GB1587921A

GB1587921A - Crystalline borosilicate and process for using same

Info

Publication number: GB1587921A
Application number: GB43106/77A
Authority: GB
Original assignee: Standard Oil Co
Current assignee: Standard Oil Co
Priority date: 1976-10-18
Filing date: 1977-10-17
Publication date: 1981-04-15
Also published as: NL7711239A; DE2746790A1; FR2367701B1; CS266302B2; PT67167A; NL187236C; YU250377A; DK153134B; FR2367701A1; IE46162B1; IN146957B; DK461477A; JPS6054243B2; DK153134C; LU78338A1; PT67167B; IE46162L; JPS5355500A; YU41571B; IN148719B

Description

(54) CRYSTALLINE BOROSILICATE AND PROCESS FOR USING SAME (71) We, STANDARD OIL COMPANY, a corporation organized and existing under the laws of the State of Indiana, United States of America of 200 East Randolph Drive, Chicago, Illinois 60601, United States of America, do hereby declare the invention for which we pray that a patent may be granted to us and the method by which it is to be performed, to be particularly described in and by the following Statement: This invention relates to crystalline borosilicates and to their use. More particularly, this invention relates to borosilicate crystalline molecular sieve materials having catalytic properties and to -various hydrocarbon conversion processes using such crystalline borosilicates.

Zeolitic materials, both natural and synthetic. have been demonstrated in the past to have catalytic capabilities for many hydrocarbon processes. The zeolitic materials are ordered porous crystalline aluminosilicates having a definite structure with large and small cavities interconnected by channels. The cavities and channels throughout the crystalline material are generally uniform in size allowing selective separation of hydrocarbons. Consequently, these materials in many instances have come to be classified in the art as molecular sieves and are utilized. in addition to the adsorptive selective processes, for certain catalytic properties. The catalytic properties of these materials are also affected to some extent by the size of the molecules which are allowed selectively to penetrate the crystal structure presumably to be contacted with active catalytic sites within the ordered structure of these materials.

Generally the term "molecular sieve" includes a wide variety of positive ion containing crystalline materials of both natural and synthetic varieties. They are generally characterized as crystalline aluminosilicates. although other crystalline materials are included in the broad definition. The crystalline aluminosilicates are made up networks of tetrahedra of SiO4 and Al04 moieties in which the silicon and aluminum atoms are cross-linked by the sharing of oxygen atoms. The electrovalence of the aluminum atom is balanced by the use of a positive ion. for example alkali metals or alkaline earth metals.

Prior art developments have resulted in the formation of many synthetic crystalline materials. Crystalline aluminosilicates are the most prevalent and as described in the patent literature and in the published journals are designated by letters or other convenient symbols.

Exemplary of these materials are Zeolite A (U.S. Patent 2.882.243), Zeolite X (U.S. Patent 2.882.244). Zeolite Y (U.S. Patent 3.130.007), Zeolite ZSM-5 (U.S. Patent 3.702.886).

Zeolite ZSM-ll (U.S. Patent 3.709.979). Zeolite ZSM-12 (U.S. Patent 3.832,449) and others.

Relevant art is the above U.S. Patent 3.702.886. claiming the crystalline aluminosilicate Zeolite ZSM-5 and the method for making the same. This patent is limited to the production of a zeolite wherein aluminum or gallium oxides are present in the crystalline structure along with silicon or germanium oxides. A specific ratio of the latter to the former are reacted to produce a class of zeolites designated ZSM-5 which is limited to crystalline alumino or gallo silicates or germanates and having a specified X-ray diffraction pattern. The above ZSM-11 and ZSM-l2 patents are similarly limited to crystalline alumino or gallo silicate or germanates also having specified X-ray diffraction patterns.

Manufacture of the ZSM materials utilizes a mixed based system in which sodium aluminate, and a silicon containing material are mixed together with sodium hydroxide and an organic base such as tetra propylammonium hydroxide or tetra propylammonium bromide under specified reaction conditions to form the desired crystalline aluminosilicate.

U.S. Patent 3,941,871 claims and teaches an organosilicate having very little aluminum in its crystalline structure and possessing an X-ray diffraction pattern similar to the ZSM-5 composition. This patent is considered relevant art.

Other relevant art includes U.S. Patents 3,329,480 and 3,329,481 which relate to "zircono-silicates" and "titano-silicates", respectively.

The present invention, however. relates to a family of stable synthetic crystalline materials charterized as borosilicates identified as AMS-1B having a specified X-ray diffraction pattern. The claimed AMS-1B crystalline borosilicates are formed by reacting a boron salt and a silicon containing material in a basic medium.

According to one aspect of the invention there are provided crystalline borosilicates having a composition in terms of mole ratios of oxides as follows: 0.9 t 0.2 M2/mO: B203 :YSiO2: ZH2O where M is at least one cation having a valence n. Y is between 4 and 500 and Z is between 0 and 160. said borosilicate showing X-ray diffraction lines substantially as set forth in Table I of the specification. Preferably. the X-ray diffraction lines have assigned strengths substantially as described in Table 1.

In a more preferred embodiment Y is a value between 4 and 200, most preferably between 50 and 160. Z preferably has a value between 0 and 40.

In the above formula M may for example be selected from tetraalkylammonium. ammonium. hydrogen. metal cations or mixtures thereof. M may for example be nickel; hydrogen and nickel; or hydrogen. nickel and an alkali metal.

In another embodiment the invention relates to a crystalline borosilicate having a composition in terms of oxides as follows: 0.9 + 0.2 (WR2O) + (1-W)M2/nO : B2O3 : YSiO2: Z2O wherein R is tetraalkylammonium. M is an alkali metal cation. W is greater than 0 and less than or equal to 1, Y is between 4 and 500. Z is between 0 and 160 and showing X-ray diffraction lines and assigned strengths substantially as described in Table II of the specification.

In a more preferred embodiment W is a value between 0.6 and 0.9 and Y and Z have the preferred values referred to above.

According to another aspect. the invention relates to a process for conversion of a hydrocarbon which comprises contacting said hydrocarbon at conversion conditions with a crystalline borosilicate as defined above. One particular example of such a conversion is the catalytic isomerization of a xylene feed.

The borosilicates of the invention. which may be designated "synthetic AMS-1B crystalline borosilicates" includes material not yet activated or calcined at high temperatures as well as such material which has been heated. e.g. to a temperature of from 500 to 1 5000F.

The original cation. "M" in the above formulations. can be replaced in accordance with techniques well-known in the art. at least in part by ion exchange with other cations.

Preferred replacing cations include tetraalkylammonium cations. metal ions. ammonium ions. hydrogen ions. and mixtures of the above. Particularly preferred cations are those which render the AMS-1B crystalline borosilicate catalytically active especially for hydrocarbon conversion. These materials include hydrogen. rare earth metals. aluminium. metals of Groups IB. IIB and VIII of the Periodic Table. noble metals and manganese and other catalytically active materials and metals known to the art. The catalytically active components can be present anywhere from 0.05 to 25 weight percent of the AMS-lB crystalline borosilicate.

Members of the family of AMS-IB crystalline borosilicates possess a specified and distinguishing crystalline structure. The reported x-ray diffraction patterns generated by these materials were obtained using standard powder diffraction techniques. The X-ray diffractometer was a Phillips instrument which utilized copper K alpha radiation in conjunction with an AMR focusing monochrometer and a theta compensating slit. in which its aperature varies with the theta angle.

The output from the diffractometer was processed through a Canberra hardware/software package and reported by way of a strip chart and tabular printout. The compensating slit and the Canberra package tend to increase the peak/background ratios while reducing the peak intensities at low theta angles [high d ( )] and increasing the peak intensities at high theta angles [low d (A)]. All of the X-ray patterns reported herein used the above analytical techniques.

The relative intensities reported were calculated as (100 I/Io) where Io is the intensity of the strongest recorded peak and I is the value actually read for the particular interplanar spacing.

For ease of reporting the relative intensities were arbitrarily assigned the following values: I/Io Assigned Strength lessthan 10 = VW less than 10- 19 = W less than 20-39 = M less than 40-70 = MS greater than 70 = VS A typical X-ray diffraction pattern displaying the significant lines which have relative intensities of 11 or higher for an AMS-1B crystalline borosilicate after calcination at 1000 F.

(535 C.) is shown in Table I below: TABLE I Interplanar Spacing Relative Assigned d( ) Intenslty Strength 11.3 #0.2 38 M 10.1 #0.2 30 M 6.01#0.07 14 W 4.35#0.05 11 W 4.26#0.05 14 W 3.8410.05 100 VS 3.7210.05 52 MS 3.65#0.05 31 M 3.44#0.05 14 W 3.33#0.05 16 W 3.04#0.05 16 W 2.97#0.02 22 M 2.48#0.02 11 W 1.99#0.02 20 M 1.66#0.02 12 W An AMS-1B borosilicate which has been only subjected to mild drying at 165 C (as produced material) possesses an X-ray diffraction pattern having the following significant lines: TABLEII Interplanar Spacing Relative Assigned d( ) Intensity Strength 11.4 10.2 19 W 10.1 +0.' 17 W 3.84#0.05 100 VS 3.7310.05 43 MS 3.66#0.05 26 M 3.4510.05 11 W 3.32#0.05 13 W 3.05#0.05 12 W 2.98#0.02 16 W 1.99#0.02 10 W 1.66#0.02 20 M The strip chart recordings of the calcined borosilicate reported in Table I above showed that this material had the following X-ray diffraction lines.

TABLE 111 Interplanar Spacing d ( ) Run 1 Run 2* 11.3 11.2 10.2 10.0 7.49 7.37 6.70 6.70 6.41 6.36 6.02 5.98 5.71 5.67 5.60 5.57 5.01 5.34 4.62 5.01 4.37 4.62 4.27 4.35 4.00 4.25 3.85 4.00 3.72 3.85 3.64 3.70 3.48 3.64 3.44 3.46 3.30 3.4' 3.14 3.30 3.04 3.25 2.98 3.12 2.86 3.04 '.71 '.97 2.60 '.86 '.48 '.71 2.39 7 37 2.22 '.00 1.99 1.95 1.91 1.86 1.75 1.66 * This run terminated at 2.71 d (A,) The AMS-lB crystalline borosilicates are useful in the catalytic cracking and hydrocracking processes. They appear to have relatively useful catalytic properties in other petroleum refining processes such as the isomerization of normal paraffins and naphthenes. the reforming of certain feedstocks, the isomerization of aromatics especially the isomerization of polyalkyl substitued aromatics such as orthoxylene, the disproportionation of aromatics such as toluene to form mixtures of other more valuable products including benzene, xylene and other higher methyl substituted benzenes and hydrodealkylation. When used as a catalyst in isomerization processes with suitable cations placed on the ion exchangeable sites within the AMS-1B crystalline borosilicate. reasonably high selectivities for production of desired isomers are obtained.

The activity for these materials to be stable under high temperatures or in the presence of other normal deactivating agents appears to make this class of crystalline materials relatively valuable for high temperature operations including the cyclical types of fluidized catalytic cracking or other processing.

The AMS-1B crystalline borosilicates can be used as catalysts or as adsorbents whetherin the alkali metal forms, the ammonium form. the hydrogen form or any other univalent or multivalent cationic form. Mixtures of cations may be employed. The AMS-1B crystalline borosilicates can also be used in intimate combination with a hydrogenating component such as tungsten. vanadium. molybdenum, rhenium. nickel, cobalt. chromium. manganese. or a noble metal such as platinum or palladium or rare earth metals where a hydrogenation dehydrogenation function is to be performed. Such components can be exchanged into the composition at the cationic sites, represented by the term "M" in the above formulas, impregnated therein or physically intimately admixed therewith. In one example, platinum can be placed on the borosilicate with a platinum metal containing ion.

The original cation associated with the AMS-1B crystalline borosilicate can be replaced as mentioned above by a wide variety of other cations according to techniques which are known in the art. Ion exchange techniques known in the art are disclosed in many patents including U.S. Patent 3.140.249. U.S. Patent 3.140.251 and U.S. Patent 3.140.253.

Following ion exchange. impregnation or contact with another material to place catalytically active materials within or on the borosilicate structure. the material can be washed and then dried at temperatures in the range of 150 to 6000F. It can then be calcined in air or nitrogen or combinations of both at closely regulated temperatures in a range from 500 to l5OO0Ffor various periods of time.

Ion exchange within the cationic site within the crystalline material will generally have a relatively insignificant effect on the overall X-ray diffraction pattern that the crystalline borosilicate material generates. Small variations may occur at various spacings on the X-ray pattern but the overall pattern remains essentially the same. Small changes in the X-ray diffraction patterns may also be the result of processing differences during manufacture of the borosilicate. however. the material will still fall within the generic class of AMS- 1 B crystalline borosilicates defined in terms of their X-ray diffraction patterns as shown in Tables I. II and III or in the Examples that follow.

The claimed crystalline borosilicate may be incorporated as a pure borosilicate in a catalyst or adsorbent or may be admixed with various binders or bases depending upon the intended process use. In many instances. the crystalline borosilicate can be pelletized or extruded. The crystalline borosilicate can be combined with active or inactive materials. synthetic or naturally occurring zeolites as well as inorganic or organic materials which would be useful for binding the borosilicate. Other well-known materials include mixtures of silica. silicaalumina. alumina sols. clays such as bentonite or kaolin or other binders well known in the art.

The crystalline borosilicate can also be mixed intimately with porous matrix materials such as silica-zirconia. silica-magnesia. silica-alumina. silica-thoria. silica-beryllia. silica-titania as well as three component compositions including but not limited to silica-alumina-thoria and many other materials well known in the art. The crystalline borosilicate content can vary anywhere from a few up to 100 per cent of the total finished product.

The AMS-1B crystalline borosilicate can be generally prepared by mixing in an aqueous medium oxides of boron. sodium or any other alkali metal and silicon. and tetraalkylammonium compound. The mole ratios of the various reactants can be varied considerably to produce the AMS-IB crystalline borosilicates. In particular. reactant mole ratios in terms of the various oxides for producing the borosilicate can vary as is indicated in Table IV below.

TABLEIV Mole Ratios SiO2/B2O3 5-600 (or higher) R4N+/(R4N+ + Na+) 0.1-1 OH-/ SiG2 0.01-10 where R is alkyl and preferably propyl. The above quantities can be varied in concentration in the aqueous medium. It is generally preferred that the mole ratio of water to the hydroxyl ion vary anywhere from about 10 to about 500 higher. By simple regulation of the quantity of boron (as B203) in the reaction mixture, it is possible to vary the SiO2/B203 molar ratio in the final product in a range of from 40 to 500. In instances where a deliberate effort is made to eliminate aluminum from the borosilicate crystal structure because of its adverse influence on particular conversion processes the molar ratios of SiO2/Al2O3 can easily exceed 2000-3000.

This ratio is generally only limited by the availability of aluminum-free raw materials.

Molar ratios of SiO2/B203 in the final crystalline product can vary from 4 to 500. Actual laboratory preparations under the general conditions described herein produce SiO2/B2o3 molar ratios starting around 40 or lower. Lower ratios can generally be produced using production methods which still are in the scope of the teachings of this specification.

Based on known properties of mordenite and ferrierite aluminosilicates, the present crystalline borosilicates will have about 4.5 BO4 tetrahedra per unit cell at SiO2/B203 molar ratios around 80. In view of this it would appear that a single BO4 exists at SiO2/B203 ratios around 500. Above this ratio there would be many unit cells which did not contain a BO4 tetrahedron and the resulting crystalline structure might not be considered a borosilicate.

There are no established criteria for establishing at what SiO2/B2o3 molar ratio the crystalline material ceases to be a borosilicate. It seems safe to assume that at high SiO2/ B2O3 values (above 1000 or more) the influence of the BO4 tetrahedra in the crystalline structure becomes somewhat diminished and the crystalline material would no longer be referred to as a borosilicate.

Under reasonably controlled conditions using the above information the claimed AMS- 1 B crystalline borosilicate will be produced. Typical reaction conditions include heating the reactants to a temperature of 90 to 2500C for a period of time of from about a few hours to a few weeks or more temperatures higher than 250"C may be used if desired. Preferred temperature ranges are anywhere from 150 to 180"C with an amount of time necessary for the precipitation of the AMS-lB crystalline borosilicate. Especially preferred conditions include a temperature around 165 0C for a period of about 7 days.

The material thus formed can be separated and recovered by well-known means such as filtration. This material can be mildly dried for anywhere from a few hours to a few days at varying temperatures to form a dry cake which itself can then be crushed to a powder or to small particles and extruded. pelletized or made into forms suitable for its intended use.

Typically the material prepared after the mild drying conditions will contain the tetraalkylammonium ion within the solid mass and a subsequent activation or calcination procedure is necessary if it is desired to remove this material from the formed product.

Typically the high temperature calcination conditions will take place at temperatures anywhere from 800 to 1600"F or higher. Extreme calcination temperatures may prove detrimental to the crystal structure or may totally destroy it. There is generally no need for going beyond about 1700"F in order to remove the tetraalkylammonium cation from the original crystalline material formed.

When the AMS-1B crystalline borosilicate is used as a hydrocracking catalyst. hydrocracking charge stocks can pass over the catalyst at temperatures anywhere from 450 to 900"F using known molar ratios of hydrocarbon to hydrogen e.g. a hydrogen: hydrocarbon ratio of from I to 100 and varying pressures anywhere from 20 to 2500 psig. The liquid hourly space velocity and other process parameters can be varied consistent with the well-known teachings of the art, e.g. the liquid hourly space ratio may be from 0. I to 50.

In employing the borosilicate for fluidized catalytic cracking processing. well known operating conditions can be used including temperatures anywhere from 500 to I 2000F in the reaction zone and temperatures anywhere from 500 to 1200 F in the reaction zone and temperatures anywhere from 800 to 1300"F in the regeneration zone. Contact times. feedstocks and other process conditions are known in the art. The pressure in the reaction zone may for example be in the range from atmospheric to 2500 psig. and the liquid hourly space ratio from 0. l to 75.

The specified AMS- I B crystalline borosilicate is also suitable as a reforming catalyst to be used with the appropriate hydrogenation components at well known reforming conditions including temperatures of anywhere from about 500 to 10500F or more. pressures anywhere from a few up to 300 to 1000 psig and liquid hourly space velocities and hydrocarbon to hydrogen mole ratios consistent with those well known in the reforming art.

The present composition is also suitable for hydrocarbon isomerization and disproportionation. It is especially useful for liquid or vapor phase isomerization of xylenes and especially the isomerization of mixed xylenes to predominately paraxylene products.

Isomerization conditions include temperatures of anywhere from 200 to 1000"F, hydrogen to hydrocarbon mole ratios of from 0 to 20, liquid hourly space velocities in the range of from 0.01 to 90. The choice of catalytically active metals to be placed on the AMS-lB crystalline borosilicate can be selected from any of those well known in the art. Nickel seems to be especially appropriate for isomerization of aromatics: The claimed AMS-iB crystalline borosilicates can also be used as adsorbents to selectively adsorb specific isomers or hydrocarbons in general from a liquid or vapor stream.

The following examples are presented as specific embodiments of the present invention.

EXAMPLE I An AMS-1B crystalline borosilicate was prepared by dissolving 0.25 gm of H3BO3 and 1.6 gm of NaOH in 60 gm of distilled H20. Then 9.4 gms of tetra-n-propylammonium bromide (TPABr) were added and again dissolved. Finally. 12.7 gm of Ludox-AS (30% solids) were added with vigorous stirring. The addition of Ludox (Registered Trade Mark) gave a curdy. gelatinous, milky solution. This solution was placed in a reaction bomb and sealed. The bomb was placed in a 165 0C oven and left there for 7 days. At the end of this time it was opened and its contents were filtered. The recovered crystalline material was washed with copious quantities of H20 and was then dried at 165"C in a forced air oven. The dried material was identified by X-ray diffraction as a crystalline material having the typical AMS-1B pattern with 100 % crystallinity. The yield was approximately 2 grams.

EXAMPLE H In this example the ASM-1B crystalline borosilicate of Example I was used to produce a catalyst having isomerization capabilities.

The material from Example I was calcined at 1100 F (535 C) in air for 4 hours to remove the organic base. The calcined sieve was exchanged one time with a solution of 20 gm of NH4NO3 in 200 ml of H20 and then a second time with 20 gm ofNH4OAc in 200 ml of H20 at 190"F for 2 hours. The exchanged borosilicate was dried and calcined in air by heating it to 900"F in 4 hours, maintaining the borosilicate at 900"F for 4 hours and then cooling to 1000F in 4 hours. The calcined material was exchanged with 100 ml of a 5% Ni(N03)2 . 6H20 solution for 2 hours at 1900F. The sieve was washed with H2O and the Ni was completely washed out of the sieve. The sieve was dried and calcined again using the above procedure.

About 2 grams of the borosilicate was dispersed in 16.9 gm of PHF-AI203 hydrosol (8.9% solids) and mixed thoroughly. One milliliter of distilled H20 and 1 ml of conc. NH40H were mixed and added to the slurry with intensive mixing. The AMS- 1 B-AI203 mix was placed in a drying oven at 165"C for 4 hours. The dried material was again calcined using the above procedure. The calcined catalyst was crushed 30-50 mesh (U.S. Seive Series) and impregnated with 2 ml of a 5% (Ni(N03)2 . 6H20 in distilled H20. The catalyst was again dried and activated by a fourth programmed calcination.

The calcined catalyst contained 65 weight percent borosilicate and 35 weight percent amorphous alumina with approximately 0.5 weight percent of the total solid as nickel.

One gram of the sized and activated catalyst was placed in the microreactor and sulfided with H2S for 20 minutes at room temperature. The catalyst was then placed under H2 pressure and heated to 600"F. After 1 hour feed was passed through the microreactor under the following conditions: Temperature 800"F Pressure 150 psig WHSV 6.28 hers.

H/ HC. mole ratio 7 The liquid feed and effluent streams for this operation are shown below. Because of the equipment limitations on the screening unit. only analysis on liquid streams were performed and reported. The light-end production over this catalyst was low from the gas chromatographic analysis made on the off-gas stream from the unit. The volume of off-gas was determined to not substantially reduce overall liquid yields over the catalyst.

Component Liquid Feed, wt. % Liquid Product, 11 t. % Paraffins and .03 .08 naphthenes Benzene 1.51 Toluene .077 .26 Ethylbenzene 19.71 17.35 paraxylene -- 19.43 metaxylene 79.80 46.40 orthoxylene .38 14.96 C9 + * - * Approximate values only EXAMPLE III A solution of 600 gm H20. 2.5 gm H3BO3 and 7.5 gm of NaOH was prepared. 94.3 gm of TP ABr was added to the original mixture and dissolved, Then 114.5 gm of Ludox-AS (30 wt. %solids) were added to the original liquid mixture with vigorousstirring.

The resuliting mixture was placed in a reaction bomb and sealed. The bomb was placed in an oven at 1 650C for 7 days.

After washing and drying of the recovered solids as described in Example I. The crystalline borosilicate was identified as AMS- 1 B and showed an X-ray diffraction pattern similar to that of Table II.

EXAMPLE IV A borosilicate similar to that prepared in Example I was calcined at about 1100 F and then analyzed to determine its overall composition. The results are shown below.

Component SiO2. wt.% 94.90 B203 1.06 Na2O 0.97 Al203 0.057 Fe203 0.029 Volatiles* 2.984 Total 100.000 Mole Ratios SiO2/B203 104.5 Na20/B:03 1.0 SiO2/Al2O3 2824.4 SiO2/Fe203 8787.0 SiO2/ (Al203 + Fe203) 2146.2 * Assumed value to total 100% Other borosilicates were produced as generally described in Example I except that the H.lBO4 content ration was varied resulting in SiO3/ B203 molar ratios varying from 50 to 160 or higher before the borosilicate was calcined or exchanged. After exchange with suitable catalytic materials the SiO2/B203 molar ratio generally increased to a value of 80- 100 for an as prepared borosilicate which had a SiO/ B203 molar ratio of around 50.

EXAMPLE V Three borosilicate materials were prepared similar to the method described in Example I.

The recovered materials were calcined at 1000 F (535 C) and then analyzed for boron and silicon

Wt. % Molar Ratio Borosilicate Boron SiO2/B203 A 0.66 47.4 B 0.64 49.1 C 0.71 44.5 After ion exchange with ammonium acetate the borosilicate was calcined at 535 C. The following was then determined: Molar Ratio Borosilicate SiO2/B203 A 75.1 B 71.2 C 64.2 Powder X-ray diffraction analysis was performed on samples of the above borosilicates after they had been calcined at 1000 F but prior to ion exchange. The reported patterns are shown below for relative intensities (I/Io) of 10 or greater. Table III above shows the interplanar spacings indicated from a strip chart for two runs of borosilicate A after 1000 F (535 C) calcination but before ion exchange.

TABLE V (Borosilicate A) Interplanar Spacing d ( ) Relatiive Intensity (I/b) 11.34 38 10.13 30 6.01 14 4.35 11 4.26 14 3.84 100 3.72 52 3.65 31 3.44 14 3.04 16 2.97 22 2.48 11 1.99 20 1.66 12 TABLE VI (Borosilicate B) Interplanar Spacing d ( ) Relative Intensity (I/Io) 11.35 41 10.14 31 6.02 15 4.26 15 3.84 100 3.72 52 3.65 33 3.44 13 3.32 15 3.04 16 2.97 22 2.48 11 1.99 20 1.66 12

Claims

TABLE VII (Borosilicate C) Interplanar Spacing d ( ) Relative Intensity (I/b) 11.40 33 10.17 29 6.03 13 5.62 10 4.27 14 3.84 100 3.73 51 3.65 30 3.44 13 3.32 16 3.05 16 2.98 21 1.99 19 1.66 12 WHAT WE CLAIM IS:

1. A crystalline borosilicate having a composition in terms of mole ratios of oxides as follows: 0.9 t 0.2 M2 +0: B203 : YSiO2: ZH2O where M is at least one cation having a valence n. Y is between 4 and 500 and Z is between 0 and 160, said borosilicate showing X-ray diffraction lines substantially as set forth in Table I of the specification.

2. A borosilicate according to Claim 1 in which Y is in the range of from 4 to 200.

3. A borosilicate according to Claim 2 in which Y is in the range of from 50 to 160.

4. A borosilicate according to any preceding claim in which Z is in the range of from 0 to 40.

5. A borosilicate according to any preceding claim wherein the X-ray diffraction lines have assigned strengths substantially as described in Table I of the specification.

6. A borosilicate according to any preceding claim in which M is selected from tetraalkylammonium. ammonium. hydrogen. metal cations or mixtures thereof.

7. A borosilicate according to Claim 6 in which M comprises hydrogen and nickel.

8. A borosilicate according to Claim 6 in which M comprises hydrogen. nickel and an alkali metal.

9. A borosilicate according to Claim 6 in which M comprises nickel.

10. A borosilicate according to any preceding claim characterized in that it shows the X-ray diffraction lines of Table III (Run l) of the specification.

11. A borosilicate according to Claim 1 and substantially as hereinbefore described and exemplified.

12. A crystalline borosilicate having a composition in terms of oxides as follows: 0.9 t 0.2. (WR2O + (I-W) M2 +O): B203: YSiO2: ZH20 wherein R is tetraalkylammonium. M is an alkali metal cation. W is greater than 0 and less than or equal to 1. Y is between 4 and 500. Z is between 0 and 160. said borosilicate showing X-ray diffraction lines and assigned strengths substantially as described in Table II of the specification.

13. A borosilicate according to Claim 12 in which Y is in the range of from 4 to 200.

14. A borosilicate according to Claim 12 and substantially as hereinbefore described and exemplified.

15. The composition formed by heating a borosilicate according to any one of Claims I 2 to 14 at a temperature in the range of from 500 to 1500 F.

16. A process for conversion of a hydrocarbon which comprises contacting said hydrocarbon at conversion conditions with a crystalline borosilicate as claimed in any one of Claims I to IlandlS.

17. A process according to Claim 16 in which the conversion is cracking and said conversion conditions include a temperature in the range of from 500"F to 1200"F, a pressure in the range of from atmospheric to 2500 psig and a liquid hourly space velocity in the range of from 0.1 to 75.

18. A process according to Claim 16 in which the conversion is hydrocracking and said conversion conditions include a temperature in the range of from 450 to 9000F, a mole ratio of hydrogen to hydrocarbon in the range of from 1 to 100, a pressure in the range of from 20 psig to 2500 psig and a liquid hourly space velocity in the range of from 0.1 to 50.

19. A process according to Claim 16 in which the conversion is isomerization and said conversion conditions include a temperature in the range of from 200"F to 1000"F, a pressure in the range of from atmospheric to 3000 psig, a liquid hourly space velocity in the range of from 0.1 to 50 and a molar ratio of hydrogen to hydrocarbon in the range of from 0 to 20.

20. A process for catalytic isomerization of a xylene feed which comprises contacting said feed at isomerization conditions with a crystalline borosilicate as claimed in any one of claims 1 to 14.

21. A process according to Claim 20 in which said isomerization conditions include a temperature in the range of from 250"F to 9000F, a pressure in the range of from zero psig to 1000 psig, a mole ratio of hydrogen to hydrocarbon in the range of from 0 to 20 and a weight hourly space velocity in the range of from 1 to 20.

22. A process for conversion of a hydrocarbon according to Claim 16 and substantially as hereinbefore described and exemplified.