MXPA99009962A - Process for the conversion of hydrocarbons to olefins and aromatics - Google Patents

Abstract

A catalyst composition and a process for converting a hydrocarbon stream such as, for example, gasoline to olefins and C6 to C8 aromatic hydrocarbons such as toluene and xylenes are disclosed. The catalyst composition comprises a zeolite, a binder, and boron wherein the weight of boron is in the range of from about 0.01 to about 10 weight%. The process comprises contacting a hydrocarbon stream with the catalyst composition under a condition sufficient to effect the conversion of a hydrocarbon to an olefin and a C6 to C8 aromatic hydrocarbon. Also disclosed is a process for producing the catalyst composition which comprises:(1) combining a zeolite with a coke-reducing amount of a binder under a condition effective to produce a zeolite-binder mixture;(2) contacting said zeolite-binder mixture with coke-reducing amount of a boron compound under a condition effective to produce a boron-incorporated or -impregnated zeolite;and (3) calcining the boron-incorporated or -impregnated zeolite.

Description

PROCESS FOR THE CONVERSION OF HYDROCARBONS TO OLEFINS AND AROMATICS FIELD OF THE INVENTION The present invention relates to a composition useful for converting a hydrocarbon to a C6 to C aromatic hydrocarbon and an olefin, to a process for producing the composition and to a process for using the composition for converting a hydrocarbon to a C6 aromatic hydrocarbon to Ce and an olefin.

BACKGROUND OF THE INVENTION - • It is well known to those skilled in the art that aromatic hydrocarbons and olefins are each a class of very important industrial chemicals that find a variety of uses in the petrochemical industry. It is well known to those skilled in the art that catalytically thermoforming hydrocarbons in the range of gasoline produces lower olefins such as, for example, propylene; and aromatic hydrocarbons, such as, for example, benzene, toluene and xylenes (collectively referred to subsequently as BTX) in the presence of zeolite-containing catalysts. The product of this R? F .: 31675 catalytic thermofraction process contains a multitude of hydrocarbons including unconverted C5 alkanes; lower alkanes such as methane, ethane and propane; lower alkenes such as ethylene and propylene and C9 + aromatic compounds containing 9 or more carbons per molecule. Recent efforts to convert gasoline to more valuable petrochemicals have focused, therefore, on improving the conversion of gasoline to olefins and aromatic hydrocarbons through catalytic thermofraction in the presence of zeolite catalysts. For example, a zeolite promoted by gallium ZSM-5 has been used in the so-called Cyclar Process to convert a hydrocarbon to BTX. Olefins and aromatic hydrocarbons may be feeds used to produce various organic compounds and polymers. However, the weight ratio of the olefins to the aromatic compounds produced by the conversion process is generally less than 50%. Therefore, the development of a catalyst and a process to convert hydrocarbons to the most valuable olefins would be a significant contribution for art and economics.

BRIEF DESCRIPTION OF THE INVENTION According to a first aspect of the present invention, there is provided a composition that can be used as a catalyst to convert a hydrocarbon or a mixture of hydrocarbons to an olefin and a C6 to C8 aromatic hydrocarbon. The composition comprises a zeolite, a binder and boron wherein the boron is present in the composition in the range of about 0.01 to about 10 weight percent (%) According to a second aspect of the present invention, there is provided a process that can be used to produce a catalyst composition. The process comprises the steps: (1) combining a zeolite with a reduced amount of coke of a binder under an effective condition to produce a zeolite-binder mixture; (2) contacting the binder zeolite mixture with a reduced amount of coke of a boron compound under an effective condition to produce a zeolite impregnated or incorporated with boron; and (3) calcining the zeolite impregnated or incorporated with boron.

According to a third aspect of the present invention, there is provided a process that can be used to convert a hydrocarbon or mixture of hydrocarbons to an olefin and to a C6 to C8 aromatic hydrocarbon comprising, consisting essentially of, or consisting of, putting into contacting a fluid comprising a hydrocarbon or a mixture of hydrocarbons with a catalyst composition that is the same as that set forth above in the first embodiment of the invention, under an effective condition for converting a hydrocarbon to an olefin and an aromatic hydrocarbon containing 6 to 8 carbon atoms per molecule, wherein the weight ratio of the olefin to the aromatic compound is improved.

DETAILED DESCRIPTION OF THE INVENTION The catalyst composition of the first embodiment of the present invention may comprise, consist essentially of, or consist of a zeolite, a binder and boron. The boron is impregnated or coated preferably on the zeolite or zeolite-binder mixture. According to the present invention, the weight of the boron element in the composition of the invention may be in the range of from about 0.01 to about 10, preferably from about 0.05 to about 8, and more preferably 0.1 to 5 grams per 100 grams of the composition. The weight of the binder in general may be in the range of about 50, preferably from about 5 to about 40 and more preferably 10 to 30 grams per 100 grams of the composition. The zeolite in general, represents the rest of the composition. The composition can also be characterized as having the following physical characteristics: a surface area determined by the BET method using nitrogen in the range of about 300 to about 600, preferably 350 to 500 m2 / g; at a pore volume in the range of about 0.4 to about 0.8, preferably from about 0.5 to about 0.75, and more preferably 0.6 to 0.75 ml / g; an average pore diameter in the range of from about 70 to about 300, preferably from about 100 to about 250, and more preferably 125 to 200 or A; and a porosity of more than about 50%.

Any commercially available zeolite can be used as a process initiating material of the second embodiment of the invention. Examples of the appropriate zeolites include, but are not limited to, those described in Kir -Othmer Encyclopedia of Chemical Technology, third edition, volume 15 (John Wiley &Sons, New York, 1991) in W.M. Meier and D.H. Olson, "Atlas of Zeolite Structure Types," pages 138-139 (Butterworth-Heineman, Boston, Mass., 3rd ed., 1992). Presently preferred zeolites are those having average pore sizes having the physical characteristics discussed above. ZSM-5 and similar zeolites that have been identified as having a structure topology identified as MFI are particularly preferred because of their shape selectivity.

Any of the binders known to one skilled in the art for use with a zeolite are suitable for use herein. Examples of suitable binders include, but are not limited to, clays such as, for example, kaolinite, halloysite, vermiculite, chlorite, attapulgite, smectite, montmorillonite, illite, saconite, sepiolite, paligoretus, diatomaceous earth and combinations of any two or more of them; aluminas such as for example α-alumina and α-alumina; silicas; alumina-silica; aluminum phosphate; aluminum chlorohydrate and combinations of two or more thereof. Because these binders are well known to one skilled in the art, the description of which is omitted here. The currently preferred binder is bentonite because it is readily available.

The composition of the present invention can be prepared by combining a zeolite, a binder and boron in the percent by weight discussed above, under any conditions sufficient to effect the production of such a composition.

However, it is currently preferred that the composition of the present invention be produced by the process set forth in the second embodiment of the invention. In the first step of the second embodiment of the invention, a zeolite is combined with a binder set forth above under a condition sufficient to produce a mixture of zeolit a-binder.

According to the present invention, a zeolite, preferably a ZSM-5 zeolite, and the binder can be easily mixed by any means known to one skilled in the art, such as agitation, mixing, kneading or extruding after which the zeolite-binder mixture can be dried in the air at a temperature in the range of about 20 to about 800 ° C, for about 0.5 to about 50 hours under any pressure adjusting the temperatures, preferably under atmospheric pressure. Subsequently, the dried zeolite-binder mixture may also be calcined, if desired, in * air at a temperature in the range of about 300 to 1000 ° C, preferably from about 350 to about 750 ° C and more preferably 450 to 650. C. for about 1 to about 30 hours to prepare a calcined α-agglutinated zeolite. Before a binder is combined with a zeolite, the zeolite can also be calcined under similar conditions to remove any contaminants, if present, to prepare a calcined zeolite.

A zeolite, a calcined zeolite, or a mixture of calcined zeolite and ta-agglutinate can be treated with a compound containing an exchange ammonium ion to prepare an ammonium exchange zeolite. If a zeolite is calcined or contains a binder, the process or treatment of the second mode is the same for each. For the interest of brevity, only one zeolite is described later. Examples of suitable ammonium-containing compounds include, but are not limited to, ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium bromide, ammonium fluoride, and combinations of any two or more thereof. The treatment of the zeolite replaces the original ions such as, for example, alkali metal or alkaline earth ions of the zeolite with predominantly ammonium ions. The techniques for such treatment are well known to one skilled in the art such as, for example, ion exchange of the original ions. For example, a zeolite can be contacted with a solution containing a salt of the desired ion or ion replacement.

In general, a zeolite can be suspended in an aqueous solution of a compound containing ammonium. The concentration of the zeolite in the aqueous solution may be in the range of about 0.01 to about 800, preferably from about 0.1 to about 500, more preferably from about 1 to about 400, and more preferably 5 to 100 grams per liter. The amount of the ammonium-containing compound required depends on the amount of the original ions that are to be exchanged. In the preparation of the solution, the solution may be subjected to a temperature in the range of about 30 ° C to about 200 ° C, preferably about 40 ° C to about 150 ° C, and more preferably 50 ° C to 125 ° C during about 1 to about 100 hours, preferably about 1 to about 50 hours, and more preferably 2 to 25 hours depending on the desired degrees of ion exchange. The treatment can be carried out at a pressure in the range of about 1 to about 10 atmospheres (atm), preferably about 1 atm or any pressure that can maintain the required temperature. Subsequently, the treated zeolite can be washed with tap water for 1 to about 60 minutes followed by drying and calcining to produce zeolite in the form of calcined hydrogen. The calcining and drying processes can be carried out in substantially the same manner as those exposed for the preparation of a calcined zeolite or a zeolite binder.

In general, the ammonium exchange zeolite becomes hydrogen exchange due to calcination or high temperature treatment, such that a predominant proportion of its interchangeable cations are hydrogen ions. The ion exchange described above of the interchangeable ions in a zeolite is well known to one skilled in the art. See, for example, Pat. U.S. No. 5,516,956, the disclosure of which is incorporated by reference. Because the ion exchange process is well known, the description of which is omitted here for the sake of brevity.

In the second embodiment of the invention, a mixture of zeolite-binder in a desired ionic form, whether calcined or not, is contacted with a boron compound, under a condition known to those skilled in the art to incorporate a compound of boron in a zeolite. Preferably, the boron compound is impregnated on the zeolite or the zeolite-binder mixture. Because the methods for incorporating or impregnating a boron compound into a zeolite or mixtures of zeolite-binder such as, for example, impregnation by the method of dryness incipient are well known to those skilled in the art, the description which is also omitted here for the interest of brevity.

According to the present invention, any boron-containing compound which, because it is incorporated in, or impregnated or coated on, a zeolite or a zeolite-binder mixture can be converted to a boron oxide in the present invention can be used in the present invention. the calcination. A boron compound having a formula of BR3.J :, (R'BO) 3, BWz, B (OR) 3 or combinations of two or more thereof may be used in the present invention in which R may be hydrogen , an alkyl radical, an alkenyl radical, an aryl radical, an aryl alkyl radical, an alkyl arayl radical and combinations of two or more thereof, wherein each radical can have from 1 to about 20 carbon atoms, R 'can be R, RO, RS, R2N, R3Si or combinations of two or more thereof, W may be a halogen, N03, N02, S04, P04 or combinations of two or more thereof, and z is an integer of 1 to 3. Examples of suitable boron compounds include, but are not limited to, boric acid, borane-ammonium complex, boron trichloride, boron phosphate, boron nitride, triethyl borane, trimemethyl borane, tripropyl borane, borate trimethyl, triethyl borate, tripropyl borate, trimethyl boroxine, triethyl boroxine, tripropyl boroxine and combinations of two or more of them.

Due to the incorporation or impregnation of the boron compound in the zeolite or the zeolite-binder mixture to produce a zeolite incorporated or impregnated with boron, the zeolite incorporated or impregnated with boron can be subjected to calcination under a condition which can include a temperature in the range of about 300 ° C to about 1000 ° C, preferably about 350 ° C to about 750 ° C, and more preferably 400 ° C to 650 ° C under a pressure that adjusts the temperature, generally in the range of about 1 to about 10 atmospheres (atm), preferably about 1 atm for a period in the range of about 1 to about 30, preferably about 1 to about 20, and more preferably 1 to 15 hours to produce the composition of the invention.

The composition of the invention can then, if desired, be pretreated with a reducing agent before being used in a hydrodealkating process. The presently preferred reducing agent is a hydrogen-containing fluid comprising molecular hydrogen (H2) in the range of about 1 to about 100, preferably about 5 to about 100 and more preferably 10 to 100 volume%. The reduction can be carried out at a temperature, in the range of about 250 ° C to about 800 ° C for about 0.1 to about 10 hours, preferably about 300 ° C to about 700 ° C for about 0.5 to about 7 hours, and more preferably 350 ° C to 650 ° C for 1 to 5 hours.

According to the third embodiment of the present invention, a process used to convert a hydrocarbon or mixture of hydrocarbons rich in olefins and aromatic hydrocarbons C6 to C6 comprises, consists essentially of, or consists of contacting a fluid stream comprising a hydrocarbon or mixture of hydrocarbons which may comprise paraffins, olefins, naphthalenes and aromatics with a catalyst composition under a condition sufficient to effect the conversion of a mixture of hydrocarbons to a mixture rich in olefins and aromatic hydrocarbons C6 to C8 or to improve the weight ratio of olefins (ethylene and propylene) to the aromatic compounds C6 to C8. The catalyst composition is the same as the one disclosed in the first embodiment of the invention. The term "fluid" is used herein to represent gas, liquid, vapor or combinations thereof. The term "hydrocarbon" generally refers, unless otherwise indicated, to one or more hydrocarbons having about 4 carbon atoms to about 30 carbon atoms, preferably to about 5 to about 20 carbon atoms and more preferably to 16 carbon atoms per molecule. The term "improved" refers to an increased weight ratio of olefins to BTX which employs the catalyst composition compared to that employed by a zeolite such as commercially available ZSM-5 and in general the weight ratio is greater than 1: 1, preferably 2: 1. Examples of a hydrocarbon include, but are not limited to butane, isobutane, pentane, isopentane, hexane, isohexane, cyclohexane, heptane, isoheptane, octane, isooctane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, butenes , isobutene, pentenes, hexenes, benzene, toluene, ethylbenzene, xylenes and combinations of any of two or more thereof.

Any fluid containing a hydrocarbon as set forth above, can be used as the feed for the process of this invention. In general, the fluid feed stream may also contain olefins, naphthenes (cycloalkanes), or some aromatics. Examples of suitable fluid feeds available include, but are not limited to, gasolines from petroleum catalytic thermofraction processes, gasoline pyrolysis from the thermal fractionation of saturated hydrocarbons, naphthas, petroleum gases, reformates and combinations of any two or more of them. The origin of this fluid feed is not critical. Although the particular composition of a feed is not critical, a preferred fluid feed is derived from gasolines which generally contain more paraffins (alkanes) than the combined content of olefins and aromatics (if present).

The contact of a fluid feed stream containing a hydrocarbon with the catalyst composition can be carried out in any technically appropriate manner, in a batch or semi-continuous or continuous process, under an effective condition to convert a hydrocarbon to a hydrocarbon. Cg to C8 aromatic hydrocarbon. In general, a fluid stream as discussed above, preferably in the vaporized state, is introduced into an aromatization reactor having a fixed catalyst bed or a moving catalyst bed, or a fluidized catalyst bed or combinations of any of two or more thereof by any means known to one skilled in the art such as, for example, pressure, metering pump and other similar means. Because an aromatization reactor and aromatization are well known to one skilled in the art, the description of which is omitted here for the sake of brevity. The condition may include a space velocity per hour of the fluid stream in the range of about 0.01 to about 100, preferably about 0.05 to about 50, and more preferably 0.1 to 30 g of feed / g of catalyst / hour. In general, the pressure may be in the range of about 0 to about 1000 psig, preferably about 0 to about 200 psig and more preferably 0 to 50 psig, and the temperature is about 250 to about 1000 ° C, preferably about 350 to about 750 ° C and more preferably 450 to 650 ° C.

The process effluent generally contains a light gas fraction comprising hydrogen and methane; a C2-C3 fraction containing ethylene, propylene, ethane and propane; an intermediate fraction which contains higher non-aromatic compounds of 3 carbon atoms; and a fraction of BTX aromatic hydrocarbons (benzene, toluene, ortho-xylene, meta-xylene and para-xylene). In general, the effluent can be separated into these main fractions by any known method such as, for example, fractional distillation. Because the separation methods are well known to one skilled in the art, the description of which is omitted here. The intermediate fraction can be recirculated to the aromatization reactor described above, methane, ethane and propane can be used as the fuel gas or as a feed for other reactions such as, for example, in a thermal fractionation process to produce ethylene and propylene. The olefins can be further recovered and separated into the individual olefins by any method known to one skilled in the art. Individual defines can be recovered and sold. The BTX fraction can also be separated into the C6 to C8 aromatic hydrocarbon fractions. Alternatively, the BTX fraction may be subjected to one or more reactions either before or after separation to the individual C6 to C8 hydrocarbons to increase the content of the majority of the desired BTX aromatic hydrocarbon. Suitable examples of such conversions of C6 to C6 aromatic hydrocarbons are the disproportionation of toluene (to form benzene and xylenes), the transalkylation of benzene and xylenes (to form toluene), and the isomerization of meta-xylene and / or ortho-xylene to para-xylene.

After the catalyst composition has been deactivated by, for example, coke deposition or feed contaminations, to an extent that the feed conversion and / or the selectivity of the desired olefin to BTX ratios have become insat is factories, the composition of the catalyst can be reactivated by any method known to one skilled in the art such as, for example, calcination in air to burn the deposited coke and other carbonaceous materials, such as oligomers or polymers, preferably at a temperature of about 400 to about 650 ° C. The optimal calcination time periods generally depend on the types and amounts of deactivation deposits in the catalyst composition and at the calcination temperatures. These optimal time periods can be easily determined by those skilled in the art and are omitted here for the purpose of brevity.

The following examples are presented to further illustrate this invention and are not elaborated as to unduly limit the scope of the present invention.

EXAMPLE I This example illustrates the preparation of the catalyst composition of the invention.

A ZSM-5 zeolite obtained from CU Chemie Uetikon AG, Uetikon, Switzerland having a designated product of Zeocat PZ 2 / 50H (obtained as powder) was used in the preparation of the catalyst composition of the invention. Twenty g of the zeolite was mixed well with 5 g of bentonite in a vessel followed by the addition of sufficient water to make a paste. The paste was then extruded at room temperature (25 ° C) to completely mix the mixture of zolol and t-bent on i t a. Subsequently, the extrusion of zeolit a-bent oni t was dried at 125 ° C in an oven. The zeolite-bentonite extrudate after drying was subjected to calcination at 500 ° C for 3 hours to produce an extrudate of calcined zeolite-bentonite (control catalyst).

In a separate run, 40 g of Zeocat zeolite was mixed with 10 g of bentonite to produce a second mixture of calcined zeolite-bentonite. Subsequently, a solution containing 5 g of boric acid in 100 ml of water was prepared. A portion (9 g) of the solution was added to 10 g of the second mixture of calcined zeolite-bentonite to impregnate the second mixture of zeolite-bentonite with boric acid to produce an acid-impregnated zeolite-bentonite. After the addition of sufficient water to completely wet the acid impregnated zeolite-bentonite to form a paste, the pulp was dried and calcined as described above to produce a boron promoted (impregnated) zeolite (catalyst of the invention) which it contained 0.775% by weight of boron by calculation.

In a comparative run, a comparative catalyst was produced by the procedure described to produce the control catalyst except that 5 g of boric acid was also added, at the same time with the addition of bentonite, to the zeolite powder. The resulting comparative catalyst contained 3.219% by weight of boron by calculation.

EXAMPLE II This example illustrates the use of the catalyst compositions described in Example I as the catalysts in the conversion of hydrocarbons to olefins and BTX.

A quartz tube of the reactor (internal diameter 1 centimeter, length 60 centimeters was filled with a base layer of 20 centimeters of Alundum® alumina (inert alumina, low surface area), 5 grams of one of the catalysts in the middle of the 20-centimeter tube, and a 20-centimeter top layer of Alundum® alumina. The liquid feed was a gasoline obtained from the Phillips Petroleum Company, Bartlesville, Oklahoma and contained the hydrocarbons shown in Table I. The liquid feed shown in Table I is summarized as: 38.7 percent by weight (%) of light (C5s and C6s), 1.3% of benzene, 5.4% of toluene, 8.1% of aromatic C8; 38.9% of non-aromatics in the BTX boiling range and 25.9% of heavy (C8 +). The feed was introduced into the reactor at a rate of 14 ml / hour (10.44 g / hour). The reaction temperature was 600 ° C. The effluent from the reactor was cooled and separated into a gas phase and a liquid phase. Both phases were analyzed by gas chromatographers at intervals of approximately 1 hour. Approximately 2 hours after the feeding was started, the reactor effluent was sampled again and analyzed by gas chromatography to determine the content of olefins and BTX. The results of runs at about 6 hours were shown in Table II below, which illustrates the production of olefins and BTX from the feed of Table I and the individual catalyst compositions produced in Example I.

Table I (continued) Analysis of Gasoline Hydrocarbons by Thermal Fractionation Catalitically Isoparaffins Aromatic Nafteños Olefins Total paraffin s Total 0.10 c15 + Totals 1,704 unknown The results presented in Table II demonstrate that untreated zeolite (control) produced significantly more BTX than olefins. The catalyst of the invention significantly increased the ratio of olefins produced to BTX, e.g. ex. , increased olefin production. However, with the comparative catalyst composition that was produced by mixing boric acid, bentonite and ZSM-5 zeolite at the same time, the olefin and BTX productions were surprisingly low.

The results shown in the previous examples clearly demonstrated that the present invention is well suited to carry out the objectives and achieve the ends and advantages mentioned, as well as those inherent herein while modifications could be made by those skilled in the art, such modifications being they encompass within the spirit of the present invention as defined by the description and the claims.

It is noted that in relation to this date, the best method known to the applicant to carry out the afontioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, the content of the following is claimed as property.

Claims (18)

1. A process for the conversion of a hydrocarbon to an olefin and a C6 to C8 aromatic hydrocarbon, the process comprises contacting a fluid comprising the hydrocarbon with a catalyst composition under conditions sufficient to effect the conversion, characterized in that the composition of the Catalyst is produced by the steps comprising: (1) combining a ZSM-5 zeolite with a binder under an effective condition to produce a binder zeolite mixture; (2) contacting the zeolite-binder mixture with a reduced amount of coke of a boron compound under an effective condition to produce a zeolite incorporated or impregnated with boron; and (3) calcining the zeolite incorporated or impregnated with boron, and the boron compound is selected from the group consisting of boric acid, borane-ammonium complex, boron trichloride, boron nitride, triethyl borane, trimethyl borane, tripropyl borane. , trimethyl borate, triethyl borate, tripropyl borate, trimethyl boroxine, triethyl boroxine, tripropyl boroxine and combinations of two or more thereof.

A process according to claim 1 characterized in that the fluid comprises a gasoline of a process of catalytic thermofraction of petroleum, a gasoline of pyrolysis of the thermal fractionation of saturated hydrocarbons, a naphtha, a petroleum gas, a reformate or a combination of any of two or more of the fluids.

3. A process according to any of the preceding claims, characterized in that the hydrocarbon contains at least 4 carbon atoms.

4. A process according to any of the preceding claims, characterized in that the hydrocarbon contains about 4 to about 30 carbon atoms.

5. A process according to any of the preceding claims, characterized in that the hydrocarbon contains 5 to 16 carbon atoms.

6. A process according to any of the preceding claims, characterized in that the hydrocarbon is a gasoline.

7. A process according to any of the preceding claims, characterized in that the hydrocarbon is butane, isobutane, pentane, isopentane, hexane, isohexane, cyclohexane, heptane, isoheptane, octane, isooctane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, butenes, isobutene, pentenes, hexenes, benzene, toluene, ethylbenzene, xylenes or a combination of any two or more of the hydrocarbons.

8. A process according to any of claims 1, 2, 3, 4, 5, 6 or 7, characterized in that the weight of the boron present in the catalyst composition is in the range of about 0.01 to about 10% by weight.

9. A process according to claim 8, characterized in that the weight of the boron present in the catalyst composition is in the range of about 0.1 to about 5% by weight.

10. A process according to any preceding claim, characterized in that the boron compound has the formula BR 3_z Wz, (R'B0) 3, BW2, B (OR) 3 or a combination of any two or more of the formulas wherein R is hydrogen, an alkyl radical, an alkenyl radical, an aryl radical, an aryl alkyl radical, an alkyl arayl radical or a combination of two or more of the radicals. radicals, R 'is a substituent that is R, RO, RS, R2N, R2P, R3Si, or a combination of any two or more substituents, is a substituent that is halogen, N03, N02, S04 or a combination of any of two or more substituents and z is an integer from 1 to 3.

11. A process according to any preceding claim, characterized in that the binder is kaolinite, halloysite, vermiculite, chlorite, attapulgite, smectite, montmorillonite, illite, saconite, sepiolite, paligoresquita, diatomaceous earth, -alouraine,? -alumina; silicas; alumina-silica; aluminum phosphate; aluminum chlorohydrate or a combination of any two or more binders.

12. A process according to the indication 11, characterized in that the binder of montmorillonite is bentonite.

13. A process according to any preceding claim, characterized in that the zeolite-binder mixture produced in step (1) is calcined before being contacted with the boron compound.

14. A process according to any preceding claim, characterized in that the mixture of binder zeolite is impregnated with an aqueous solution of boron compound.

A process according to any preceding claim, characterized in that the condition comprises a space velocity for each hour by weight of the fluid in the range of about 0.01 g / g of li zador / hor to approximately 100 g / g of aliquator cat. / hour, one pressure in the range of approximately 0 psig to approximately 200 psig, and a temperature in the range of approximately 250 ° C to approximately 1,000 ° C.

16. A process for producing a cpq catalyst composition comprises (1) combining a ZSM-zeolite with a binder to produce a zeolite-binder mixture; (2) calcining the zeolite-binder mixture to produce a calcined zeolite-binder; (3) contacting the calcined zeolite-binder with an aqueous solution of a boron compound under a condition sufficient to produce one impregnated with boron compound; and (4) calcining the zeolite impregnated with the boron compound, and the boron compound is selected from the group consisting of boric acid, borane-ammonium complex, boron trichloride, boron nitride, triethyl borane, trimethyl borane, tripropyl borane, trimethyl borate, triethyl borate, tripropyl borate, trimethyl boroxine, triethyl boroxine, tripropyl boroxine and combinations of two or more thereof.

17. A process according to claim 16, characterized in that the binder is selected from the group consisting of kaolinite, halloysite, vermiculite, chlorite, attapulgite, smectite, montmorillonite, illite, saconite, sepiolite, paligoresqui ta, diatomaceous earth, α-alumina, ?-alumina; silicas; alumina-silica / aluminum phosphate; aluminum chlorohydrate and combinations of two or more thereof and the boron compound is selected from the group consisting of boric acid, borane-ammonium complex, boron trichloride, boron nitride, triethyl borane, trimethyl borane, tripropyl borane, trimethyl borate, triethyl borate, tripropyl borate, trimethyl boroxine, triethyl boroxine, tripropyl boroxine and combinations of two or more thereof.

18. A process according to claim 16, characterized in that the binder is bentonite and the boron compound is boric acid.