RU2806830C1 - Methods for obtaining aromatization catalyst - Google Patents

Abstract

FIELD: chemical industry.

SUBSTANCE: present invention relates to the aromatization of hydrocarbons using an aromatization catalyst. In particular, the present invention relates to methods for producing an aromatization catalyst. An aromatization catalyst is described containing: a zeolite support, wherein the zeolite support contains a KL zeolite, which is associated with silica and fluorine derived from the first fluorine-containing compound; platinum deposited on a zeolite substrate; chlorine deposited on a zeolite support; and fluorine derived from the second fluorine-containing compound supported on the zeolite support. A method for producing a catalyst includes: calcining an extruded base to form a calcined extruded base, wherein the extruded base contains KL zeolite and a silica binder; contacting the calcined extruded base with a first fluorine-containing compound to form a fluorinated calcined extruded base; washing the fluorinated calcined extruded base to form a washed fluorinated calcined extruded base; drying the washed fluorinated calcined extruded base to form a dried washed fluorinated calcined extruded base; calcining the dried washed fluorinated calcined extruded base to form a bonded zeolite support; and contacting the bonded zeolite support with a platinum-containing compound, a chlorine-containing compound, and a second fluorine-containing compound, wherein the first fluorine-containing compound and the second fluorine-containing compound may be the same or different, wherein the average crush strength of the resulting catalyst is greater than 12 pounds based on at least two samples of catalyst granules.

EFFECT: creation of an improved method for producing an aromatization catalyst with high catalytic selectivity and conversion.

21 cl, 5 tbl

Description

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation in part of and claims priority to U.S. Patent Application No. 15/386,129, filed December 21, 2016 and published as U.S. Patent Application Publication No. US 2018/0170837 A1, entitled “Methods of Preparing an Aromatization.” Catalyst", which application is incorporated herein by reference in its entirety.

TECHNICAL FIELD

[0002] The present invention relates to the aromatization of hydrocarbons using an aromatization catalyst. In particular, the present invention relates to methods for producing an aromatization catalyst.

BACKGROUND OF THE ART

[0003] The catalytic conversion of hydrocarbons into aromatic compounds, called aromatization, is an important industrial process used to produce the basic chemical building block compounds on which much of the chemical industry is based. Aromatization reactions may include dehydrogenation, isomerization, and hydrocracking of hydrocarbons. These reactions are typically carried out in one or more aromatization reactors containing aromatization catalysts. These catalysts can improve selectivity for desired aromatic compounds and/or conversion rates of reactions to desired aromatic compounds. Given their commercial importance, there is a continuing need for improved methods for producing aromatization catalysts with high selectivity and conversion.

[0004] In addition, movement of catalyst particles during catalyst loading and during reactor operation results in the formation of fine catalyst particles. For example, transferring catalyst from catalyst storage drums to an aromatization reactor causes the catalyst particles to be brought into contact with each other and with the transfer equipment. Contact may lead to destruction of catalyst particles. Fine particles are formed when small pieces of catalyst break off from either broken or intact catalyst particles. Fine particles can also be generated during process failures, which can cause movement in the catalyst bed, leading to breakdown and attrition of the catalyst particles. Fine catalyst particles are abrasive to the reactor interior and can clog reactor-related equipment such as strainers and pumps.

SUMMARY OF THE INVENTION

[0005] Described herein is a catalyst comprising a zeolite support; Group VIII metal on zeolite support; and at least two halides bonded to a zeolite support, a Group VIII metal, or both, wherein the average crush strength of the catalyst is greater than 11.25 pounds based on at least two catalyst pellet samples measured in accordance with ASTM D4179.

[0006] Also described herein is a method for preparing a catalyst, comprising calcining an extruded base to form a calcined extruded base, wherein the extruded base comprises a KL zeolite; contacting the calcined extruded base with a first fluorine-containing compound to form a fluorinated calcined extruded base; washing the fluorinated calcined extruded base to form a washed fluorinated calcined extruded base; drying the washed fluorinated calcined extruded base to form a dried washed fluorinated calcined extruded base; calcining the dried washed fluorinated calcined extruded base to form a bonded zeolite support; and contacting the bonded zeolite support with the Group VIII metal and a second fluorine-containing compound, wherein the first fluorine-containing compound and the second fluorine-containing compound may be the same or different.

DETAILED DESCRIPTION OF THE INVENTION

[0007] At the outset, it should be understood that while an exemplary implementation of one or more aspects is provided below, the systems and/or methods described may be implemented using any number of techniques currently known or existing. The present invention is not to be limited in any way to the illustrative implementations, drawings and methods illustrated below, including the illustrative designs and implementations illustrated and described herein, but may be varied within the scope of the appended claims along with their full scope of equivalents.

[0008] Methods for preparing catalysts are described herein. In one aspect, the catalyst is an aromatization catalyst that is used to convert hydrocarbons to aromatic compounds. Typically, such conversions of hydrocarbons to aromatic compounds are carried out in one or more aromatization reactors. Hereinafter, the present invention will focus on the production of an aromatization catalyst, which may be referred to generally as a "catalyst". However, it is contemplated that one skilled in the art, taking advantage of the present invention, can use similar techniques to prepare other types of catalyst. In one aspect, the catalysts described herein contain a bonded zeolite support, one or more catalytically active metals, and one or more halides.

[0009] To more clearly define the terms used herein, the following definitions are provided. Unless otherwise stated, the following definitions apply to the present invention. If a term is used in the present invention but is not specifically defined therein, the definition from the IUPAC Compendium of Chemical Terminology, 2nd ed. may apply. (1997), provided that this definition does not conflict with any other invention or definition applied herein or render undefined or invalid any claim to which this definition applies. To the extent that any definition or application set forth in any document incorporated herein by reference conflicts with a definition or application set forth herein, the definition or application set forth herein shall control.

[0010] As used herein, although compositions and methods are often described by terms such as “comprising” various components or steps, compositions and methods may also “consist primarily of” or “consist of” various components or steps, if not otherwise indicated.

[0011] Terms in the singular form are intended to include plural alternatives, such as at least one. For example, the present description of “transition metal” or “halogen” is intended to cover one, or mixtures or combinations of more than one transition metal or halogen, unless otherwise indicated.

[0012] For any particular compound or group described herein, any name or structure (general or specific) presented is intended to cover all conformational isomers, regioisomers, stereoisomers, and mixtures thereof that may arise from a particular set of substituents unless otherwise specified other. The name or structure (general or specific) also covers all enantiomers, diastereomers and other optical isomers (if any) in enantiomeric or racemic forms, as well as mixtures of stereoisomers as recognized by one skilled in the art, unless otherwise noted. For example, a common reference to hexane includes n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane and 2,3-dimethylbutane; and a general reference to a butyl group includes an n-butyl group, a sec-butyl group, an isobutyl group and a tert-butyl group.

[0013] In one aspect, a chemical "group" may be defined or described in accordance with how the group is formally derived from the reference or "parent" compound, for example, by the number of hydrogen atoms removed from the parent compound to form the group, even if this band is literally not synthesized that way. These groups can be used as substituents, or matched, or bonded to metal atoms. As an example, an "alkyl group" can formally be formed by removing one hydrogen atom from an alkane. The present invention, namely a substituent, ligand or other chemical moiety that may constitute a particular "group", implies that when using that group as described, well-known rules of chemical structure and bonding are followed. When describing a group as “derived by,” “derived from,” “formed by,” or “derived from,” such terms are used in a formal sense and are not intended to represent any specific synthetic methods or procedures unless otherwise noted or the context is clear. demands otherwise.

[0014] Various numerical ranges are described herein. When a range of any type is described or stated herein, the intent is to describe or state separately each possible number, which range may reasonably include the endpoints of the range as well as any subranges and combinations of subranges covered herein. document unless otherwise indicated. As a representative example, the present application describes that the bonded zeolite support contains fluoride present in an amount of about 0.1 wt. % to about 5 wt. %. According to the invention, in which the bound zeolite support contains an amount of fluoride, which may be present in the range of about 0.1 wt. % to about 5 wt. %, the intent is to indicate that the amount of fluoride may be any amount within a range and, for example, may be about 0.5 wt. %, about 1.0 wt. %, about 1.5 wt. %, about 2.0 wt. %, about 2.5 wt. %, about 3.0 wt. %, about 3.5 wt. %, about 4.0 wt. %, about 4.5 wt. % or about 5.0 wt. %. In addition, the amount of fluoride can be in any range from about 0.1 wt. % to about 5 wt. % (for example, the amount of fluoride may vary from about 0.2 wt.% to about 1.5 wt.%) and this also includes any combination of ranges, for example from about 0.3 wt. % to about 1.8 wt. %. Likewise, all other ranges described herein should be interpreted similarly to this example.

[0015] As used herein, the term “hydrocarbon” refers to a compound containing only carbon and hydrogen atoms. Other identifiers may be used to indicate the presence of specific groups, if any, in the hydrocarbon (eg, halogenated hydrocarbon indicates the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the hydrocarbon).

[0016] An "aromatic" compound is a compound containing a cyclically conjugated double bond system that follows Hückel's rule (4n+2) and contains (4n+2) pi electrons, where n is an integer from 1 to 5. Aromatic compounds include "arenes" (hydrocarbon aromatic compounds such as benzene, toluene and xylenes) and "heteroaromatic compounds" (heteroaromatic compounds formally derived from arenes by replacing one or more methane (C=) carbon atoms of a cyclically conjugated double bond system with a trivalent or divalent heteroatom in such a way as to preserve the continuous system of pi-electrons characteristic of the aromatic system, and the number of pi-electrons out of plane, corresponding to Hückel's rule (4n+2)). As described herein, the term “substituted” can be used to describe an aromatic group, an arene, or a heteroarene, wherein the non-hydrogen moiety formally replaces a hydrogen atom in the compound and is intended to be non-limiting unless otherwise noted.

[0017] As used herein, the term “alkane” refers to a saturated hydrocarbon compound. Other identifiers may be used to indicate the presence of specific groups, if any, on the alkane (eg, halogenated alkane indicates the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the alkane). The term "alkyl group" is used herein as defined by IUPAC: a monovalent group formed by the removal of a hydrogen atom from an alkane. An alkane or alkyl group may be straight or branched unless otherwise specified.

[0018] "Cycloalkane" is a saturated cyclic hydrocarbon with or without side chains, such as cyclobutane, cyclopentane, cyclohexane, methylcyclopentane and methylcyclohexane. Other identifiers may be used to indicate the presence of specific groups, if any, on the cycloalkane (eg, halogenated cycloalkane indicates the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the cycloalkane).

[0019] The term "halogen" has its usual meaning. Examples of halogens include fluorine, chlorine, bromine and iodine.

[0020] Molar selectivity is defined as:

Selectivity for benzene:

Toluene selectivity:

Selectivity for benzene and toluene:

Selectivity for aromatic compounds:

[0021] Conversion is defined as the number of moles converted per mole of "converted" components supplied: where indicates the molar flow rate in a continuous reactor or the number of moles in a batch reactor.

eC6 conversions:

eC7 conversions:

Conversion C6+C7:

[0022] In one aspect, the bonded zeolite support comprises one or more zeolite powders bonded together by a binder. The term "zeolite" primarily refers to a specific group of crystalline metal aluminosilicates. These zeolites have a network of SiO ₄ and AlO ₄ tetrahedra, in which aluminum and silicon atoms are cross-linked into a three-dimensional framework by sharing oxygen atoms. In the framework, the ratio of oxygen atoms to the total number of aluminum and silicon atoms is 2. The framework has a negative electrovalence, which is usually balanced by the inclusion of cations such as metals, alkali metals, alkaline earth metals, or hydrogen in the crystal. Thus, zeolites are a group of natural or synthetic aluminosilicate minerals that typically contain alkali and alkali metals. Zeolites are characterized by a framework structure that contains interconnected cavities occupied by ion-exchangeable large metal cations, such as potassium and water molecules, allowing reversible dehydration. The actual formula of the zeolite can be varied without changing the crystal structure. In one aspect, the molar ratio of silicon to aluminum (Si/Al) in the zeolite can range from about 1.0 to about 3.5.

[0023] In one aspect, the bonded zeolite support comprises a large-pore zeolite. The term "large-pore zeolite" as used herein refers to a zeolite having an effective pore diameter of from about 6 angstroms (Å) (0.6 nm) to about 15 Å (1. 5 nm), alternatively, from about 7 Å (0.7 nm) to about 9 Å (0.9 nm). Large pore crystalline zeolites suitable for use in the present invention include, but are not limited to, L-zeolite, X-zeolite, Y-zeolite, omega zeolite, beta zeolite, ZSM-4, ZSM-5, ZSM-10, ZSM- 12, ZSM-20, REY, USY, RE-USY, LZ-210, LZ-210-A, LZ-210-M, LZ-210-T, SSZ-24, ZZA-26, SSZ-31, SSZ- 33, SSZ-35, SSZ-37, SSZ-41, SSZ-42, SSZ-44, MSM-58, mordenite, faujasite or combinations thereof. In one aspect, the large-pore zeolite has an isotypic framework structure. In one aspect, the bonded zeolite support contains L-zeolite.

[0024] L-type zeolite catalysts are a subset of zeolite catalysts. Typical L-type zeolites contain oxide molar ratios according to the following formula:

M. _2/n O⋅Al. ₂ O ₃ ⋅xSiO ₂ ⋅yH. ₂ O,

where "M" denotes at least one exchangeable cation such as barium, calcium, cerium, lithium, magnesium, potassium, sodium, strontium and zinc, as well as non-metallic cations such as hydronium and ammonium ions, which may be replaced by other exchangeable cations cations without causing a significant change in the basic crystal structure of the L-type zeolite. The "n" indicated in the formula represents the valence of "M", "x" is 2 or more; and "y" represents the number of water molecules contained in the channels or interconnecting voids with the zeolite. L-zeolite, its diffraction pattern; The X-ray diffraction pattern, its properties and methods for its preparation are described in detail in US Pat. No. 3,216,789, the contents of which are incorporated herein by reference. In one aspect, the bonded zeolite support contains an L-zeolite, wherein M represents potassium and is hereinafter referred to as a KL-zeolite.

[0025] In one aspect, the catalyst comprises a crystalline zeolite powder, such as a KL-zeolite powder, having an average particle size of less than about 6 microns, alternatively less than about 5 microns, alternatively less than about 4 microns, alternatively less than about 3 microns, or alternatively from about 5 microns up to about 2 microns; an average particle size of less than about 5 microns, alternatively less than about 4 microns, alternatively less than about 3 microns, alternatively less than about 2 microns, alternatively from about 5 microns to about 2 microns; or combinations thereof. Zeolite powders having the average and median particle sizes described can be prepared using any suitable zeolite preparation technique. For example, zeolite can be produced by methods such as spray drying or crystallization. In one aspect, the zeolite can then be contacted with other components to form a bonded zeolite support.

[0026] In one aspect, the binder for use with the zeolite includes synthetic or naturally occurring zeolites; aluminium oxide; clays such as montmorillonite and kaolin; refractory metal oxides of groups IVA and IVB of the Periodic Table of Elements; oxides of silicon, titanium, zirconium; or combinations thereof. In one aspect, the binder contains silica. In one aspect, the silica may be in the form of a silicic acid sol. The silicic acid sol may contain dispersed silica particles in water. The silicic acid sol can be offered in the form of an aqueous solution with a concentration of about 20 wt. % to about 30 wt. %, having a pH of from about 9.0 to about 10.5 and a viscosity equal to or less than about 20 mPa⋅s at 25°C, alternatively from about 1 mPa⋅s to about 20 mPa⋅s at 25°C.

[0027] The catalyst compositions of the present invention may contain a zeolite support, as described herein, a Group VIII metal, as described herein, on the zeolite support, and at least two halides described herein, which are associated with the zeolite support, with a Group VIII metal or with both a zeolite support and a Group VIII metal. In aspects, the at least two halides are a fluoride and a second halide selected from chloride, bromide or iodide. In additional aspects, the at least two halides are fluoride and chloride. In aspects in which the fluoride is one of two halides, these catalyst compositions may be referred to as pre-fluorinated (metal)-(halide)-F catalysts or doubly fluorinated catalysts because their supports have been contacted with the fluorine-containing compound prior to loading the metal, and were then brought into contact with a fluorine-containing compound and another halide-containing compound during metal loading. Specific examples of prefluorinated (metal)-(halide)-F catalysts include prefluorinated Pt-Cl-F catalysts.

[0028] The average crush strength for the catalysts described herein can be calculated. Typically, the average crush strength is calculated by averaging the crush strength of at least two catalyst samples. Each catalyst sample contains a specified number of catalyst beads, for example 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100 beads. The crush strength of a sample can be calculated by averaging the crush strength of the individual granules for each granule in the sample. The crushing strength of each individual granule can be measured according to ASTM D4179; alternatively, the crush strength of each individual granule can be measured in accordance with ASTM D4179, except that the drying step in the standard is performed at 538°C instead of 400°C.

[0029] In some aspects, the average crush strength of the catalyst may be greater than 11.25 pounds; alternatively, more about £11.79; alternatively, more than about £12.00; alternatively, over about £13.00; alternatively, more about £13.20; alternatively, more around £13.40. In some additional aspects, the average crush strength may be less than about 15.00 pounds; alternatively, less than about £14.00; alternatively, less around £13.90; alternatively, less than about £13.70; alternatively, less around £13.50.

[0030] In some aspects, the crush strength of the catalyst sample may exceed 11.91 pounds; alternatively, over about £12.00; alternatively, over about £13.00; alternatively, more around £13.10. In some additional aspects, the crush strength of the catalyst sample may be less than about 15.00 pounds; alternatively, less than about £14.00; alternatively, less around £13.90; alternatively, less than about £13.80; alternatively, less around £13.70.

[0031] In some aspects, the average crush strength per length of catalyst extrudate (eg, pellet) may be greater than 2.25 lb/mm; alternatively, greater than 2.48 lb/mm; alternatively, more than about 2.50 lb/mm; alternatively, more than about 2.60 lb/mm; alternatively, more than about 2.70 lb/mm; alternatively, more than about 2.80 lb/mm; alternatively, more than about 2.90 lb/mm; alternatively, more than about 3.00 lb/mm. In some additional aspects, the average crush strength per length of catalyst extrudate may be less than about 3.50 lb/mm; alternatively, less than about 3.40 lb/mm; alternatively, less than about 3.30 lb/mm; alternatively, less than about 3.20 lb/mm; alternatively, less than about 3.10 lb/mm.

[0032] In some aspects, the crush strength of the sample per catalyst extrudate length may be greater than 2.65 lb/mm; alternatively, more than about 2.70 lb/mm. In some additional aspects, the crush strength of the sample per catalyst extrudate length may be less than about 3.50 lb/mm; alternatively, less than about 3.40 lb/mm; alternatively, less than about 3.30 lb/mm.

[0033] In some aspects, less than 22% of the catalyst pellets, measured in accordance with ASTM D4179, have an individual pellet crush strength of less than 10 lbs/pellet; alternatively, less than 21% of the pellets measured in accordance with ASTM D4179 have an individual pellet crush strength of less than 10 lbs/pellet.

[0034] In some aspects, exactly or less than 14% of the catalyst pellets that are measured in accordance with ASTM D4179 have an individual pellet crush strength of less than 9 lbs/pellet; alternatively, less than 13% of the pellets measured in accordance with ASTM D4179 have an individual pellet crush strength of less than 9 lbs/pellet.

[0035] In one aspect, a method of preparing a catalyst includes mixing a zeolite of the type described herein, a binder of the type described herein, and water to form a paste and form the paste into a wet extruded base or extrudate. In one aspect, the wet extruded base can be in any suitable shape. Any suitable molding process or technology may be used, which may include, but is not limited to, extrusion, spray drying, granulation, agglomeration, and the like. In one aspect, shaping the paste into a wet extruded base or extrudate is, for example, described in US Pat. Nos. 8,263,518, 7,902,105, 6,190,539, and 5,558,851, each of which is incorporated herein by reference in its entirety.

[0036] The zeolite and binder (eg, silica) can be combined to produce a zeolite-binder weight ratio of about 95:5 to about 50:50; alternatively, zeolite: binder from about 90:10 to about 70:30; or, alternatively, a zeolite binder of about 88:12 to about 78:22 in a bound zeolite support. The amount of water required to form the extrudable paste can be determined by one skilled in the art. The amount of water may be sufficient to form a paste having a paste-like consistency. Such a paste may be characterized by its resistance to coloring (i.e., not being brittle) and its ability to maintain a cohesive shape (i.e., not having a soupy consistency). The paste may further be characterized by the ability to form a plug at the interface of the extruder, which can then be forced out through the die openings in a cylindrical shape, resembling spaghetti strands, which can be cut or crushed into cylinders or granules having the required dimensions and being solid or hollow.

[0037] In one aspect, the paste further comprises an extrusion aid. An extrusion aid can improve the rheology of the paste. This improvement in paste rheology can help improve paste flow during the molding process (eg, through the extrusion die). Improved flow during the molding process results in easier machine startup, smoother extrusion, faster processing, lower extrusion pressure and improved product appearance. In one aspect, the extrusion aid comprises cellulose-based materials, ethylene glycol, stearic acid, or combinations thereof. In one aspect, the extrusion aid comprises a cellulose ether such as methylcellulose, arboxymethylcellulose, ethylhydroxyethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylhydroxyethylcellulose, methylhydroxypropylcellulose, or combinations thereof. An example of an extrusion aid suitable for use in the present invention includes, but is not limited to, METHOCEL®, a cellulose-based material commercially available from Dow Chemical Company. Extrusion auxiliaries, effective amounts thereof, and methods of inclusion in the base catalyst composition can be varied and selected as needed to achieve the specific user and/or process objectives. In the following, the molded paste coming out of the die and having the required dimensions will be called a “wet extruded base” (WEB).

[0038] Excess water in the wet extruded base can be removed by drying to form an extruded base (EB) before further processing. For drying WEB, any suitable method for drying wet solids can be used, which may include, for example, drying in air or in an inert gas such as nitrogen or argon. Drying temperatures can range from about 93.3°C (200°F) to about 204°C (400°F), alternatively, from about 93.3°C (200°F) to about 149°C (300°F ) or, alternatively, from about 107°C (225°F) to about 135°C (275°F). The drying time may vary from about 1 hour or more, alternatively from about 1 hour to about 10 hours, or alternatively from about 2 hours to about 5 hours.

[0039] In one aspect, WEB or EB can be contacted with a fluorine-containing compound in a process commonly referred to as fluorination. The fluorine-containing compound may be in a solid phase, a liquid phase, a gas phase, or combinations thereof.

[0040] Examples of fluorine-containing compounds suitable for use in the present invention include, but are not limited to, tetramethylammonium fluoride (TMAF), ammonium fluoride (NH ₄ F or AF), or combinations thereof.

[0041] In some aspects, the fluorine-containing compound may be an organic ammonium halide compound and may include one or more compounds represented by the general formula N(R) ₄ F, where R represents hydrogen or a substituted or unsubstituted carbon chain molecule having from 1 to 20 carbon atoms, each R may be the same or different. In one aspect, R is methyl, ethyl, propyl, butyl, or combinations thereof. Alternatively, R is methyl. Examples of suitable organic ammonium fluoride compounds include, but are not limited to, ammonium fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride, methyltriethylammonium fluoride, or combinations thereof.

[0042] The organic ammonium halide compound may also contain at least one hydrofluoric acid and at least one ammonium hydroxide represented by the formula N(R') ₄ OH, where R' represents hydrogen or a substituted or unsubstituted carbon chain molecule containing from 1 to 20 carbon atoms, where each R' may be the same or different. In one aspect, R' is methyl, ethyl, propyl, butyl, or combinations thereof. Alternatively, R is methyl. Examples of organic ammonium hydroxides suitable for use in the present invention include tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or combinations thereof.

[0043] In one aspect, WEB is contacted with a fluorine-containing compound of the type described herein to form a fluorinated washed extruded base (F-WEB). In an alternative aspect, the EB is contacted with a fluorine-containing compound of the type described herein to form a fluorinated extruded base (F-EB).

[0044] In one aspect, neither the WEB nor the EB are contacted with a fluorine-containing compound. In such aspects, the extruded base (EB) can be calcined to form a calcined extruded base (CEB). Calcination temperatures may range from about 260°C (500°F) to about 816°C (1500°F), alternatively, from about 371°C (700°F) to about 593°C (1100°F), or alternatively , from about 454°C (850°F) to about 593°C (1100°F). The calcination time may vary from about 0.5 to about 5 hours, or alternatively from about 0.5 to about 1.5 hours. In such aspects, calcination can be carried out in an oxygen-containing atmosphere at a flow rate of from about 4.7 L/min (10 cubic feet per hour (cfm)) to about 9.4 L/min (20 cfm) Alternatively, the calcination can be carried out in air at a flow rate of from about 4.7 L/min (10 cu ft/hr) to about 9.4 L/min (20 cu ft/hr) or, alternatively, the calcination can be carried out in “dry” air at flow rates from about 4.7 L/min (10 cu ft/hr) to about 9.4 L/min (20 cu ft/hr). Dry air refers to air whose dew point is less than about minus 40°C (minus 40°F). In one aspect, the CEB can be contacted with a fluorine-containing compound of the type described herein to form a fluorinated calcined extruded base (F-CEB).

[0045] In one aspect, the extruded base is calcined (in the absence of a previous drying step as described previously) to form a calcined extruded base (CEB). Calcination temperatures may range from about 260°C (500°F) to about 816°C (1500°F), alternatively, from about 371°C (700°F) to about 593°C (1100°F), or alternatively , from about 454°C (850°F) to about 593°C (1100°F). The calcination time may vary from about 0.5 to about 5 hours, or alternatively from about 0.5 to about 1.5 hours. In such aspects, calcination can be carried out in an oxygen-containing atmosphere at a flow rate of from about 10 cubic feet per hour (cfm) to about 20 cc. ft/hour (9.4 l/min), alternatively, calcination can be carried out in air at a flow rate of about 10 cc. ft/hr (4.7 L/min) to about 20 cu.m. ft/hour (9.4 l/min), alternatively, calcination can be carried out in “dry” air at a flow rate of about 10 cc. ft/hr (4.7 L/min) to about 20 cu.m. ft/hr (9.4 L/min). Dry air refers to air whose dew point is less than about minus 40°C (minus 40°F). In one aspect, the CEB can be contacted with a fluorine-containing compound of the type described herein to form a fluorinated calcined extruded base (F-CEB).

[0046] In one aspect, the SEB can be washed to form washed SEB (WCEB). Flushing with SEB can reduce the amount of “easy to remove” alkali that may be present. The term "washing", as used herein, includes any process in which a liquid (eg water) exceeding the pore volume of a material is brought into contact with the SEV. "Easily removable" alkali is defined herein as alkali that can be washed out of the CER after 5 washes by contacting a volume of liquid of approximately 1:1 with the bulk of the extrudate at ambient temperature. It may take several washes to significantly reduce the amount of easily removed alkali. In some aspects, the SEB may be subjected to at least 5 washes to remove a significant amount of easily removable alkali. In one aspect, the rinse water is distilled or deionized water having a pH of from about 5 to about 9. The rinse temperature can range from about 21°C (70°F) to about 93.3°C (200°F), alternatively, from about 27°C (80°F) to about 54°C (130°F), alternatively, from about 32°C (90°F) to about 43°C (110°F). The rinsing time may vary from about 5 to about 60 minutes per rinse, alternatively from about 15 to about 30 minutes per rinse.

[0047] After washing, to reduce the amount of easily removed alkali, the washed WCEB can be dried to form washed and dried SEB. The drying temperature may vary from about 93.3°C (200°F) to about 204°C (400°F), alternatively, from about 93.3°C (200°F) to about 149°C (300°F ) or, alternatively, from about 107°C (225°F) to about 135°C (275°F). The drying time may vary from at least about 1 hour, alternatively from about 1 to about 10 hours, or alternatively from about 2 to about 5 hours.

[0048] The washed and dried SEB can be calcined to form washed, dried and calcined SEB. The calcination temperature may range from about 260°C (500°F) to about 649°C (1200°F), alternatively, from about 371°C (700°F) to about 593°C (1100°F), or alternatively , from about 454°C (850°F) to about 593°C (1000°F). The calcination time may vary from about 0.5 to about 5.0 hours, or alternatively from about 0.5 to about 1.5 hours. In such aspects, calcination can be carried out in an oxygen-containing atmosphere at a flow rate of from about 4.7 L/min (10 cu ft/hr) to about 9.4 liter/min (20 cu ft/hr), alternatively, calcination can be carried out in air at a flow rate of about 4.7 L/min (10 cu ft/hr) to about 9.4 L/min (20 cu ft/hr) or, alternatively, calcination can be carried out in “dry” air at flow rates from about 4.7 L/min (10 CFM) to about 9.4 L/min (20 CFM).

[0049] F-WEB, F-EB, F-CEB and/or F-WCEB may be collectively referred to as fluorinated base materials (FBM). In one aspect, a method of producing an aromatization catalyst includes contacting at least one of its WEB, EB, CEB or WCEB with a fluorine-containing compound to produce one or more FBMs. In one aspect, a fluorine-containing compound can be contacted with at least two of WEB, EB, CEB, or WCEB to produce one or more FBMs. In one aspect, the fluorine-containing compound can be contacted with any combination of WEB, EB, CEB and/or WCEB to produce one or more FBMs. In one aspect, the contact of WEB, EB, SEB and/or WCEB with a fluorine-containing compound to produce FBM occurs in a temperature range of about 20°C to about 100°C, alternatively, from about 22°C to about 80°C, or, alternatively, from about 25°C to about 50°C.

[0050] It should be understood that contact of the fluorine-containing compound results in the binding of fluoride to subsequent materials formed during the preparation of the aromatization catalyst. For example, fluoridation of WEB produces F-WEB, which can then be dried to produce F-EB, which can be calcined to produce F-CEB. Likewise, fluorination of EB produces F-EB, which can be calcined to produce F-CEB. As noted earlier, each of these FBMs can be further washed, dried and calcined. Therefore, fluorinating a wet extruded base produces a fluorinated wet extruded base, followed by a fluorinated extruded base, a baked fluorinated extruded base, a washed baked fluorinated extruded base, a dried washed baked fluorinated extruded base, and so on. In aspects in which the extruded base is brought into contact with a fluorine-containing compound, a fluorinated extruded base is formed, and then a calcined fluorinated extruded base, a washed calcined fluorinated extruded base, a dried washed calcined fluorinated extruded base, and so on. In aspects in which the calcined extruded base is brought into contact with a fluorine-containing compound, a fluorinated calcined extruded base is formed, followed by a washed fluorinated calcined extruded base, a dried washed fluorinated calcined extruded base, and so on. Again, any of the resulting FEB, F-EB, F-CEB or F-WCEB may be collectively referred to as fluorinated base materials (FBM).

[0051] FBMs can be subjected to further processing steps to produce bonded zeolite supports and/or catalysts (eg, aromatization catalysts) as described herein. For example, the FBM may be further washed, dried and calcined to form an associated zeolite support (which may also be referred to as a catalyst support, catalyst precursor, precursor support, support material, etc., each of which indicates that one or more catalyst materials have not yet been added to the support).

[0052] In one aspect, the FBM can be washed to form washed FBM. The term "washing", as used herein, includes any process in which a liquid (eg water) exceeding the pore volume of the material is brought into contact with the FBM. Several washes can be carried out. In some aspects, the FBM may undergo 1 to 5 washes. In one aspect, the rinse water is distilled or deionized water having a pH of from about 5 to about 9. The rinse temperature can range from about 21°C (70°F) to about 93.3°C (200°F), alternatively, from about 27°C (80°F) to about 54°C (130°F), alternatively, from about 32°C (90°F) to about 43°C (110°F). The rinsing time may vary from about 5 to about 60 minutes per rinse, alternatively from about 15 to about 30 minutes per rinse. [0053] In one aspect, potassium (K ⁺ ) ions can be included in the wash liquid (eg, water) to neutralize any proton sites that may have formed during the wash and/or to prevent the formation of proton sites. Any suitable K-containing compound that is soluble in water may be used, including, but not limited to, KOH, KNO ₃ , KHCO ₃ , K ₂ CO ₃ , K-acetate, K-salts of common organic acids such as oxalic, citric, acetic, propionic acid, etc. K ⁺ may be present in amounts ranging from about 100 to about 1000 ppm. Protic or Brønsted acid sites can result in acidic properties with an adverse effect on catalytic activity and/or deactivation rate. In one aspect, the fluorine-containing compound is brought into contact with the SEB prior to washing.

[0054] After washing, the washed FBM can be dried to form a washed and dried FBM. The drying temperature may vary from about 93.3°C (200°F) to about 204°C (400°F), alternatively, from about 93.3°C (200°F) to about 149°C (300°F ), alternatively from about 107°C (225°F) to about 135°C (275°F). The drying time may vary from at least about 1 hour, alternatively from about 1 to about 10 hours, or alternatively from about 2 to about 5 hours.

[0055] The washed and dried FBM can be calcined to form washed, dried and calcined FBM. The calcination temperature may range from about 260°C (500°F) to about 649°C (1200°F), alternatively, from about 371°C (700°F) to about 593°C (1100°F), or alternatively , from about 454°C (850°F) to about 593°C (1000°F). The calcination time may vary from about 0.5 to about 5.0 hours, or alternatively from about 0.5 to about 1.5 hours. In such aspects, calcination can be carried out in an oxygen-containing atmosphere at a flow rate of from about 4.7 L/min (10 cu ft/hr) to about 9.4 liter/min (20 cu ft/hr), alternatively, calcination can be carried out in air at a flow rate of about 4.7 L/min (10 cfm) to about 9.4 L/min (20 cfm), alternatively, calcination can be carried out in "dry" air at a speed of flow from about 4.7 L/min (10 CFM) to about 9.4 L/min (20 CFM).

[0056] In one aspect, the washed, dried and calcined FBM may be referred to as a bonded zeolite support and may be used as a support material for preparing an aromatization catalyst having one or more catalyst materials supported thereon. In one aspect, the bound zeolite support contains fluoride present in an amount of from about 0.1 wt. % to about 5 wt. %, alternatively, from about 0.1 wt. % to about 3 wt. %, alternatively, from about 0.3 wt. % about 1.8 wt. %, as determined by any suitable technique such as x-ray fluorescence.

[0057] The method of producing an aromatization catalyst may further include impregnating a bonded zeolite support with one or more catalyst compounds, such as a Group VIII metal (eg, platinum) and one or more halides (eg, chloride).

[0058] The bonded zeolite support prepared as previously described herein may be further processed to include one or more catalyst materials. In one aspect, the addition of a metal and a chloride to a bonded zeolite support forms a catalyst capable of catalyzing reactions such as the conversion of hydrocarbons to aromatic compounds.

[0059] In one aspect, one or more Group VIII metals are added to a bonded zeolite support to form a metallized catalyst support. The metal can be added to the bonded zeolite support using any suitable method, such as ion exchange, moisture impregnation or pore filling impregnation. In one aspect, the metal is added to a bonded zeolite support by impregnation with a metal-containing solution. The metal in the metal-containing solution may be at least one Group VIII metal; alternatively, Pt, Pd, Rh, Ir, Ru, Os or combinations thereof; alternatively, platinum.

[0060] In one aspect, the metal includes platinum, which is added to a bonded zeolite support by contact with a metal-containing solution containing at least one platinum-containing compound. Examples of suitable platinum-containing compounds for contact with the bonded zeolite support include, but are not limited to, platinum compounds that form positively charged complex platinum ions in solution, such as, for example, platinum salts such as chlorides and nitrates; platinum complexes with amines; or combinations thereof. For example, the platinum-containing compound may be any degradable platinum-containing compound, including, but not limited to, ammonium tetrachloroplatinate, hydrochloroplatinic acid, diammineplatinum(II) nitrite, bis(ethylenediamine)platinum(II), platinum(II) chloride, acetylacetonate, platinum dichlorodiammine, platinum(II) chloride, tetraammineplatinum(II) hydroxide, tetraammineplatinum chloride and tetraammineplatinum(II) nitrate. In one aspect, the platinum source is tetraammine platinum chloride (TAPC). The amount of platinum in the metallized catalyst support can vary from about 0.1 to about 5 wt. %, alternatively, from about 0.1 to about 3 wt. %, alternatively, from about 0.3 to about 1.8 wt. %.

[0061] In one aspect, one or more halides are added to a bonded zeolite support by contacting a halide-containing compound to form a halogenated catalyst support. One or more halides may be added separately to the bonded zeolite support; alternatively, one or more halides may be added to the bonded zeolite support at the same time. Such halides may also be introduced during metal addition; alternatively, one or more halides are introduced in a separate step, which may be performed before or after metal addition, to form a halogenated metallized catalyst support. Examples of suitable halides include, but are not limited to, chloride, fluoride, bromide, iodide, or combinations thereof. Such halides may be introduced in the form of an organic ammonium halide compound.

[0062] An organic ammonium halide compound may include one or more compounds represented by the formula N(R) ₄ X, where X is a halide and where R is hydrogen or a substituted or unsubstituted carbon chain molecule containing 1 to 20 carbon atoms, each R can be the same or different. In one aspect, R is selected from the group consisting of methyl, ethyl, propyl, butyl, and combinations thereof, more specifically, methyl. In one aspect, the halide is a chloride and is added to a bonded zeolite support by contact with a chlorine-containing compound.

[0063] Suitable chlorine-containing compounds may be organic ammonium chloride compounds and may include one or more compounds represented by the general formula N(R) ₄ Cl, where R represents hydrogen or a substituted or unsubstituted carbon chain molecule containing from 1 to 20 atoms carbon, and each R may be the same or different. In one aspect, R is methyl, ethyl, propyl, butyl, or combinations thereof. Alternatively, R is methyl. Examples of suitable organic ammonium chloride compounds include, but are not limited to, ammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, methyltriethylammonium chloride, or combinations thereof.

[0064] In one aspect, the halogenated metallized catalyst support contains chloride present in an amount of from about 0.1 wt. % to about 5 wt. %, alternatively, from about 0.1 wt. % to about 3 wt. % or, alternatively, from about 0.3 wt. % to about 1.8 wt. %. In one aspect, the halogenated metallized catalyst support contains both chloride and fluoride, which may be present in a C1:F ratio of from about 1:10 to 10:1, alternatively from about 1:5 to 5:1, or alternatively from about 1:2 to 2:1.

[0065] In one aspect, the halogenated metallized catalyst support is allowed to solidify for several hours before further processing. In one aspect, the halogenated metallized catalyst support is allowed to solidify for about 1 to about 24 hours, alternatively about 2 to about 8 hours, or alternatively about 3 to about 6 hours. In one aspect, the catalyst comprises a metallized halogenated support.

[0066] After impregnating the bonded zeolite support with a metal and one or more halides to form a halogenated metallized catalyst support, the halogenated metallized catalyst support can then be subjected to further processing as described herein. The halogenated metallized catalyst support can be treated to remove unwanted compounds remaining after impregnation steps, for example, by drying to remove compounds and/or heating to decompose compounds. In one aspect, the halogenated metallized catalyst support is dried and calcined as described below.

[0067] The halogenated metallized catalyst support can be dried to form a dried halogenated metallized catalyst support. The drying temperature may range from about 38°C (100°F) to about 149°C (300°F), alternatively, from about 66°C (150°F) to about 121°C (250°F), or alternatively , from about 93.3°C (200°F) to about 104°C (220°F). The drying time may vary from about 0.1 to about 6 hours, alternatively from about 0.2 to about 4 hours, or alternatively from about 0.2 to about 3 hours. The halogenated metallized catalyst support can be dried using any suitable drying equipment under the conditions described. For example, a halogenated metallized catalyst support can be dried using a rotary evaporation technique at temperatures above about 38°C (100°F) under a pressure of about 102 kPa (30 inHg).

[0068] The dried halogenated metallized catalyst support can be calcined to form a dried and calcined halogenated metallized catalyst support. The calcination temperature may range from about 204°C (400°F) to about 282°C (900°F), alternatively, from about 260°C (500°F) to about 371°C (700°F), or alternatively , from about 288°C (550°F) to about 316°C (600°F). The calcination time may vary from about 0.5 to about 5 hours, or alternatively from about 0.5 to about 2.5 hours. Calcination can be carried out in an oxygen-containing atmosphere at a flow rate of from about 2.4 L/min (5 cu.ft./hour) to about 9.4 L/min. (20 cu.ft./hour). Alternatively, calcination can be carried out in air at a flow rate of from about 2.4 L/min (5 cu ft/hr) to about 9.4 L/min (20 cu ft/hr), alternatively, in dry air at flow from about 2.4 l/min (5 cfm) to about 9.4 l/min (20 cfm). After completion of the processing of the halogenated metallized catalyst support (eg, washing, drying and calcination), the resulting treated halogenated metallized catalyst support can be called a catalyst (eg, an aromatization catalyst) and used in a suitable chemical reaction and process.

[0069] Specific methods for preparing the catalyst are discussed next.

[0070] In one aspect, a method for preparing a catalyst may include mixing a zeolite of the type described herein, a binder of the type described herein, and water to form a paste and form the paste into a wet extruded base (WEB) or extrudate. Excess water may be removed from the WEB or it may otherwise be dried to form a dried extruded base (EB). After removing excess water or drying, the method may include contacting the EB with a fluorine-containing compound to form a fluorinated dried extruded base (F-EB). The F-EB can then be calcined to form a fluorinated calcined extruded base (F-CEB). The F-CEB can then be washed, dried and calcined again to form a bonded zeolite support. The bound zeolite support may then be contacted with a metal as described herein and a chlorine-containing compound as described herein, and then dried and then calcined again to form a catalyst. In one aspect, F-EB can be dried before calcining the F-EB to form F-CEB.

[0071] In another aspect, a method for preparing a catalyst may include mixing a zeolite of the type described herein, a binder of the type described herein, and water to form a paste and form the paste into a wet extruded base (WEB) or extrudate. Excess water may be removed from the WEB or it may otherwise be dried to form a dried extruded base (EB). The EB can then be calcined to form a calcined extruded base (CEB). The CEB can then be contacted with a fluorine-containing compound to form a fluorinated calcined extruded base (F-CEB). The F-CEB can then be washed, dried and calcined to form a bonded zeolite support. The bound zeolite support may then be contacted with a metal as described herein and a chlorine-containing compound as described herein, and then dried and then calcined again to form a catalyst. In one aspect, the F-CEB may be dried and/or calcined prior to washing, drying and subsequent calcination.

[0072] In another aspect, a method for preparing a catalyst may include mixing a zeolite of the type described herein, a binder of the type described herein, and water to form a paste and form the paste into a wet extruded base (WEB) or extrudate. Excess water may be removed from the WEB or it may otherwise be dried to form a dried extruded base (EB). The EB can then be calcined to form a calcined extruded base (CEB). The SEB can then be washed, dried and calcined again to form a double baked extruded base (2CEB). 2CEB can then be contacted with a fluorine-containing compound to form a bound zeolite support. The bound zeolite support may then be contacted with a metal as described herein and a chlorine-containing compound as described herein, and then dried and then calcined again to form a catalyst.

[0073] In one aspect, a method for preparing a catalyst may include mixing a zeolite of the type described herein, a binder of the type described herein, and water to form a paste and form the paste into a wet extruded base (WEB) or extrudate. Excess water may be removed from the WEB or it may otherwise be dried to form a dried extruded base (EB). After removing excess water or drying, the method may include contacting the EB with a first fluorine-containing compound to form a fluorinated dried extruded base (F-EB). F-EB can then be calcined to form fluorinated calcined extruded base (F-CEB). The F-CEB can then be washed, dried and re-calcined to form a bonded zeolite support. The bonded zeolite support may then be contacted with a metal as described herein, a chlorine-containing compound as described herein, and a second fluorine-containing compound as described herein, and then dried and then calcined again to form a catalyst. In one aspect, F-EB can be dried before calcining the F-EB to form F-CEB.

[0074] In another aspect, a method for preparing a catalyst may include mixing a zeolite of the type described herein, a binder of the type described herein, and water to form a paste and form the paste into a wet extruded base (WEB) or extrudate. Excess water may be removed from the WEB or it may otherwise be dried to form a dried extruded base (EB). The EB can then be calcined to form a calcined extruded base (CEB). The CEB may then be contacted with the first fluorine-containing compound to form a fluorinated calcined extruded base (F-CEB). The F-CEB can then be washed, dried and re-calcined to form a bonded zeolite support. The bound zeolite support may then be contacted with a metal as described herein, a chlorine-containing compound as described herein, and a second fluorine-containing compound as described herein, and then dried and then calcined again to form a catalyst. In one aspect, the F-CEB can be dried and/or calcined before washing, drying and then calcining the F-CEB to form a bonded zeolite support.

[0075] In another aspect, a method for preparing a catalyst may include mixing a zeolite of the type described herein, a binder of the type described herein, and water to form a paste and form the paste into a wet extruded base (WEB) or extrudate. Excess water may be removed from the WEB or it may otherwise be dried to form a dried extruded base (EB). The EB can then be calcined to form a calcined extruded base (CEB). The CEB can then be washed, dried and calcined again to form a double-fired extruded base (2CEB). The 2CEB may then be contacted with the first fluorine-containing compound and then dried and/or calcined to form a bound zeolite support. The bound zeolite support may then be contacted with a metal as described herein, a chlorine-containing compound as described herein, and a second fluorine-containing compound as described herein, and then dried and then calcined again to form a catalyst.

[0076] In one aspect, the catalyst prepared as described herein is used as a catalyst in an aromatization reactor system comprising at least one aromatization reactor and its associated process equipment. As used herein, the terms “aromatization,” “flavorization,” and “reforming” refer to the processing of hydrocarbon feedstocks to produce an aromatics-enriched product, which in one aspect is a product in which the aromatics content exceeds the aromatics content of the feedstock. Typically, one or more feed components undergo one or more reforming reactions to produce aromatic compounds. Some hydrocarbon reactions that occur during the aromatization operation include dehydrogenation of cyclohexanes to produce aromatics, dehydroisomerization of alkylcyclopentanes to produce aromatics, dehydrocyclization of acyclic hydrocarbons to produce aromatics, or combinations thereof. A number of other reactions also occur, including dealkylation of alkylbenzenes, isomerization of paraffins, hydrocracking reactions, which produce light hydrocarbon gases such as methane, ethane, propane and butane, or combinations thereof.

[0077] The aromatization reaction occurs under process conditions that thermodynamically favor the dehydrocyclization reaction and limit undesirable hydrocracking reactions. The pressure may range from about 0 kPa (0 psig) to about 3447 kPa (500 psig) or, alternatively, from about 172 kPa (25 psig) /sq.ig.) to about 2068 kPa (300 psig.). The molar ratio of hydrogen to hydrocarbons may be from about 0.1:1 to about 20:1, alternatively from about 1:1 to about 6:1. Operating temperatures include reactor inlet temperatures from about 371°C (700°F) to about 566°C (1050°F) or, alternatively, from about 482°C (900°F) to about 538°C (1000° F). The hourly space velocity of the hydrocarbon feed liquid over the aromatization catalyst may be from about 0.1 h ^-1 to about 10 h ^-1 or, alternatively, from about 0.5 h ^-1 to about 2.5 h ^-1 .

[0078] Feed composition is an important factor in the development of catalytic aromatization systems. In one aspect, the hydrocarbon feedstock includes non-aromatic hydrocarbons containing at least six carbon atoms. The raw material for the aromatization system is a mixture of hydrocarbons containing C ₆ -C ₈ hydrocarbons containing up to about 10 wt. %, and, alternatively, up to about 15 wt. % C ₅ and lighter hydrocarbons (C ₅ ^- ) and containing up to about 10 wt. % C ₉ and heavier hydrocarbons (C ₉ ⁺ ).

Such low levels of C ₉ ⁺ and C ₅ ^- hydrocarbons maximize the yield of valuable aromatic compounds. In some aspects, the optimal hydrocarbon feedstock provides the maximum percentage of _C6 hydrocarbons. Such feedstocks can be produced by separating a hydrocarbon feedstock, such as crude naphtha, into a light hydrocarbon feedstock fraction and a heavy hydrocarbon feedstock fraction and using the light fraction.

[0079] In another aspect, the feedstock is a naphtha feedstock. The naphtha feedstock may be a light hydrocarbon with a boiling point from about 21°C (70°F) to about 232°C (450°F). Naphtha feedstock may contain aliphatic, naphthenic or paraffinic hydrocarbons. These aliphatic and naphthenic hydrocarbons are converted, at least in part, to aromatic compounds in the aromatization reactor system. Although catalytic aromatization typically refers to the conversion of naphtha, other feedstocks can also be processed to produce an aromatic-enriched product. Therefore, although naphtha conversion is one aspect, the present invention may be applicable to the activation of catalysts for the conversion or aromatization of a wide variety of feedstocks, such as paraffinic hydrocarbons, olefinic hydrocarbons, acetylene hydrocarbons, cyclic paraffinic hydrocarbons, cyclic olefinic hydrocarbons and mixtures thereof, and especially saturated hydrocarbons.

[0080] In one aspect, the feedstock is substantially free of sulfur, nitrogen, metals and other known aromatization catalyst poisons. In one aspect, the feedstock contains less than about 100 ppb sulfur. If present, such poisons can be removed using any suitable method. In some aspects, the feedstock can be purified first using conventional hydrotreating methods and then using sorbents to remove remaining poisons.

[0081] In one aspect, aromatization catalysts of the type described herein exhibit increased catalytic selectivity as determined by the ratio of benzene to toluene produced using naphtha feedstocks. In such aspects, selectivity may range from about 10% to about 100%, alternatively from about 20% to about 90%, or alternatively from about 30% to about 80%.

EXAMPLES

[0082] The present invention will be described in more detail with the help of specific examples. The following examples are offered for illustrative purposes only and are not intended to limit the present invention in any way. Those skilled in the art will readily recognize many non-critical parameters that can be changed or modified to obtain substantially the same results.

EXAMPLES OF SUBSTRATE

[0083] Substrate A was a dried extruded silica bound KL zeolite base containing about 80 wt. % KL-zeolite. A mixture was prepared from about 609 grams (g) of KL-zeolite crystalline powder and about 30 g of methylcellulose. This mixture was thoroughly mixed in the sand apparatus. To this mixture was added about 714 g of about 20 wt. % aqueous silica solution (SI-350, obtained from CCIC (Japan)) and mixed thoroughly. To ensure thorough mixing, the silicic acid sol was added to the sand apparatus over a period of about 11 minutes. After the silicic acid sol was added to the mixture, water was added to bring the moisture content to about 35 wt. % to about 40 wt. % loss on ignition (LOI) for extrusion. Loss on ignition is the percentage of mass lost when a sample is heated at about 538°C (1000°F) for about 1 hour in dry air. The mixture was then extruded through a 1.6 mm (1/16 inch) diameter die. The extrudates were then dried at a temperature of about 121°C (250°F) for about 4 hours to obtain substrate A, extruded base (EB).

[0084] Substrate A was then calcined for about 1 hour at about 482°C (900°F) to form Substrate B, a calcined extruded base (CEB). During calcination, the temperature was increased at a rate of 300°F/4 to a final set point of 482°C (900°F) and an air flow of 4.7 L/min (10 scf/hr) was maintained through the particle bed.

[0085] Substrate C was a washed baked extruded base (WCEB). About 100 g of the calcined extruded base (substrate B) was washed with about 250 ml of deionized water at about 37.8°C (100°F). This flushing time was sufficient to achieve proper solid-liquid contact. This washing was repeated for a total of three washes. The washed extrudate was then dried for about 4 hours at about 121°C (250°F) and then air calcined at about 482°C (900°F) for about 1 hour under a stream of dry air.

[0086] Fluorinated support 1 was prepared by contacting 12 grams of support A with 2.33 grams of 20 wt. % tetramethylammonium fluoride (TMAF) solution using initial wetting methods. The substrate was allowed to settle for 16 hours and then dried at 150°C for 2 hours, after which the temperature was raised to 500°C for two hours and then held at 500°C for 1 hour.

[0087] Fluorinated support 2 was prepared by contacting 11 grams of support B with a mixture of 2.33 grams of 20 wt. % tetramethylammonium fluoride (TMAF) solution and 1.67 grams of water using initial wetting methods. The substrate was allowed to settle for 16 hours and then dried at 150°C for 2 hours, after which the temperature was raised to 500°C for two hours and then held at 500°C for 1 hour.

[0088] Fluorinated supports 3-7 were prepared by contacting 64.36 grams of support C with a mixture of about 15 grams of 20 wt. % tetramethylammonium fluoride (TMAF) solution and about 15 grams of water using initial wetting methods. The substrate was allowed to settle for 4 hours. The substrate was then divided into four parts, with each part being dried separately at 150°C for 2 hours, followed by increasing the temperature to a final holding temperature of six hours. The processing temperatures used to prepare fluorinated supports 3-7 are given in Table 1. An analysis of these fluorinated base materials is given in Table 2.

CATALYST EXAMPLES

[0089] Platinum-impregnated KL zeolite catalysts were prepared as follows. An impregnating mixture was obtained from about 0.18 g of tetraammine platinum (II) chloride (TAPC), about 0.36 g of 50 wt. % aqueous solution of tetramethylammonium chloride (TMAC) and about 3.5 g of water, which was added to a container containing about 10 g of bonded zeolite support (EB, CEB or WCEB) using initial wetting methods. The impregnated bonded zeolite support was then allowed to sit for about 16 hours at room temperature. The impregnated bonded zeolite support was dried in vacuum for about 4 hours at about 85°C. The resulting material was then calcined to an initial holding temperature of about 150°C for about 2 hours, then the temperature was increased over about 4 hours to a second holding temperature of about 350°C for 6 hours in dry air. The resulting catalysts were analyzed for wt. % Pt, Mac.%°F and wt. % O using X-ray fluorescence (XRF), and porosity was determined from nitrogen adsorption and calculated using the Brunauer-Emmett-Teller (BET) method. The analysis of these catalysts is given in Table 3.

EXAMPLES OF FLAVORS CHARACTERISTICS

[0090] In the following examples, the catalysts prepared above were aromatization catalysts of the type described previously herein. Each of the catalysts was evaluated for effectiveness as an aromatization catalyst. In each of the following examples, the following standard test conditions were used: the catalysts were crushed, screened through about 20 to 40 mesh, and 1 gram was placed in a reactor containing a 1/4 inch outside diameter (OD) stainless steel reaction vessel in an oven with adjustable temperature. After the catalyst was reduced in a stream of hydrogen, an incoming stream of aliphatic hydrocarbon and hydrogen was introduced into the reaction vessel at a flow rate of 22 ml/min; pressure 50 psi. inch (345 kPa); the molar ratio of H ₂ : hydrocarbon is 3:1, the hourly space velocity of the liquid is 9 h ^-1 , to obtain performance characteristics. The aliphatic hydrocarbon contained the following weight percentages of normal paraffins and isoparaffins: about 8 wt. % C ₈ paraffins, about 28 wt. % C ₇ paraffins and about 62 wt. % C ₆ paraffins. The composition of the reactor effluent was analyzed by gas chromatography to determine the amount of benzene and toluene present in the product, as well as the amount of light hydrocarbons with four or fewer carbon atoms (C ₄ ^- wt.%). Low stringency conditions were adjusted to give a total of 60 wt. % for the sum of wt. % benzene and wt. % toluene in the reactor effluent while high stringency conditions were adjusted to give a total of 75 wt. % for the sum of wt. % benzene and wt. % toluene in the reactor effluent. The catalyst performance was determined by plotting the temperature required to maintain the total yield of benzene and toluene at 60 wt. % for low severity conditions (75 wt % for high severity conditions) versus time under standard test conditions. In each of the following examples, the procedure for obtaining the catalyst, the production parameters and/or changes in process conditions are assessed by the effects observed in T ₆₀ or T ₇₅ , as well as by C ₄ ^- wt. %. Other parameters listed in the table include time on stream (h) (also referred to as TOS); and the benzene-toluene molar ratio of the product as shown in Table 4.

[0091] The results show that treating the extruded base, calcined extruded base, or washed calcined extruded base with fluoride reduces the microporosity of the support and the resulting aromatization catalyst and that treatment of the extruded base (Catalyst A) and the calcined extruded base (Catalyst B) provides greater catalyst selectivity aromatization, based on lower wt. % C ₄ ^- in the product.

[0092] The following listed aspects are presented as non-limiting examples of the subject matter of the present invention.

EXAMPLES OF CRUSHING STRENGTH

[0093] In the following examples, doubly fluorinated catalysts were tested for crush strength and compared with the crush strength of catalysts fluorinated only once.

[0094] The Pt-Cl-F catalyst on F-CEB was prepared by mixing KL zeolite powder, silica binder and water to form a paste and forming the paste into a wet extruded base (WEB). The WEB was dried to form a dried extruded base (EB). The EB was then calcined to form a calcined extruded base (CEB). The CEB was then contacted with NH ₄ F to form a fluorinated calcined extruded base (F-CEB). The F-CEB was then calcined, washed, dried and calcined again to form a bonded zeolite support. The bound zeolite support was then contacted with Pt, NH ₄ Cl and NH ₄ F, then dried and then calcined again to form a Pt-Cl-F catalyst on F-CEB. Thus, "Pt-Cl-F on F-CEB" indicates that the support was brought into contact with the fluorine compound at two points during catalyst preparation: 1) the fluorine compound was added to the calcined extruded base and 2) the fluorine compound was added to Pt and the chlorine-containing compound while adding the metal to the bonded zeolite support. "Pt-Cl-F catalyst on F-CEB" may also be referred to as doubly fluorinated Pt-Cl-F catalyst or pre-fluorinated Pt-Cl-F catalyst.

[0095] Pt-Cl-F catalyst on SEB was prepared by mixing KL zeolite powder, silica binder and water to form a paste and forming the paste into a wet extruded base (WEB). The WEB was dried to form a dried extruded base (EB). The EB was then calcined to form a calcined extruded base (CEB). The SEB was then washed, dried and calcined again to produce a bonded zeolite support. The bound zeolite support was then contacted with Pt, NH ₄ Cl and NH ₄ F, dried and then calcined again to form a Pt-Cl-F SEB catalyst. Thus, "Pt-Cl-F on CEB" indicates that the fluorine compound was added to the Pt and chlorine compound during metal addition to the bonded zeolite support, but was not added to the WEB, EB, or CEB prior to metal addition. “SEB Pt-Cl-F catalyst” may also be referred to as a singly fluorinated Pt-Cl-F catalyst that has not been pre-fluorinated.

[0096] The Pt-Cl catalyst on F-CEB was prepared by mixing KL zeolite powder, silica binder and water to form a paste and forming the paste into a wet extruded base (WEB). The WEB was dried to form a dried extruded base (EB). The EB was then calcined to form a calcined extruded base (CEB). The CEB was then brought into contact with NH ₄ F to form a fluorinated calcined extruded base (F-CEB). The F-CEB was then calcined, washed, dried and calcined again to form a bound zeolite support. The bound zeolite support was then contacted with Pt and NH ₄ Cl, then dried and then calcined again to form a Pt-Cl catalyst on F-CEB. Thus, "Pt-Cl on F-SEB" indicates that the fluorine compound was added to the calcined extruded base, but was not added to the Pt and chlorine compound during the addition of the metal to the bonded zeolite support. “Pt-Cl on F-CEB catalyst” may also be referred to as singly fluorinated Pt-Cl-F catalyst or pre-fluorinated Pt-Cl catalyst.

[0097] Table 5 below presents data related to crush strength for each of the Pt-Cl-F catalyst on F-CEB, the Pt-Cl-F catalyst on CEB, and the Pt-Cl catalyst on F-CEB.

[0098] The average crush strength for each catalyst was obtained by i) obtaining two samples of each catalyst, each sample containing 50 catalyst pellets, ii) measuring the individual crush strength of each catalyst pellet in accordance with ASTM D4179, excluding the drying stage, required by ASTM D4179 was carried out at 538°C instead of 400°C, iii) calculating the sample crushing strength as the average crushing strength of individual granules for each sample, and iii) calculating the average crushing strength for each catalyst as the average crushing strength of two samples. In Table 5, the crushing strength value indicated for each of “Sample A”, “Sample B”, “Sample C”, “Sample D”, “Sample E” and “Sample F” represents the crushing strength of the sample or the average crush strength value of individual granules for each of samples A-F. Crushing strength values presented as “avg. AB", "avg. CD" and "medium. EF" represent the average crush strength or the average crush strength of two corresponding samples (ie AB, CD or EF) for each catalyst.

[0099] "Length crush strength" was determined by i) measuring the length of each granule before measuring its individual crush strength as described above, ii) dividing the individual crush strength measured for each granule in accordance with ASTM D4179 by the measured length, to obtain the individual granule lengthwise crushing strength for each granule, iii) calculating the lengthwise crushing strength of the sample as the average of the individual granule lengthwise crushing strengths for each sample, and iv) calculating the lengthwise average crushing strength for each catalyst as the average lengthwise crush strength for two samples of each catalyst. In Table 5, the lengthwise crushing strength value listed for each of “Sample A”, “Sample B”, “Sample C”, “Sample D”, “Sample E” and “Sample F” represents the crushing strength of the sample along the length or the average crush strength of individual granules along the length for each of samples A-F. Length crushing strength values presented as “avg. AB", "avg. CD" and "medium. EF" represent the average lengthwise crush strength or the average lengthwise crush strength of two corresponding samples (ie AB, CD or EF) for each catalyst.

[00100] Table 5 also shows the "<10 lb crush strength" for "Sample A", "Sample B", "Sample C", "Sample D", "Sample E" and "Sample F", which represents % number of 50 beads in each sample of each catalyst that had a crush strength of less than 10 lbs. “<10 lb crush strength” values reported as “avg. AB", "avg. CD" and "medium. EF" represent the average "<10 lb crush strength" of the two corresponding samples for each catalyst.

[00101] Also in Table 5, "<9 lb crush" for "Sample A", "Sample B", "Sample C", "Sample D", "Sample E" and "Sample F" is the % amount of 50 pellets in each sample of each catalyst that had a crush strength of less than 9 lbs. "Crush Strength<9 lb" values reported as "Avg. AB", "avg. CD" and "medium. EF" represent the average "<9 lb crush strength" of the two corresponding samples for each catalyst.

[00102] As can be seen, the average crush strength and crush strength of each sample for the Pt-Cl-F catalyst on F-SEB is higher than the corresponding crush strength values of the Pt-Cl-F catalyst on SEB and the Pt-Cl catalyst on F -CEB. The average lengthwise crushing strength and lengthwise crushing strength of the sample for the Pt-Cl-F catalyst on F-SEB are also higher than the corresponding values for the lengthwise crushing strength of the Pt-Cl-F catalyst on SEB and the Pt-Cl catalyst on F -SEV. The Pt-Cl-F catalyst on F-CEB had fewer granules with crush strengths <10 lb and <9 lb compared to the Pt-Cl-F catalyst on CEB and the Pt-Cl catalyst on F-CEB.

[00103] It is believed that the higher crush strength, as well as the lower % of granules having a crush strength of less than 10 lbs and 9 lbs, indicate that the Pt-Cl-F catalyst on F-CEB will produce fewer catalyst fines particles when moving catalyst particles (e.g. loading and unloading catalyst), and thus the severity of problems associated with fine particles will be reduced compared to the amount of fine particles that would be generated when using a Pt-Cl-F catalyst on SEB and Pt-Cl catalyst on F-CEB.

ADDITIONAL DESCRIPTION

[00104] The following is provided as further description of combinations of features and aspects of the present invention.

[00105] The first aspect, which is a method of producing a bonded zeolite support, comprising contacting zeolite powder with a binder and water to form a paste; shaping the paste into a wet extruded base; removing excess water from the wet extruded base to form an extruded base; contacting the extruded base with a fluorine-containing compound to form a fluorinated extruded base; calcining the extruded base to form a calcined fluorinated extruded base; washing the calcined fluorinated extruded base to form a washed calcined fluorinated extruded base; drying the washed calcined fluorinated extruded base to form a dried washed calcined fluorinated extruded base; and calcining the dried, washed, calcined fluorinated extruded base to form a bonded zeolite support.

[00106] The second aspect, which is a method of producing a bonded zeolite support, comprising contacting zeolite powder with a binder and water to form a paste; shaping the paste into a wet extruded base; removing excess water from the wet extruded base to form an extruded base; calcining the extruded base to form a calcined extruded base; bringing the calcined extruded base into contact with a fluorine-containing compound to form a fluorinated calcined extruded base; washing the fluorinated calcined extruded base to form a washed fluorinated calcined extruded base; drying the washed fluorinated calcined extruded base to form a dried washed fluorinated calcined extruded base; and calcining the dried washed fluorinated calcined extruded base to form a bonded zeolite support.

[00107] The third aspect, which is a method of producing a bonded zeolite support, comprising contacting zeolite powder with a binder and water to form a paste; giving the paste the shape of an extruded base; calcining the extruded base to form a calcined extruded base; bringing the calcined extruded base into contact with a fluorine-containing compound to form a fluorinated calcined extruded base; washing the fluorinated calcined extruded base to form a washed fluorinated calcined extruded base; drying the washed fluorinated calcined extruded base to form a dried washed fluorinated calcined extruded base; and calcining the dried washed fluorinated calcined extruded base to form a bonded zeolite support.

[00108] The fourth aspect, which is the method of any preceding aspect, wherein the fluorine-containing compound is in a gas phase.

[00109] The fifth aspect, which is a method according to any preceding aspect, in which the binder contains synthetic or naturally occurring zeolites, alumina, silica, clays, refractory metal oxides of groups IVA and IVB of the periodic table of elements; oxides of silicon, titanium, zirconium; or combinations thereof.

[00110] The sixth aspect, which is the method of any preceding aspect, wherein the bonded zeolite support has a zeolite to binder weight ratio ranging from about 90:10 to about 70:30.

[00111] The seventh aspect, which is a method according to any preceding aspect, wherein the zeolite includes a large pore zeolite.

[00112] The eighth aspect, which is the method of any preceding aspect, wherein the zeolite includes a KL zeolite.

[00113] The ninth aspect, which is the method of any preceding aspect, wherein the fluorine-containing compound is an organic ammonium halide compound represented by the general formula N(R) ₄ F, wherein R represents hydrogen or a substituted or unsubstituted carbon chain molecule having from 1 to 20 carbon atoms, and each R may be the same or different.

[00114] The tenth aspect, which is the method of any preceding aspect, wherein R is methyl, ethyl, propyl, butyl, or combinations thereof.

[00115] The eleventh aspect, which is a method according to any preceding aspect, wherein the fluorine-containing compound contains ammonium fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride, methyltriethylammonium fluoride, or combinations thereof.

[00116] The twelfth aspect, which is the method of any preceding aspect, wherein the bonded zeolite support contains fluoride present in an amount of about 0.1 wt. % to about 5 wt. % based on X-ray fluorescence.

[00117] A thirteenth aspect comprising contacting the bonded zeolite support of any preceding aspect with a Group VIII metal and at least one chlorine-containing compound to form an aromatization catalyst.

[00118] The fourteenth aspect, which is the method of the thirteenth aspect, wherein the Group VIII metal includes platinum.

[00119] The fifteenth aspect, which is a method according to any of the fourteenth to fifteenth aspects, in which the chlorine-containing compound is an organic ammonium halide compound represented by the general formula N(R) ₄ Cl, where R represents hydrogen or a substituted or unsubstituted carbon molecule chain containing from 1 to 20 carbon atoms, and each R may be the same or different.

[00120] The sixteenth aspect, which is a catalytic reforming process for converting hydrocarbons to aromatic compounds, comprising contacting the aromatization catalyst of any preceding aspect with a hydrocarbon feedstock in a reaction zone under reforming conditions and recovering aromatic compounds from the reaction zone.

[00121] The seventeenth aspect, which is the catalytic reforming process of the sixteenth aspect, wherein the hydrocarbon feedstock contains less than 100 ppb sulfur.

[00122] The eighteenth aspect, which is the catalytic reforming process of any one of the sixteenth to seventeenth aspects, wherein the aromatization catalyst has a selectivity of from about 20% to 100%, as determined by C5 ⁺ yield in weight percent.

[00123] The nineteenth aspect, which is a catalyst comprising: a zeolite support; Group VIII metal on zeolite support; and at least two halides bonded to a zeolite support, a Group VIII metal, or both, wherein the average crush strength of the catalyst is greater than 11.25 pounds based on at least two catalyst pellet samples measured in accordance with ASTM D4179.

[00124] The twentieth aspect, which is the catalyst of the nineteenth aspect, wherein each of the at least two bead samples has 50 beads.

[00125] The twenty-first aspect, which is the catalyst of any of the nineteenth and twentieth aspects, wherein the average crush strength is greater than 12 pounds based on at least two catalyst pellet samples measured in accordance with ASTM D4179.

[00126] The twenty-second aspect, which is the catalyst of any of the nineteenth to twenty-first aspects, wherein the average crush strength along the length of the catalyst is greater than about 2.48 lb/mm.

[00127] The twenty-third aspect, which is the catalyst of any of the nineteenth to twenty-second aspects, wherein the average crush strength along the length of the catalyst is in the range of about 3.00 lb/mm to about 3.10 lb/mm.

[00128] The twenty-fourth aspect, which is the catalyst of any of the nineteenth through twenty-third aspects, wherein less than 22% of the pellets, measured in accordance with ASTM D4179, have an individual pellet crush strength of less than 10 lbs/pellet.

[00129] The twenty-fifth aspect, which is the catalyst of any of the nineteenth through twenty-fourth aspects, wherein less than 21% of the pellets, measured in accordance with ASTM D4179, have an individual pellet crush strength of less than 10 lbs/pellet.

[00130] The twenty-sixth aspect, which is the catalyst of any of the nineteenth through twenty-fifth aspects, wherein less than 14% of the pellets, measured in accordance with ASTM D4179, have an individual pellet crush strength of less than 9 lbs/pellet.

[00131] The twenty-seventh aspect, which is the catalyst of any of the nineteenth through twenty-sixth aspects, wherein less than 13% of the pellets, measured in accordance with ASTM D4179, have an individual pellet crush strength of less than 9 lbs/pellet.

[00132] A twenty-eighth aspect, which is a catalyst according to any one of the nineteenth to twenty-seventh aspects, wherein the zeolite support contains a KL zeolite.

[00133] The twenty-ninth aspect, which is a catalyst according to any of the nineteenth to twenty-eighth aspects, in which the zeolite support further contains a binder, and the binder contains synthetic zeolites or zeolites of natural origin, aluminum oxide, silicon dioxide, clays, refractory oxides of metal groups IVA and IVB of the Periodic Table of Elements; oxides of silicon, titanium, zirconium; or combinations thereof.

[00134] A thirtieth aspect, which is a catalyst according to any of the nineteenth to twenty-ninth aspects, wherein the Group VIII metal is Pt.

[00135] The thirty-first aspect, which is a catalyst according to any of the nineteenth to thirtieth aspects, wherein at least two halides contain fluoride and chloride.

[00136] Thirty-second aspect, which is a method of producing a catalyst, comprising calcining an extruded base to form a calcined extruded base, wherein the extruded base contains a KL zeolite, contacting the calcined extruded base with a first fluorine-containing compound to form a fluorinated calcined extruded base, washing fluorinated calcined extruded base to form a washed fluorinated calcined extruded base, drying the washed fluorinated calcined extruded base to form a dried washed fluorinated calcined extruded base, calcining the dried washed fluorinated calcined extruded base to form a bonded zeolite support, and contacting the bonded zeolite support with a Group VIII metal and a second fluorine-containing compound, wherein the first fluorine-containing compound and the second fluorine-containing compound may be the same or different.

[00137] The thirty-third aspect, which is the method of the thirty-second aspect, further comprising contacting a bonded zeolite support with a chlorine-containing compound.

[00138] The thirty-fourth aspect, which is the method of the thirty-third aspect, wherein the bound zeolite support is contacted with a chlorine-containing compound, while the bound zeolite support is brought into contact with a Group VIII metal and a second fluorine-containing compound.

[00139] The thirty-fifth aspect, which is the method of the thirty-third or thirty-fourth aspects, wherein the chlorine-containing compound is an organic ammonium halide compound represented by the general formula N(R) ₄ Cl, wherein R represents hydrogen or a substituted or unsubstituted molecule carbon chain containing from 1 to 20 carbon atoms, and each R may be the same or different.

[00140] The thirty-sixth aspect, which is the method of any of the thirty-second to thirty-fifth aspects, wherein the first fluorine-containing compound and the second fluorine-containing compound are independently selected from tetramethylammonium fluoride (TMAF) and ammonium fluoride (NH ₄ F).

[00141] The thirty-seventh aspect, which is the method of any of the thirty-second to thirty-sixth aspects, wherein the Group VIII metal is Pt.

[00142] The thirty-eighth aspect, which is a method according to any of the thirty-second through thirty-seventh aspects, further comprising, after contacting the bound zeolite support with the Group VIII metal and the second fluorine-containing compound, drying and subsequently calcining the bound zeolite support to form a catalyst.

[00143] While aspects of the present invention have been shown and described, modifications thereto may be made by one skilled in the art without departing from the spirit and teachings of the present invention. The aspects described herein are illustrative only and are not intended to be limiting. Many variations and modifications of the present invention are possible and fall within the scope of the present invention. The use of the term “optional” in relation to any element of a claim means that the object element is required or, alternatively, not required. Both embodiments are intended to be within the scope of the claims. It should be understood that the use of broader terms such as “comprises”, “includes”, “having”, etc. provides support for narrower terms such as “consisting of”, “consisting essentially of”, “consisting mostly from."

[00144] Accordingly, the scope of protection is not limited to the description set forth above, but is limited only by the following claims, which scope includes all equivalents of the subject matter of the claims. Each claim is incorporated herein as an aspect of the present invention. Thus, the claims provide further description and are in addition to the preferred aspects of the present invention. A discussion of a reference in the Background section is not an admission that it is prior art to the present invention, especially any reference that may have a publication date after the priority date of this application. The descriptions of all patents, patent applications and publications set forth herein are hereby incorporated by reference to the extent that they provide illustrative, procedural or other details in addition to those set forth herein.

[00145] For purposes of any U.S. national stage filing of this application, all publications and patents mentioned herein are incorporated herein by reference in their entirety for the purpose of describing and disclosing the designs and methodologies described in these publications that may be used in connection with the methods of the present invention. Any publications and patents discussed above and throughout the text are provided solely for the purpose of disclosure prior to the filing date of this application. Nothing herein should be construed as an admission that the inventors are not entitled to postdate such description by virtue of an earlier invention.

[00146] Unless otherwise indicated, when a range of any type is described or claimed, each possible number that could reasonably be covered by such range, including any subranges covered therein, is intended to be disclosed or stated separately. When describing a measurement range, each possible number that could reasonably cover such a range could, for example, refer to values within the specified range with one significant digit in excess of what is present at the end points of the range. In addition, when a range of values is described or claimed and Applicants intend to display separately each possible number that could reasonably encompass such range, Applicants also provide that the description of the range will reflect all possible sub-ranges and combinations of sub-ranges included therein and will be interchangeable with their description. Accordingly, applicants reserve the right to reserve or exclude any individual elements of any such group, including any subranges or combinations of subranges within a group, if for any reason applicants decide to claim less than the full scope of the present invention.

Claims (32)

1. An aromatization catalyst containing: a zeolite support, the zeolite support comprising a KL zeolite which is associated with silica and fluorine derived from the first fluorine-containing compound; platinum deposited on a zeolite substrate; chlorine deposited on a zeolite support; And fluorine derived from the second fluorine-containing compound supported on a zeolite support. 2. The catalyst of claim 1, wherein the average crush strength of the catalyst is greater than 12 pounds based on at least two catalyst pellet samples. 3. The catalyst according to claim 2, wherein each of the at least two granule samples has 50 granules. 4. The catalyst of claim 1 or 2, wherein the average crush strength along the length of the catalyst is greater than about 2.48 lb/mm. 5. The catalyst of claim 4, wherein the average crush strength along the length of the catalyst ranges from about 3.00 lb/mm to about 3.10 lb/mm. 6. The catalyst of claim 2, wherein less than 22% of the pellets have an individual pellet crush strength of less than 10 lbs/pellet. 7. The catalyst of claim 6, wherein less than 21% of the pellets have an individual pellet crush strength of less than 10 lbs/pellet. 8. The catalyst of claim 2, wherein less than 14% of the pellets have an individual pellet crush strength of less than 9 lbs/pellet. 9. The catalyst of claim 8, wherein less than 13% of the pellets have an individual pellet crush strength of less than 9 lbs/pellet. 10. The catalyst of claim 4, wherein less than 22% of the pellets have an individual pellet crush strength of less than 10 lbs/pellet. 11. The catalyst of claim 5, wherein less than 21% of the pellets have an individual pellet crush strength of less than 10 lbs/pellet. 12. The catalyst of claim 4, wherein less than 14% of the pellets have an individual pellet crush strength of less than 9 lbs/pellet. 13. The catalyst of claim 5, wherein less than 13% of the pellets have an individual pellet crush strength of less than 9 lbs/pellet. 14. The catalyst of claim 10, wherein less than 14% of the pellets have an individual pellet crush strength of less than 9 lbs/pellet. 15. The catalyst of claim 11, wherein less than 13% of the pellets have an individual pellet crush strength of less than 9 lbs/pellet. 16. The catalyst of claim 1, wherein the fluorine derived from the second fluorine-containing compound is brought into contact with the zeolite support following the fluorine derived from the first fluorine-containing compound being brought into contact with the zeolite support. 17. A method for producing a catalyst, including: calcining the extruded base to form a calcined extruded base, wherein the extruded base contains KL zeolite and a silica binder; contacting the calcined extruded base with a first fluorine-containing compound to form a fluorinated calcined extruded base; washing the fluorinated calcined extruded base to form a washed fluorinated calcined extruded base; drying the washed fluorinated calcined extruded base to form a dried washed fluorinated calcined extruded base; calcining the dried washed fluorinated calcined extruded base to form a bonded zeolite support; And contacting a bonded zeolite support with a platinum-containing compound, a chlorine-containing compound, and a second fluorine-containing compound, wherein the first fluorine-containing compound and the second fluorine-containing compound may be the same or different, wherein the average crush strength of the resulting catalyst is greater than 12 pounds based on at least two samples of catalyst granules. 18. The method of claim 17, wherein the bound zeolite support is brought into contact with the chlorine-containing compound at the same time as the bound zeolite support is brought into contact with the Group VIII metal and the second fluorine-containing compound. 19. The method of claim 18, wherein the chlorine-containing compound is an organic ammonium halide compound represented by the general formula N(R)4Cl, wherein R represents hydrogen or a substituted or unsubstituted carbon chain molecule having from 1 to 20 carbon atoms, and and each R can be the same or different. 20. The method of claim 17, wherein the first fluorine-containing compound and the second fluorine-containing compound are independently selected from tetramethylammonium fluoride (TMAF) and ammonium fluoride (NH4F). 21. The method according to claim 17, additionally including: drying and then calcining the bound zeolite support to obtain a catalyst after contacting the bound zeolite support with the platinum-containing compound and the second fluorine-containing compound.