, iridium, and mixtures thereof or at least one from the group consisting of nickel, molybdenum, cobalt, tungsten, titanium, chromium, and mixtures thereof. Reference to the catalytically active metal or metals is intended to encompass such metal or metals in the elemental state or in some form such as an oxide, sulfide, halide, carboxylate, and the like. The hydrogenation component of the hydrodewaxing catalyst is present in an effective amount to provide an effective hydrodewaxing catalyst preferably in the range of from about 0.05 to 5% by weight. (B)SSZ-24 can be used to convert straight run naphthas and similar mixtures to highly aromatic mixtures. Thus, normal and slightly branched chained hydrocarbons, preferably having a boiling range above about 40°C and less than about 200°C, can be converted to products having a substantial aromatics content by contacting the hydrocarbon feed with the zeolite at a temperature in the range of from about 400°C to 600°C, preferably 480°C to 550°C at pressures ranging from atmospheric to 10 bar, and LHSV ranging from 0.1 to 15. The hydrogen to hydrocarbon ratio will range between 1 and 10. (B)SSZ-24 can be used in a fixed, fluid, or moving bed reformer. -18- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 234403 The reforming catalyst preferably contain a Group viii metal compound to have sufficient activity for commercial use. By Group viii metal compound as used herein is meant the metal itself or a compound thereof. The Group viii noble metals and their compounds, platinum, palladium, and iridium, or combinations thereof can be used. The most preferred metal is platinum. The amount of Group viii metal present in the conversion catalyst should be within the normal range of use in reforming catalysts, from about 0.05 to 2.0 wt. %, preferably 0.2 to 0.8 wt. %. The catalyst may also contain a second metal selected from rhenium or tin. The zeolite/Group VIII metal conversion catalyst can be used without a binder or matrix. The preferred inorganic matrix, where one is used, is a silica-based binder such as Cab-O-Sil or Ludox. Other matrices such as magnesia and titania can be used. The preferred inorganic matrix is nonacidic. It is critical to the selective production of aromatics in useful quantities that the conversion catalyst be substantially free of acidity, for example, by poisoning the zeolite with a basic metal, e.g., alkali metal, compound. The zeolite is usually prepared from mixtures containing alkali metal hydroxides and thus, have alkali metal contents of about 1-2 wt. %. These high levels of alkali metal, usually sodium or potassium, are unacceptable for most catalytic applications because they greatly deactivate the catalyst for cracking reactions. Usually, the alkali metal is removed to low levels by ion exchange with hydrogen or ammonium ions. By alkali metal compound as used herein is meant elemental or ionic alkali metals or their basic compounds. Surprisingly, unless the zeolite itself is substantially free of acidity, the basic compound is -19- 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 23 4 4 0 required in the present process to direct the synthetic reactions to aromatics production. The amount of alkali metal necessary to render the zeolite substantially free of acidity can be calculated using standard techniques based on the aluminum, gallium or iron content of the zeolite. If a zeolite free of alkali metal is the starting material, alkali metal ions can be ion exchanged into the zeolite to substantially eliminate the acidity of the zeolite. An alkali metal content of about 100%, or greater, of the acid sites calculated on a molar basis is sufficient. Where the basic metal content is less than 100% of the acid sites on a molar basis, the test described in U.S. Patent No. 4,347,394 which patent is incorporated herein by reference, can be used to determine if the zeolite is substantially free of acidity. The preferred alkali metals are sodium, potassium, and cesium. The zeolite itself can be substantially free of acidity only at very high silica:alumina mole ratios; by "zeolite consisting essentially of silica" is meant a zeolite which is substantially free of acidity without base poisoning. Hydrocarbon cracking stocks can be catalytically cracked in the absence of hydrogen using (B)SSZ-24 at LHSV from 0.5 to 50, temperatures from about 260°F to 1625°F and pressures from subatmospheric to several hundred atmospheres, typically from about atmospheric to about five atmospheres. For this purpose, the (B)SSZ-24 catalyst can be composited with mixtures of inorganic oxide supports as well as traditional cracking catalyst. -20- 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 23 4 4 0,; The catalyst may be employed in conjunction with traditional cracking catalysts, e.g., any aluminosilicate heretofore employed as a component in cracking catalysts. Representative of the zeolitic aluminosilicates disclosed heretofore as employable as component parts of cracking catalysts are Zeolite Y (including steam stabilized chemically modified, e.g., ultra-stable Y), Zeolite X, Zeolite beta (U.S. Patent No. 3,308,069), Zeolite ZK-20 (U.S. Patent No. 3,445,727), Zeolite ZSM-3 (U.S. Patent No. 3,415,736), faujasite, LZ-10 (U.K. Patent 2,014,970, June 9, 1982), ZSM-5-Type Zeolites, e.g., ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48, crystalline silicates such as silicalite (U.S. Patent No. 4,061,724), erionite, mordenite, offretite, chabazite, FU-l-type zeolite, NU-type zeolites, LZ-210-type zeolite and mixtures thereof. Traditional cracking catalysts containing amounts of Na20 less than about one percent by weight are generally preferred. The relative amounts of the (B)SSZ-24 component and traditional cracking component, if any, will depend at least in part, on the selected hydrocarbon feedstock and on the desired product distribution to be obtained therefrom, but in all instances, an effective amount of (B)SSZ-24 is employed. When a traditional cracking catalyst (TC) component is employed, the relative weight ratio of the TC to the (B)SSZ-24 is generally between about 1:10 and about 500:1, desirably between about 1:10 and about 200:1, preferably between about 1:2 and about 50:1, and most preferably between about 1:1 and about 20:1. The cracking catalysts are typically employed with an inorganic oxide matrix component which may be any of the inorganic oxide matrix components which have been employed heretofore in the formulation of FCC catalysts including: amorphous catalytic inorganic oxides, e.g., catalytically -21- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 2 3 4 4 0 active silica-aluminas, clays, silicas, aluminas, silica-aluminas, silica-zirconias, silica-magnesias, alumina-borias, alumina-titanias, and the like and mixtures thereof- The traditional cracking component and (B)SSZ-24 may be mixed separately with the matrix component and then mixed or the TC component and (B)SSZ-24 may be mixed and then formed with the matrix component. The mixture of a traditional cracking catalyst and (B)SSZ-24 may be carried out in any manner which results in the coincident presence of such in contact with the crude oil feedstock under catalytic cracking conditions. For example, a catalyst may be employed containing the traditional cracking catalyst and a (B)SSZ-24 in single catalyst particles or (B)SSZ-24 with or without a matrix component may be added as a discrete component to a traditional cracking catalyst. (B)SSZ—24 can also be used to oligomerize straight and branched chain olefins having from about 2-21 and preferably 2-5 carbon atoms. The oligomers which are the products of the process are medium to heavy olefins which are useful for both fuels, i.e., gasoline or a gasoline blending stock and chemicals. The oligomerization process comprises contacting the olefin feedstock in the gaseous state phase with (B)SSZ-24 at a temperature of from about 450°F to about 1200°F, a WHSV of from about 0.2 to about 50 and a hydrocarbon partial pressure of from about 0.1 to about 50 atmospheres. Also, temperatures below about 450°F may be used to oligomerize the feedstock, when the feedstock is in the liquid phase when contacting the zeolite catalyst. Thus, -22- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 2 3 4 4 0 v when the olefin feedstock contacts the zeolite catalyst in the liquid phase, temperatures of from about 50°F to about 450°F, and preferably from 80 to 400°F may be used and a WHSV of from about 0.05 to 20 and preferably 0.1 to 10. It will be appreciated that the pressures employed must be sufficient to maintain the system in the liquid phase. As is known in the art, the pressure will be a function of the number of carbon atoms of the feed olefin and the temperature. Suitable pressures include from about 0 psig to about 3000 psig. The zeolite can have the original cations associated therewith replaced by a wide variety of other cations according to techniques well known in the art. Typical cations would include hydrogen, ammonium, and metal cations including mixtures of the same. Of the replacing metallic cations, particular preference is given to cations of metals such as rare earth metals, manganese, calcium, as well as metals of Group II of the Periodic Table, e.g., zinc, and Group VIII of the Periodic Table, e.g., nickel. One of the prime requisites is that the zeolite have a fairly low aromatization activity, i.e., in which the amount of aromatics produced is not more than about 20 wt. %. This is accomplished by using a zeolite with controlled acid activity [alpha value] of from about 0.1 to about 120, preferably from about 0.1 to about 100, as measured by its ability to crack n-hexane. Alpha values are defined by a standard test known in the art, e.g., as shown in U.S. Patent No. 3,960,978 which is incorporated herein by reference. If required, such zeolites may be obtained by steaming, by use in a conversion process or by any other method which may occur to one skilled in this art. -23- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 23 4 4 0 v (B)SSZ—24 can be used to convert light gas C2~C6 paraffins and/or olefins to higher molecular weight hydrocarbons including aromatic compounds. Operating temperatures of 100-700°C, operating pressures of 0-1000 psig and space velocities of 0.5-40 hr~* WHSV can be used to convert the C2~Cg paraffin and/or olefins to aromatic compounds. Preferably, the zeolite will contain a catalyst metal or metal oxide wherein said metal is selected from the group consisting of Group IB, IIB, IIIA, or VIII of the Periodic Table, and most preferably, gallium or zinc and in the range of from about 0.05-5 wt. %. (B)SSZ-24 can be used to condense lower aliphatic alcohols having 1-10 carbon atoms to a gasoline boiling point hydrocarbon product comprising mixed aliphatic and aromatic hydrocarbons. Preferred condensation reaction condition using (B)SSZ-24 as the condensation catalyst include a temperature of about 500-1000°F, a pressure of about 0.5-1000 psig and a space velocity of about 0.5-50 WHSV. U.S. Patent No. 3,984,107 describes the condensation process conditions in more detail. The disclosure of U.S. Patent No. 3,984,107 is incorporated herein by reference. The (B)SSZ-24 catalyst may be in the hydrogen form or may be base exchanged or impregnated to contain ammonium or a metal cation complement, preferably in the range of from about 0.05-5 wt. %. The metal cations that may be present include any of the metals of the Groups I-VIII of the Periodic Table. However, in the case of Group IA metals, the cation content should in no case be so large as to effectively inactivate the catalyst. -24- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 2 3 4 4 0 v The (B)SSZ-24 catalyst is highly active and highly selective for isomerizing C4 to Cj hydrocarbons. The activity means that the catalyst can operate at relatively low temperatures which thermodynamically favors highly branched paraffins. Consequently, the catalyst can produce a high octane product. The high selectivity means that a relatively high liquid yield can be achieved when the catalyst is run at a high octane. The isomerization process comprises contacting the isomerization catalyst with a hydrocarbon feed under isomerization conditions. The feed is preferably a light straight run fraction, boiling within the range of 30-250°F and preferably from 60-200°F. Preferably, the hydrocarbon feed for the process comprises a substantial amount of C^ to Cy normal and slightly branched low octane hydrocarbons, more preferably Cg and Cg hydrocarbons. The pressure in the process is preferably between 50-1000 psig, more preferably between 100-500 psig. The LHSV is preferably between about 1 to about 10 with a value in the range of about 1 to about 4 being more preferred. It is also preferable to carry out the isomerization reaction in the presence of hydrogen. Preferably, hydrogen is added to give a hydrogen to hydrocarbon ratio (H2/HC) of between 0.5 and 10 H2/HC, more preferably between 1 and 8 H2/HC. The temperature is preferably between about 200°F and about 1000°F, more preferably between 400-600°F. As is well known to those skilled in the isomerization art, the initial selection of the temperature within this broad range is made primarily as a function of the desired conversion level considering the characteristics of the feed and of the catalyst. Thereafter, to provide a relatively constant -25- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 2 3 4 4 C value for conversion, the temperature may have to be slowly increased during the run to compensate for any deactivation that occurs. A low sulfur feed is especially preferred in the isomerization process. The feed preferably contains less than 10 ppm, more preferably less than 1 ppm, and most preferably less than 0.1 ppm sulfur. In the case of a feed which is not already low in sulfur, acceptable levels can be reached by hydrogenating the feed in a presaturation zone with a hydrogenating catalyst which is resistant to sulfur poisoning. An example of a suitable catalyst for this hydrodesulfurization process is an alumina-containing support and a minor catalytic proportion of molybdenum oxide, cobalt oxide and/or nickel oxide. A platinum on alumina hydrogenating catalyst can also work. In which case, a sulfur sorber is preferably placed downstream of the hydrogenating catalyst, but upstream of the present isomerization catalyst. Examples of sulfur sorbers are alkali or alkaline earth metals on porous refractory inorganic oxides, zinc, etc. Hydrodesulfurization is typically conducted at 315-455°C, at 200-2000 psig, and at a LHSV of 1-5. It is preferable to limit the nitrogen level and the water content of the feed. Catalysts and processes which are suitable for these purposes are known to those skilled in the art. After a period of operation, the catalyst can become deactivated by coke. Coke can be removed by contacting the catalyst with an oxygen-containing gas at an elevated temperature. -26- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 23440; The isomerization catalyst preferably contains a Group VIII metal compound to have sufficient activity for commercial use. By Group VIII metal compound as used herein is meant the metal itself or a compound thereof. The Group VIII noble metals and their compounds, platinum, palladium, and iridium, or combinations thereof can be used. Rhenium and tin may also be used in conjunction with the noble metal. The most preferred metal is platinum. The amount of Group VIII metal present in the conversion catalyst should be within the normal range of use in isomerizing catalysts, from about 0.05-2.0 wt. %. (B)SSZ-24 can be used in a process for the alkylation or transalkylation of an aromatic hydrocarbon. The process comprises contacting the aromatic hydrocarbon with a C2 to C2q olefin alkylating agent or a polyalkyl aromatic hydrocarbon transalkylating agent, under at least partial liquid phase conditions, and in the presence of a catalyst comprising SSZ-24. For high catalytic activity, the (B)SSZ-24 zeolite should be predominantly in its hydrogen ion form. Generally, the zeolite is converted to its hydrogen form by ammonium exchange followed by calcination. If the zeolite is synthesized with a high enough ratio of organonitrogen cation to sodium ion, calcination alone may be sufficient. It is preferred that, after calcination, at least 80% of the cation sites are occupied by hydrogen ions and/or rare earth ions. The pure (BJSSZ-24 zeolite may be used as a catalyst, but generally, it is preferred to mix the zeolite powder with an inorganic oxide binder such as alumina, silica, silica-alumina, or naturally occurring clays and form the -27- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 23440. mixture into tablets or extrudates. The final catalyst may contain from 1-99 wt. % (B)SSZ-24 zeolite. Usually the zeolite content will range from 10-90 wt. %, and more typically from 60-80 wt. %. The preferred inorganic binder is alumina. The mixture may be formed into tablets or extrudates having the desired shape by methods well known in the art. Examples of suitable aromatic hydrocarbon feedstocks which may be alkylated or transalkylated by the process of the invention include aromatic compounds such as benzene, toluene, and xylene. The preferred aromatic hydrocarbon is benzene. Mixtures of aromatic hydrocarbons may also be employed. Suitable olefins for the alkylation of the aromatic hydrocarbon are those containing 2-20 carbon atoms, such as ethylene, propylene, butene-1, trans-butene-2, and cis-butene-2, and higher olefins, or mixtures thereof. The preferred olefin is propylene. These olefins may be present in admixture with the corresponding C2 to C2q paraffins, but it is preferable to remove any dienes, acetylenes, sulfur compounds or nitrogen compounds which may be present in the olefin feedstock stream to prevent rapid catalyst deactivation. When transalkylation is desired, the transalkylating agent is a polyalkyl aromatic hydrocarbon containing two or more alkyl groups that each may have from two to about four carbon atoms. For example, suitable polyalkyl aromatic hydrocarbons include di-, tri-, and tetra-alkyl aromatic hydrocarbons, such as diethylbenzene, triethylbenzene, diethylmethylbenzene (diethyltoluene), di-isopropylbenzene, di-isopropyltoluene, dibutylbenzene, and the like. -28- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 234 4 03 Preferred polyalkyl aromatic hydrocarbons are the dialkyl benzenes. A particularly preferred polyalkyl aromatic hydrocarbon is di-isopropylbenzene. Reaction products which may be obtained include ethylbenzene from the reaction of benzene with either ethylene or polyethylbenzenes, cumene from the reaction of benzene with propylene or polyisopropylbenzenes, ethyltoluene from the reaction of toluene with ethylene or polyethyltoluenes, cymenes from the reaction of toluene with propylene or polyisopropyltoluenes, and sec-butyl benzene from the reaction of benzene and n-butenes or polybutylbenzenes. The production of cumene from the alkylation of benzene with propylene or the transalkylation of benzene with di-isopropylbenzene is especially preferred. When alkylation is the process conducted, reaction conditions are as follows. The aromatic hydrocarbon feed should be present in stoichiometric excess. It is preferred that molar ratio of aromatics to olefins be greater than four-to-one to prevent rapid catalyst fouling. The reaction temperature may range from 100-600°F, preferably, 250-450°F. The reaction pressure should be sufficient to maintain at least a partial liquid phase in order to retard catalyst fouling. This is typically 50-1000 psig depending on the feedstock and reaction temperature- Contact time may range from 10 seconds to 10 hours, but is usually from five minutes to an hour. The WHSV, in terms of grams (pounds) of aromatic hydrocarbon and olefin per gram (pound) of catalyst per hour, is generally within the range of about 0.5 to 50. When transalkylation is the process conducted, the molar ratio of aromatic hydrocarbon will generally range from about 1:1 to 25:1, and preferably from about 2:1 to 20:1. -29- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 234 4 0 The reaction temperature may range from about 100-600°f, but it is preferably about 250-450°f. The reaction pressure should be sufficient to maintain at least a partial liquid phase, typically in the range of about 50-1000 psig, preferably 300-600 psig. The WHSV will range from about 0.1-10. The conversion of hydrocarbonaceous feeds can take place in any convenient mode, for example, in fluidized bed, moving bed, or fixed bed reactors depending on the types of process desired. The formulation of the catalyst particles will vary depending on the conversion process and method of operation. Other reactions which can be performed using the catalyst of this invention containing a metal, e.g., platinum, include hydrogenation-dehydrogenation reactions, denitrogenation, and desulfurization reactions. Some hydrocarbon conversions can be carried out on SSZ-24 zeolites utilizing the large pore shape-selective behavior. For example, the substituted (B)SSZ-24 zeolite may be used in preparing cumene or other alkylbenzenes in processes utilizing propylene to alkylate aromatics. Such a process is described in our U.S. Serial No. 134,410 (1987), using beta zeolite. (B)SSZ-24 can be used in hydrocarbon conversion reactions with active or inactive supports, with organic or inorganic binders, and with and without added metals. These reactions are well known to the art, as are the reaction conditions. -30- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 23 4 4 0 (B)SSZ-24 can also be used as an adsorbent, as a filler in paper, paint, and toothpastes, and as a water-sofnening agent in detergents. The following examples illustrate the preparation of {B)SSZ—24. EXAMPLES Example 1 Preparation of N,N,N-Trimethyl-1-Adamantane [3.3.1.1]Tricyclodecane Ammonium Hydroxide (Template ) The quaternary ammonium compound used in the SSZ-24 synthesis is prepared by an adaptation of an amino acid alkylation method (Can. J. Chem. 54 3310, 1976). One hundred grams of 1-adamantanamine (1-amino tricyclot3.3--l.l]decane, Aldrich) is dissolved in 1.5 L of methanol. One hundred seventy-two grams of potassium bicarbonate is slurried into solution. The solution is chilled in an ice bath and 400 g of methyl iodide is added dropwise with stirring. The reaction is allowed to come to room temperature and is stirred for a few days. The reaction is concentrated to dryness by removing methanol and unreacted methyl iodide. The residue is treated with chloroform to extract the organic salts from the inorganics. The chloroform extracts are stripped down leaving an off-white solid. This is recrystallized from a minimum of hot methanol to yield N,N,N,-trimethyl-l-adamantammonium iodide (decomposes at 309°C by DSC analysis). -31- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 23 4 4 0 v The crystalline salt is conveniently converted to the hydroxide form by stirring overnight in water with AGI-X8 hydroxide ion exchange resin to achieve a solution ranging from 0.25-1.5 molar. Example 2 2.25 millimoles of the hydroxide form of the template from Example 1 and 0.10 g koh (solid) in a total of 12 mL 1^0 are stirred until clear. 0.90 grams Cabosil M-5 is stirred in. 0.60 g of NH^+ boron beta (aluminum free and described in our U.S. Serial Application) is added and the reaction is heated at 150°C for seven days and at 0 rpm. The product after filtration and washing, drying at 100°C, and XRD analysis is found to be (b)SSZ-24. Changes in lattice parameters (see below) demonstrate boron incorporation. No remaining beta zeolite is observed. Example 3 The same experiment as Example 2 is set up except the boron beta zeolite is added to the reaction at three days of heating. Heating is carried out for another four days. The product is still (B)SSZ-24. Example 4 An experiment is run to see if the boron beta contribution to the product can be increased. 1.12 millimoles of template hydroxide and 0.05 g KOH(s) are mixed in 6 mL ^0. 0.45 grams Cabosil is added and the reaction is heated for four days at 150°C and 0 rpm. The reaction produces a gel. 0.60 grams of NH^+ boron beta is added and the reaction is heated for three more days. A crystalline product is -32- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 23 4 4 0 obtained and is (B)SSZ-24 upon analysis. The contribution of boron beta has been doubled in this reaction relative to Examples 2 and 3. Example 5 The same reaction is run using boron beta made originally from Ludox AS-30; hence, 500 ppm aluminum is introduced into the reaction. But again, the crystalline product is (B)SSZ-24 with the aluminum carried along in the hydrothermal conversion. Example 6 In this reaction, the amorphous silica is replaced by a much smaller quantity of seed material. The solution phase consists of 6.82 g of 0.33 molar template, 0.10 g KOH(s) and 5.2 g ^O. 1.00 g of NH4+ boron beta and 0.10 g of all silica SSZ-24, as synthesized, is added as seed material (the SSZ-24 is prepared as described in U.S. Patent No. 4,665,110). The reaction is run for four days at 0 rpm and 150°C. The product is well-crystallized (B)SSZ-24. XRD data is given in Table II. This reaction approaches a straight transformation of boron beta to boron SSZ-24 in the presence of the correct template and base. However, we note that in the absence of an all-silica source, the transformation does not occur at all. Several reactions were carried out with the intention of replacing boron beta with a boron-containing glass. A finely powered Pyrex material was used. It contained aluminum as well as boron. All reactions contained the same amount of template, KOH and water as the reaction in Example 6. Heating was at 150°C. -33- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 23 4 4 0 TABLE II 2 9 d/n int. 100 x I/IQ 7.58 11.66 45 13.08 6.77 6 15.12 5.86 32 20.04 4.431 75 21.56 4.122 64 22.80 3.900 100 25.31 3.519 7 26.33 3.385 35 29.55 3.023 16 30.50 2.931 21 Examples 7 through 12 It can be seen in Examples 7-12 (see Table III) that Pyrex does not afford as pure a product and reaction rates are slower than when boron beta zeolite is used. In Examples 11 and 12, when Pyrex is the major silica source, the presence of aluminum becomes important enough to give SS2-13 (a chabazite phase) as the exclusive product. Example 13 Not only does the boron beta yield a pure boron SSZ-24 as described in Examples 2-6, but the crystallization rate is even greatly enhanced over the all-silica synthesis from Cabosil. A reaction is set up as in Example 2. The reaction is run at 150°C, 0 rpm, but for only one day. A crystalline product is already produced which analyzed as pure boron SSZ-24. The all-silica SSZ-24 usually requires 7-10 days to crystallize. -34- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 O 0.) o o :-'tv ■o \ TABLE III Reactions Using Powdered Pyrex Glass (150-250 Hesh) Example No. Cabosil, g SSZ-24 Seeds, g Glass, g (Added at X Days) Rpm Major Total Run, Phase Days XRD., Others XRD„ 7 0.90 - 0.60 To 45 11 SSZ-24 SSZ-31 Trace3 8 0.90 - 0.60 To 0 12 SSZ-24 SSZ-23 Traceb 9 0.90 - 0.60 3 45 11 SSZ-24 SSZ-23 Trace 10 0.90 - 0.60 3 0 12 SSZ-24 SSZ-23 Minor 11 - 0.05 0.90 To 45 6 SSZ-130 None 12 _ 0.05 0.90 To 0 7 SSZ-13 None aDescribed in our U.S. Serial No. 260,439 application. described in E.P. 231 018 A2. cDescribed in U.S. Patent No. 4,665,110. Osl 4S 4>* O 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 23 4 4 0 Example 14 The product of Example 2 was calcined as follows. The sample was heated in a muffle furnace from room temperature up to 540°C at a steadily increasing rate over a 7-hour period. The sample was maintained at 540°C for four more hours and then taken up to 600°C for an additional four hours. Nitrogen was passed over the zeolite at a rate of 20 standard cubic feet per minute (cfm) during heating (a small amount of oxygen is also present). The calcined product had the X-ray diffraction lines indicated in Table IV below. TABLE IV 2 6 d/n Int. 100 x I/IQ 7.50 11.79 100 13.00 6.81 16 15.03 5.894 8 19.93 4.455 35 21.42 4.148 48 22.67 3.922 60 25.15 3.541 3 26.20 3.401 22 29.38 3.040 12 30.43 2.947 12 Example 15 Ion exchange of the calcined material from Example 14 was carried out using NH^NO^ to convert the zeolites from K form to NH^. Typically the same mass of NH^NO^ as zeolite was slurried into h20 at ratio of 50:1 H20:zeolite. The exchange solution was heated at 100°C for two hours and then -36- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 23 4 4 0 3 filtered. This process was repeated two times. Finally, after the last exchange, the zeolite was washed several times with i^O and dried. Example 16 Constraint Index Determination 0.50 g of the hydrogen form of the zeolite of Example 3 (after treatment according to Examples 14 and 15) was packed into a 3/8-inch stainless steel tube with alundum on both sides of the zeolite bed. A lindburg furnace was used to heat the reactor tube. Helium was introduced into the reactor tube at 10 cc/minute and atmospheric pressure. The reactor was taken to 250°F for 40 minutes and then raised to 800°F. Once temperature equilibration was achieved, a 50/50, w/w feed of n-hexane and 3-methylpentane was introduced into the reactor at a rate of 0.62 cc/hour. Feed delivery was made via syringe pump. Direct sampling onto a gas chromatograph was begun after 10 minutes of feed introduction. Constraint Index values were calculated from gas chromatographic data using methods known in the art. Example Conversion No. C.I. at 10 Min. Temp., °F 16 -- 0 800 Example 17 The product of Example 3 after treatment as in Examples 14 and 15 is refluxed overnight with Al(N03)3*9H20 with the latter being the same mass as the zeolite and using the same dilution as in the ion exchange of Example 15. The product is filtered, washed, and calcined to 540°C. After pelletizing the zeolite powder and retaining the 20-40 mesh -37- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 23 4 4 0 fraction, the catalyst is tested as in Example 16. Data for the reaction is given in Table V along with a variety of catalysts made from analogous treatments with other metal salts. TABLE V Constraint Index Determination For Metal-Treated (B)SSZ-24 Example No. Metal Salt C.I. Conversion, % {10 Min.) Temp., °F 16 17 18 19 None akno3)3 Ga(n03)3 Zn(AC) -> 0.30 0.20 0.08 0 70 33 18 800 700 700 800 Table VI gives the lattice parameter changes for samples of (B)SSZ—24 unsubstituted, substituted with aluminum or boron and with and without calcination. TABLE VI Lattice Constants for (B)SSZ-24 Example No. Framework Calcined Substitution Volume 2 No B 13.57 8.27 3956 2 Yes B 13.61 8.30 3994 3 No B 13.55 8.26 3940 6 No B 13.54 8.24 3925 From ACS No. 368 No None 13.62 8.30 4000 From ACS No. 368 Yes None 13.62 8.32 4010 6-»14-»17 Yes Al, B 13.66 8.33 4038 21 (Before Pt) Yes Al, B 13.68 8.34 4055 -38- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 23 4 4 0 Example 20 The borosilicate version of (B)SSZ-24 was evaluated as a reforming catalyst. The zeolite powder was impregnated with Pt(NH2)^*2N02 to give 0.8 wt. % Pt. The material was calcined up to 550°F in air and maintained at this temperature for three hours. The powder was pelletized on a Carver press at 1000 psi and broken and meshed to 24-40. The catalyst was evaluated at 800°F to 900°F in hydrogen after reduction at 950°F (1 hr, 300 cc/min.) under the following conditions: The feed was an iC^ mixture (Philips Petroleum Company). The data for the run is given in Table VII. psig h2/hc WHSV 200 6.4 6 TABLE VII Product, % 800 °F 900 °F Conversion Toluene Cg-Cg Octane Cg+ Yield 79.6 100.0 22.1 21.9 86.8 105.2 54.9 35.4 Aromatization Selectivity Toluene in 32.1 30.2 Cg+ Aromatics 86.6 72.7 -39- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 2 3 4 4 0 v Example 21 The product of Example 17 now contained acidity due to aluminum incorporation. Two back ion exchanges with KNO^ were performed and the catalyst was calcined to 1000°F. Next, a reforming catalyst was prepared as in Example 20. The catalyst was evaluated under the following conditions: psig h2/hc whsv Temperature = 200 = 6.4 = 6 = 800, 900 °F The feed was an iC^ mixture (Philips Petroleum Company). The data for the run is given in Table VIII. After 23 hours onstream, the temperature was raised to 900°F and this data also appears in the table. By comparison with Example 20, the incorporation of aluminum into the zeolite gives a more aromatic selective reforming catalyst and a higher C^+ yield. TABLE VIII 1 Hr (After 91 Hr (After Time 23 Hr 23 Hr at 800°F) 23 Hr at 800°F) Temperature, °F 800 900 900 Conversion, % 53 95.1 85.3 Aromatization Select., % 47.1 35.7 38.2 Toluene in Product, % 22.6 26.6 27.3 Toluene in C^+ Aromatics, % 90.6 78.1 83.8 -40- 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 2 3 4 4 0 » TABLE VIII (Cont.) 1 Hr (After 91 Hr (After Time 23 Hr 23 Hr at 800°F) 23 Hr at 800°F) C5-Cg RON 78.1 99.6 92.4 C5+ Yield % 81.5 46.2 55.1 Example 22 A product was prepared as in Example 17. Next, the catalyst was dried at 600°F, cooled in a closed system, and then vacuum impregnated with an aqueous solution of Pd (NH^J^^NO^ to give 0.5 wt. % loading of palladium. The catalyst was then calcined slowly, up to 900°F in air and held there for three hours. Table IX gives run conditions and product data for the hydrocracking of hexadecane. The catalyst is quite stable at the temperatures given. table ix Temperature, °F 570 587 WHSV 1.55 1.55 psig 1200 1200 Conversion 77.8 83.7 Isom. Select. 21.8 16.0 Crack. Select- 78.2 84.0 C5+/C4 11.2 11.5 C5+C6/C5+ % 22,3 22 *3 The data shows that the catalyst has isomerization activity and that the liquid yield is high compared with the gas make. -41- 23 4 4 0 . 01 Example 23 02 03 Benzene/Propylene Alkylation With (B)SSZ-24 Catalyst 04 05 The ability of the aluminum containing (B)SSZ-24 zeolite to 06 catalyze the alkylation of an aromatic hydrocarbon by an 07 olefin was demonstrated as follows. Aluminum containing 08 (B)SSZ-24 powder from Example 17 was pressed to form tablets 09 which were crushed and sieved to obtain 10-20 mesh granules 10 for testing. The granular catalyst was weighed and charged 11 to a tubular microreactor. The catalyst was heated to 450°F 12 in flowing nitrogen at atmospheric pressure. Nitrogen flow 13 was continued for four hours to dry and activate the 14 catalyst. After the drying period, the nitrogen flow was 15 continued while the reactor was cooled to 325°F and 16 pressurized to 600 psig. When the pressure had stabilized 17 at 600 psig, the nitrogen flow was stopped and liquid 18 benzene was passed upflow through the reactor- After the 19 reactor was filled with liquid benzene, liquid propylene was 20 injected into the benzene feed stream to give 21 benzene/propylene feed molar ratio of 7.2 to 1 and a total 22 feed rate of 5.7 g per gram of dry zeolite per hour. During 23 the run, the reaction temperature was raised from 325°F to 24 3508F. 25 26 Periodic analysis of the reactor effluent by capillary 27 gas-liquid-chromatography (Table X) showed that all of the 28 propylene was converted to make a product comprised of 84-86 29 wt. % cumene and 15-13 wt. % diisopropylbenzenes on a 30 benzene-free weight basis. It is anticipated that the 31 diisopropylbenzene can be reacted in a separate reactor with 32 benzene to make additional cumene. The conversion to useful 33 product was thus about 99 wt. % based on propylene and 34 benzene reacted. -42- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 234 4 0 A high sensitivity GLC analysis (Table XI) of the liquid products showed that they contained very little ethylbenzene or n-propylbenzene and thus cumene made with this (B)SSZ-24 catalyst would easily meet a 99.9% specification for cumene purity. TABLE X Benzene/Propylene Alkylation Over (B)SSZ-24 Zeolite Catalyst Hours Onstream 6-18 20-42 49-67 Temperature, °F 325 325 350 Pressure, psig 600 600 600 BZ/C3 Molar Ratio 7.2 7.2 7.2 WHSV % Propylene Conversion 100.0 100.0 100.0 Product Wt. % Ethlybenzene Cumene n-Propylbenzene 1.3-Diisopropylbenzene 1.4-Diisopropylbenzene 1,3,5-Triisopropylbenzene Other iH O • o 0.01 o • o h-* 85.7 83.7 86.0 0.02 0.03 0.03 4.7 4.4 4.4 8.7 10.8 8.6 0.02 0.01 0.01 0.8 1.1 0.9 -43- 01 02 03 <T4 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 234403 TABLE XI Analysis of Cumene Impurities In Reactor Effluent Hours Onstream 18-19 67-6S Reaction Temperature, 325 350 Cumene Impurities In Reactor Effluent Wt-ppm Based Cumene; Sthylbensene 81 107 Xylenes 5 6 n-Propylbensene 258 349 Tert-Butvlbenzene 190 174 Sec-Butylbenzene 71 72 Alpha-Methylstyrene 42 13 m-Cvmene 51 30 p-Cymene 56 51 Total 754 802 Note: Same Run as TABLE X. Example 24 The acid form of (B)SSZ-24 was prepared as in Example 17 and tested for the conversion of methanol to liquid products. 0.5 g of catalyst was loaded into a 3/8-inch stainless steel reactor tube which was heated in a Lindberg furnace to 1000°F. The temperature was reduced to 700®F in a stream of helium at 20 cc/min. Methanol was introduced into the reactor at a rate of 1.25 cc/hr. The conversion at 10 -44- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 23 4 4 0 TABLE XI Analysis of Cumene Impurities In Reactor Effluent Hours Onstream 18-19 67-68 Reaction Temperature, °F 325 350 Cumene Impurities In Reactor Effluent Wt-ppm Based Cumene: Ethylbenzene 81 107 Xylenes 5 6 n-Propylbenzene 258 349 Tert-Butylbenzene 190 174 Sec-Butylbenzene 71 72 Alpha-Methylstyrene 42 13 m-Cymene 51 30 p-Cymene 56 51 Total 754 802 Note: Same Run as TABLE X. Example 24 The acid form of (B)SSZ-24 was prepared as in Example 17 and tested for the conversion of methanol to liquid products. 0.5 g of catalyst was loaded into a 3/8-inch stainless steel reactor tube which was heated in a Lindberg furnace to 1000°F. The temperature was reduced to 700°F in a stream of helium at 20 cc/min. Methanol was introduced into the reactor at a rate of 1.25 cc/hr. The conversion at 10 -44- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 23 4 4 C minutes was close to 100% and dropped only slightly over several hours. The product distribution is given in Table XII below. TABLE XII Products determined by gas chromatography at 5 minutes on-stream at 700°F (100% conversion) Product % Methane 0. .56 Ethylene 5. .60 Ethane 0. .15 Propylene 0. .61 Propane 10, .30 Butanes and Butenes 27. .63 Pentanes and Pentenes 7. .20 Hexanes and Hexenes 1. .45 Benzene 0. .18 Toluene 1. .22 Xylenes and Ethylbenzene 8. .35 Mesitylene 8. .04 Other Cg Aromatics 22. .35 Diethylbenzene 1. .62 The catalyst has surprising life and is capable of making higher molecular weight products than can be analyzed by the poropak Q column. The catalyst is run constantly over a 2-day period and liquid product is collected in a trap including a considerable amount of waxy solid. This product includes aromatics alkylated to the extent of producing pentamethyl benzenes. A simulated distillation sequence is -45- </div>

Claims

<div id="claims" class="application article clearfix printTableText"> 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 23 4 4 0 v given in Table XIII and demonstrates that products in the range of to C^g are being produced by the large pore zeolite catalyst. TABLE XIII Simulated Distillation of Product Collected at Room Temperature from SSZ-24 Conversion of Methanol Cut Temp., °F Cumulative wt. % 350-400 1.31 400-450 13.16 450-500 36.20 500-550 94.73 550-600 97.01 600-650 99.15 -46- ■s 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 >34403 ■ CLAft? VTi.

1. A zeolite having a mole ratio of an oxide selected from silicon oxide, germanium oxide, and mixtures thereof to an oxide selected from boron oxide or mixtures of boron oxide with aluminum oxide, gallium oxide, and iron oxide, between 20:1 and 100:1 and having the X-ray-diffraction lines of Table I. r" ~

2. A zeolite having a mole ratio of silicon oxide to boron oxide between 20:1 and 100:1 and having the X-ray diffraction lines of Table I.

3. A zeolite having a mole ratio of silicon oxide to aluminum oxide between 20:1 and 100:1 and having the X-ray diffraction lines of Table I.

4. A zeolite having a composition, and in the anhydrous state in terms of mole ratios of oxides as follows: (1.0 to 5)Q20:(0.1 to 1.0)M20:W203(20 to 100)Y02 wherein M is an alkali metal cation, W is selected from boron, Y is selected from silicon, germanium, and mixtures thereof, Q is an adamantane quaternary ammonium ion and having the X-ray diffraction lines of Table I.

5. A zeolite prepared by thermally treating the zeolite of Claim 4 at a temperature from 200°C to 820°C.

6. A zeolite in accordance with Claim 4 wherein the adamantane quaternary ammonium ion is derived from an adamantane compound of the formula: -47- • 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 234 4 0v Nw(y1/Y2/Y3)A e (a) wherein each of Y, 0 2> and Y^ independently is lower is an anion which is not detrimental to the formation of the zeolite; and each of R^, R2, and R3 independently is hydrogen, or lower alkyl; and (b) rr'(Y1,Y2,Y3)A 0 wherein each of R^, R^, and Rg independently is hydrogen or lower alkyl; each of Y^, Y2, and Y3 independently is lower alkyl; and A® is an anion which is not detrimental to the formation of the zeolite.

7. A zeolite in accordance with Claim 6 wherein in formula (a) each of Y^, Y2, and Y3 independently is methyl or ethyl; A® is OH or halogen; and each of R^, R2, and R3 is hydrogen; and in formula (b) each of Y^f Y2, and Y3 independently is methyl or ethyl; A® is OH or halogen; and each of R^, R^, and Rg is hydrogen. -48- 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 23 4 4 0 v

8. A zeolite in accordance with Claim 6 wherein Y,, Y?, and Y^ are the same and each is methyl; and A is OH or I.

9. A zeolite in accordance with Claim 1 or 2 which after calcination has undergone ion exchange with hydrogen, ammonium, rare earth metal, Group IIA metal, or Group VIII metal ions.

10. A zeolite in accordance with Claim 1 or 2 wherein rare earth metals, Group IIA metals, or Group VIII metals are occluded in the zeolite.

11. A zeolite composition, comprising the zeolite of Claim 1 or 2 and an inorganic matrix.

12. A method for preparing the zeolite of Claim 1, comprising: (a) preparing an aqueous mixture containing sources of an adamantane quaternary ammonium ion, an oxide selected from boron oxide in a borosilicate form, and an oxide selected from silicon oxide, germanium oxide, and mixtures thereof; (b) maintaining the mixture at a temperature of at least 140°C until the crystals of said zeolite form; and (c) recovering said crystals.

13. A method in accordance with Claim 12 wherein the borosilicate is borosilicate glass, or boron beta zeolite or other boron zeolites. -49- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 23 4 4 0

14. The method in accordance with Claim 12 wherein the aqueous mixture has a composition in terms of mole ratios of oxides falling in the ranges: Y02/W203, 20 to 100; Q/Y02, 0.05:1 to 0.50:1; wherein Y is selected from silicon, germanium, and mixtures thereof, W is selected from boron and Q is an adamantane compound.

15. A method in accordance with Claims 12 and 13 wherein the adamantane quaternary ammonium ion is derived from an adamantane compound of the formula: wherein each of Y^, Y2, and Y^ independently is lower alkyl and a® is an anion which is not detrimental to the formation of the zeolite; and each of R^, R2/ an|3 Rj independently is hydrogen, or lower alkyl; and n®(y1,y2,y3)a9 (a) R, 2 I 4 r (b) r 6 n®(y,,y,,y,)a9 1' 2' 3 wherein each of R^, R^, and Rg independently is hydrogen or lower alkyl; each of Y^, Y2, and Y^ -50- 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 2 3 4 4 0 3 0 independently is lower alkyl; and A is an anion which is not detrimental to the formation of the zeolite.

16. A method in accordance with Claim 14 wherein in formula (a) each of Y^, Y^, and Y^ independently is methyl or ethyl; A® is OH or halogen; and each of and R^ is hydrogen; and in formula (b) each of Y^, Y2* and Y^ independently is methyl or ethyl; A® is OH or halogen; and each of R^, R^, and Rg is hydrogen.;

17. A method in accordance with Claim 15 wherein Y^, Y;0;and Y^ are the same and each is methyl; and A is OH, or I.;

18. A method for replacing the boron in the zeolite of Claim 5 comprising contacting this boron-containing zeolite with an aqueous solution of a Group IIIA metal or a transition metal.;

19. A process for converting hydrocarbons comprising contacting a hydrocarbonaceous feed at hydrocarbon converting conditions with the zeolite of Claim 1.;

20. The process of Claim 19 which is a hydrocracking process comprising contacting the hydrocarbon feedstock under hydrocracking conditions with the zeolite of Claim 1.;

21. The process of Claim 19 which is a process for preparing a product having an increased aromatics content comprising:;-51-;01;02;03;04;05;06;07;08;09;10;11;12;13;14;15;16;17;18;19;20;21;22;23;24;25;26;27;28;29;30;31;32;33;34;? 3 < 4 0 3;(a) contacting a hydrocarbonaceous feed, which comprises normal and slightly branched hydrocarbons having a boiling range above 40°C and less;40°C and less than;200°C under aromatic conversion conditions with the zeolite of Claim 1, wherein said zeolite is substantially free of acidity; and;(b) recovering an aromatic-containing effluent.;

22. The process of Claim 21 wherein the zeolite contains a Group VIII metal component.;

23. The process of Claim 19 which is a dewaxing process comprising contacting the hydrocarbon feedstock under dewaxing conditions with the zeolite of Claim 1.;

24. The process of Claim 19 which is a process for;• alkylating an aromatic hydrocarbon which comprises contacting under alkylating conditions at least a mole excess of an aromatic hydrocarbon with a C2 to C2g olefin under at least partial liquid phase conditions and in the presence of a zeolite according to Claim 1.;

25. The process of Claim 19 which is an isomerizing process for isomerizing to C^. hydrocarbons, comprising contacting a catalyst, comprising at least one Group VIII metal and the zeolite of Claim 1, with a feed having normal and slightly branched C^ to C^ hydrocarbons under isomerization conditions.;

26. A process in accordance with Claim 25 wherein the catalyst has been calcined in a steam/air mixture at an elevated temperature after impregnation of the Group VIII metal.;-52-;234403;01;02;03;04;05;06;07;08;09;10;11;12;13;14;15;16;17;18;19;20;21;24;25;26;27;^ 28;29;30;31;32;33;34;

27. A process in accordance with Claim 25 wherein Group VIII metal is platinum.;

28. The process of Claim 19 which is a process for transalkylating an aromatic hydrocarbon which comprises contacting under transalkylating conditions an aromatic hydrocarbon with a polyalkyl aromatic hydrocarbon under at least partial liquid phase conditions and in the presence of a zeolite according to Claim 1.;

29. The process of Claim 28 wherein said aromatic hydrocarbon and said polyalkyl aromatic hydrocarbon are present in a molar ratio of 1:1 to 25:1, respectively.;

30. The process of Claim 19 which is an oligomerization process comprising contacting an olefin feed under oligomerization conditions with the zeolite of Claim 1.;

31. The process of Claim 19 which is a process for the catalytic conversion of lower aliphatic alcohols having 1 to 8 carbon atoms to form gasoline boiling range and higher molecular weight hydrocarbons which comprises contacting the alcohols under converting conditions with a zeolite of Claim 1.;

32. A process of Claim 19 which is a catalytic cracking process comprising the step of contacting the hydrocarbon feedstock in a reaction zone under catalytic cracking conditions in the absence of added hydrogen with a catalyst composition comprising a;'AJE&S.;\ "*3 APR 1992 ~ ? -53- 234403 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 component which is the zeolite of Claim 1 and a large pore size crystalline aluminosilicate cracking component.

33. The process of Claim 32 wherein the catalyst compositions comprise a physical mixture of the two components.

34. The process of Claim 32 wherein the two catalyst components are incorporated in an inorganic matrix.

35. A zeolite as clained in any one of claims 1-11 substantially as hereinbefore described with reference to any example thereof.

36. A method as clained in any one of claims 12-15 when performed substantially as herein before described with reference to any example thereof.

37. A zeolite produced by a method as claimed in any one of claims 12-18 and 36.

38. A process as claimed in any one of the claims 19 to 34 when performed substantially as hereinbefore described.

39. A converted hydrocarbon product when produced by a process as claimed in any one of claims 19 to 34 and 38. ~ By ter/Their Authorised Sger.ts, A. J. PARK & SON Per. -54- MEW ZEALAND . I PA"; ;\T OFFICE -6JUL1990 ! RECEIVED </div>