NZ231524A - Zeolite ssz-26 optionally containing a hexamethylpropellane diammonium ion and its use in hydrocarbon conversion - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £31 5£4 2M.5 Priority Date(s): Compl*»« Specification Fifed: .2rAk...).i.7.^5| Class: (5). pqi jIvy* i 2-SJ co~7<^2.

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WO DRAWINGS NEW ZEALAND PATENTS ACT, 1953 No.: Date: COMPLETE SPECIFICATION NEW ZEOLITE SSZ-26 2 4 NO]f 1989 jWWe, CHEVRON RESEARCH COMPANY, a corporation duly organised under the laws of the State of Delaware, USA, of 100 West Tenth Street, Wilmington, Delaware, USA, and having a place of business at 555 Market Street, San Francisco, California 94105, United States of America hereby demlare the invention for which jbc/ we pray that a patent may be granted to*Hgtfus, and the method by which it is to be performed, to be particularly described in and by the following statement: - 2315 24 WO 89/09185 PCT/US89/01179 01 05 IS 3b 40 - NEW ZEOLITE SSZ-26 BACKGROUND OP THE INVENTION Natural and synthetic xeolitic crystal Una alumnosilicates ara useful at catalyst* and adsorbents. These aluitinosi licates have distinct crystal structures which are demonstrated by x-ray di (fraction. Pm crystal structure defines cavities and pores wMcfc are character • Istic of the different soecies. The adsocp*i«e a«*3 catalytic properties of each crystalline al'wuwR-o-s; Urate are determined in part oy the dltaensions of its p»ret cavities. Thus, the utility of a partsc^Sar a««U<* s* a particular application depends at least partly a* its crystal structure.

Because of their wniflrw* «©lecsil*r sie*-&nw® characteristics, as well as their catalytic pr-ooert&es. crystalline aluitinosi licates are especially is «-^cn, applications as gas drying and separation a«d JiySroearsofl conversion. Although many different crystalline alwsnsifto-silicates and silicates have been disclosed* there ts 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-trimethyl cyclopentylammo-nium iodide in the preparation of Zeolite SSZ-15 molecular sieve is disclosed in U.S. Patent No. 4,610,85'. ; use of 1-azoniaspiro (4.4] nonyl bromide and N,N,N-trimethyl neo-pentylaiwonium iodide in the preparation of a molecular sieve teraed "Losod" is disclosed in Helv. Chira. Acta i If*), Vol. 57, page 1533 (W. Sieber and W. M. Meier); t use of quinuclidinium compounds to prepare a zeolite termed "NU-3" is disclosed in European Patent Publication OS No. 40016; use of 1,4-di(1-azoniabicyclo 12.2.2.]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-l-adamantamine in the preparation of zeolite SSZ-13 molecular sieve is disclosed in U.S. Patent 10 No. 4,544,538. aluminosilicate molecular sieves with unique properties, referred to herein as "Zeolite SSZ-26", or simply 15 "SSZ-26", and have found a highly effective method for preparing SSZ-26. from silicon oxide, germanium oxide, and mixtures thereof to an oxide selected from aluminum oxide, gallium oxide, iron oxide, and mixtures thereof greater than about 10:1, and preferably in the range of 10:1 to 200:1, and having the X-ray diffraction lines of Table 1 below. The zeolite further has a composition, as synthesized and in the anhydrous state, in terms of mole ratios of oxides as follows: (0.1 to 2.0)Q20:(0.1 to 25 2.0)M20:W203s(10 to 200)Y02 wherein M is an alkali metal cation, W is selected from aluminum, gallium, iron, and mixtures thereof, Y is selected from silicon, germanium and mixtures thereof, and 0 is a hexamethyl 14.3.3.0] propellane-8,11-diammonium cation. SSZ-26 zeolites can *0 have a mole ratio in the range of 10 to 200. As prepared, the silicas alumina mole ratio is typically in the range of 12:1 to about 100:1. Higher mole ratios can be obtained by treating the zeolite with chelating agents or acids to extract aluminum from the zeolite lattice.

This includes reagents such as (NH^)2SiFg or acidic ion exchange resins. The silica:alumina mole ratio can also be increased by using silicon and carbon halides and other similar compounds. Preferably# SSZ-26 is an aluminosilicate wherein W is aluminum and Y is silicon.

SUMMARY OF THE INVENTION We have prepared a family of crystalline SSZ-26 has a mole ratio of an oxide selected 40 231 52 WO 89/09185 PCT/US89/01179 01 IS Our invention also involves a method for preparing SSZ-26 zeolites, comprising preparing an aqueous mixture containing sources of a hexamethyl {4.3.3.0] propellane-8,11-diammonium cation, an oxide selected from aluminum oxide, gallium oxide, iron oxide, and mixtures thereof, 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: Y02/W203, 10:1 to 200:1? and Q/Y02 0.05:1 to 0.50:1; wherein Y is selected from silicon, germanium, and mixtures thereof, W is selected from aluminum, gallium, iron, and mixtures thereof, and 0 is a hexamethyl [4.3.3.0] propellane-8,11-diammonium cation; maintaining the mixture at a temperature of at least 100'C until the crystals of said zeolite are formed; and recovering said crystals.

DETAILED DESCRIPTION OF THE INVENTION SSZ-26 zeolites, as synthesized, have a crystalline structure whose X-ray powder diffraction pattern shows the following characteristic lines: Table 1 2 e d/n I/In x 100 7.78 11.36 100 .33 4.389 63 21.37 4.158 25 21.99 4.042 53 22.85 3.890 46 Sh 23.00 3.867 64 26.49 3.365 33 Sh « Shoulder Typical SSZ-26 aluminosilicate zeolites have the X-ray diffraction pattern of Tables 3-7, The X-ray powder diffraction patterns were 40 determined by standard techniques. The radiation was the 231 52 WO 89/09185 PCT/US89/01179 01 IS JO K-alpha/doublet of copper and a scintillation countcr spectrometer with a strip-chart pen recorder wa* used. The peak heights I and the positions, as a {unction of 2 e where e is the Braga angle, were read froai the spectrometer chart. Fro* these Measured values, the relative intensities, 100j/lo, where I0 is the intensity of tne strongest line or peak, and d, the interolanar specift3 rnt Angstroas correspond!no to the recorded lines, can b* calculated. The X-ray diffraction pattern of Tattle I t» characteristic of SSZ-26 zeolites. The teolite by exchanging the Metal or other cations present in zeolite with various other cations yields substemteUr the saw diffraction pattern although there can ti* shifts in interplanar spacing and sinor variations relative intensity. Minor variations in the di ffraction pattern can also result fran variations in the ar^aftic compound used in the preparation and fro* variations ts the ailica-to-alu«in« sole ratio fro® sample to sample. Calcination can also cause Minor shifts in the X-ray diffraction pattern. Notwithstanding these Minor perturbations, the basic crystal lattice structure renains unchanged.

After calcination the SSZ-26 zeolites have a crystalline structure whose X-ray powder diffraction pattern shows the following characteristic lines as indicated in Table 2 below: Table 2 2 e d/n I/Irt x 100 7.78 11.36 100 .22 4.392 18 21.34 4.164 21.98 4.044 22.93 3.878 13 Sh 23.01 3.853 19 2t.4t 3.366 12 • ft • SfH»vi$er 231524 WO 89/09185 PCT/US89/01179 01 SSZ-26 zeolites can be suitably prepared from an aqueous solution containing sources of an alkali metal oxide, a hexamethyl [4.3.3.0] propellane-8,11-dianunonium cation, an oxide of aluminum, gallium, iron, or mixtures thereof, 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 IS 2S 3 b Y02/W203 10-200 20-100 0H"/Y02 0.10-1.0 0.20-0.50 Q/Y02 0.05-0.50 0.05-0.20 M+/Y02 0.05-0.50 0.15-0.30 H20/Y02 15-300 25-60 q/q+m+ 0.20-0.70 0.30-0.67 wherein Q is a hexamethyl [4.3.3.0] propellane-8,11-diammonium cation, Y is silicon, germanium or both, and w is aluminum, gallium, iron, or mixtures thereof. M is an alkali metal ion, preferably sodium. The organic propellane compound which acts as a source of the propellane quaternary ammonium ion employed can provide hydroxide ion. Anions which are associated with the organic cation are those which are not detrimental to the formation of the zeolite.

The hexamethyl [4.3.3.0] propellane-8,11-diammonium cation component Q, of the crystallization mixture, is preferably derived from a compound of the formula: n(ch3)3 2Ae n(ch3)3 40 including syn,syn; syn,anti; and anti,anti orientations and wherein A® is an anion which is not £315 2* WO 89/09185 PCT/US89/01179 01 05 IS 2b ib 40 detrimental to the formation of the zeolite. Representative o£ the anions include halogen, e.g., fluoride, chloride, bromide and iodide, hydroxide, acetate, sulfate, tetra-fluoroborate, carboxylate, and the like. Hydroxide is the most preferred anion.

The reaction mixture is prepared using standard zeolitic preparation techniques. Typical sources of aluminum oxide for the reaction mixture include alumi-nates, alumina, and aluminum compounds such as AICI3, AI2(SO^)^, kaolin clays, and other zeolites. Typical sources of silicon oxide include silicates, silica hydrogel, silicic acid, colloidal silica, fumed silicas, tetraalkyl orthosilicates, and silica hydroxides.

Gallium, iron, and germanium can be added in forms corresponding to their aluminum and silicon counterparts. Salts, particularly alkali metal halides such as sodium chloride, can be added to or formed in the reaction mixture. They are disclosed in the literature as aiding the crystallization of zeolites while preventing silica occlusion in the lattice.

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 140*C to about 200°C, preferably from about 150°C to about 180°C and most preferably from about 150°C to about 170°C. The crystallization period is typically greater than 1 day and preferably from about 5 days to about 10 days.

Preferably the zeolite is prepared using mild stirring or aqitation. High speed stirring may lead to co-crystallization of at least one other zeolite.

Stirring at less than 100 RPM is preferred.

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 Y-_> *J0 - ro,4 * a.j • t 01 -7- raechanical separation techniques such as filtration. The crystals are water-washed and then dried, e.g., at 90°C to 05 150°C for from 8 to 24 hours, to obtain the as synthesized, SSZ-26 zeolite crystals. The drying step can be performed at atmospheric or subatmospheric pressures.

During the hydrothermal crystallization step, the SSZ-26 crystals can be allowed to nucleate spontane-ously from the reaction mixture. The reaction mixture can also be seeded with SSZ-26 crystals both to direct, and accelerate the crystallization, as well as to minimize the formation of undesired aluminosilicate contaminants.

If the reaction mixture is seeded with SSZ-26 crystals, the concentration of the organic compound can be greatly » reduced.

The synthetic SSZ-26 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., GDTA or dilute acid solutions, to increase the silica:alumina mole ratio. These methods may also include the use of (NH^^SiFg or acidic ion-exchange ^ resin treatment. The zeolite can also be steamed; steaming helps stabilize the crystalline lattice to attack from acids. The zeolite can be used in intimate combination 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 IA, 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, Ga, Cd, Pt, Pd, Ni , Co, Ti, Al, Sn, Fe and Co are particularly preferred.

The version of the Periodic Table to which the definitions of the groups of the various metal ions relate is that found in the Handbook of Chemistry and Physics, 63rd Edition, 1982-1983, CRC Press Inc.

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 A -A physically intimately admixed with the zeolite using standard methods known to the art. And, the metals can be occluded in the crystal lattice by having the desired metals present as ions in the reaction mixture from which the SSZ-26 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. Ion exchange can take place either before or after the zeolite is calcined.

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, steam, a mixture thereof or inert qas at temperatures ranqinq from about 200°C to 820°C for 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 SSZ-26 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. 01 OS IS 2S 3S 40 The zeolite can be conposited with other materials resistant to the temperatures and other conditions employed in organic conversion processes. Such matrix aaterials include active and inactive Materials and synthetic or naturally occurring teoli tes as well as mof qanic Materials such as clays, silica and netal oxides. The latter may occur naturally or My be in the (arm of gelatinous precipitates, sols, or gels, including Mixtures of silica and Metal oxides. Use of mm active Material in conjunction with the synthetic teolite, I.e., c«rJSi«e4 with it, tends to iMprove the conversion and selectivity of the catalyst in certain organic conversion processes. Inactive Materials can suitably serve as ditvencs to control the aaount of conversion in a oiven process so that products can be obtained economically wltitout using other Means for controlling the rate of reaction. Frequently, zeolite Materials have been incorporated into naturally occurring clays, e.g., bentonite and kaolin. These Materials, i.e., clays, oxides, etc., function, m 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 alsr> 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-26 zeolites can be composited with porous matrix materials and Mixtures of matrix Materials such as 231524 wo 89/09185 PCT/US89/01179 01 OS lb 3b silica, alumina, titania, magnesia, silica:alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia as we11 as ternary compositions such as silica-alumina-thoria, silica-alumina-zi rconia, si lica-alumina-maanesia and silica-magnesia-zirconia. The Matrix can be in the form of a cogel.

The SSZ-26 zeolites can also be cooposited other zeolites such as synthetic and natural faujatite« (e.g., X and ¥)* erionites. and mordenltes. T»ey can atsa be coaposited with purely synthetic zeolite* such at those of the ZSH, EU, FU, and MU series. The combination of zeolites can also be composited In a porous Inorganic matrix.

SSZ-26 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., metaxylene), and disproportionating aromatics (e.g., toluene) to provide mixtures of benzene, xylenes and higher methylbenzenes. The SSZ-26 catalysts have high selectivity, and under hydrocarbon conversion conditions can provide a high percentage of desired products relative to total products.

SSZ-26 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, u< •*«.* ell. i*4, i» general. c*» M any carbon SCO I y <- ' 01 _n_ OS 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 in qeneral processing will be sore efficient (and the catalyst aore active) the lower the veta1. nitrogen, and sulfur content of the feedstock.

The conversion of hydrocarbonaceous feeds can take place in any convenient mode. for example. In fluid-ized 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 tfte catalyst of this invention containing a metal, e.g.. a Group VIII metal such as platinum, include hydrogenation-dehydrogenation reactions, denitrogenation and desulfurization reactions.

SSZ-26 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.

Using SSZ-26 catalyst which contains a hydrogenation promoter, heavy petroleum residual feedstocks, cyclic stocks and other hydrocrackate charge 30 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 catalysts contain an effective amount of at least one hydrogenation catalyst (component) of the type commonly employed in hydrocracking catalysts. Tfee hydrogenation component is generally selected from the of hydroxjenati on catalysts consisting of one or acre «• I ^ WO 89/09185 PCT/US89/01179 01 IS ib metals of Group VIB and Group VIII, including the salts, complexes and solutions containing such. The hydrogena-tion catalyst is preferably selected froc* th# group of metals, salts and ccmplexes thereof of the group consisting of *t least on* of platinu*. palladium, rhodium, iridium and *ixtur*s thereof or the group co«**i*tittg of *». least one of nickel, Molybdenum, cobalt, tungsten, tit*niu*t« chroaiua and mixture* thereof. Htf*r*««* tu cstalytically *ctiv* natal or wrtal* i* t, ft tended xo •n-ciwi-pas* such **tal or **t*l* In the *8***«t*i *t*t* or ;n son* font such as an oxide, sulfide, halide. c*ro«*Yl*t« and the Ilk*.

The hydrogenation c*t*ly*t is presant lit «a effective awmnt to provide the hydrogenation function off th* hydrocracking catalyst, and preferably in the range of from 0.0S to 25% by weight.

The catalyst asy be employed in co»ju«noft witft traditional hydrocracking catalysts, e.g.# any aluaunosi l-icate heretofore eaployed as a component in hydrocracking catalysts. Representative of the zeolitic aluaunosi licates disclosed heretofore as employable as component parts of hydrocracking catalysts are Zeolite y (including steam stabilized, 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, ZSH-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 NajO less than about one percent by weight are generally preferred. The relative amounts of the SSZ-26 component and traditional hydrocracking component, if any, will depend *t l*ast in part, on th* **l*ct*d hydrocarbon Im4*ic<» **d dm the dealr*d product dl ttri button to be *vt U *11 »*•«**«•* i J WO 89/09185 PCT/US89/01179 01 OS IS amount of SSZ-26 is employed. When a traditional hydrocracking catalyst (THC) component is employed the relative weight ratio of the THC to the SSZ-26 is generally between about 1:10 and about S00:1, desirably between about 1:13 and about 200:1, preferably between about it2 and about 50:1, and most preferably is between about lit and about 20:1.

The hydrocracking catalysts are typically employed with an inorganic oxide Mtrt« eo*po«e*t wnt<c* may be any of the inorgani c odd# mstris components wni zn have been employed heretofore m the fattjUuoft of hydrocracking catalysts including* amorphous* catalytic inorganic oxides# e.g.* cataiyticaily act & we si Uca-aluminas, clays, silicas, aluminas* si lice-etu*une*. si lica-zirconias, silica-magnesias* alumina-borias. alunina-titanias and the Like and mixtures thereof. The traditional hydrocracking catalyst and SSZ-26 may be suited separately with the matrix component end then mixed or the THC component and SS2-26 may be mixed and then formed with the matrix component.

SSZ-26 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 liquid hourly space velocity (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 1000 to about 20,000 SCf/bbl. Generally, »?4r<»9e* will fee separated from the product and recycled u »ft* *o*e. Typical feedstock* include light «• 23 1 5 24 WO 89/09185 PCT/US89/01179 01 05 IS 2S 3S 40 gas oil, heavy gas oils and reduced crudes boiling about 350#F.

The SSZ-26 hydrodewaxing catalyst may optionally contain a hydrogenation component of the type commonly employed in dewaxing catalysts. The hydrogenation component may be selected from the group of hydrogenation catalysts consisting of one or more metals of Group VIB and Group VIZI, 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 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.

SSZ-26 can be used to convert light 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 higher octane 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-550*C at pressures ranging from atmospheric to 10 bar, and liquid hourly space velocities (LHSV) ranging from 0.1 to 15.

The conversion 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, £315 24 WO 89/09185 PCT/US89/01179 01 palladium, and iridium, or combinations thereof can be used. Rhenium or tin or a mixture thereof may also be 0^ used in conjunction with the Group VIII metal compound and preferably a noble metal compound. 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 weight percent, preferably 0.2 to 0.8 weight percent.

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 1-3 weight percent. These high levels of alkali metal, usually sodium, potassium or cesium, 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 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 content of the zeolite. Under normal circumstances, the zeolite as prepared and without ion-exchange will contain sufficient alkali metal to neutralize the acidity of the 40 WO 89/09185 PCT/US89/01179 01 05 IS 2S Jb 40 catalyst. 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 totally herein by reference, can be used to determine if the zeolite is substantially free of acidity.

The preferred alkali metals are sodiusa, potassium, and cesium. The zeolite itself can be substantially free of acidity only at very high silica:aluodna aol 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 SSZ-26 »t liquid hourly space velocities from 0.5 to 50, temperatures froa about 260°F to 1625*F and pressures from subataospheric to several hundred atmospheres, typically from about atmospheric to about 5 atmospheres.

For this purpose, the SSZ-26 catalyst can be composited with mixtures of inorganic oxide supports as well as traditional cracking catalyst.

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 2315 24 WO 89/09185 PCT/US89/01179 01 IS silicates such as silicalite (U.S. Patent No. 4.061,724), erionite, mordenite, offretlte, chabazite, FU-l-type 05 zeolite, NU-type zeolites, LZ-210-type zeolite end mixtures thereof. Traditional cracking catalysts containing amounts of Na20 less than about one percent by weight are generally preferred. The relative wounti of the SSZ-26 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 ell instances an effective amount of SSZ-26 is employed. Mhtn • traditional cracking catalyst (TC) component is employed ttte relative weight ratio of the TC to the SSZ-26 is generally between about It 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 is 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 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 SSZ-26 may be mixed separately with the matrix component and then mixed or the TC component and SSZ-26 may be mixed and then formed with the matrix component.

The mixture of a traditional cracking catalyst and SSZ-26 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 SSZ-26 in single catalyst particles or SSZ-26 with or without a matrix component may be added as a discrete component to a traditional cracking catalyst. 40 231524 rermsmoim 01 IS SSZ-26 can also be used to oligomerize straight and branched chain olefins having from about 2 to 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 SSZ-26 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, 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 .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% by weight. This is accomplished by using a 40 231524 WO 89/09185 PCT/US89/01179 01 05 40 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 value are defined by a standard test known in the art, e.q., as shown in U.S. Patent No. 3,960,978 which is incorporated totally 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.

SSZ-26 can be used to convert light gas c2"<-6 paraffins and/or olefins to hiqher molecular weight hydrocarbons including aromatic compounds. Operating temperatures of 100*C-700*C, operating pressures of 0 to 1000 psig and space velocities of 0.5-40 hr~* WHSV (weight hourly space velocity) can be used to convert the Cj-C^ 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, VIII and IIIA of the Periodic Table, and most preferably gallium or zinc and in the range of froes about 0.05 to 5% by weight.

SSZ-26 can. be used to condense lower aliphatic alcohols having 1 to 10 carbon atoms to a gasoline boiling point hydrocarbon product comprising mixed aliphatic and aromatic hydrocarbon. The condensation reaction proceeds at a temperature of about 500°F to 1000*F, a pressure of about 0.5 to 1000 psig and a space velocity of about 0.5 to 50 WHSV. The process disclosed in U.S. Patent No. 3,984,107 more specifically describes the process conditions used in this process, which patent is incorporated totally herein by reference.

The 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 to 5t by weight. The metal cations that may be present include any of the metals of the Groups I through VIII of the Periodic Table. However, in the case of Id 1 t) L 4 WO 89/09185 PCT/US89/01179 01 05 Group IA metals the cation content should in no case be so large as to effectively inactivate the catalyst.

The present catalyst is highly active and highly selective for isomerizing to C7 hydrocarbons. The activity means that the catalyst can operate at relatively low temperature which thermodynamically favors highly branched paraffins. Consequently# the catalyst can produce a high octane product. The high selectivity Mans that a relatively high liquid yield can be achieved when the catalyst is run at a high octane.

The present process comprises contacting the isomerization catalyst with a hydrocarbon feed under isomerization conditints. The feed is preferably a lignt straight run fraction, boiling within the range of 10*F to 250°F and preferably from 60*F to 200*F. Preferably* the hydrocarbon feed for the process comprises a substantial amount of C^ to C7 normal and slightly branched low octane hydrocarbons, more preferably C5 and Cg hydrocarbons.

The pressure in the process is preferably between 50 psig and 1000 psig, more preferably between 100 and 500 psig. The liquid hourly space velocity (LHSVJ 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 (Hj/HC) of between 0.5 and 10 Hj/HC, more preferably between 1 and 8 I^/HC. The temperature is preferably between about 200°F and about 1000°F, more preferably between 400°F and 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 value for conversion, the temperature may have to be slowly increased during the run to compensate for any deactivation that occurs. 4 G 1 0 i. t WO 89/09185 PCT/US89/01179 01 OS IS 2S JS 40 A low sulfur feed is especially preferred in the present process. The feed preferably contains less than 10 ppra, more preferably less than 1 pon. and nott prefer-ably less than 0.1 ppm sulfur. In the esse of a feed which is not already low in sulfur* acceptable levels can be reached by hydrogenating the feed in a pres4turatto« tone with a hydrooenatmg catalyst which is rest stent to sulfur pot soning. An et«sple of a sui table catalyst for this hydrodesulfuri ration process is an afiwukt as support and a minor catalytic prcportt o« of «»o L##<«♦«. *n oxide, cobalt oxide and/or nick# 1 oxide. A p&ei t <m alumina hydrogenating catalyst c*» also *©**. case a sulfur sorber is preferably pt#c#4 a( the hydrogenating catalyst, but upstream of t $«-•««« t isomerization catalyst, examples of sulfur sorbet* alkali or alkaline earth aetals on porous refractory inorganic oxides, sine* etc. ftydrodesv! furl istion »s typically conducted at 315*C to 455*C, at to 2000 psig, and at a liquid hourly space velocity of I to S.

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 sulfur or coke. Sulfur and coke can be removed by contacting the catalyst with an oxygen-containing gas at an elevated temperature. If the Group VIII metal(s) have agglomerated, then it can be redispersed by contacting the catalyst with a chlorine gas under conditions effective to redisperse the metal(s). The method of regenerating the catalyst may depend on whether there is a fixed bed, moving bed, or fluidized bed operation. Regeneration methods and conditions are well known in the art.

The conversion catalyst preferably contains a Group VIII metal compound to have sufficient activity for commercial use. By Group VIII metal compound as used 231524 WO 89/09185 PCT/US89/01179 01 OS IS ^0 2S 3S 40 herein is meant the Mtal i t *e 1 f or a compound thereof. The Croup Viii noble aetels end their compound*. pUitnuit, palladium, and iridiun, or conbinatlons thereof ca« be used. Rheniua and tin My also be used in co«i)uii£tio*-with the noble metal. The aoit preferred met*! t* platinum. The aaount of Croup VI SI aetal present conversion catalyst should be wt thin tit* aomt r«A«* <af use in isonerixing catalysts, fro» about $.$$ <«• 1.$ weight percent, preferably 0.2 to 0.1 wet 9%t perxe«t.

SSI-26 can be vaed in a proce** (m alkylation or tr»n*alkyl*ti oa ©f *n aroaettt fcySffl***aun. The process coop rises contacting ttm ar«m*tsc »f*®r with a Cj to C4 olefin alkylating *o*nt «* a petyaStyS aroMtic hydrocarbon transalkylstlng *f*o<t, q*kder at Beats partial liquid phase conditions, and m the presentee of a catalyst comprising SSZ-26.

For high catalytic activity, tft« MJ-J* te3 It ».♦ should be predominantly in it* hydrogen 1for®* Generally, the teoli te is converted to it# hydrogen f am by anmoniua exchange followed by calcination. SS the zeolite is synthesized with a high enough ratio of or<?a«c-nitrogen cation to sodiua ion, calcination alone My 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 SSZ-26 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 mixture into tablets or extrudates. The final catalyst may contain from 1 to 99 wt % SSZ-26 zeolite. Usually the zeolite content will range from 10 to 90 wt %, and more typically from 60 to 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 My be alkylated or transalkylated by the 231524 WO 89/09185 PCT/US89/01179 01 IS 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 to 4 carbon atoms# such as ethylene# propylene# butene-1# trans-butene-2 and cis-butene-2# or mixtures thereof. The preferred olefin is propylene. These olefins may be present in admixture with the corresponding C2 to C4 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 2 to about 4 carbon atoms. For example# suitable polyalkyl aromatic hydrocarbons include di-f tri- and tetra-alkyl aromatic hydrocarbons# such as diethylbenzene# triethylbenzene# diethylmethylbenzene (diethyltoluene)# di-isopropylbenzene, di-isopropyltoluene# dibutylbenzene, and the like. 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# ethyl-toluene from the reaction of toluene with ethylene or polyethyltoluenes, cymenes from the reaction of toluene with propylene or polyisopropyltoluenes, and sec-butylbenzene 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. "7 '■> '> ' r- --- 01 -24- When alkylation is the process conducted, reaction conditions are as follows. The aromatic 05 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°F to 600°F, preferably, 250°F to 450°F. The reaction 10 pressure should be sufficient to maintain at least a partial liquid phase in order to retard catalyst fouling.

This is typically 50 to 1000 psig depending on the feedstock and reaction temperature. Contact time may range from 10 seconds to 10 hours, but is usually from 5 minutes 15 to an hour. The weight hourly space velocity (WHSV), in *1 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 20 aromatic hydrocarbon to pol.yalkyl aromatic hydrocarbon will qenerally range from about 1:1 to 25:1, and preferably from about 2:1 to 20:1. The reaction temperature may range from about 100°F to 600°F, but it is preferably about 250®F to 450°F. The reaction pressure should be sufficient to 25 maintain a least a partial liquid phase, typically in the range of about 50 psig to 1000 psig, preferably 300 psig to 600 psiq. The weight hourly space velocity will range from about 0.1 to 10.

SSZ-26 can also be used as an adsorbent, as 30 a filler in paper, paint, and toothpastes, and as a water-softening agent in detergents.

The present invention will be more fully understood by reference to the following examples. They are intended to be purely exemplary and are not intended 35 to limit the scope of the invention in any way.

EXAMPLES Example 1 [4.3.3.0] Propellane-8,11-dione was prepared according to the Cook and Weiss [J. Org. Chem. 4_1_ 4053 40 (1976)]. The dione was then heated for 16 hours in a 2315 2 4 WO 89/09185 PCT/US89/01179 01 -25- closed pressure vessel with Dimethylformamide and Fonaic acid (88%) in a Leukart-type reaction. The reaction is OS cooled to room temperature, dissolved in water# brought to a pH of 12 with alkali, and extracted twice with equal volumes of diethyl ether. The extract is dried over sodium sulfate and the solvent removed. The N#N,N*»K'~ tetramethyl (4.3.3.0} prooellane-8.11-diaaine product 10 (which has an elemental analysis consistent with the theoretical structure of the diamine) is dissolved in chloroform and an excess of methyl iodide is addeS tft# reaction is stirred overnight to produce the crystal E i»e diquaternary anaoniua product Ca saal 1 amount of IS amine is also produced in this reaction sequence. tt be carried through all steps without adversely ef<eett«*$ the xeolite synthesis or can be removed by fractional crystallization fran hot ethanol once the qwateraited product has been achieved). The crystalline product Diwtms 20 a melting point of 304*-306*C is »3<* .Ji'-ftexawethyI (4.3.3.0) Propel lane-8,ll-diaaaoniu* diiodide. At tftis stage three isomeric forms of the coopound may be possible. The orientation of the diammonium qroups relative to the carbocyclic skeleton may be syn,syn or syn,anti, or 25 anti,anti. The template can be further purified by recrystallization from Ethanol/water (20/1). This greatly diminishes the formation of other zeolite impurities.

Example 2 The product of Example 1 was dissolved in water 30 (so as to produce a 0.5 to 1.0 M solution) and stirred overnight with an excess of Dowex 1 AG-X8 hydroxide ion-exchange resin. The resin was filtered and the basic solution was titrated with an analytical solution of HC1.

Similarly, other anions such as acetate, 3b sulfate, bromide, carboxylate and tetrafluoroborate may be substituted for the hydroxy by using the appropriate ion-exchange resin.

Example 3 76 Grams of a 0.45 N solution of Template from Example 2 in its hydroxide form were mixed with 1.58 gms of NaOH (solid). After dissolution 0.89 gm of sodium L o I □ e-1 WO 89/09185 PCT/US89/01179 01 IS aluminate (75% solids) were added with stirring using a magnetic stir bar. Finally 9.08 gas of Cabosil NS tuatd silica was added. The reactants were loaded into a Parr 300 cc reactor, sealed and heated. The reactor was stirred at 60 RPfl while being heated at 17S*C for 6 days. The product after filtration, washing wi th distilled water, drying in air and then at 100*C was the crystalline 10 Material designated SSZ-26. The x-ray 6i f(ra^tio* of the as-Mde material is tabulated i« Table 1 treliow.

Table I 2 9 d/n 100 * !/!tt 7.83 11.300 100 14.19 6.240 S .65 S.660 1 .28 4.380 61 .93 4.240 9 mi 21.39 4.150 22.00 4.040 55 22.82 3.900 45 S ft 23.05 3.860 70 .26 3.530 9 26.50 3.360 36 26.68 3.340 54 QTZ QTZ » Quartz Sh « Shoulder Example 4 75 Grams of a 0.45 M solution of Template were -mixed with 1.70 gms NaOH(s), and 2.70 gms of SK-40 Y zeolite (sold by Union Carbide) as source of alumina.

After thorough mixing 7.20 gms of Cabosil was blended in as silica source. The reaction mixture was heated in a 3^ Parr 300 cc reactor at 175°C at 45 RPM for 6 days. Workup as in Example 3 produced crystalline SSZ-26 and a minor amount of quartz.

Example 5 In this example Na-Y zeolite (SK-40) was used 40 again but the initial 0H"/Si02 ratio was lowered to 0.20, 231524 01 OS IS 40 0.28 gms of SK-40, as source of alumina, was used and dispersed in 6 ml H20, 0.07 gm NaOH, and 2.4 gins of a 0.5 M Template solution. 0.72 Crams of Cabosil was used and the reaction was run at 170*C but at 30 ftpn. At 6 days of reaction the product was crystalline SSJ-J6. The Si02/Al20} value of the zeolite is 3S.

Eiwplt 6 2.4 Crams of a 0.S ft solution of Template was mixed with (ml of ft20# 0.21 gm* of WaOttts). O.Ji ymt Na-Y zeolite, as source of alumina* and finally -J. of Cabosil US. The mixture was heated at t4®*C for 6 day* with 30 RPM agitation. T*e crystalline pro-Swct *** 5SJ-J* and has a Si02/Al203 ratio of 2S.

Example ? A reaction like Csampl* 6 was set up a«*i<s.

This time the reactants were increased IS fold. Th# mixture was seeded with a small quantity from Cxanole 4. and heated static at 160*C. The crystalline product after 12 days of reaction and the usual workup was SSZ-26, «*itn minor quantities of analcime and quarts.

Example 8 The template is prepared as described in Example 1, but instead of using Ethanol/water in the final recrystallization step, Acetonitrile/water is used (15/1). A lower yield of crystals are recovered but it gives a correct microanalysis for the desired product.

Even though the integrations are correct for the various protons as seen in the NMR, the coupling constants are now markedly different. Also the IR pattern contains some new bands. Clearly a different isomer has been recovered from the potential mixture. This new product is converted to the hydroxide form as in Example 2. 1.2 mmoles of this form of the template in 7 ml of water are combined with 0.20 gms of NaOH(s), 0.28 gms of SK-40 zeolite, and finally 0.72 gms of Cabosil. A Teflon ball (3/4 in.) is placed in the reactor to aid in stirring. The reactor is tumbled at 30 RPM while being heated to 170°C for 6 days. The product after the usual workup was well-crystallized o 2315 WO 89/09185 PCT/US89/01179 01 OS IS 2S SSZ-26. The data for the XRD analysis appears in Table 4. This example demonstrates that more than one isomeric conformation is capable of producing SSZ-26 in the present invention.

Table 4 2 © d/n 100 x I/I SL 7.77 11.38 76 8.92 9.91 11 B 9.42 9.39 8 B 13.15 6.73 7 B 14.10 6.28 4 14.77 6.00 6 B .25 5.84 6 .58 5.69 11 19.68 4.51 14 B .20 4.396 80 21.24 4.183 38 21.84 4.069 72 22.77 3.905 63 Sh 22.92 3.880 100 .12 3.545 10 26.50 3.363 51 28.38 3.145 6 28.86 3.094 8 .33 2.947 7 B * Broad Sh » Shoulder Example 9 3.75 gms of the template prepared as in Example 2 (0.63 M) is combined with 0.30 gms of NaOH(s) and 9.3 ml water. 0.53 gms of SK-40 are added and then 1.35 gms of Cabosil. After placing a Teflon-coated stir bar in the reactor it is sealed and heated at 170°C for 6 days while tumbling at 30 RPM. The product after the usual workup was SSZ-26 and the XRD data appears in Table 5. 40 C U I 4- -T 01 OS 'J -29-T«bl» S 2 8 d/n 100 x I/Io 7.74 11*420 9® 8.30 10.6S0 * t 8.88 9.960 10 • 11.20 6.70? * t 14.08 6.290 * IS.22 S.«2S * t IS.SS S.698 W 16.61 S.IJI 1 19.59 4. Sit It ** 20.17 4.<02 5#® 21.26 «.17t «# 21.87 4.064 •• 22.77 3.90S 6® Sft 22.92 3.8*0 109 20 25.14 1.S42 I* 26.4S 3.170 63 27.62 3.230 * t 27.93 3.194 « # 28.43 3.139 11 2S 28.90 3.089 10 29.60 3.018 3 B 30.33 2.947 11 31.43 2.846 8 31.93 2.803 7 33.19 2.699 12 .32 2.541 10 .63 2.520 5 36.30 2.475 3 36.80 2.442 8 3S 37.23 2.415 5 40. 17 2.245 6 41.95 2.154 2 43.06 2.101 7 B ■ Broad 40 Sh ■ Shoulder 231524 WO 89/09185 PCT/US89/01179 01 Exawpl* 10 1.2 tm of ctw template f roti Example 2 and m 8 nl water is conbinad with 0.12 gas of K»0H(«t. 0.29 fM of SK-40, and finally 0.72 qm of Cabosi 1. Aftar addt^3 tha TafIon-coatad atirrar and closing th* r**ctor. th* raaction is run for about 9 days at IWC and J® tW tumbling. Tit* product was a nic*ly crystal 11 **d saanpt* -o! SSZ-26. Th* product ahow*d a **ry «io*09#«k*ows dt«5flection in th* scanning *i*ctron aictotcop*. Tim *»0' data «* giv*n in Tabl* i.

IS *•»>« * As Pr*&ar*d 2 0 d/n la® * J/j _ 7.78 11.16 100 8.32 .63 • 0 8.90 9.94 B 13.20 6.71 14.15 6.26 S .26 .81 4 B .62 .67 8 .92 .57 7 16.74 .30 2 19.63 4.52 6 B .23 4.389 63 B 21.37 4.158 21.99 4.042 53 22.85 3.89 46 Sh 23.00 3.867 64 .20 3.534 9 26.15 3.408 8 26.49 3.365 33 28.51 3.131 8 28.95 3.084 7 B ■ Broad Sh • Shoulder 40 .WI •' " 4 231524 WO 89/09185 PCT/US89/01179 01 Example 11 The crystalline products of Examples 3-10 were subjected to calcination as follows. The samples were heated in a muffle furnace from room temperature up to 540#C at a steadily increasing rate over a 7-hour period. The samples were maintained at 540°C for four more hours and then taken up to 600°C for an additional 10 four hours. A 50/50 mixture of air and nitrogen was passed over the zeolites at a rate of 20 standard cubic feet per minute during heating. Representative X-ray diffraction data for the calcined product of Example 8 appears in Table 7.

IS 3S 40 Z3 4 D * 01 -32- Tabl* 7 05 " ~ C«wwM»t» T •«9U<* IS 3b 2 0 d/n 100 * 6.18 14.300 3 7.74 11.420 100 9.30 .950 3 9.93 .250 ) 9.95 9.990 4 9.44 9.170 £2 9.92 9.007 4 11.12 9.749 1) 14.09 9.290 St 14.7$ 9.009 4 .53 .759 9 19.00 .539 1 19.93 .331 19.7$ 4.495 9 .19 4.400 94 .95 4.290 21.27 4.177 21 21.90 4.059 55 22.90 3.993 49 23.03 3.962 99 .17 3.539 19 26.45 3.370 59 26.60 3.351 36 28.42 3.140 12 28.90 3.089 29.63 3.015 4 .40 2.940 31.41 2.848 8 32.00 2.797 7 33.27 2.693 11 .38 2.537 9 .62 2.520 4 36.32 2.473 4 39.79 2.443 37.33 2.409 2 38.32 2.349 4 40. 15 2.246 4 42.00 2.151 1 42.42 2.131 1 43.76 2.069 7 mt is. mi 40 QTZ » Quartz Sh ■ Shoulder WO 89/09185 PCT/US89/01179 01 Example 12 lon-exchange of the calcined SSZ-26 aaterials 0^ from Example 8 was carried out using NH4NO3 to convert trie zeolites from their Na font to NH^ and then eventually H form. Typically the saae aass of NH|SOj as zeolite was slurried into HjO at ratio of SO/1 HjO to zeolite. T*e exchange solution was heated at 100*C for two houri then filtered. This process was repeated fovr t t*«t. Finally, after the last exchange the ttohte was wasn.es several tiaes with M^O and dried. A repeat e*l<c1 om a« in Exaaple 11 was carried oat bwt witftowt t»* ire »t • aent at 600*C. This produces th* « form ci ** zeolite.

Exaaple 13 The product of Cuaplt 6« after treataent as in Exaaples 11 and tti«n 12. was subjected to a surface area and pore size distribution analysts ustn$ N2 as adsorbate and via the BET aethod. Tft* surface area of the zeolitic aaterial was S60 a^/ga and the aicrcjpore volume was 0.19 cc/ga.

Example 14 Constraint Index Determination; 0.25 Grams of the hydrogen form of the zeolite of Example 4 (after treatment according to Examples 11 and 12) was packed into a 3/8" 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 lOcc/min. and atmospheric pressure. The reactor was taken to 250°F for 40 min. and then raised to 600#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 0.62cc/hr. Feed delivery was made via syringe pump. Direct sampling onto a gas chromatograph began after 10 minutes of feed introduction. The constraint index value was calculated from gas chromatographic data using methods known in the art. It can be seen that novel zeolite 40 SSZ-26 has very high cracking activity.

CO IU«t WO 89/09185 PCT/US89/01179 01 Conversion Example No. C.I. at 10 win. Temp, 05 4 0.3 95% 600 Example 1S SSZ-26 was prepared as In Exaaple 9 and treated as in Exaaples 11 and 12. The acid fora of the xeolite was then neutralized by refluxing overnight with dilute KOH. After washing and drying the seolite it was calcined to 1000*F. The KOH treatment was repeated a second tiae with subsequent washing* drying and calcination* The K-exchanged zeolite was iapregnated (via incipient wetness) with 0*8 wt % Pt, dried overnight at 250*f and then calcined 3 hours at S00*F. The catalyst was then evaluated using a light straight run feed. Reactor conditions: 100 » psig 2 • LHSV 3 » H2/HC 800*F » Temp.

Composition, Wt % "Feed Product C4- 0.0 30.5 Total C5 4.2 12.7 i C6 11.3 11.8 n C6 17.0 4.9 Benzene 0.5 12.5 i C? 14.5 1.7 n C"j 16.7 0.6 Toluene 2.4 16.9 3«, i C8+ 0.9 0.0 n C8+ 4.9 0.6 Cg+ Aromatics 1.4 4.6 40 LV% 100 64.2 RON 62 88.3 L 0 I D L *1 As might be anticipated the liquid volume yield could be improved by further neutralization of the zeolite catalyst.

Example 16 The hydrogen form of SSZ-26 can be used in catalytic cracking. For such purposes, the catalyst prepared as in Example 9 was tested in a micro-activity 10 test (HAT) using the procedure developed by ASTN Coctautc*« D-32. The test was run at 925*F on fresh catalyst at a cat/oil ratio of 3 (based upon catalyst calcined to 1100*F) and a WHSV of 15-16. Table 8 shows inspections on the feed and the resulting products. The catalyst was run ** at 20 weight % in a kaolin matrix.

Table 8 MAT Test for SSt-26 Zeolite Peed: API 29.09 Aniline pt, F 219.1 Ramsbottom Carbon, wt % 0.3 N(T), ppn 270 N(B), ppm 159 S(T), wt « 0.54 Test Data: Conversion, wt * 61.0 Coke, wt % 7.8 C5-430°F 23.0 403-650°F 16.0 650 + 23.0 C3- 14.8 C4- 30.2 C4 olefin/C4 total 0.21 Example 17 The hydrogen form of the SSZ-26 zeolite can be used in hydrocracking conversions of hydrocarbon feeds. 40 The data shown in Table 9 is for the conversion of a feed 231524 01 OS IS made up of representative Model compounds. The dat* i llustrates the high activity and tMpt-Mltcuvity (or SSZ-26 zeolite in hydroprocesalng. Th# catalyst l* a«Uw# by itself as used in this example or wh«n a noble owtafi i. e incorporated. One grata (dry M«i»! of catalyst wit Io+4«<* Into a 1/4" reactor tube packed with al-unOus* on side of the bed. The catalyst «*» dried at S$#*f f#r 30 «in. with 1200 pst lj. The hydro?** flow rate I* S$ cc/«t«. at autocphwric pressure a«d coo* *«>**•.

The feod rat# was SO aiicroliters/Min. (»• tetafcr** <**♦« •qui librated for 2 hours at aim*# mtw analysis. 2S 3S Tatele 1 Hydroprocessing of a node I Feed mth SSt-26 Catalyst Teap.

LHSV H2 Pressure Conversion Product/Feed wt * Cl-C6 Hexamethylethane Marker Cyclohexane Isooctane(2,2,4) Toluene 3,4,Diethyl Cfi 4-Propyl heptane n-Decane t-Decalin c-Decalin n-Dodecane feed Alone 0.0 1.1 31.9 4.5 33.7 .1 5.1 5.5 4.5 3.7 5SI-24 sat *r 1200 22.6 .0 1.6 18.4 4.0 33.1 11.7 2.6 4.9 0 1.1 sss-H iOO'f 1200 37.S 33.1 1.8 9.0 3.9 31.2 12.2 0.7 3.7 0 0 40 As can be seen above the catalyst has surprising selectivity for n-paraffins, demonstrating its usefulness 231524 01 05 IS for dewaxing, and a selectivity for cis decalin over the trans isomer. The reactivity is also sonewhat pressure dependent.

Exaaple 18 Due to the strong cracking activity of the SSZ-26 zeolite it can be advantageously used in the isoaerization of pen-hex streaas to upgrade octane values. Hydrogen SSZ-26 was prepared at in Exaaple* 9. 11, and 12 and was iapregnated with 0.9 wt I platinum. Pure hexane was run over the catalyst using the to!lowing paraaeters: 100 psig 6 • Hj/HC 3 • LHSV S01*F • Temp.

The product distribution frow the reaction is given Table 10.

Table 10 Hydrocarbon Wt % Methane 0.12 Ethane 0.21 Propane 1.29 Isobutane 1.05 j0 n-Butane 0.45 Isopentane 1.37 n-Pentane 0.65 2,2 DM Butane 15.74 2, 3,DM Butane 8.66 2 ,Methylpentane 31.80 3,Methylpentane 20.99 n-Hexane 17.51 Me,Cyclopentane 0.17 Benzene 0.0 LV% 96.9 40 RON 75.7 2315 24 WO 89/09185 PCT/US89/01179 01 -38- ' ! i Example 19 A commercial pen-hex stream, characterized below, was used with a 0.3% Pt catalyst prepared similarly to the one used in Example 18, and the catalyst run conditions were: 200 * psig 10 6 ■ H2/HC 1 - LHSV 485°F * Temp.

At 22 hours on stream the product was the following: IS Feed, Product Hydrocarbon Wt % Wt % Methane 0.0 0.0 Ethane 0.0 0.0 Propane 0.0 1.81 Isobutane 0.04 6.49 n-Butane 0.28 1.15 Isopentane 12.03 22.40 n-Pentane 18.93 11.75 2,2, DM Butane 0.58 .09 Cyclopentane 4.26 3.96 2,3 DM Butane 2.26 4.48 2,Methylpentane 12.55 .14 3,Methylpentane 8.19 9.81 n-Hexane 19.74 8.33 Me,Cyclopentane .04 6.58 Benzene 3.75 O.OO Cyclohexane 1.89 1.91 Isoheptane 0.07 1.11 n-Heptane 0.15 0.00 Toluene 0.00 0.00 LV % 100 93.0 RON(GC) 74.5 79.8 -n • 23152 WO 89/09185 PCT/US89/01179 01 -39- Example 20 The SSZ-26 zeolite catalyst can be used for OS hydrocracking in conjunction with a metal component and under hydrogen. The zeolite of Example 9 was treated as in Examples 11 and 12 to produce the acidic form. About 0.6 wt % Pd was loaded onto the zeolite by ion-exchange in a buffered (pH 9.5) solution. Calcination was carried out LO in steps to 940°F where the product is held for 3 hours. Next the zeolite was bound in Catapal alumina (65/35) and meshed to 24-40. The experimental conditions and product properties are given in the tables below.

After hydrogen reduction at 600°F and titration IS at 350°F with Feed A (see Table 11) spiked with 800 ppm N using n-butylamine# Feed A was hydrocracked over the catalyst under the conditions given in Table 12. The product properties are given in Table 13.

Table 11 Properties of Feed A Nitrogen# ppm 0.3 2S Sulfur# ppm ~2 API Gravity 32.0 Boiling Range# °F 0-5% 454-544 -50% 544-716 50-90% 716-834 85-100% 866-919 Table 12 Run Conditions For Hydrocracking Feed A with Catalyst Pd H SSZ-26 3S Temperature, °F 550 WHSV 1.53 Total Pressure, psig 1185 Inlet H2 Pr psia 1129 Gas Rate, SCFB 5707 40 CO 1 01 -40 Table 13 0$ Properties of Hydrocracktd Product Pro* r««4 A Using th# Catalyst Under Conditions Ctv#n tm Ta&S# SI Conversion to 4S0*F-, wt % *1.$ Cs» Yl#ld* Ht % §3.® Cj-180*f tield, Wt I 13.* 1«0-390*F. Mt i 2t.t 3tO-4SO*F. »t % $.1 Citts 8j Coasum«6« fCft fit Boiling K«nQ«, *F 0»SI 41-?* IS S-S0I *t.JH so-70% m-itt 70-90% 95-99% 122-113 Etaagl* 21 Th# ability of th# SIMi x#ol 11# to catal/i* th# alkylation of an arooatic hydrocarbon by an el#8i« wai demonstrated as follows. SSZ-26 po>wd#r fron Exaapl# 4 after treatment as in Exaaples 11 and 12 was pressed to 25 form tablets which were crushed and si#v#d to obtain -20 mesh granules for testing. The granular catalyst was calcined for 4 hours at 1000*P in a muffle furnace, then weighed and charged to a tubular aicroreactor. The catalyst was heated to 325*F in flowing nitrogen at 30 atmospheric pressure. Nitrogen flow continued while the reactor was pressurized to 600 psig. When the unit pressure had stabilized at 600 psig, the nitrogen flow was stopped and liquid benzene was passed upflow through the reactor. After the reactor was filled with liquid 3b benzene, liquid propylene was injected into the benzene feed stream to given benzene/propylene feed molar ratio of 7.2 and a total feed rate of 5.7 grams per gram of catalyst per hour.

Analysis of the reactor effluent by capillary 40 gas-liquid-chromatography showed that all of the propylene had b#en converted to make a product comprising 93.5%

Claims (39)

2315 24 WO 89/09185 PCT/US89/01179 01 OS 10 -41- cumene and 5.9% diisopropyl benzenes on a benzene free weight basis. Since SSZ-26 is also a good transalkylation catalyst, it is anticipated that the diisopropylbenzene would be either recycled to the alkylation reactor or reacted in a separate reactor with benzene to make additional cumene. The conversion to useful product was thus better than 99 weight percent based on propylene and benzene reacted. IS 20 2S 30 3S 40 -42- what^we claim is.-

1. A zeolite having a mole ratio of an oxide, selected from silicon oxide, germanium oxide and mixtures thereof to an oxide, selected from aluminum oxide, gallium oxide, iron oxide (Fe£03), and mixtures thereof, qreater than 10:1, and having the X-ray diffraction lines of Table 1.

2. A zeolite having a composition, as synthesized and in the anhydrous state, in terms of mole ratios of oxides as follows: (0.1 to 2.0)020: (0.1 to 2.0)M20:W203:-(greater than 10) Y02 wherein M is an alkali metal cation, Wis selected from aluminum, gallium, iron and mixtures thereof, Y is selected from silicon, germanium and mixtures thereof and 0 is a hexamethyl [4.3.3.0] propellane-8,11-diammonium cation, and having the X-ray diffraction lines of Table 1.

3. The zeolite according to Claim 2 wherein W is aluminum and Y is silicon.

4. A zeolite prepared by thermally treating the zeolite of Claim 2 at a temperature of from 200°C to 820°C.

5. The zeolite according to Claim 4 having the X-ray diffraction lines of Table 2.

6. The zeolite according to Claim 1 or 2 wherein said mole ratio of silicon oxide or germanium oxide to aluminum oxide, gallium oxide, or iron oxide (Fe^) is 10:1 to 200:1.

7. A zeolite according to Claim 1, 2 or 4 which has undergone ion exchange with hydrogen, ammonium, rare earth metal, Group IIA metal, or Group VIII metal ions. 1 >01 05 10 IS 20 25 30 35 40 t } '} -4 3-

8. A zeolite according to Claim 1, 2 or 4 wherein rare earth metals, Group IIA metals, or Group VIII metals are occluded in the zeolite.

9. A zeolite composition, comprising the zeolite of Claim 1, 2 or 4 and an inorganic matrix.

10. A method for preparing a zeolite of Claim 1, comprising: (a) preparing an aqueous mixture containing sources of an alkali metal oxide, a hexamethyl [4.3.3.0] propellane-8,11-diammonium cation, an oxide selected from aluminum oxide, gallium oxide, iron oxide (Fe203) and mixtures thereof, 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.

11. The method according to Claim 10 wherein the aqueous mixture has a composition in terms of mole ratios of oxides falling in the ranges: Y02/W203, 10:1 to 200:1; and Q/Y02, 0.05:1 to 0.50:1; wherein Y is selected from j silicon, germanium and mixtures thereof, W is selected from aluminum, gallium, iron and mixtures thereof, and Q is a hexamethyl [4.3.3.0] propellane-8,11-diammonium cation.

12. The method according to Claim 10 or 11 wherein Y is silicon and W is aluminum.

13. A process for converting hydrocarbons comprising contacting a hydrocarbonaceous feed at hydrocarbon converting conditions with the zeolite of Claim 1. £-9 JAN1992 j -44- ij-> - rr-A

14. The process of Claim 13 which is a hydrocracking process comprising contacting the hydrocarbon feedstock under hydrocracking conditions with the zeolite of Claim 1.

15. The process of Claim 13 which is a dewaxing process comprising contacting the hydrocarbon feedstock under dewaxing conditions with the zeolite of Claim 1.

16. The process of Claim 13 which is a process for preparing a high octane product having an increased aromatics content comprising: (a) contacting a hydrocarbonaceous feed which , comprises normal and slightly branched hydrocarbons having a boiling range above 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 a higher octane, higher aromatic effluent.

^ 17. The process of Claim 16 wherein the zeolite contains a Group VIII metal component.

18. The process of Claim 13 which is a catalytic cracking process comprising the step of contacting the hydrocarbon feedstock in a reaction zone under catalytic 30 cracking conditions in the absence of added hydrogen with a catalyst comprising the zeolite of Claim 1.

19. A process of Claim 13 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 component which is the zeolite of Claim 1 and a large pore size crystalline aluminosilicate cracking component. 01 05 10 15 20 25 30 35 * j o ■" r: '> a •- <• » J. 5. J '1 -45-

20. The process of Claim 19 wherein the catalyst compositions comprises a physical mixture of the two components.

21. The process of Claim 19 wherein the two catalyst components are incorporated in an inorganic matrix.

22. The process of Claim 13 which is an isomerizing process for isomerizing C4 to C-j 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 hydrocarbons under isomerization conditions. ,

23. A process in accordance with Claim 22 wherein the catalyst has been calcined in a steam/air mixture at an elevated temperature after impregnation of the Group VIII metal.

24. A process in accordance with Claim 22 wherein ' Group VIII metal is platinum.

25. The process of Claim 13 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 C^ olefin under at least partial liquid phase conditions and in the presence of a zeolite according to Claim 1.

26. The process of Claim 25 wherein the aromatic hydrocarbon and olefin are present in a molar ratio of 4:1 to 20:1, respectively.

27. The process of Claim 25 wherein the aromatic j hydrocarbon is a member selected from the group consisting of benzene, toluene and xylene, or mixtures thereof. 40 01 05 LO IS 20 2S 30 3b <} -46-

28. The process of Claim 13 which is a process for transalkylating an aromatic hydrocarbon which comprises contacting under transalkylating condition 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 28 wherein the aromatic hydrocarbon is a member selected from the group consisting of benzene, toluene and xylene, or mixtures thereof.

31. The process of Claim 28 wherein the polyalkyl aromatic hydrocarbon is a dialkylbenzene.

32. A compound of the formula 2A- N(CH3)3 wherein A" is an anion.

33. The compound of Claim 32 wherein the anion is selected from the group consisting of halide, hydroxide, acetate, sulfate, tetrafluoroborate, and carboxylate.

34. The compound of Claim 32 wherein the anion is hydroxide. N r o f - ' ^ - 9 JAN 1992 \a. O - 47 -

35. A zeolite substantially as herein described with reference to any embodiment disclosed in the examples.

36. A method for preparing a zeolite substantially as herein described with reference to any embodiment disclosed in the examples.

37. A xeolite produced by the method of any one of claims 10 to 12 and claim 36.

38. A process as claimed in claim 13 substantially as herein described with reference to any embodiment disclosed.

39. Hydrocarbons when converted by the process of any one of claims 13 to 31 and 38. BATED THIS CR DAY OF A. J. PARK St SON K& AGENTS FOR THE APPLICANTS