GB1573132A

GB1573132A - Zeolite catalyst and method of manufacture and use thereof

Info

Publication number: GB1573132A
Application number: GB1287977A
Authority: GB
Original assignee: UOP LLC
Current assignee: Honeywell UOP LLC
Priority date: 1976-03-29
Filing date: 1977-03-28
Publication date: 1980-08-13
Also published as: JPS5731458B2; BR7701913A; FR2346046B1; DE2712996A1; ES457247A1; DE2712996B2; DE2712996C3; FR2346046A1; IT1075362B; JPS52117889A; CA1100468A

Description

(54) ZEOLITE CATALYST AND METHOD OF MANUFACTURE AND USE THEREOF (71) We, UOP INC, a corporation organized under the laws of the State of Delaware, United States of America, of Ten UOP Plaza, Algonquin & Mt. Prospect Roads, Des Plaines, Illinois, 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: Crystalline aluminosilicates, or zeolites, of which mordenite is one example, are well known in the art and have found extensive application as hydrocarbon conversion catalysts or as a component thereof. Such materials are of ordered crystalline structure often visualized as a three-dimensional network of fundamental structural units consisting of siliconcentered Si04 and aluminumcentered A104 tetrahedra, the tetrahedra being interconnected by a mutual sharing of apical oxygen atoms and arranged to form cages or cavities in open communication through smaller intracrystalline channels or pore openings whose narrowest cross section has essentially a uniform diameter characteristic of each crystalline aluminosilicate variety. To effect a chemical balance, each A104 tetrahedra has a cation associated therewith - usually a sodium or other exchangeable cation. The aforementioned cages or cavities are occupied by water molecules and by the last mentioned cations, both of which exhibit considerable freedom of movement permitting ion-exchange and reversable dehydration.

The crystalline aluminosilicates, or zeolites, employed in the manufacture of the catalytic composite of this invention, are of the mordenite crystal structure, highly siliceous in nature and generally characterized by a silica-alumina mole ratio of from 6 to 12 as found in nature. The mordenite crystal structure comprises four- and five-membered rings of the Si04 and A104 tetrahedra so arranged that the crystal lattice comprises pores and channels running parallel along the crystal axis to give a tubular configuration. This structure is unique among the crystalline aluminosilicates since the channels or tubes do not intersect, and access to the cages or cavities is in only one direction. For this reason, the mordenite structure is frequently referred to as two-dimensional. This is in contrast to other well-known crystalline aluminosilicates, for example faujasite, in which the cavities can be entered from three directions. Mordenite, clinoptilolite, or mordenite which has been synthesized or acid extracted, caustic extracted or otherwise treated to increase the silica-alumina mole ratio to 20:1 or more while maintaining the mordenite crystal structure, may be used in the manufacture of the catalytic composite of this invention.

Crystalline aluminosilicates having a mordenite crystal structure have heretofore been utilized composited with a refractory inorganic oxide, typically alumina, as a hydrocarbon conversion catalyst, and are particularly useful with respect to the transalkylation of alkylaromatic hydrocarbons. This invention presents a new and useful method of manufacture capable of providing a catalytic composite of high activity.

According to the present invention there is provided a method of manufacturing a zeolitic catalytic composite which comprises subjecting a zeolite of the mordenite crystal structure, containing less than 5 wt. % sodium as Na20, to an aqueous ammoniacal treatment (as hereinafter defined) at a pH of at least 9.5, and calcining the thus treated zeolite in intimate admixture with a refractory inorganic oxide to form a catalytic composite therewith.

One of the more specific embodiments of the invention is a method of manufacturing a zeolitic catalytic composite which comprises subjecting a zeolite of the mordenite crystal structure, containing less than 5 wt % sodium as Na20, to an aqueous ammoniacal treatment at a pH of from 10 to 12, and calcining the thus treated zeolite in intimate admixture with a alumina to form a catalytic composite therewith.

A still more specific embodiment of the invention is a method of manufacturing a zeolitic catalytic composite which comprises subjecting mordenite, containing less than 5 wt. % sodium as Na20, to an aqueous ammoniacal treatment with a pH of from 10 to 12 and at a temperature of from 75" to 200"C. in intimate admixture with alphaalumina monohydrate, and calcining said zeolite in intimate admixture with said alumina to form a catalytic composite therewith.

Pursuant to the present invention, the zeolite is subjected to an aqueous ammoniacal treatment at a pH of at least 9.5, and said treatment can be prior to admixture with the refractory inorganic oxide or after admixture therewith, the latter being preferred. The aqueous ammoniacal treatment is suitably effected at a temperature of from 75" to 200"C., usually for a period of from 1 to 24 hours. The treatment can be effected at substantially atmospheric pressure in an open vessel at about the reflux temperature of the aqueous ammoniacal solution, albeit over a relatively extended period up to 24 hours. The treatment is effective over a substantially shorter period, say from 1 to 10 hours, at autogenous pressures utilizing a closed vessel. Suitable aqueous ammoniacal solutions include aqueous solutions of ammonium bases such as ammonium hydroxide, hydroxylamine, hydrazine and tetramethylammonium hydroxide, and of strong organic amines like methylamine, dimethylamine, ethylamine, diethylamine, propylamine, diisopropylamine, n-butylamine, t-butylamine, diisobutylamine, n-amylamine, n-hexylamine, ethylene diamine, hexamethylenediamine, benzylamine, aniline, piperazine and piperadine, the selected base being employed in sufficient concentration to provide a pH of at least 9.5, and preferably from 10 to 12. The term "ammoniacal treatment" as used herein therefore denotes not only treatment with ammonia but also treatment with an amine, a quaternary ammonium base, hydroxylamine and hydrazine.

The crystalline aluminosilicate, or zeolite, employed herein as a starting material must contain, or must be treated to contain, less than 5 wt. %sodium as Na20. The sodium can be reduced to an acceptable level by conventional and widely practiced ion-exchange techniques. Typically, ammonium cations are substituted for sodium cations on treating the zeolite in contact with an aqueous ammonium salt solution, for example an aqueous ammonium chloride solution. The resulting ammonium-exchanged zeolite is thereafter heat-treated to effect thermal decomposition of the ammonium cations and formation of the hydrogen form of the zeolite. The treatment may be effected one or more times to reduce the sodium content to less than 5 wt. % as Na20.

Refractory inorganic oxides for use in accordance with the method of this invention include the naturally occurring as well as the synthetically prepared refractory inorganic oxides. Suitable refractory inorganic oxides are such as alumina, silica, zirconia, titania, thoria, boria, magnesia, chromia and stannic oxide, as well as combinations and composites thereof, for example alumina-silica, alumina-ziroconia and alumina-titania.

Alumina is a preferred refractory inorganic oxide for use herein, particularly with respect to the manufacture of a catalytic composite for use in the transalkylation of alkylaromatic hydrocarbons. The alumina may be any of the various hydrous aluminum oxides or alumina gels such as alpha-alumina monohydrate of the boehmite structure, alphaalumina tri-hydrate of the gibbsite structure or beta-alumina trihydrate of the bayerite structure, the first mentioned alpha-alumina monohydrate being preferred.

The zeolite may be combined in intimate admixture with the refractory inorganic oxide in any conventional or otherwise convenient manner. For example, the zeolite can be admixed with an alumina precursor which is subsequently converted to alumina to provide the zeolite in intimate admixture with the alumina. One preferred alumina precursor for use in this manner is a basic aluminum sulfate such as is precipitated from an aqueous solution of aluminum sulfate and ammonium hydroxide at a pH of about 6.

The zeolite may be combined in intimate admixture with refractory inorganic oxide in any conventional or otherwise convenient manner to form spheres, pills, pellets, granules, extrudates, or other suitable particle shape. For example, the zeolite can be admixed with an alumina sol such as results from digesting aluminum in hydrochloric acid under controlled conditions, and the mixture dispersed as droplets in a hot oil bath whereby gelation occurs with the formation of spheroidal gel particles. In this type of operation, the alumina is set chemically utilizing ammonia as a neutralizing or setting agent, typically at a pH in the 4.5-5.5 range, the ammonia being furnished by an ammonia precursor such as hexamethylenetetramine included in the alumina sol. The method is described in greater detail in U.S. Patent No.

2,620,314. A more preferred method comprises commingling the zeolite with a powdered refractory inorganic oxide, adding a binder and/or lubricant to the mixture, and compressing the mixture into pills or pellets of uniform size and shape. Alternatively, and still more preferably, the zeolite is mulled with a powdered form of the refractory inorganic oxide, and with a peptizing agent such as nitric acid, to form an extrudable dough.

The dough can be pressured through a die of predetermined size to form extrudate particles utilized as such or rolled into spheres in a spinning drum prior to calcination. In any case, the zeolite can be subjected to the aqueous ammoniacal treatment herein contemplated either before being admixed with the refractory inorganic oxide or after being admixed therewith, the latter being preferred. The zeolite is preferably calcined in intimate admixture with the selected refractory inorganic oxide in a weight ratio of from 1:3 to 3:1.

Regardless of whether the zeolite is subjected to the aqueous ammoniacal treatment before or after admixture with refractory inorganic oxide, the treated zeolite is calcined in intimate admixture therewith to form a catalytic composite. Calcination is suitably in an air atmosphere at a temperature of from 425" to 7500C., preferably at a temperature of from 475" to 5500C., over a period of from 0.5 to 10 hours.

The catalytic composite of this invention is particularly useful for the transalkylation of alkylaromatic hydrocarbons. Thus, an alkylaromatic hydrocarbon having from 7 to 15 carbon atoms per molecule may be treated at transalkylation conditions including a temperature of from 200 to 480"C. and a pressure of from atmospheric to 1500 pounds per square inch gauge (psig) in contact with a catalyst comprising essentially the catalytic composite of this invention to form products of higher and lower number of carbon atoms than said alkylaromatic hydrocarbon. The preferred composition employed as the catalytic composite comprises mordenite in admixture with alumina, said mordenite comprising from 25 to 75 wt. % of said composite.

The alkylaromatic hydrocarbon feed stock can be a substantially pure alkylaromatic hydrocarbon of from 7 to 15 carbon atoms, a mixture of such alkylaromatic hydrocarbons, or a hydrocarbon fraction rich in said alkylaromatics. Suitable alkylaromatic hydrocarbons include alkylbenzenes and alkylnaphthalenes, preferably with an alkyl group of less than 4 carbon atoms. The catalytic composite is particularly effective in the treatment of the more difficulty transalkylatable toluene to form benzene, xylenes, or other polymethylbenzenes.

The transalkylation, or disproportionation, reaction can be effected in contact with the catalytic composite of this invention in any conventional or otherwise convenient manner and may comprise a batch or continuous type of operation. A preferred type of operation is of the continuous type. For example, the above described catalyst is disposed in a fixed bed in a reaction zone of a vertical tubular reactor and the alkylaromatic feed stock charged in an upflow or downflow manner, the reaction zone being maintained at a temperature of from 200 to 480 C., preferably at a temperature of from 220 to 4600 C. Although pressure does not appear to be an important variable with respect to the transalkylation reaction, the process is generally conducted in the presence of an imposed hydrogen pressure to provide from 1 to 10 moles of hydrogen per mole of hydrocarbon. However, there is no net consumption of hydrogen in the process, and the hydrogen charge is recovered from the reactor effluent and recycled.

The transalkylation reaction can be effected over a wide range of space velocities. In general, the process is conducted at a space velocity of from 0.2 to 10. Space velocities herein referred to are liquid hourly space velocities, (LHSV), i.e., volume of charge per volume of catalyst per hour.

While the catalytic composite prepared by the present method permits unusually high space velocities indicative of high activity, the catalytic composite is particularly noteworthy because of its relatively high stability at a high activity level.

The composite prepared in accordance with the method of this invention may be employed as a component of a catalyst comprising any of the several catalytically active metallic materials in the oxidized or reduced state. Of particular interest are those catalytic composites comprising one or more metals of Group VIB (the chromium group) or VIII, namely molybdenum, tungsten, chromium, iron, nickel, cobalt, platinum, palladium, ruthenium, rhodium, osmium or iridium. Thus, the composite of this invention can be utilized advantageously as a catalyst or component thereof to effect a variety of hydrocarbon conversion reactions involving reaction conditions comprising a temperature in the 25-760 C. range. The catalysts are particularly useful in effecting the hydrocracking of heavy oils, including vacuum residuals, to form petroleum products in the middle distillate range utilizing a temperature of from 260 to 15600C. and pressures of from 500 to 1000 psig. Said hydrocarbon conversion reactions further include polymerization of olefins, particularly ethylene, propylene, 1-butene, 2-butene, isobutylene and also higher boiling olefins, at polymerization reaction conditions. The composite of this invention is also useful as a catalyst or component thereof in effecting the alkylation of isoparaffins with olefins or other alkylating agents including, for example, alkyl halides; also the alkylation of isobutane, isopentane, and/or isohexane with ethylene, propylene, 1-butene or mixtures thereof; and also the alkylation of aromatics with olefins or other alkylating agents, particularly the alkylation of benzene and/or toluene with propylene, butylene and/or higher boiling olefins, including nonenes, decenes and undecenes, the foregoing alkylation reactions being effected at alkylation conditions disclosed in the art.

The composite of this invention is further useful in the isomerization of paraffins, particularly nbutane, n-pentane, n-hexane, n-heptane and n-octane, and mixtures thereof, including isomerization of less highly branched chain saturated hydrocarbons to more highly branched chain saturated hydrocarbons such as the isomerization of 2- or 3-methyl pentane to 2,2- and 2,3dimethylbutane, isomerization of naph- thenes, for example, the isomerization of dimethylcyclopentane to methylcyclohexane, isomerization of methylclopentane to cyclohexane, at isomerization reaction conditions. Other hydrocarbon conversion reactions including the reforming of naphtha to gasoline, dehydrogenation of ethylbenzene to styrene, and hydrogenation of benzene to cyclohexane, are effectively catalyzed utilizing the composite of this invention as a catalyst or as a component thereof.

The following examples are presented in illustration of the method of this invention and are not intended as a limitation on the generally broad scope of the invention as set out in the appended claims.

EXAMPLE I (Comparative) In this example, a catalytic composite of mordenite and alumina was prepared with- out the benefit of the aqueous ammoniacal treatment herein described. Thus, 595 grams of a commercial mordenite (H Zeolon) containing about 0.16 wt. %sodium as Na20 and 16 wt. So volatile matter, as evidenced by weight loss on ignition at 900 C., was thoroughly dry-mixed with 694 grams of a commercial alpha-alumina monohydrate (Kaiser medium - KAISER is a Registered Trade Mark) containing about 28% volatile matter. Approximately 20 milliliters of concentrated nitric acid and 420 milliliters of water was admixed therewith, and the mixture mulled to form an extrudable dough.

The resulting dough was extruded through a 1/16 inch die and the extrudate segmented and balled in a spinning drum with the formation of 1/16-1/8 inch spheroidal particles.

The spheroidal product was subsequently calcined in air at 500"C. for 1 hour.

EXAMPLE II The preparation was repeated in accordance with the method of Example I except that the mordenite was subjected to an aqueous ammoniacal treatment and calcined in intimate admixture with the alumina, the aqueous ammoniacal treatment in this case being after admixture with the alumina pursuant to one preferred embodiment of this invention. In this instance, the spheroidal product of Example I was immersed in an aqueous solution of ammonium hydroxide containing 5 wt. % NH3 and having a pH of about 11.6. Five volumes of the aqueous ammoniacal solution were employed per volume of spheroidal product treated. The treatment was at atmospheric pressure conditions utilizing a glass flask with an overhead condenser. The treatment was effected at reflux temperature -- about 90"C, over a 16 hour period. The thus treated material was subsequently water-washed, dried, and calcined for 1 hour at 5000C.

EXAMPLE HI The preparation of Example I was again repeated except that the mordenite was subjected to an aqueous ammoniacal treatment and calcined in intimate admixture with the alumina, the aqueous ammoniacal treatment in this case being after admixture with the alumina and at an elevated pressure pursuant to one preferred embodiment of this invention. In this instance, the spheroidal product of Example I was sealed in a glass-lined rotating autoclave together with an aqueous ammoniacal solution substantially as described in Example II. The aqueous ammoniacal solution was employed in an amount equivalent to 2 volumes per volume of said spheroidal product. The autoclave was heated to 110 C. and the spheroidal product treated at this temperature under autogenous pressure conditions for 2 hours.

The thus treated product was recovered, water-washed, dried and calcined at 5000 C.

for 1 hour.

The above-described preparations were evaluated with respect to the transalkylation of toluene. In each case, toluene, in admixture with hydrogen to provide a hydrogen/hydrocarbon mole ratio of about 10, was charged downflow through a 50 cubic centimeter bed of approximately 1/8 inch spheroidal catalyst particles at a liquid hourly space velocity of 2.0, and at transalkylation conditions including a pressure of 500 psig.

The temperature of the catalyst bed was adjusted to effect a 40% conversion of a toluene feed stock, the temperature in each case being taken as a measure of catalyst activity.

The catalytic composites of Examples I, II and III required temperatures of 475 , 381 and 368"C., respectively, the latter two being prepared according to the method of this invention.

EXAMPLE IV The preparation of Example I was again repeated except that the mordenite therein described was subjected to an aqueous ammoniacal treatment prior to admixture with the alumina, the mordenite being subsequently calcined in intimate admixture with the alumina. In this example, the mordenite was first immersed in the aqueous ammoniacal solution of Example II. Five volumes of solution were employed per volume of mordenite. The aqueous ammoniacal treatment was effected under reflux conditions utilizing a glass flask equipped with an overhead condenser. The treatment was effected over a 16 hour period at substantially atmospheric pressure conditions, after which the mordenite was recovered and dried. The mordenite was thereafter thoroughly dry-mixed with the alphaalumina monohydrate to provide a 50-50 weight mixture with 20 milliliters of concentrated nitric acid in 420 milliliters of water being subsequently added. After thorough mulling to provide an extrudable dough, the dough was extruded, segmented, and formed into spheres as heretofore described. The spheroidal product was calcined in air for 1 hour at 5000C. and thereafter evaluated with respect to the transalkylation of toluene in the described manner. A 40% conversion was achieved at 3800C.

EXAMPLE V (Comparative) In this example, the mordenite employed was an ammonium ion-exchanged mordenite as opposed to the aqueous ammoniacal solution-treated mordenite of this invention.

Thus, a solution of 260 grams of ammonium nitrate in 2340 cubic centimeters of water was used to ammonium ion-exchange 600 grams of the mordenite. The mordenite was slurried in 600 cc portions of the solution at about 55"C. for about 1/2 hour, the mordenite being recovered by filtration after each of three such ammonium ion-exchange treatments. After the final treatment the mordenite was dried at about 95"C. The mordenite was thereafter thoroughly drymixed with the alpha-alumina monohydrate to provide a 50-50 weight mixture with 20 milliliters of concentrated nitric acid in 420 milliliters of water being subsequently added. After thorough mulling to provide an extrudable dough, the dough was extruded, segmented and formed into shperes as heretofore described. The spheroidal product was calcined in air for 1 hour at 500"C., and thereafter evaluated with respect to the transalkylation of toluene in the described manner. A 40% conversion was achieved at 463"C.

EXAMPLE VI (Comparative) A substantially pure mordenite (H Zeolon), in the form of extrudate particles was calcined in air for 1 hour at 500"C. and thereafter evaluated with respect of the transalkylation of toluene in the described manner. In this instance, a temperature of 508"C. was required to achieve a 40% conversion. In a separate experiment, the calcined extrudate was further treated with an aqueous ammoniacal solution substantially in accordance with the method of Example III, and then further calcined in air at 5000 C.

for 1 hour. Although the temperature required to effect a 40% conversion of toluene was reduced to 473"C., the temperature is substantially higher than that required when the treated mordenite is calcined in intimate admixture with alumina.

WHAT WE CLAIMS IS: 1. A method of manufacturing a zeolitic catalytic composite which comprises subjecting a zeolite of the mordenite crystal structure, containing less than 5 wt. % sodium as Nazi, to an aqueous ammoniacal treatment (as hereinbefore defined) at a pH of at least 9.5, and calcining the thus treated zeolite in intimate admixture with a refractory inorganic oxide to form a catalytic composite therewith.

2. The method of Claim 1 further characterized in that said zeolite is mordenite.

3. The method of Claim 1 further characterized in that said zeolite is clinoptilolite.

4. The method of any of Claims 1 to 3 further characterized in that said refractory inorganic oxide is alumina.

5. The method of any of Claims 1 to 3 further characterized in that said refractory inorganic oxide is an alpha-alumina monohydrate.

6. The method of any of Claims 1 to 5 further characterized in that said zeolite is calcined in intimate admixture with said refractory inorganic oxide in a weight ratio of from 1:3 to 3:1.

7. The method of any of Claims 1 to 6 further characterized in that said zeolite is calcined in intimate admixture with said refractory inorganic oxide at a temperature of from 425" to 7500C.

8. The method of any of Claims 1 to 6 further characterized in that said zeolite is clacined in intimate admixture with said refractory inorganic oxide at a temperature of from 475" to 550"C.

9. The method of any of Claims 1 to 8 further characterized in that said aqueous ammoniacal treatment is effected at a pH of from 10 to 12.

10. The method of any of Claims 1 to 9 wherein the aqueous ammoniacal treatment is effected at a temperature of from 75" to 200"C.

11. The method of any of Claims 1 to 10 wherein the zeolite is subjected to the aqueous ammoniacal treatment in intimate admixture with the refractory inorganic oxide.

12. A method of manufacturing a zeolitic catalytic composite carried out substantially as described in any of the foregoing Examples II, III or IV.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. ammoniacal treatment prior to admixture with the alumina, the mordenite being subsequently calcined in intimate admixture with the alumina. In this example, the mordenite was first immersed in the aqueous ammoniacal solution of Example II. Five volumes of solution were employed per volume of mordenite. The aqueous ammoniacal treatment was effected under reflux conditions utilizing a glass flask equipped with an overhead condenser. The treatment was effected over a 16 hour period at substantially atmospheric pressure conditions, after which the mordenite was recovered and dried. The mordenite was thereafter thoroughly dry-mixed with the alphaalumina monohydrate to provide a 50-50 weight mixture with 20 milliliters of concentrated nitric acid in 420 milliliters of water being subsequently added. After thorough mulling to provide an extrudable dough, the dough was extruded, segmented, and formed into spheres as heretofore described. The spheroidal product was calcined in air for 1 hour at 5000C. and thereafter evaluated with respect to the transalkylation of toluene in the described manner. A 40% conversion was achieved at 3800C. EXAMPLE V (Comparative) In this example, the mordenite employed was an ammonium ion-exchanged mordenite as opposed to the aqueous ammoniacal solution-treated mordenite of this invention. Thus, a solution of 260 grams of ammonium nitrate in 2340 cubic centimeters of water was used to ammonium ion-exchange 600 grams of the mordenite. The mordenite was slurried in 600 cc portions of the solution at about 55"C. for about 1/2 hour, the mordenite being recovered by filtration after each of three such ammonium ion-exchange treatments. After the final treatment the mordenite was dried at about 95"C. The mordenite was thereafter thoroughly drymixed with the alpha-alumina monohydrate to provide a 50-50 weight mixture with 20 milliliters of concentrated nitric acid in 420 milliliters of water being subsequently added. After thorough mulling to provide an extrudable dough, the dough was extruded, segmented and formed into shperes as heretofore described. The spheroidal product was calcined in air for 1 hour at 500"C., and thereafter evaluated with respect to the transalkylation of toluene in the described manner. A 40% conversion was achieved at 463"C. EXAMPLE VI (Comparative) A substantially pure mordenite (H Zeolon), in the form of extrudate particles was calcined in air for 1 hour at 500"C. and thereafter evaluated with respect of the transalkylation of toluene in the described manner. In this instance, a temperature of 508"C. was required to achieve a 40% conversion. In a separate experiment, the calcined extrudate was further treated with an aqueous ammoniacal solution substantially in accordance with the method of Example III, and then further calcined in air at 5000 C. for 1 hour. Although the temperature required to effect a 40% conversion of toluene was reduced to 473"C., the temperature is substantially higher than that required when the treated mordenite is calcined in intimate admixture with alumina. WHAT WE CLAIMS IS:

1. A method of manufacturing a zeolitic catalytic composite which comprises subjecting a zeolite of the mordenite crystal structure, containing less than 5 wt. % sodium as Nazi, to an aqueous ammoniacal treatment (as hereinbefore defined) at a pH of at least 9.5, and calcining the thus treated zeolite in intimate admixture with a refractory inorganic oxide to form a catalytic composite therewith.

13. A zeolitic catalytic composite

whenever manufactured by the method of any of Claims 1 to 12.

14. A catalytic process for transalkylating an alkylaromatic hydrocarbon wherein a zeolitic catalytic composite as claimed in Claim 13 is used as the catalyst of the process.

15. A process as claimed in Claim 14 wherein an alkylaromatic hydrocarbon having from 7 to 15 carbon atoms per molecule is treated at 200 to 480"C and 0 to 1500 psig in contact with the catalyst.

16. A catalyst comprising a zeolitic catalytic composite as claimed in Claim 13 and a catalytically active metallic material of Group VIB (the chromium group) or VIII of the Periodic Table.

17. A catalytic process for hydrocracking a heavy oil wherein a catalyst as claimed in Claim 16 is used as the catalyst of the process.