BACKGROUND OF THE INVENTION

Natural and synthetic zeolitic crystalline aluminosilicates are useful as catalysts and adsorbents. These aluminosili- cates have distinct crystal structures which are demon- strated 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 alumino- silicates 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 con- taining 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 cyclopentylammonium iodide in

i the preparation of Zeolite SSZ-15 molecular sieve is dis- 2 closed in U.S. Patent No. 4,610,854; use of 1-azoniaspiro 3 [4.4] nonyl bromide and N,N,N-trimethyl neopentylammonium 4 iodide in the preparation of a molecular sieve termed 5 "Losod" is disclosed in Helv. Chim. Acta (1974); Vol. 57, 6 P« 1533 ( . Sieber and W. M. Meier); use of quinuclidinium 7 compounds to prepare a zeolite termed "NU-3" is disclosed in 8 European Patent Publication No. 40016; use of 9 1,4-di(l-azoniabicyclo[2.2.2. Joctane) lower alkyl compounds 0 in the preparation of Zeolite SSZ-16 molecular sieve is 1 disclosed in U.S. Patent No. 4,508,837; use of 2 N,N,N-trialkyl-l-adamantamine in the preparation of Zeolite 3 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. 5 5 Synthetic zeolitic crystalline borosilicates are useful as 7 catalysts. Methods for preparing high silica content zeo- liteε that contain framework boron are known and disclosed 9 in U.S. Patent No. 4,269,813. The amount of boron contained 0 ^{n tne} zeolite may be made to vary by incorporating i different amounts of borate ion in the zeolite-forming 2 solution. 3 4 The use of a quaternary ammonium compound in the preparation 5 of a boron-containing zeolite is disclosed in European 6 Patent Application No. 188,913. A method for treating a 7 zeolite containing aluminum and boron with a silicon substi- 8 tution treatment,is disclosed in U.S. Patent No. 4,701,313. 9 _Q The present invention relates to a novel family of stable 1 synthetic crystalline materials characterized as borosili- 2 cates identified as SSZ-24 and having a specified X-ray 3 diffraction pattern, and also to the preparation and use of 4 such materials.

1 SUMMARY OF INVENTION 2 3 We have prepared crystalline borosilicate molecular sieves 4 with unique properties, referred to herein as "zeolite 5 (B)SSZ-24" or simply "(B)SSZ-24" and have found highly 6 effective methods for preparing this zeolite. The boron in 7 the crystalline network may be replaced by other metals. 8 Advantageous uses for (B)SSZ-24 have also been discovered. 9 0 Thus, according to the present invention, a zeolite composition, (B)SSZ-24, is provided. (B)SSZ-24 has a mole 2 ratio of an oxide selected from silicon oxide, germanium 3 oxide, and mixtures thereof to an oxide selected from boron 4 oxide or mixtures of boron oxide with aluminum oxide, 5 gallium oxide or iron oxide between 20:1 and 100:1, and 6 having the X-ray diffraction lines of Table I below. This 7 zeolite further has a composition, as synthesized and in the 8 anhydrous state, in terms of mole ratios of oxides as 9 follows: (1.0 to 5)Q ₂ O:(0.1 to 1.0)M ₂ O:W ₂ O-: (20 to 100)YO ₂ wherein M is an alkali metal cation, W is selected from boron, gallium oxide or iron oxide, Y is selected from 2 silicon, germanium and mixtures thereof, and Q is an 3 adamantammonium quaternary ammonium ion. (B)SSZ-24 zeolites 4 can have a Y0 ₂ :W ₂ 0, mole ratio between 20:1 to 100:1 and can 5 be made essentially alumina free. As prepared, the 6 εilica:boron ratio is typically in the range of 20:1 to 7 about 100:1. Higher mole ratios can be obtained by treating 8 the zeolite with chelating agents or acids to extract boron g from the zeolite lattice. The silica:boron mole ratio can ø also be increased by using silicon and carbon halides and 1 other similar compounds. 2 3 4

01 A portion of the boron in the crystalline network may be 02 replaced by aluminum. For example, aluminum insertion may 03 occur by thermal treatment of the zeolite in combination 04 with an aluminum binder or dissolved source of aluminum. 0 Such procedures are described in U.S. Patent Nos. 4,559,315

06 and 4,550,092. 07 08 According to one embodiment of the present invention, a øg method is provided for making (B)SSZ-24 zeolites, comprising

10 preparing an aqueous mixture containing sources of an 1 adamantane quaternary ammonium ion, an alkali oxide, an

1 oxide selected from boron as a borosilicate, not simply a

13 boron oxide, and an oxide selected from silicon oxide,

14 germanium oxide, and mixtures thereof, and having a

1 ₅ composition, in terms of mole ratios of oxides, falling g within the following ranges: Y0 ₂ /W ₂ 0 ₃ , 20:1 to 100; wherein

1 ₇ Y is selected from silicon, germanium, and mixtures thereof,

IP W is selected from boron, and Q is an adamantane quaternary

,g ammonium ion; maintaining the mixture at a temperature of at

2o least 100 ^β C until the crystals of said zeolite are formed;

2i and recovering said crystals.

22

23 A zeolite _s having the same X-ray diffraction pattern as the 24 (B)SSZ-24 zeolite is described in our U.S. Patent

₂₅ No. 4,834,958 entitled "New Zeolite SSZ-24". As synthesized

₂₆ using the method described therein, this zeolite contains a

₂₇ mole ratio of 0 ₂ /W ₂ 0 ₃ greater than 100:1. The method for

28 preparing SSZ-24 described in this application cannot be 29 used to make (B)SSZ-24. The mole ratio of Y0 ₂ /W ₂ 0 ₃ cannot 30 be reduced by using large quantities of aluminum, gallium,

,. iron, or boron.

32 33

A preferred borosilicate source is boron beta zeolite described in commonly assigned co-pending application U.S. Serial No. (Docket No. B-3924), filed concurrently herewith, and entitled "Low-Aluminum Boron Beta Zeolite".

We now find that by using a suitable borosilicate source, the Y0 ₂ / ₂ 0 ₃ mole ratio can be decreased to 20:1 where W is boron. Aluminum, gallium, iron and other metals can replace boron in the (B)SSZ-24 framework by post-synthetic treatment 0 as described herein. This type of framework substitution extends the range of catalytic applications for (B)SSZ-24. 2 3 Among other factors, the present invention is based on our finding that (B)SSZ-24 with a 0 ₂ /W ₂ 0 ₃ mole ratio between 5 20:1 and 100:1 can be synthesized using a new borosilicate 6 source. Surprisingly, we have found that the mole ratio of 7 Y0 ₂ /W ₂ 0 ₃ can be decreased below 100:1 by using certain 3 borosilicate sources. We have found that the (B)SSZ-24 g zeolite has unexpectedly outstanding hydrocarbon conversion 0 properties, particularly including hydrocracking, chemicals i production, and oxygenate conversion properties. 2 3 DETAILED DESCRIPTION OF THE INVENTION 4 5 SSZ-24 zeolites, as synthesized, have a crystalline struc- 6 ture whose X-ray powder diffraction pattern shows the 7 following characteristic lines: 8 9 0 1 2 3 4

TABLE I

Typical SSZ-24 borosilicate and aluminoεilicate 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 θ where θ is the Bragg angle, were read from the spectrometer chart. From these measured values, the relative intensities, 100I/I , where I 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 rations yields substantially the same diffraction pattern although

i there can be minor shifts in interplanar spacing and minor 2 variations in relative intensity. Minor variations in the 3 diffraction pattern can also result from variations in the organic compound used in the preparation and from variations 5 in the silica-to-alumina mole ratio from sample to sample. 6 Calcination can also cause minor shifts in the X-ray 7 diffraction pattern. Notwithstanding these minor 8 perturbations, the basic crystal lattice structure remains 9 unchanged. 0 1 (B)SSZ-24 zeolites can be suitably prepared from an aqueous 2 solution containing sources of an alkali metal oxide, a 3 tricyclof3.3.1.1Jdecane quaternary ammonium ion, 4 borosilicate, and an oxide of silicon or germanium, or 5 mixture of the two. The reaction mixture should have a 6 composition in terms of mole ratios falling within the 7 following ranges: 8 9 0 1 2 3 4 5 6 7 3 wherein Q is an adamantane (or tricyclo[3.3.1.1Jdecane) g quaternary ammonium ion, Y is silicon, germanium or both, 0 and W is boron. M is an alkali metal, preferably potassium. « The organic compound which acts as a source of the ₂ quaternary ammonium ion employed can provide hydroxide ion. ₃ W is shown as boron, but is provided to the reaction as ₄ borosilicate.

When using the quaternary ammonium hydroxide compound as a template, it ha.s 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[3.3.1.1Jdecane quaternary ammonium ion is derived from a compound of the formula:

wherein each of Y., Y ₂ , 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- R ₂ , and R- independently is hydrogen, or lower alkyl and most preferably hydrogen; and

wherein each of ^~ H . , Rς, and g independently is hydrogen or lower alkyl; and most preferably hydrogen; each of Y-, Y ₂ ,

and Y- independently is lower alkyl and most preferably methyl; and A is an anion which is not detrimental to the formation of the zeolite.

The quaternary ammonium compounds are prepared by methods known in the art .

^β "lower alkyl" is meant alkyl of from about 1 to 3 carbon atoms. 0 Aθ is an anion which is not detrimental to the formation of 2 the zeolite. Representative of the anions include halogen, 3 e.g., fluoride, chloride, bromide and iodide, hydroxide, 4 acetate, εulfate, carboxylate, etc. Hydroxide is the most 5 preferred anion. It may be beneficial to ion exchange, for 6 example, the halide for hydroxide ion, thereby reducing or 7 eliminating the alkali metal hydroxide quantity required. 8 9 The reaction mixture is prepared using standard zeolitic 0 preparation techniques. Sources of borosilicates for the i reaction mixture include borosilicate glasεeε and most 2 particularly, other reactive borosilicate molecular sieves. 3 One very reactive source is boron beta zeolite described in 4 commonly assigned copending application U.S. Serial 5 No. (Docket No. B-3924), filed concurrently 6 herewith, and entitled "Low-Aluminum Boron Beta Zeolite". 7 Typical εourceε of silicon oxide include silicates, silica 3 hydrogel, silicic acid, colloidal silica, fumed silica, 9 tetra-alkyl orthosilicates, and silica hydroxides. 0 1 The reaction mixture is maintained at an elevated 2 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

01 200 ^β C, preferably from about 130°C to about 170°C and most

02 preferably from .about 135 ^β C to about 165 ^β C. The

03 crystallization period is typically greater than one day and 04 preferably from about three days to about seven days. 05 06 The hydrothermal crystallization is conducted under pressure 07 and usually in an autoclave so. that, the reaction mixture is 08 subject to autogenous preεsure. The reaction mixture can be 09 stirred during crystallization.

10

11 Once the zeolite crystals have formed, the solid product is

12 separated from the reaction mixture by standard mechanical

₁ separation techniques such as filtration. The crystals are 24 water-washed and then dried, e.g., at 90 ^β C to 150°C from 8 •c to 24 hourε, to obtain the as synthesized, (B)SSZ-24 zeolite

16 crystals. The drying step can be performed at atmospheric or εubatmoεpherip preεsureε.

18 _j o During the hydrothermal cryεtallization εtep, the (B)SSZ-24

20 crystals can be allowed to nucleate spontaneously from the 21 reaction mixture. The reaction mixture can also be seeded

₂₂ with (B)SSZ-24 crystals both to direct, and accelerate the

₂₃ crystallization, aε well aε to minimize the formation of

₂₄ undeεired boroεilicate contaminants.

25

_ _fi The synthetic (B)SSZ-24 zeolites can be used as synthesized

27 or can be thermally treated (calcined). Usually, it is 28 deεirable to remove the alkali metal cation by ion exchange - _g and replace it with hydrogen, ammonium, or any deεired metal _ ₀ ion. The zeolite can be leached with chelating agentε, ₃₁ e.g., EDTA or dilute acid solutions, to increase the

32 εilica:boron mole ratio. The zeolite can also be steamed; 33 εteaming helpε stabilize the crystalline lattice to attack 34 from acids. The zeolite can be used in intimate combination

with hydrogenating components, such aε 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, aε. well a_s.th.eir. mix.tuxes. Of the replacing metallic cations, cations of metals such aε 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 componentε can be exchanged into the zeolite. The zeolite can alεo 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 deεired metals present as ionε in the reaction mixture from which the (B)SSZ-24 zeolite iε prepared.

Typical ion exchange techniqueε involve contacting the εynthetic zeolite with a εolution containing a εalt of the desired replacing cation or cations. Although a wide variety of saltε can be employed, chlorideε and other halides, nitrates, and sulfateε are particularly preferred. Repreεentative ion exchange techniqueε are diεcloεed in a wide variety of patents including U.S. Nos. 3,140,249; 3,140,251; and 3,140,253.

Following contact with the εalt εolution of the deεired 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 temperatureε ranging from about 200°C to 820°C for

1 periods of time ranging from 1 to 48 hours, or more, to 2 produce a catalytically active product especially useful in 3 hydrocarbon conversion procesεeε. 4 5 Regardleεε of the cations present in the εyntheεized form of 6 the zeolite, the εpatial arrangement of the atoms which form 7 the basic crystal lattice of the zeolite remains essentially 8 unchanged. The exchange of cations has little, if any, 9 effect on the zeolite lattice εtructureε. 0 1 The (B)SSZ-24 boroεilicate and aluminosilicate can be formed 2 into a wide variety of physical shapes. Generally speaking, 3 the zeolite can be in the form of a powder, a granule, or a 4 molded product, such aε extrudate having particle size 5 sufficient to paεε through a 2-mesh (Tyler) screen and be 6 retained on a 400-meεh (Tyler) εcreen. In caεeε where the 7 catalyεt iε molded, εuch aε by extruεion with an organic 3 binder, the ¹ aluminoεilicate can be extruded before drying, g or, dried or partially dried and then extruded. The zeolite 0 ^{can De} compoεited with other aterialε resistant to the i temperatureε and other conditionε employed in organic 2 converεion proceεεeε. Such matrix materials include active 3 and inactive materials and synthetic or naturally occurring 4 zeolites as well as inorganic materials εuch as clays, silica and metal oxides. The latter may occur naturally or 6 may be in the form of gelatinous precipitates, solε, or 7 gelε, including mixtures of εilica and metal oxideε. Use of 8 an active material in conjunction with the εynthetic 9 zeolite, i.e., combined with it, tends to improve the con- 0 version and selectivity of the catalyst in certain organic conversion procesεeε. Inactive materialε can suitably serve ₂ as diluents to control the amount of conversion in a given ₃ proceεε εo that productε can be obtained economically with- 4 out uεing other means for controlling the rate of reaction.

1 Frequently, zeolite materials have been incorporated into 2 naturally occurring clayε, e.g., bentonite and kaolin. 3 Theεe materials, i.e., clays, oxides, etc., function, in 4 part, as binders for the catalyst. It is desirable to 5 provide a catalyst having good crush strength, because in petroleum refining the catalyst is often subjected to rough 7 handling. This tends to break the catalyst down into powders which cause problems in processing. 9 0 Naturally occurring clays which can be compoεited with the 1 εynthetic zeoliteε of this invention include the 2 montmorillonite and kaolin families, which families include ₃ the εub-bentonites and the kaolins commonly known as Dixie, McNamee, Georgia, and Florida clays or others in which the 5 main mineral constituent is halloyεite, kaolinite, dickite, 6 nacrite, or anauxite. Fibrous clays εuch aε εepiolite and

27 attapulgite can alεo be used aε supports. Such clays can be

18 used in the raw state aε originally mined or can be - _g initially εubjected to calcination, acid treatment or ₂₀ chemical modification.

21

₂₂ In addition to the foregoing materialε, the SSZ-24 zeoliteε

₂₃ can be compoεited with porouε matrix materialε and mixtureε _. of matrix materialε εuch aε εilica, alumina, titania,

25 magnesia, εilica:alumina, silica-magnesia, εilica-zirconia, 26 εilica-thoria, silica-beryllia, silica-titania, ₇ _ titania-zirconia as well as ternary compositions εuch as _2β silica-alumina-thoria, silica-alumina-zirconia, 2« silica-alumina-magnesia, and silica-magneεia-zirconia. The - ₀ matrix can be in the form of a cogel.

31

The (B)SSZ-24 zeoliteε can alεo be compoεited with other zeolites εuch as εynthetic and natural faujasites (e.g., X and Y), erioniteε, and mordenites. They can also be

compoεited with purely εynthetic zeoliteε εuch aε thoεe of the ZSM εerieε. The combination of zeolites can also be composited in a porous inorganic matrix.

(B)SSZ-24 zeolites are useful in hydrocarbon converεion reactionε. Hydrocarbon converεion reactionε are chemical and catalytic proceεεeε in which carbon-containing compounds are changed to different carbon-containing compounds. Exampleε of hydrocarbon converεion reactionε include catalytic cracking, hydrocracking, and olefin and aromaticε formation reactionε. The catalyεtε are useful in other petroleum refining and hydrocarbon conversion reactions εuch aε iεomerizing n-paraffinε and naphtheneε, polymerizing and oligomerizing olefinic or acetylenic compoundε εuch aε isobutylene and butene-1, reforming, alkylating, isomerizing polyalkyl subεtituted aromatics (e.g., ortho xylene), and diεproportionating aromaticε (e.g., toluene) to provide mixtures of benzene, xyleneε, and higher methylbenzenes. The (B)SSZ-24 catalystε have high εelectivity, and under hydrocarbon converεion conditions can provide a high percentage of deεired productε relative to total productε.

(B)SSZ-24 zeoliteε can be used in proceεεing hydrocarbonaceouε feedεtockε. Hydrocarbonaceouε feedεtockε contain carbon compoundε and can be from many different sources, εuch aε virgin petroleum fractionε, recycle petroleum fractionε, shale oil, liquefied coal, tar sand oil, and in general, can be any carbon containing fluid suεceptible to zeolitic catalytic reactionε. Depending on the type of proceεεing the hydrocarbonaceous feed iε to undergo, the feed can contain metal or be free of metals, it can alεo have high or low nitrogen or sulfur impurities. It can be appreciated, however, that processing will generally

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 ^β C to 485°C, molar ratios of hydrogen to hydrocarbon charge from 1 to 100, a preεεure in the range of from 0.5 to 350 bar, and a liquid hourly εpace velocity (LHSV) in the range of from 0.1 to 30.

Hydrocracking catalyεts 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 εelected from the group of hydrogenation catalysts consiεting of one or more metalε of Group VIB and Group VIII, including the salts, complexes, and solutionε containing εuch. The hydrogenation catalyεt iε preferably εelected from the group of metalε, salts, and complexes thereof of the group conεiεting of at leaεt one of platinum, palladium, rhodium, iridiu , and mixtureε thereof or the group conεiεting 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 encompasε εuch metal or metals in the elemental state or in some form such as an oxide, sulfide, halide, carboxylate, and the like.

A hydrogenation component iε present in the hydrocracking catalyεt in an effective amount to provide the hydrogenation function Of the hydrocracking catalyεt and preferably in the range of from 0.05% to 25% by weight.

The (B)SSZ-24 catalyεt may be employed in conjunction with traditional hydrocracking catalyεtε, e.g., any aluminosilicate heretofore employed as a component in hydrocracking catalysts. Representative of the zeolitic aluminosilicatjss diεcloεed heretofore aε employable aε component parts of hydrocracking catalystε are Zeolite Y (including εteam εtabilized, e.g., ultra-εtable 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), rauj site, 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 εilicateε εuch aε εilicalite (U.S. Patent No. 4,061,724), erionite, mordenite, offretite, chabazite, FU-1-type zeolite, NU-type zeoliteε, LZ-210-type zeolite, and mixtureε thereof. Traditional hydrocracking catalyεtε containing amountε of ^Na 2° ^eεε than about one percent by weight are generally preferred. The relative amounts of the (B)SSZ-24 component and traditional ^hydrocracking component, if any, will depend at leaεt in pact?, on the selected hydrocarbon feedstock and ^on the desired product distribution to be obtained therefrom, but in all instanceε an effective amount of (B)SSZ-24 iε employed.

The hydrocracking catalyεtε 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 hydrocracking catalysts including: amorphous catalytic inorganic oxides, e.g..

catalytically active silica-aluminas, clays, silicas, aluminas, silica-aluminas, silica-zirconiaε, εilica-magneεiaε, alumina-boriaε, alumina-titaniaε, 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.

0 (B)SSZ-24 can be used to dewax hydrocarbonaceous feeds by selectively removing straight chain paraffins. The catalytic dewaxing conditionε are dependent in large meaεure 3 on the feed uεed and upon the desired pour point. 4 5 Generally, the temperature will be between about 200°C and about 475 ^β C, preferably between about 250 ^β C and about 450°C. The presεure iε typically between about 15 pεig and about 3 3000 pεig, preferably between about 200 pεig and 3000 pεig. 9 The LHSV preferably will be from 0.1 to 20, preferably 0 between about 0.2 and about 10. 1 2 Hydrogen iε preferably preεent in the reaction zone during 3 the catalytic dewaxing proceεε. The hydrogen to feed ratio 4 iε typically between about 500 and about 30,000 SCF/bbl 5 (εtandard cubic feet per barrel), preferably about 1,000 to 6 about 20,000 SCF/bbl. Generally, hydrogen will be εeparated 7 from the product and recycled to the reaction zone. Typical 3 feedεtockε include light gaε-oil, heavy gaε-oilε, and g reduced crudes boiling about 350°F. 0 i The (B)SSZ-24 hydrodewaxing catalyst may optionally contain 2 a hydrogenation component of the type commonly employed in 3 dewaxing catalystε. The hydrogenation component may be 4

εelected from the group of hydrogenation catalysts consiεt- ing of one or more metalε of Group VIB and Group VIII, including the salts, complexes and solutionε containing εuch metalε. The preferred hydrogenation catalyεt is at least one of the group of metals, saltε, and complexeε εelected from the group conεiεting of at leaεt one of platinum, palladium, rhodfmm, iridium, and mixtureε thereof or at leaεt one from the group consisting of nickel, molybdenum, cobalt, tungsten, titanium, chromium, and mixtures thereof. Reference to th - catalytically active metal or metals iε intended to encompaεε εuch metal or metalε in the elemental state or in εome form εuch aε an oxide, εulfide, halide, carboxylate, anfe the like.

The hydrogenation component of the hydrodewaxing catalyst is present in an effective amount to provide an effective hydrodewaxing catalyεt preferably in the range of from about 0.05 to 5% by weight.

(B)SSZ-24 can be uεed to convert εtraight run naphthaε and εimilar mixtureε to highly aromatic mixtures. Thus, normal a°d slightly branched chained hydrocarbons, preferably having a boiling range above about 40°C and less than about 200 ^β 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 ^β C to 600 ^β C, preferably 480 ^β C to 550°C at pressureε 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.

The reforming catalyst preferably contain a Group VIII metal compound to have εufficient activity for commercial uεe. By Group VIII metal compound aε 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 uεe 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 εelected from rhenium or tin.

The zeolite/Group VIII metal converεion catalyεt can be used without a binder or matrix. The preferred inorganic matrix, where one is used, is a εilica-based binder εuch aε Cab-O-Sil or Ludox. Other matriceε εuch aε magneεia and titania can be uεed. The preferred inorganic matrix iε nonacidic.

It iε critical to the εelective production of aromatics in useful quantities that the conversion catalyst be εubεtantially free of acidity, for example, by poiεoning the zeolite with a baεic metal, e.g., alkali metal, compound. The zeolite iε uεually prepared from mixtureε containing alkali metal hydroxideε and thuε, have alkali metal contentε of about 1-2 wt. %. Theεe high levelε of alkali metal, uεually εodium or potaεsium, are unacceptable for most catalytic applicationε becauεe they greatly deactivate the catalyεt for cracking reactions. Usually, the alkali metal is removed to low levels by ion exchange with hydrogen or ammonium ions. By alkali metal compound aε uεed herein is meant elemental or ionic alkali metalε or their baεic compoundε. Surpriεingly, unleεε the zeolite itεelf iε substantially free of acidity, the basic compound is

required in the preεent proceεε to direct the εynthetic reactionε to aromaticε production.

The amount of alkali metal neceεεary to render the zeolite εubεtantially free of acidity can be calculated uεing εtandard techniqueε baεed 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 subεtantially eliminate the acidity of the zeolite. An alkali metal content of about 100%, or greater, of the acid εiteε calculated on a molar baεiε iε εufficient.

Where the baεic metal content iε leεε than 100% of the acid εiteε on a molar baεiε, the teεt deεcribed in U.S. Patent No. 4,347,394 which patent iε incorporated herein by reference, can be uεed to determine if the zeolite iε εubεtantially free of acidity.

The preferred alkali metalε are εodium, potassium, and cesium. The zeolite itself can be subεtantially free of acidity only at very high εilica:alumina mole ratioε; by "zeolite conεiεting eεεentially of εilica" is meant a zeolite which iε εubεtantially free of acidity without baεe poiεoning.

Hydrocarbon cracking εtockε 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 εubatmoεpheric to εeveral hundred atmoεphereε, typically from about atmoεpheric to about five atmoεphereε. For this purpose, the (B)SSZ-24 catalyst can be composited with mixtures of inorganic oxide supports aε well as traditional cracking catalyst.

The catalyεt may be employed in conjunction with traditional 2 cracking catalyεtε, e.g., any aluminosilicate heretofore 3 employed aε a component in cracking catalyεtε. 4 Representative of the zeolitic aluminosilicates disclosed 5 heretofore as employable as component parts of cracking 6 catalysts are Zeolite Y (including steam stabilized 7 chemically modified, e.g., ultra-stable Y), Zeolite X, 8 Zeolite beta (U.S. Patent No. 3,308,069), Zeolite ZK-20 9 (U.S. Patent No. 3,445,727), Zeolite ZSM-3 (U.S. Patent No. 0 3,415,736), faujasite, LZ-10 (U.K. Patent 2,014,970, June 9, 1 .1982), ZSM-5-Type Zeolites, e.g., ZSM-5, ZSM-11, ZSM-12, 2 ZSM-23, ZSM-35, ZSM-38, ZSM-48, crystalline silicates such 3 as silicalite (U.S. Patent No. 4,061,724), erionite, 4 mordenite, offretite, chabazite, FU-1-type zeolite, NU-type 5 zeolites, LZ-210-type zeolite and mixtures thereof. Traditional cracking catalysts containing amounts of Na ₂ 0 7 lesε than about one percent by weight are generally 8 preferred. The relative amountε of the (B)SSZ-24 component 9 and traditional cracking component, if any, will depend at 0 leaεt in part, on the εelected hydrocarbon feedεtock and on i the deεired product diεtribution to be obtained therefrom, 2 but in all inεtanceε, an effective amount of (B)SSZ-24 iε 3 employed. When a traditional cracking catalyst (TC) 4 component is employed, the relative weight ratio of the TC 5 to the (B)SSZ-24 is generally between about 1:10 and about 6 500:1, deεirably between about 1:10 and about 200:1, 7 preferably between about 1:2 and about 50:1, and moεt 8 preferably between about 1:1 and about 20:1. 9 0 The cracking catalyεts are typically employed with an 1 inorganic oxide matrix component which may be any of the 2 inorganic oxide matrix components which have been employed 3 heretofore in the formulation of FCC catalystε including: 4 amorphouε catalytic inorganic oxideε, e.g., catalytically

Oi* active εilica-aluminaε, clayε, εilicaε, aluminas,

-*ø2 εilica-aluminaε, εilica-zirconiaε, εilica-magneεiaε,

03 alumina-boriaε, alumina-titanias, and the like and mixtures

04 thereof. The traditional cracking component and (B)SSZ-24

05 may be mixed separately with the matrix component and then

06 mixed or the TC component and (B)SSZ-24 may be mixed and

07 then formed with the matrix component.

08

09 The mixture of a traditional cracking catalyst and (B)SSZ-24 0 may be carried out in any manner which resultε in the

11 coincident preεence of εuch in contact with the crude oil

12 feedεtock under catalytic cracking conditionε. For example,

13 a catalyεt may be employed containing the traditional

14 cracking catalyεt and a (B)SSZ-24 in single catalyst

15 particles or (B)SSZ-24 with or without a matrix component

16 may be added aε a diεcrete component to a traditional

17 cracking catalyεt.

18

19 (B)SSZ-24 can alεo be uεed to oligomerize εtraight and

20 branched chain olefinε having from about 2-21 and preferably 2i 2-5 carbon atomε. The oligomerε which are the productε of

22 the proceεε are medium to heavy olefinε which are uεeful for

23 both fuelε, i.e., gaεoline or a gasoline blending stock and

24 chemicals.

25

26 The oligomerization proceεε comprises contacting the olefin

27 feedstock in the. gaseous state phase with (B)SSZ-24 at a

28 temperature of from about 450°F to about 1200°F, a WHSV of 2g from about 0.2 to about 50 and a hydrocarbon partial

30 presεure of from about 0.1 to about 50 atmoεphereε.

31

32 Alεo, temperatureε below about 450°F may be uεed to

22 oligomerize the feedεtock, when the feedstock is in the

2 liquid phase when contacting the zeolite catalyst. Thuε,

when the olefin feedstock contacts the zeolite catalyst in the liquid phase, temperatureε of from about 50°F to about 450 ^β F, and preferably from 80 to 400°F may be uεed 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 εufficient to maintain the εyεtem in the liquid phaεe. As is known in the art, the presεure will be a function of the number of carbon atoms of the feed olefin and the temperature. Suitable presεureε include from about 0 pεig to about 3000 psig.

The zeolite can have the original cations asεociated therewith replaced by a wide variety of other cationε according to techniqueε well known in the art. Typical cations would include hydrogen, ammonium, and metal cations including mixtureε of the εame. Of the replacing metallic cationε, particular preference iε given to cationε of metalε εuch aε rare earth metalε, manganeεe, calcium, aε well aε metalε 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 aromaticε produced iε not more than about 20 wt. %. Thiε iε accompliεhed by uεing a zeolite with controlled acid activity [alpha value] of from about 0.1 to about 120, preferably from about 0.1 to about 100, aε meaεured by itε ability to crack n-hexane.

Alpha valueε are defined by a εtandard teεt known in the art, e.g., aε shown in U.S. Patent No. 3,960,978 which is incorporated herein by reference. If required, such zeolites may be obtained by εteaming, by uεe in a converεion proceεε or by any other method which may occur to one skilled in thiε art.

24 (B)SSZ-24 can be uεed to convert light gaε C ₂ -C ₈ paraffinε and/or olefinε .to higher molecular weight hydrocarbonε including aromatic compounds. Operating temperatures of 100-700 ^β C, operating pressureε of 0-1000 pεig and space velocities of 0.5-40 hr~ WHSV can be used to convert the C _j -C _f - paraffin and/or olefins to aromatic compounds. Preferably, the zeolite will contain a catalyst metal or metal oxide wherein said metal iε εelected 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 uεed to condenεe lower aliphatic alcoholε having 1-10 carbon atomε to a gaεoline boiling point hydrocarbon product compriεing mixed aliphatic and aromatic hydrocarbons. Preferred condensation reaction condition using (B)SSZ-24 aε the condensation catalyst include a temperature of about 500-1000 ^β 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 proceεε conditionε in more detail. The diεcloεure of U.S. Patent ^N °« 3,984,107 iε incorporated herein by reference.

The (B)SSZ-24 catalyst may be in the hydrogen form or may be baεe exchanged or impregnated to contain ammonium or a metal cation complement, preferably in the range of from about 0.05-5 wt. %. The metal cationε that may be preεent include any of the metals of the Groupε I-VIII of the Periodic Table. However, in the caεe of Group IA metalε, the cation content should in no case be so large as to effectively inactivate the catalyst.

The (B)SSZ-24 catalyst is highly active and highly selective for isomerizing C. to C ₇ hydrocarbonε. The activity means that the catalyst can operate at relatively low temperatures 4 which thermodynamically favors highly branched paraffins. 5 Consequently, the catalyεt can produce a high octane 6 product. The high selectivity means that a relatively high 7 liquid yield can be achieved when the catalyst is run at a high octane. 9 o The isomerization process comprises contacting the i isomerization catalyst with a hydrocarbon feed under 2 iεomerization conditionε. The feed is preferably a light 2 straight run fraction, boiling within the range of 30-250°F and preferably from 60-200°F. Preferably, the hydrocarbon ₅ feed for the process compriseε a εubstantial amount of C. to 6 Cη normal and slightly branched low octane hydrocarbonε, ₇ more preferably Cς and C _g hydrocarbonε. 8 _Q The preεεure in the proceεε iε preferably between 50-1000 ₀ pεig, more preferably between 100-500 pεig. The LHSV iε ₁ preferably between about 1 to about 10 with a value in the ₂ range of about 1 to about 4 being more preferred. It iε ₃ alεo preferable to carry out the iεomerization reaction in ₄ the preεence of hydrogen. Preferably, hydrogen iε added to _ς give a hydrogen to hydrocarbon ratio (H ₂ /HC) of between 0.5 ₆ and 10 H ₂ /HC, more preferably between 1 and 8 H ₂ /HC. The ₇ temperature iε preferably between about 200 ^β F and about 8 1000°F, more preferably between 400-600°F. Aε is well known 9 to those skilled in the isomerization art, the initial 0 selection of the temperature within thiε broad range iε made ₁ primarily as a function of the desired conversion level 2 considering the characteristicε of the feed and of the catalyεt. Thereafter, to provide a relatively conεtant 3 4

i value for conversion, the temperature may have to be slowly 2 increased during the run to compensate for any deactivation 3 that occurs. 4 5 A low εulfur feed iε eεpecially preferred in the 6 iεomerization proceεε. The feed preferably containε leεε 7 than 10 ppifi, more preferably leεε than 1 ppm, and moεt 8 preferably leεε than 0.1 ppm εulfur. in the caεe of a feed 9 which iε not already low in εulfur, acceptable levels can be 0 reached by hydrogenating the feed in a preεaturation zone 1 with a hydrogenating catalyεt which iε reεiεtant to εulfur 2 poiεoning. An example of a εuitable catalyεt for thiε hydrodeεulfurization proceεε is an alumina-containing 4 support and a minor catalytic proportion of molybdenum 5 oxide, cobalt oxide and/or nickel oxide. A platinum on alumina hydrogenating catalyst can alεo work. in which ₇ case, a εulfur εorber iε preferably placed downstream of the hydrogenating catalyst, but upεtream of the preεent g iεomerization catalyεt. Exampleε of εulfur εorberε are 0 alkali or alkaline earth metalε on porouε refractory inorganic oxides, zinc, etc. Hydrodeεulfurization iε 2 typically conducted at 315-455°C, at 200-2000 pεig, and at a 3 LHSV of 1-5. 4 5 I is preferable to limit the nitrogen level and the water 6 content of the feed. Catalysts and processeε which are 7 εuitable for these purposes are known to those skilled in 3 the art.

29 _Q After a period of operation, the catalyεt can become

22 deactivated by coke. Coke can be removed by contacting the

_2 catalyst with an'Λ&xygen-containing gas at an elevated

,_ temperature.

34

i The isomerization catalyεt preferably contains a Group viii 2 metal compound to have sufficient activity for commercial 3 use. By Group VIII metal compound as used herein iε meant 4 the metal itself or a compound thereof. The Group VIII 5 noble metals and their compounds, platinum, palladium, and 6 iridium, or combinations thereof can be used. Rhenium and 7 tin may also be used in conjunction with the noble metal. 8 The most preferred metal is platinum. The amount of Group 9 VIII metal present in the conversion catalyεt εhould be 0 within the normal range of use in isomerizing catalyεts, 1 from about 0.05-2.0 wt. %. 2 3 (B)SSZ-24 can be used in a process for the alkylation or 4 transalkylation of an aromatic hydrocarbon. The proceεs 5 comprises contacting the aromatic hydrocarbon with a C- to 6 ^c 20 ° ^efin alkylating agent or a polyalkyl aromatic 7 hydrocarbon transalkylating agent, under at least partial 3 liquid phase conditions, and in the presence of a catalyst g compriεing SSZ-24. 0 2 For high catalytic activity, the (B)SSZ-24 zeolite εhould be 2 predominantly in itε hydrogen ion form. Generally, the 3 zeolite iε converted to itε hydrogen form by ammonium 4 exchange followed by calcination. If the zeolite iε syntheεized with a high enough ratio of organonitrogen 6 cation to εodium ion, calcination alone may be sufficient. 7 It iε preferred that, after calcination, at leaεt 80% of the 8 cation εiteε are occupied by hydrogen ionε and/or rare earth 9 ions.

30

32 The pure (B)SSZ-24 zeolite may be used as a catalyεt, but

22 generally, it iε preferred to mix the zeolite powder with an

_, inorganic oxide binder εuch aε alumina, silica,

24 εilica-alumina, or naturally occurring clays and form the

mixture into tabletε or extrudateε. The final catalyεt may contain from 1-99 wt. % (B)SSZ-24 zeolite. Uεually the 3 zeolite content will range from 10-90 wt. %, and more 4 typically from 60-80 wt. %. The preferred inorganic binder 5 iε alumina. The mixture may be formed into tabletε or 6 extrudateε having the deεired εhape by methodε well known in the art. 8 9 Exampleε of suitable aromatic hydrocarbon feedεtockε which 0 may be alkylated or tranεalkylated by the proceεε of the 1 invention include aromatic compoundε εuch aε benzene, 2 toluene, and xylene. The preferred aromatic hydrocarbon is 3 benzene. Mixtures of aromatic hydrocarbons may also be 4 employed. 5 6 Suitable olefins for the alkylation of the aromatic 7 hydrocarbon are those containing 2-20 carbon atomε, εuch aε 3 ethylene, propylene, butene-1, tranε-butene-2, and g ciε-butene-2, and higher olefinε, or mixtureε thereof. The 0 preferred olefin iε propylene. These olefins may be preεent i in admixture with the correεponding C ₂ to C _2Q paraffinε, but 2 it iε preferable to remove any dieneε, acetyleneε, εulfur 3 compounds or nitrogen compoundε which may be preεent in the olefin feedεtock stream to prevent rapid catalyεt 5 deactivation. 6 7 When transalkylation iε deεired, the tranεalkylating agent 3 is a polyalkyl aromatic hydrocarbon containing two or more 9 alkyl groups that each may have from two to about four 0 carbon atoms. For example, εuitable polyalkyl aromatic 1 hydrocarbonε include di-, tri-, and tetra-alkyl aromatic 2 hydrocarbons, εuch aε diethylbenzene, triethylbenzene, 2 diethylmethylbenzene (diethyltoluene) , di-isopropylbenzene, 4 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 polyisopropylbenzeneε, ethyltoluene from the reaction of toluene with ethylene or polyethyltoluenes, cymeneε from the reaction of toluene with propylene or polyiεopropyltolueneε, and εec-butyl benzene from the reaction of benzene and n-buteneε or polybutylbenzenes. The 3 production of cumene from the alkylation of benzene with 4 propylene or the transalkylation of benzene with 5 di-isopropylbenzene is eεpecially preferred. 6 7 When alkylation iε the proceεε conducted, reaction 3 conditionε are aε followε. The aromatic hydrocarbon- feed εhould be preεent in εtoichiometric exceεε. It iε preferred o that molar ratio of aromaticε to olefinε be greater than i four-to-one to prevent rapid catalyεt fouling. The reaction 2 temperature may range from 100-600°F, preferably, 250-450°F. 3 The reaction preεεure should be sufficient to maintain at 4 least a partial liquid phaεe in order to retard catalyεt c fouling. Thiε iε typically 50-1000 pεig depending on the 6 feedεtock and reaction temperature. Contact time may range 7 from 10 εeconds to 10 hours, but is usually from five 3 minutes to an hour. The WHSV, in terms of grams (pounds) of g aromatic hydrocarbon and olefin per gram (pound) of catalyst o per hour, is generally within the range of about 0.5 to 50. 1 2 When transalkylation is the process conducted, the molar 2 ratio of aromatic hydrocarbon will generally range from 4 about 1:1 to 25:1, and preferably from about 2:1 to 20:1.

The reaction temperature may range from about 100-600°F, but it iε preferably about 250-450°F. The reaction preεεure εhould be εufficient to maintain at leaεt a partial liquid phaεe, typically in the range of about 50-1000 pεig, preferably 300-6O0 pεig. The WHSV will range from about 0.1-10.

The converεion 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 procesε deεired. The formulation of the catalyεt particles will vary depending on the conversion procesε and method of operation.

Other reactionε which can be performed uεing the catalyεt of thiε invention containing a metal, e.g., platinum, include hydrogenation-dehydrogenation reactionε, denitrogenation, and deεulfurization reactionε.

Some hydrocarbon coπverεionε can be carried out on SSZ-24 zeoliteε utilizing the large pore εhape-εelective behavior. ^For example, the ^' εubεtituted (B)SSZ-24 zeolite may be uεed in preparing cumene or other alkylbenzeneε in proceεses utilizing propylene to alkylate aromaticε. Such a proceεε iε deεcribed in "our U.S. Serial No. 134,410 (1987), uεing beta zeolite.

(B)SSZ-24 can be ^* uεed in hydrocarbon converεion reactions with active or inactive supportε, with organic or inorganic binderε, and with and without added metalε. Theεe reactionε are well known to the art, aε are the reaction conditionε.

(B)SSZ-24 can also be used aε an adsorbent, as a filler in paper, paint, and toothpasteε, and aε a water-εoftening agent in detergents.

The following examples illustrate the preparation of (B)SSZ-24.

EXAMPLES

Example 1

Preparation of N,N,N-Trimethyl-1-Adamantane [3.3.1.1jTricyclodecane Ammonium Hydroxide (Template )

5 The quaternary ammonium compound used in the SSZ-24 6 syntheεiε iε prepared by an adaptation of an amino acid 7 alkylation method (Can. J. Chem. 54 3310, 1976). One 3 hundred gramε of 1-adamantanamine (1-amino tricyclo[3.3.- g l.ljdecane, Aldrich) is dissolved in 1.5 L of methanol. One o hundred seventy-two grams of potasεium bicarbonate iε i εlurried into εolution. The solution iε chilled in an ice 2 bath and 400 g of methyl iodide iε added dropwiεe with 3 εtirring. The reaction iε allowed to come to room tempera- 4 ture and iε εtirred for a few dayε. The reaction iε 5 concentrated to dryness by removing methanol and unreacted 6 methyl iodide. The residue is treated with chloroform to 7 extract the organic εaltε from the inorganicε. The chloro- 8 form extractε are εtripped down leaving an off-white εolid. 9 0 This is recrystallized from a minimum of hot methanol to 1 yield N,N,N,-trimethyl-l-adamantammonium iodide (decompoεeε 2 at 309°C by DSC analyεiε). 3 4

The cryεtalline εalt iε conveniently converted to the hydroxide form by εtirring overnight in water with AGI-X8 hydroxide ion exchange reεin to achieve a εolution ranging from 0.25-1.5 molar.

Example 2 7 2.25 millimoleε of the hydroxide form of the template from Example 1 and 0.10 g KOH (εolid) in a total of 12 mL H ₂ 0 are 0 εtirred until clear. 0.90 gramε Caboεil M-5 is stirred in. 0.60 g of NH.+ boron beta (aluminum free and described in 2 our U.S. Serial Application) is added and the reaction is 3 heated at 150°C for seven dayε and at 0 rp . The product 4 after filtration and washing, drying at 100°C, and XRD 5 analysis is found to be (B)SSZ-24. Changes in lattice 6 parameters (εee below) demonεtrate boron incorporation. No 7 remaining beta zeolite iε obεerved. 8 9 Example 3 0 i The εame experiment aε Example 2 iε εet up except the boron 2 beta zeolite iε added to the reaction at three days of 3 heating. Heating is carried out for another four dayε. The 4 product iε still (B)SSZ-24. 5 6 Example 4 7 3 An experiment iε run to see if the boron beta contribution 9 to the product can be increaεed. 1.12 millimoleε of 0 template hydroxide and 0.05 g KOH(ε) are mixed in 6 mL H-O. 2 0.45 grams Cabosil is added and the reaction is heated for 2 four days at 150°C and 0 rpm. The reaction produces a gel. 2 0.60 grams of NH,+ boron beta is added and the reaction iε 4 heated for three more dayε. A cryεtalline product is

Oi obtained and is (B)SSZ-24 upon analysis. The contribution

02 of boron beta has been doubled in thiε reaction relative to

03 Examples 2 and 3.

04

05 Example 5

06

07 The same reaction is run using boron beta made originally

08 from Ludox AS-30; hence, 500 ppm aluminum is introduced into Og the reaction. But again, the crystalline product is

10 (B)SSZ-24 with the aluminum carried along in the

11 hydrothermal conversion.

12

13 Example 6

14

15 In thiε reaction, the amorphouε εilica is replaced by a much 6 smaller quantity of seed material. The solution phase

17 consiεtε of 6.82 g of 0.33 molar template, 0.10 g KOH(s) and 3 5.2 g H ₂ 0. 1.00 g of NH.+ boron beta and 0.10 g of all

19 silica SSZ-24, as syntheεized, iε added aε εeed material

20 (the SSZ-24 iε prepared as described in U.S. Patent No.

2i 4,665,110). The reaction is run for four days at 0 rpm and

22 150°C. The product iε well-crystallized (B)SSZ-24. XRD

23 data is given in Table II. This reaction approaches a

24 straight transformation of boron beta to boron SSZ-24 in the 25 presence of the correct template and base. However, we note 26 that in the absence of an all-silica source, the 27 transformation does not occur at all. 28 29 Several reactions were carried out with the intention of 30 replacing boron beta with a boron-containing glass. A 2i finely powered Pyrex material was used. It contained 22 aluminum as well as boron. All reactions contained the same 22 amount of template, KOH and water as the reaction in Example - ₄ 6. Heating was at 150°C.

TABLE II

it can be εeen in Exampleε 7-12 (εee Table III) that Pyrex doeε not afford as pure a product and reaction rates are slower than when boron beta zeolite is uεed. In Examples 11 and 12, when Pyrex is the major silica source, the presence of aluminum becomes important enough to give SSZ-13 (a chabazite phase) as the excluεive product.

Example 13

Not only doeε the boron beta yield a pure boron SSZ-24 aε deεcribed in Exampleε 2-6, but the cryεtallization rate iε even greatly enhanced over the all-silica synthesiε from Caboεil. A reaction is set up aε in Example 2. The reaction iε run at 150°C, 0 rpm, but for only one day. A cryεtalline product iε already produced which analyzed aε pure boron SSZ-24. The all-silica SSZ-24 usually requireε 7-10 dayε to cryεtallize.

Example 14

The product of Example 2 waε calcined aε followε. The εample waε heated in a muffle furnace from room temperature up to 540°C at a εteadily increasing rate over a 7-hour period. The sample waε maintained at 540°C for four more hourε and then taken up to 600°C for an additional four hourε. Nitrogen waε paεεed over the zeolite at a rate of 20 εtandard cubic feet per minute (cfm) during heating (a small amount of oxygen iε alεo present). The calcined product had the X-ray diffraction lines indicated in Table IV below.

TABLE IV

ion exchange of the calcined material from Example 14 was carried out using NH.N0 ₃ to convert the zeoliteε from K form to NH4. Typically the εame mass of NH.N0 ₃ as zeolite waε slurried into H ₂ 0 at ratio of 50:1 H ₂ 0:zeoiite. The exchange εolution wa ^' s heated at 100°C for two hourε and then

filtered. Thiε proceεε was repeated two times. Finally, after the last exchange, the zeolite was washed several times with H ₂ 0 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 presεure. The 5 reactor was taken to 250°F for 40 minutes and then raised to 6 800 ^β F. Once temperature equilibration was achieved, a 7 50/50, w/w feed of n-hexane and 3-methylpentane was 8 introduced into the reactor at a rate of 0.62 cc/hour. Feed g delivery waε made via εyringe pump. Direct εampling onto a 0 9 ^a s chromatograph waε begun after 10 minuteε of feed i introduction. Constraint Index values were calculated from 2 9 ^a s chromatographic data using methods known in the art. 3

Example Conversion 4 No. C.I. at 10 Min. Temp., °F 5

16 — 0 800 6 7

Example 17 8 9

The product of Example 3 after treatment as in Examples 14 0 and 15 is refluxed overnight with Al(N0 ₃ )- ^* 9H ₂ 0 with the 1 latter being the εame maεε aε the zeolite and uεing the εame 2 dilution aε in the ion exchange of Example 15. The product 3 iε filtered, washed, and calcined to 540°C. After 4 pelletizing the zeolite powder and retaining the 20-40 mesh

38

fraction, the catalyεt iε teεted aε in Example 16. Data for the reaction iε given in Table V along with a variety of catalyεtε made from analogouε treatmentε with other metal εaltε.

TABLE V

Constraint Index Determination For Metal-Treated (B)SSZ-24

Conversion, % Temp. (10 Min. ) °F

0 800 70 700 33 700 18 800

Table VI gives the lattice parameter changeε for εampleε of (B)SSZ-24 unεubεtituted, εubεtituted with aluminum or boron and with and without calcination.

TABLE VI Lattice Conεtantε for (B)SSZ-24

Framework Calcined Subεtitution

No B 13.57 8.27

Yeε B 13.61 8.30

No B 13.55 8.26

No B 13.54 8.24

No None 13.62 8.30

Yeε None 13.62 8.32

Yeε Al, B 13.66 8.33 Yeε Al, B 13.68 8.34

Example 20

The borosilicate version of (B)SSZ-24 was evaluated aε a reforming catalyεt. The zeolite powder waε impregnated with Pt(NH ₃ ). ^* 2N0 ₃ to give 0.8 wt. % Pt. The material waε calcined up to 550°F in air and maintained at thiε temperature for three hours. The powder waε pelletized on a Carver press at 1000 psi and broken and meshed to 24-40.

The catalyεt waε evaluated at 800°F to 900°F in hydrogen after reduction at 950°F (1 hr, 300 cc/min.) under the following conditionε:

psig « 200 H ₂ /HC - 6.4 WHSV - 6

The feed waε an iC ₇ mixture (Philips Petroleum Company). The data for the run iε given in Table VII.

TABLE VII

Product, %

800°F 900°F

Converεion 79.6 100.0 Toluene 22.1 21.9 ^C 5" ^C 8 ^{0ctane 86} -8 105.2 C ₅ + Yield 54.9 35.4 Aromatization Selectivity 32.1 30.2 Toluene in C ₅ + Aromaticε 86.6 72.7

Example 21

The product of Example 17 now contained acidity due to aluminum incorporation. Two back ion exchangeε with KNO- 5 were performed and the catalyεt waε calcined to 1000°F. 6 Next, a reforming catalyεt waε prepared aε in Example 20. 8' The catalyεt waε evaluated under the following conditionε:

0

3 4 5 The feed waε an iC, mixture (Philipε Petroleum Company). 6 The data for the run is given in Table VIII. After 23 hours 7 onstream, the temperature was raised to 900°F and this data 8 alεo appearε in the table. By compariεon with Example 20, g the incorporation of aluminum into the zeolite giveε a more 0 aromatic εelective reforming catalyεt and a higher C _g + 1 yield. 2 3 TABLE VIII 4

1 Hr (After 91 Hr (After 5 Time 23 Hr 23 Hr at 800°F) 23 Hr at 800°F) 6

900 900 7

95.1 85.3 8 9

35.7 38.2 0 1

26.6 27.3 2 3 78.1 83.8 4

TABLE VI I I ( Cont . )

1 Hr (After 91 Hr (After

Time 23 Hr 23 Hr at 800°F) 23 Hr at 800°F) C _C -C _Q RON 92.4 b o C _c + Yield % 55.1 5

A product was prepared aε in Example 17. Next, the catalyεt was dried at 600°F, cooled in a closed εyεtem, and then vacuum impregnated with an aqueous εolution of Pd (NH_). ^* 2N0 ₃ to give 0.5 wt. % loading of palladium. The catalyεt was then calcined slowly, up to 900°F in air and held there for three hourε.

Table IX giveε run conditions and product data for the hydrocracking of hexadecane. The catalyst iε quite εtable at the temperatureε given.

The data εhows that the catalyst has iεomerization activity and that the liquid yield is high compared with the gas make.

42 Example 23

Benzene/Propylene Alkylation With (B)SSZ-24 Catalyεt

The ability of the aluminum containing (B)SSZ-24 zeolite to catalyze the alkylation of an aromatic hydrocarbon by an olefin waε demonεtrated aε followε. Aluminum containing (B)SSZ-24 powder from Example 17 waε preεεed to form tabletε which were cruεhed and εieved to obtain 10-20 mesh granules for testing. The granular catalyεt waε weighed and charged to a tubular microreactor. The catalyεt waε heated to 450°F in flowing nitrogen at atmoεpheric preεsure. Nitrogen flow was continued for four hourε to dry and activate the catalyεt. After the drying period, the nitrogen flow waε continued while the reactor waε cooled to 325°F and pressurized to 600 psig. When the presεure had εtabilized at 600 pεig, the nitrogen flow waε εtopped and liquid benzene waε paεsed upflow through the reactor. After the reactor waε filled with liquid benzene, liquid propylene waε injected into the benzene feed εtream to give benzene/propylene feed molar ratio of 7.2 to 1 and a total feed rate σf 5.7 g per gram of dry zeolite per hour. During the run, the reaction temperature waε raiεed from 325 ^β F to 350 ^β F.

Periodic analyεiε of the reactor effluent by capillary gaε-liquid-chromatography (Table X) showed that all of the propylene waε converted to make a product comprised of 84-86 wt. % cumene and 15-13 wt. % diiεopropylbenzeneε on a benzene-frle weight basis. It is anticipated that the diiεopropylbenzene can be reacted in a εeparate reactor with benzene to make additional cumene. The converεion to uεeful product waε thuε ^" about 99 wt. % baεed on propylene and benzene reacted.

A high sensitivity GLC analysis (Table XI) of the liquid products εhowed that they contained very little ethylbenzene or n-propylbenzene and thuε cumene made with thiε (B)SSZ-24 catalyst would easily meet a 99.9% εpecification 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/C- 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-Diiεopropylbenzene 1,3,5-Triiεopropylbenzene Other

01 TABLE XI 02

Analyεiε of Cumene Impuritieε 03 In Reactor Effluent 04 05 Hours Onstream 18-19 67-68 06 Reaction Temperature, °F 325 350 -07 08 Cumene Impurities 09 In Reactor Effluent 10 Wt-ppm Based Cumene: 11 12 13 14 15 16 17 18 19 20 21 Total 754 802 22 23 Note: Same Run aε TABLE X. 24 25 Example 24 26 27 The acid form of (B)SSZ-24 was prepared as in Example 17 and 28 tested for the converεion of methanol to liquid productε. 29 0.5 g of catalyεt waε loaded into a 3/8-inch εtainleεε εteel 30 reactor tube which waε heated in a Lindberg furnace to 31 1000 ^β F. The temperature waε reduced to 700°F in a εtream of 32 he.lium at 20 cc/min. Methanol waε introduced into the 33 reactor at a rate of 1.25 cc/hr The conversion at 10 34

minuteε was close to 100% and dropped only slightly over several hours. The product distribution iε given in Table XII below.

TABLE XII

Produjtε, determined by gaε chromatography at 5 minutes on-εtream at 700 ^o F (100% conversion)

Product %

Methane 0.56 Ethylene 5.60 Ethane 0.15 Propylene 0.61 Propane 10.30

Butanes and Butenes 27.63

Pentaneε and Penteneε 7.20 Hexaneε and Hexeneε 1.45

Benzene 0.18

Toluene 1.22 Xyleneε and Ethylbenzene 8.35 Meεitylene 8.04 Other C _g Aromatics 22.35 Diethylbenzene 1.62

The catalyεt haε εurpriεing life and iε capable of making higher molecular weight productε than can be analyzed by the poropak Q column. The catalyεt iε run conεtantly over a 2-day period and liquid product iε collected in a trap including a conεiderable amount of waxy εolid. Thiε product includeε aromatics alkylated to the extent of producing pentamethyl benzenes. A simulated distillation sequence is

given in Table XIII and demonstrateε that productε in the range of C ₁₅ to C ₁₈ are being produced by the large pore zeolite catalyεt.

TABLE XIII

Simulated Diεtillation 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