Improvement in aromatization catalyst activity and selectivity with alcohol addition during catalyst preparation

Abstract

Methods of preparing supported catalysts containing a transition metal and a bound zeolite substrate are disclosed. These methods employ the steps of impregnating the bound zeolite substrate with a transition metal precursor, a chlorine precursor, and a fluorine precursor in a solvent composition containing water and from about 5 wt % to about 50 wt % of a C1 to C3 alcohol compound. The resulting supported catalyst has improved catalyst activity and selectivity, as well as lower fouling rates in aromatization reactions.

Description

[0001] This application was filed as a PCT international patent application on July 15, 2021 and claims priority and benefits to U.S. Provisional Patent Application No. 63 / 053,006 filed on July 17, 2020, the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0002] The present disclosure relates to methods for preparing supported catalysts, and more particularly to preparing supported aromatization catalysts containing a transition metal and a bound zeolite matrix using a catalyst impregnation step in which a water / alcohol mixture is used. Background Art

[0003] The catalytic conversion of non-aromatic hydrocarbons into aromatic compounds, commonly referred to as aromatization or reforming, is an important industrial process that can be used to produce benzene, toluene, xylenes, etc. The aromatization or reforming process is usually carried out in a reactor system, which may include one or more reactors containing transition metal-based catalysts. These catalysts can increase the selectivity and / or yield of the desired aromatic compounds. These catalysts also slowly lose their activity over time, which is usually indicated by a loss of selectivity and / or a decrease in conversion of the desired aromatic compounds.

[0004] It would be beneficial to have an improved aromatization catalyst that provides high catalyst activity and selectivity, low fouling rates, and stability in long term production runs. Accordingly, the present disclosure is primarily directed to these objects. Summary of the invention

[0005] Disclosed herein are methods for preparing supported catalysts. Such methods may include (a) preparing a supported catalyst in a mixture containing water and about 5 wt % to about 50 wt % C 1 To C 3 The invention relates to a method for preparing a supported catalyst, wherein the supported catalyst comprises: (a) impregnating a bound zeolite substrate with a transition metal precursor, a chlorine precursor, and a fluorine precursor in any order in a solvent composition of an alcohol compound to form an impregnated zeolite substrate, and (b) drying and then calcining the impregnated zeolite substrate to prepare the supported catalyst. Typically, the supported catalyst may comprise from about 0.1 wt % to about 10 wt % of a transition metal, from about 0.1 wt % to about 5 wt % of chlorine, and from about 0.1 wt % to about 5 wt % of fluorine, based on the total weight of the supported catalyst.

[0006] The supported catalyst prepared by the method provided herein can be used in an aromatization process to prepare aromatic compounds from non-aromatic hydrocarbons. Such catalysts can have an unexpected combination of increased catalyst activity and reduced fouling rate while maintaining excellent selectivity (e.g., to benzene and toluene).

[0007] The foregoing summary of the invention and the following detailed description all provide examples and are illustrative only. Therefore, the foregoing summary of the invention and the following detailed description should not be considered restrictive. In addition, in addition to the features or variations listed herein, other features or variations may also be provided. For example, some aspects may be directed to various feature combinations and sub-combinations described in the detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1 A graph of the yield regulation temperature versus reaction time for the supported catalyst of Example 1 is shown.

[0009] Figure 2 A graph of molar aromatics selectivity versus reaction time for the supported catalyst of Example 1 is shown.

[0010] Figure 3 A graph of the yield regulation temperature versus reaction time for the supported catalyst of Example 2 is shown.

[0011] Figure 4 A graph of molar aromatics selectivity versus reaction time for the supported catalyst of Example 2 is shown.

[0012] Figure 5 A graph of the yield regulation temperature versus reaction time for the supported catalyst of Example 3 is shown.

[0013] Figure 6 A graph of molar aromatics selectivity versus reaction time for the supported catalyst of Example 3 is shown.

[0014] Figure 7 A graph of the yield regulation temperature versus reaction time for the supported catalyst of Example 3 is shown.

[0015] Figure 8 A graph of molar aromatics selectivity versus reaction time for the supported catalyst of Example 3 is shown.

[0016] Fig. 9 A graph of the yield regulation temperature versus reaction time for the supported catalyst of Example 4 is shown.

[0017] Fig.10 A graph of molar aromatics selectivity versus reaction time for the supported catalyst of Example 4 is shown.

[0018] Fig.11 A graph of the yield regulation temperature versus reaction time for the supported catalyst of Example 5 is shown.

[0019] Fig.12 A graph of molar aromatics selectivity versus reaction time for the supported catalyst of Example 5 is shown.

[0020] Fig.13A graph of the yield adjustment temperature versus reaction time for the supported catalyst of Example 6 is shown.

[0021] Fig.14 A graph of molar aromatics selectivity versus reaction time for the supported catalyst of Example 6 is shown.

[0022] Fig.15 A graph of the yield adjustment temperature versus reaction time for the supported catalyst of Example 7 is shown.

[0023] Fig.16 A graph of the hydrogen / hydrocarbon (methane) ratio versus time for the supported catalyst of Example 7 is shown.

[0024] Fig.17 A graph of the yield adjustment temperature versus reaction time for the supported catalyst of Example 8 is shown.

[0025] Fig.18 A graph showing the molar benzene + toluene selectivity for the supported catalyst of Example 8 is shown.

[0026] Fig.19 A graph of percent drying versus drying time for the supported catalyst of Example 9 is shown.

[0027] Fig. 20 A graph of percent drying versus drying time for the supported catalyst of Example 11 is shown.

[0028] Fig.21 A graph of the yield adjustment temperature versus reaction time for the supported catalyst of Example 11 is shown.

[0029] Fig. 22 A graph of the yield adjustment temperature versus reaction time for the supported catalyst of Example 12 is shown.

[0030] definition

[0031] In order to more clearly define the terms used herein, the following definitions are provided. Unless otherwise indicated, the following definitions apply to the present disclosure. If a term is used in the present disclosure but is not specifically defined in this article, the definition in the 2nd edition (1997) of IUPAC Compendium of Chemical Terminology can be applied, as long as the definition does not conflict with any other disclosure or definition used herein, or any claim applying the definition is unclear or invalid. If any definition or usage provided by any file incorporated herein by reference conflicts with the definition or usage provided herein, then the definition or usage provided herein shall prevail.

[0032] Herein, features of the subject matter are described such that within a particular aspect, combinations of different features are contemplated. For each aspect and each feature disclosed herein, all combinations that do not adversely affect the designs, compositions, processes, or methods described herein are contemplated with or without explicit description of a particular combination. In addition, unless expressly stated otherwise, any aspect or feature disclosed herein may be combined to describe a design, composition, process, or method of the invention consistent with the present disclosure.

[0033] In the present disclosure, although compositions and methods are often described as "comprising" various components or steps, unless otherwise specified, the compositions and methods may also "consist essentially of" or "consist of" the various components or steps.

[0034] The terms "a", "an" and "the" are intended to include plural alternatives, such as at least one. For example, unless otherwise specified, disclosure of "a transition metal" or "a chlorine precursor" is meant to encompass mixtures or combinations of one or more than one of the transition metals or chlorine precursors.

[0035] Generally, element groups are referred to using the numbering scheme indicated in the version of the periodic table published in Chemical and Engineering News, 63(5), 27, 1985. In some cases, element groups may be referred to using the common name assigned to the group; for example, alkali metals refer to Group 1 elements, transition metals refer to Groups 3-12 elements, and halogens or halide ions refer to Group 17 elements.

[0036] For any particular compound or group disclosed herein, unless otherwise indicated, any name or structure (general or specific) presented is intended to encompass all conformational isomers, positional isomers, stereoisomers, and mixtures thereof that may result from a particular set of substituents. Unless otherwise indicated, the name or structure (general or specific) also includes all enantiomers, diastereomers, and other optical isomers, if any, in both enantiomeric and racemic forms, as well as mixtures of stereoisomers, as known to those skilled in the art. For example, a general reference to hexane includes n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, and 2,3-dimethylbutane; and a general reference to butyl includes n-butyl, sec-butyl, isobutyl, and tert-butyl.

[0037] On the one hand, a chemical "group" can be defined or described according to how the group is formally derived from a reference or "parent" compound, for example, by the number of hydrogen atoms removed from the parent compound to produce the group, even if the group is not literally synthesized in this way. These groups can be used as substituents or coordinated or bonded to metal atoms. For example, an "alkyl group" can be obtained by removing a hydrogen atom from an alkane. The disclosure that a substituent, a ligand or other chemical part can constitute a specific "group" means that when the group is used as described, well-known chemical structures and bonding rules are followed. When a group is described as "derived from", "derived from...", "formed from" or "formed from...", these terms are used in a formal sense and are not intended to reflect any specific synthesis method or procedure, unless otherwise specified or the context requires otherwise.

[0038] Various numerical ranges are disclosed herein.When any type of scope is disclosed or claimed herein, it is intended to disclose or claim each possible numeral that such scope can reasonably cover separately, including the endpoint of the scope and any sub-range and the combination of sub-ranges covered therein, unless otherwise specified.As a representative example, the application discloses the gross weight based on supported catalyst, and supported catalyst can contain about 1.8 weight % to about 3.2 weight % of chlorine in some aspects.The chlorine content of supported catalyst disclosed can be in the range of about 1.8 weight % to about 3.2 weight %, it is intended to state that chlorine content can be any amount in the range, and for example can be equal to about 1.8 weight %, about 2 weight %, about 2.2 weight %, about 2.4 weight %, about 2.6 weight %, about 2.8 weight %, about 3 weight % or about 3.2 weight %.In addition, chlorine content can be in any range of about 1.8 weight % to about 3.2 weight % (for example, chlorine content can be in the range of about 2 weight % to about 3 weight %), and this is also included in any combination of the scope between about 1.8 weight % and about 3.2 weight %. Further, in all cases, if "about" a particular value is disclosed, the value itself is disclosed. Thus, a disclosure that the chlorine content can be from about 1.8 wt % to about 3.2 wt % also discloses a chlorine content within the range of 1.8 wt % to 3.2 wt % (e.g., 2 wt % to 3 wt %), and this also includes any combination of ranges between 1.8 wt % and 3.2 wt %. Likewise, all other ranges disclosed herein should be interpreted in a manner similar to this example.

[0039] The term "about" means that the amount, size, formula, parameter and other quantities and characteristics are not and need not be exact, but may be approximate, including larger or smaller as needed, reflecting tolerances, conversion factors, rounding, measurement errors, etc., and other factors known to those skilled in the art. In general, whether or not explicitly stated as "about" or "approximately", the amount, size, formula, parameter or other quantity or characteristic is "about" or "approximately". The term "about" also encompasses amounts that vary due to different equilibrium conditions of the composition produced by a particular initial mixture. Whether or not modified by the term "about", the claims include equivalents of the stated amounts. The term "about" may mean within 10% of the reported value, preferably within 5% of the reported value.

[0040] 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 (e.g., a halogenated hydrocarbon indicates the presence of one or more halogen atoms replacing an equal number of hydrogen atoms in the hydrocarbon).

[0041] An "aromatic" compound is a compound containing a cyclic conjugated double bond system that follows the Hückel (4n+2) rule and contains (4n+2) π electrons, where n is an integer from 1 to 5. Aromatic compounds include "arenes" (hydrocarbon aromatic compounds such as benzene, toluene and xylene) and "heteroarene" (heteroaromatic compounds formally derived from arenes by replacing one or more methine (-C=) carbon atoms in the cyclic conjugated double bond system with trivalent or divalent heteroatoms, in such a way that the continuous π electron system characteristic of the aromatic system and the number of out-of-plane π electrons corresponding to the Hückel rule (4n+2) are maintained). As disclosed herein, unless otherwise indicated, the term "substituted" may be used to describe an aromatic group, arene or heteroarene, in which a non-hydrogen moiety formally replaces a hydrogen atom in the compound, and is intended to be non-limiting.

[0042] 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) in the alkane (e.g., a haloalkane indicates the presence of one or more halogen atoms that replace an equal number of hydrogen atoms in the alkane). The term "alkyl group" is used herein according to the definition specified by IUPAC: a monovalent group formed by removing one hydrogen atom from an alkane. Unless otherwise specified, an alkane or alkyl group may be straight or branched.

[0043] A "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) in the cycloalkane (e.g., a halocycloalkane indicates the presence of one or more halogen atoms replacing an equal number of hydrogen atoms in the cycloalkane).

[0044] As used herein, the terms "convertible hydrocarbons", "convertible C 6 species" or "convertible C 7 "Species" refers to hydrocarbon compounds that readily react to form aromatic hydrocarbons under aromatization process conditions. "Non-convertible hydrocarbons" are highly branched hydrocarbons that do not readily react to form aromatic hydrocarbons under aromatization process conditions. "Non-convertible hydrocarbons" may include highly branched hydrocarbons having six or seven carbon atoms and internal quaternary carbons, or hydrocarbons having six carbon atoms and two adjacent internal tertiary carbons, or mixtures thereof. "Convertible C 6 "Species" are hydrocarbons containing six carbons without an internal quaternary carbon or two adjacent internal tertiary carbons, such as n-hexane, 2-methylpentane, 3-methylpentane, cyclohexane, and methylcyclopentane. "Convertible C 7 "Species" are hydrocarbons containing seven carbons without internal quaternary carbons, such as n-heptane, 2-methylhexane, 3-methylhexane, 2,3-dimethylpentane, 2,4-dimethylpentane, methylcyclohexane, and dimethylcyclopentane. Highly branched hydrocarbons with six or seven carbon atoms and internal quaternary carbons may include, for example, 2,2-dimethylbutane, 2,2-dimethylpentane, 3,3-dimethylpentane, and 2,2,3-trimethylbutane. Highly branched hydrocarbons with six carbon atoms and adjacent internal tertiary carbons may include, for example, 2,3-dimethylbutane. Unconvertible highly branched hydrocarbons are not easily converted to aromatic products, but tend to be converted to light hydrocarbons under aromatization process conditions.

[0045] The term "halogen" has its usual meaning. Examples of halogen include fluorine, chlorine, bromine and iodine.

[0046] The molar selectivity is defined as:

[0047] Benzene selectivity:

[0048] Toluene selectivity:

[0049] Benzene + Toluene Selectivity:

[0050] Aromatic Compound Selectivity:

[0051] The conversion is defined as the number of moles of "convertible" hydrocarbon converted per mole of feed:

[0052] C6 conversion rate: C7 conversion rate: C6+C7 conversion rate:

[0053] In these formulas, It indicates the molar flow rate in a continuous reactor or the number of moles in a batch reactor.

[0054] Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, typical methods and materials are described herein.

[0055] All publications and patents mentioned herein are incorporated herein by reference for the purpose of describing and disclosing, for example, the constructs and methodologies that are described in the publications, which might be used in connection with the presently described invention. DETAILED DESCRIPTION

[0056] Disclosed herein is a method for preparing a supported catalyst wherein a transition metal is impregnated onto a bound zeolite substrate using a mixture of water and an alcohol compound. Chlorine and fluorine may be co-impregnated with the transition metal or may be impregnated separately using water alone or a mixture of water and an alcohol compound.

[0057] The impregnation step is conducted for a period of time sufficient to allow for diffusion and deposition of the transition metal and halogen components into the pores of the bound zeolite substrate, followed by drying and calcining of the impregnated zeolite substrate to form the supported catalyst.

[0058] Advantageously, the supported catalysts described herein have unexpectedly improved catalyst activity and selectivity and lower fouling rates due to the use of an alcohol-water mixture during impregnation, compared to conventional aromatization catalysts prepared using only water during impregnation.

[0059] Method for preparing supported catalyst

[0060] Various methods for preparing supported catalysts such as supported aromatization catalysts are disclosed and described. One such method for preparing a supported catalyst may comprise (or consist essentially of or consist of): (a) preparing a supported catalyst in a solution containing water and about 5 wt % to about 50 wt % of C 1 To C 3 The invention relates to a method for preparing a supported catalyst, wherein the supported catalyst comprises: (a) impregnating a bound zeolite substrate with a transition metal precursor, a chlorine precursor, and a fluorine precursor in any order in a solvent composition of an alcohol compound to form an impregnated zeolite substrate, and (b) drying and then calcining the impregnated zeolite substrate to prepare a supported catalyst. The supported catalyst may comprise from about 0.1 wt % to about 10 wt % of a transition metal, from about 0.1 wt % to about 5 wt % of chlorine, and from about 0.1 wt % to about 5 wt % of fluorine, based on the total weight of the supported catalyst.

[0061] In general, features of any of the methods disclosed herein (e.g., bound zeolite matrix, alcohol compound, amount of alcohol compound, transition metal precursor, transition metal and transition metal content, chlorine precursor, chlorine content, fluorine precursor, fluorine content, conditions for performing the impregnation step, and conditions for performing drying and calcining, etc.) are described independently herein, and these features may be combined in any combination to further describe the disclosed methods. In addition, unless otherwise indicated, other process steps may be performed before, during, and / or after any of the steps listed in the disclosed methods. In addition, supported catalysts (such as supported aromatization catalysts) prepared according to any disclosed method / process are within the scope of the present disclosure and are encompassed herein.

[0062] Referring now to step (a) of the method for preparing the supported catalyst (commonly referred to as the impregnation step), a bonded zeolite substrate may be impregnated with a transition metal precursor, a chlorine precursor, and a fluorine precursor in any order in a solvent composition to form an impregnated zeolite substrate. The bonded zeolite substrate in step (a) may be prepared by any technique known to those skilled in the art. For example, a bonded zeolite substrate comprising a zeolite and a binder may be prepared by a method comprising the steps of mixing or combining the zeolite with the binder to form a mixture, then extruding the mixture to form an extrudate, subsequently drying and calcining the extrudate to form a calcined substrate, then washing, drying, and calcining the calcined substrate to form a bonded zeolite substrate.

[0063] The transition metal precursors, chlorine precursors, and fluorine precursors in the impregnation step encompass any compound that can deposit transition metals, chlorine, and / or fluorine in or on the bound zeolite matrix to form an impregnated zeolite matrix. The present specification is meant to encompass (1) compounds that serve as precursors to only one material—for example, ammonium chloride can be a chlorine precursor to chlorine—and (2) compounds that serve as precursors to more than one material—for example, platinum (II) chloride can be a transition metal precursor and a chlorine precursor to platinum and chlorine, while chlorofluorocarbon compounds can be both chlorine precursors and fluorine precursors to chlorine and fluorine.

[0064] Illustrative and non-limiting examples of transition metal precursors suitable for impregnating the bound zeolite matrix with platinum include, but are not limited to, tetraamine platinum (II) chloride, tetraamine platinum (II) nitrate, platinum (II) acetylacetonate, platinum (II) chloride, ammonium tetrachloroplatinate (II), chloroplatinic acid, platinum (II) nitrate, and the like, and mixtures or combinations thereof. Illustrative and non-limiting examples of chlorine precursors include hydrochloric acid, carbon tetrachloride, tetrachloroethylene, chlorobenzene, methyl chloride, methylene chloride, chloroform, allyl chloride, trichloroethylene, chloramine, chlorine oxide, chlorine acid, chlorine dioxide, dichlorine monoxide, dichlorine heptoxide, chloric acid, perchloric acid, ammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, methyltriethylammonium chloride, and the like, and combinations thereof. Illustrative and non-limiting examples of fluorine precursors include hydrofluoric acid, 2,2,2-trifluoroethanol, tetrafluoroethylene, carbon tetrafluoride, carbon trifluoride, fluoromethane, heptafluoropropane, decafluorobutane, hexafluoroisopropanol, tetrafluoropropanol, pentafluoropropanol, hexafluorophenylpropanol, perfluorobutanol, hexafluoro-2-propanol, pentafluoro-1-propanol, tetrafluoro-1-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, ammonium fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride, methyltriethylammonium fluoride, and the like, and combinations thereof.

[0065] Any suitable method or technique known to those skilled in the art that results in a transition metal being fully dispersed on a supported catalyst may be used in the impregnation step. When only water is used as a carrier for the precursor, the method may involve mixing the bonded zeolite matrix with any suitable transition metal precursor, wherein the transition metal precursor is present in an aqueous solution. Similarly, for halogens, the impregnation step may include mixing the bonded zeolite matrix with any suitable chlorine precursor and / or fluorine precursor in any order or sequence. For example, the bonded zeolite matrix may be mixed with a solution of a chlorine precursor, a solution of a fluorine precursor, or a solution of both a chlorine precursor and a fluorine precursor in water. An incipient wetness technique may be used.

[0066] Advantageously, in the disclosed method, a mixture containing water and about 5 wt % to about 50 wt % C 1 To C 3In the solvent composition of alcohol compound (rather than independent water), in any order, the zeolite matrix of bonding is impregnated with transition metal precursor, chlorine precursor and fluorine precursor, to form the zeolite matrix of impregnation. On the one hand, the zeolite matrix of bonding can be impregnated with chlorine precursor and / or fluorine precursor before the transition metal precursor. Any suitable carrier solvent can be used, such as independent water, or with the mixture of water and alcohol compound of any suitable blending ratio. Therefore, on the one hand, the zeolite matrix of bonding can be impregnated with solution containing water and chlorine precursor and / or fluorine precursor, and on the other hand, the zeolite matrix of bonding can be impregnated with solution containing water, alcohol compound and chlorine precursor and / or fluorine precursor.

[0067] In this context, the present invention can be carried out in a mixture containing water and about 5 wt % to about 50 wt % of C 1 To C 3 The bound zeolite substrate is impregnated with a transition metal precursor in a solvent composition containing about 5 wt % to about 50 wt % of a C 1 To C 3 The bound zeolite substrate is impregnated with a transition metal precursor and a chlorine precursor (or a transition metal precursor and a fluorine precursor, or all of the transition metal precursors, chlorine precursors, and fluorine precursors) in a solvent composition containing an alcohol compound. Thus, for example, the bound zeolite substrate can be mixed with a combination of transition metal precursors, chlorine precursors, and fluorine precursors (i.e., all together), such as by mixing the bound zeolite substrate with a solvent composition containing a transition metal precursor, a chlorine precursor, and a fluorine precursor, wherein the solvent composition contains water and from about 5 wt % to about 50 wt % of C 1 To C 3 Alcohol compounds.

[0068] Any suitable amount of the alcohol compound can be used in the solvent composition, and this can vary based on the precursor compound used, solubility considerations, and desired aromatization catalyst performance, among other factors. However, typically, the solvent composition contains from about 5 wt % to about 50 wt % of the alcohol compound, and illustrative and non-limiting ranges may include from about 5 wt % to about 45 wt %, from about 10 wt % to about 40 wt %, from about 10 wt % to about 35 wt %, from about 10 wt % to about 30 wt %, from about 15 wt % to about 50 wt %, or from about 15 wt % to about 35 wt % of the alcohol compound.

[0069] The solvent composition may contain any C 1 To C 3Alcohol compounds, either alone or in combination. The alcohol compound may include methanol, ethanol, n-propanol, isopropanol, or any combination thereof, and thus, the solvent composition may contain methanol; alternatively, ethanol; alternatively, n-propanol; alternatively, isopropanol; alternatively, methanol and ethanol; or alternatively, n-propanol and isopropanol; and the like.

[0070] Referring now to step (b), the impregnated zeolite substrate may be dried and then calcined to produce a supported catalyst.Any suitable temperature, pressure, time period and atmosphere may be used in the drying and calcining steps.

[0071] In one aspect, the drying step may comprise contacting the impregnated zeolite substrate with a drying gas stream comprising (or consisting essentially of or consisting of) an inert gas (e.g., nitrogen), oxygen, air, or any mixture or combination thereof; alternatively, nitrogen; alternatively, helium; alternatively, neon; alternatively, argon; alternatively, oxygen; or alternatively, air. Although not limited thereto, the drying step may generally be performed at a drying temperature in the range of about 30°C to about 200°C; alternatively, about 100°C to about 200°C; alternatively, about 85°C to about 175°C; or alternatively, about 30°C to about 100°C. In these and other aspects, these temperature ranges are also meant to encompass situations in which the drying step is performed at a range of different temperatures falling within the corresponding ranges rather than at a single fixed temperature. In some aspects, the drying step may be performed at atmospheric pressure or at any suitable subatmospheric pressure, such as less than about 150 Torr, less than about 125 Torr, less than about 100 Torr, or less than about 50 Torr.

[0072] The duration of the drying step is not limited to any particular time period. Typically, the drying step can be performed in a time period as short as 30 minutes to as long as 8 hours (or longer), but more typically, the drying step can be performed in a time period ranging from about 1 hour to about 8 hours, for example, from about 1 hour to about 7 hours, from about 1 hour to about 6 hours, from about 2 hours to about 7 hours, or from about 2 hours to about 6 hours.

[0073] The calcining step can be carried out at various temperatures and time periods. Typical peak calcining temperatures generally fall within the range of about 200°C to about 600°C, such as about 200°C to about 500°C, about 230°C to about 450°C, or about 230°C to about 350°C. In these and other aspects, these temperature ranges also mean to cover the situation where the calcining step is carried out at a series of different temperatures (e.g., initial calcining temperature, peak calcining temperature) falling within the corresponding range rather than at a single fixed temperature. For example, the calcining step can start at the same initial temperature as the drying temperature in the drying step. Subsequently, the calcining temperature can be increased to the peak calcining temperature over time, for example, within the range of about 230°C to about 350°C, about 275°C to about 425°C, or about 300°C to about 400°C.

[0074] The duration of the calcining step is not limited to any specific time period. Therefore, the calcining step can be carried out, for example, in a time period as short as 30-45 minutes to as long as 10-12 hours or longer. Suitable calcining time can depend on, for example, the conditions of the initial / peak calcining temperature and the drying step, and other variables. However, usually, the calcining step can be carried out in a time period ranging from about 45 minutes to about 12 hours, for example, from about 1 hour to about 12 hours, from about 1 hour to about 10 hours, from about 1 hour to about 5 hours, or from about 1 hour to about 3 hours.

[0075] The calcining step can be carried out in a calcining gas stream comprising (or consisting essentially of or consisting of) an inert gas (e.g., nitrogen), oxygen, air, or any mixture or combination thereof. In some aspects, the calcining gas stream can comprise air, while in other aspects, the calcining gas stream can comprise a mixture of air and nitrogen. However, in certain aspects, the calcining gas stream can be an inert gas, such as nitrogen and / or argon.

[0076] The method for preparing a supported catalyst disclosed herein may also include a reduction step after step (b), i.e., after drying and calcining the impregnated zeolite substrate to prepare a supported catalyst. The reduction step may include contacting the supported catalyst with a reducing gas stream comprising hydrogen to prepare a reduced (or activated) supported catalyst. Typically, the reducing gas stream comprises molecular hydrogen alone or together with an inert gas such as helium, neon, argon, nitrogen, etc., and this includes a combination of two or more of these inert gases. In some aspects, the reducing gas stream may comprise molecular hydrogen and nitrogen (or substantially consisting of or consisting of). In addition, molecular hydrogen may be the main component (greater than 50mol%) of the reducing gas stream, while in other aspects, molecular hydrogen may be a minor component (between 5-35mol%, or between 1-6mol%). On the other hand, the reducing gas stream may comprise molecular hydrogen and hydrocarbons (or substantially consisting of or consisting of).

[0077] The reduction step can be performed at various temperatures and time periods. For example, the reduction step can be performed at a reduction temperature in the range of about 100°C to about 700°C; alternatively, about 200°C to about 600°C; alternatively, about 200°C to about 575°C; alternatively, about 350°C to about 575°C; alternatively, about 400°C to about 550°C; or alternatively, about 450°C to about 550°C. In these and other aspects, these temperature ranges are also meant to cover situations where the reduction step is performed at a range of different temperatures falling within the corresponding ranges rather than at a single fixed temperature.

[0078] The duration of the reduction step is not limited to any specific time period. Therefore, the reduction step can be carried out, for example, in a time period as short as 1 hour to as long as 48-72 hours or longer. For example, the reduction step can be carried out in a time period ranging from about 1 hour to about 48 hours, from about 3 hours to about 36 hours, from about 5 hours to about 36 hours, from about 2 hours to about 30 hours or from about 10 hours to about 30 hours.

[0079] In one aspect, the reduction step can be performed non-in situ. In this aspect, the supported catalyst is converted to a reduced (or activated) supported catalyst according to the above procedure. The reduction can occur at the catalyst manufacturing site or another site. The reduced (or activated) supported catalyst can then be packaged under air or under an inert gas and then stored before being loaded into the aromatization reactor and used in the aromatization reactor system. Prior to use, a reduction step can be performed to reduce any supported catalyst that was oxidized after the first reduction, such as during storage, transportation, and loading. This second reduction may require the same or less time as the in situ reduction described below.

[0080] In another aspect, the reduction step can be performed in situ. In this aspect, the supported catalyst is packaged after the calcination step. The supported catalyst can be stored for a longer period of time before being loaded into the aromatization reactor. After loading, the supported catalyst is then converted to a reduced (or activated) supported catalyst according to the above procedure.

[0081] It is contemplated that non-alcohol compounds (e.g., ketones) may be present in the solvent composition with water and the alcohol compound, or with water and in place of the alcohol compound. For example, certain ketone compounds may have a carbonyl group similar to C 1 To C 3The property of alcohol compound, and therefore can be used in solvent composition to prepare supported catalyst disclosed herein. Suitable ketone compound can be selected based on miscibility with water and based on volatility. Non-limiting examples can include butanone (methyl ethyl ketone, MEK), pentanone, hexanone etc. Therefore, another method for preparing supported catalyst consistent with the present disclosure can include (a) in a solvent composition containing water and about 5 wt % to about 50 wt % of ketone compound, impregnating the bonded zeolite matrix with transition metal precursor, chlorine precursor and fluorine precursor in any order, to form the impregnated zeolite matrix, and (b) drying, then calcining the impregnated zeolite matrix to prepare supported catalyst. Based on the gross weight of supported catalyst, supported catalyst comprises about 0.1 wt % to about 10 wt % of transition metal, about 0.1 wt % to about 5 wt % of chlorine and about 0.1 wt % to about 5 wt % of fluorine.

[0082] Supported Catalyst

[0083] Consistent with aspects disclosed herein are supported catalysts comprising (or consisting essentially of or consisting of): a bound zeolite matrix, from about 0.1 wt % to about 10 wt % transition metal, from about 0.1 wt % to about 5 wt % chlorine, and from about 0.1 wt % to about 5 wt % fluorine. These weight percentages are based on the total weight of the supported catalyst.

[0084] Referring first to the bound zeolite matrix, any suitable bound zeolite matrix can be used in the methods for preparing the supported catalysts described herein. Generally, the bound zeolite matrix can comprise an inorganic oxide, examples of which can include, but are not limited to, bound medium and / or large pore zeolites (aluminosilicates), amorphous inorganic oxides, and mixtures thereof. Large pore zeolites often have a diameter in the range of about 100 to about 100 mm. to about The average pore diameter of the large pore zeolite is in the range of about 100 to about 100, and non-limiting examples of large pore zeolites include L-zeolite, Y-zeolite, mordenite, ω-zeolite, β-zeolite, etc. Medium pore zeolites often have an average pore diameter in the range of about 100 to about 100, and non-limiting examples of large pore zeolites include L-ze to about The amorphous inorganic oxide may include, but is not limited to, aluminum oxide, silicon oxide, titanium dioxide, and combinations thereof.

[0085] The term "zeolite" generally refers to a specific group of hydrated crystalline metal aluminosilicates. These zeolites exhibit SiO 4 and AlO 4 A network of tetrahedra in which aluminum and silicon atoms are cross-linked in 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 may be equal to 2. The framework exhibits a negative charge, which can usually be balanced by including cations such as metals, alkali metals, and / or hydrogen in the crystal.

[0086] In some aspects, the bound zeolite matrix may include an L-type zeolite. An L-type zeolite support is a subset of zeolite supports that may have a molar ratio of oxides according to the formula: 2 / n OA1 2 O 3 xSiO 2 y 2 O. In the formula, "M" represents exchangeable cation(s), such as barium, calcium, cerium, lithium, magnesium, potassium, sodium, strontium and / or zinc, and non-metallic cations such as hydronium and ammonium, which can be replaced by other exchangeable cations without causing substantial changes in the basic crystal structure of L-type zeolite. In the formula, "n" represents the valence of "M"; "x" is 2 or greater; and "y" is the number of water molecules contained in the channels or interconnected voids of the zeolite.

[0087] In one aspect, the bonded zeolite matrix may include a bonded potassium L-type zeolite, also referred to as K / L-zeolite, while in another aspect, the bonded zeolite matrix may include a barium ion-exchanged L-zeolite. As used herein, the term "K / L-zeolite" refers to an L-type zeolite in which the major cation M incorporated into the zeolite is potassium. The K / L-zeolite may be cation exchanged (e.g., with barium) prior to forming the bonded zeolite matrix to form an exchanged zeolite (e.g., Ba / L-zeolite). The bonded zeolite matrix comprising the L-zeolite may be impregnated with a transition metal and one or more halides to produce a transition metal-impregnated halogenated zeolite or a K / L supported transition metal-halide zeolite catalyst.

[0088] In the bonded zeolite matrix, the zeolite can be bonded to a carrier matrix (or binder), and non-limiting examples of the binder can include, but are not limited to, inorganic solid oxides, clays, etc., and combinations thereof. Any method known in the art can be used to bond the zeolite to a binder or carrier matrix. For example, a bonded zeolite matrix comprising a zeolite and a binder can be prepared by a method comprising the following steps: a zeolite such as K / L-zeolite is mixed with a binder such as silica sol, then the mixture is extruded to form an extrudate, then the extrudate is dried and calcined to form a calcined matrix, then the calcined matrix is ​​washed, dried and calcined to form a bonded zeolite matrix.

[0089] In some aspects, the binder may include alumina, silica, magnesia, boria, titania, zirconia, or mixed oxides thereof (e.g., aluminosilicates), or mixtures thereof, while in other aspects, the binder may include montmorillonite, kaolin, cement, or combinations thereof. In one specific aspect contemplated herein, the binder may include silica, alumina, or mixed oxides thereof; alternatively, silica; alternatively, alumina; or alternatively, silica-alumina. Thus, the bonded zeolite matrix may include a silica-bonded L-zeolite, such as a silica-bonded Ba / L-zeolite, a silica-bonded barium ion-exchanged L-zeolite, or a silica-bonded K / L-zeolite.

[0090] Although not limited thereto, the bonded zeolite substrate (or supported catalyst) contemplated herein may contain from about 3 wt % to about 35 wt % of a binder. For example, the bonded zeolite substrate (or supported catalyst) may contain from about 5 wt % to about 30 wt % or from about 10 wt % to about 30 wt % of a binder. These weight percentages are based on the total weight of the bonded zeolite substrate, or based on the total weight of the supported catalyst, as the context requires.

[0091] Illustrative examples of bound zeolite matrices and their use in supported catalysts are described in U.S. Pat. Nos. 5,196,631, 6,190,539, 6,406,614, 6,518,470, 6,812,180, and 7,153,801, the disclosures of which are incorporated herein by reference in their entireties.

[0092] The supported catalyst may contain from about 0.25 wt % to about 5 wt % of the transition metal. For example, the supported catalyst may contain from about 0.5 wt % to about 3 wt %, from about 0.5 wt % to about 2 wt %, or from about 0.7 wt % to about 1.5 wt % of the transition metal. These weight percentages are based on the total weight of the supported catalyst.

[0093] Non-limiting examples of suitable transition metals may include iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, gold, silver, copper, etc., or a combination of two or more transition metals. In one aspect, the transition metal may include a Group 8-11 transition metal or a Group 8-10 transition metal (one or more), while in another aspect, the transition metal may include platinum (Pt). In yet another aspect, the bonded zeolite substrate is impregnated with only one transition metal, and the transition metal is platinum.

[0094] Where the transition metal comprises platinum, the supported catalyst may comprise from about 0.1 wt % to about 10 wt % platinum; alternatively, from about 0.25 wt % to about 5 wt % platinum; alternatively, from about 0.5 wt % to about 3 wt % platinum; or alternatively, from about 0.7 wt % to about 1.5 wt % platinum. In one specific aspect contemplated herein, the supported catalyst may comprise platinum on a bound K / L-zeolite.

[0095] The supported catalyst described herein may have any suitable chlorine (Cl) loading, based on the gross weight of the supported catalyst, generally in the range of about 0.1 wt % to about 5 wt %. On the one hand, the supported catalyst may include about 0.3 wt % to about 4 wt % chlorine, or about 0.4 wt % to about 3.5 wt % chlorine. On the other hand, the supported catalyst may include about 0.5 wt % to about 3.3 wt % chlorine. On the other hand, the supported catalyst may include about 0.5 wt % to about 1.5 wt % chlorine. On the other hand, the supported catalyst may include about 1.8 wt % to about 3.2 wt % chlorine, or about 2 wt % to about 3 wt % chlorine. The high loading of chlorine in the supported catalyst can provide improved catalyst activity and stability, as well as lower fouling rate.

[0096] The supported catalyst also comprises fluorine (F), which is generally in the range of about 0.1 wt % to about 5 wt %, or about 0.3 wt % to about 4 wt %, based on the total weight of the supported catalyst. For example, the supported catalyst may comprise about 0.4 wt % to about 3 wt % fluorine, about 0.3 wt % to about 2 wt % fluorine, or about 0.4 wt % to about 1.5 wt % fluorine.

[0097] Although not limited thereto, the supported catalyst may be characterized by a chlorine:fluorine weight ratio that generally falls within the range of about 1:5 to about 8:1, or about 1:5 to about 5:1. In some aspects, the chlorine:fluorine weight ratio may be in the range of about 1:3 to about 3:1, while in other aspects, the weight ratio may be in the range of about 1:2 to about 2:1.

[0098] Likewise, although not limited thereto, supported catalysts may be characterized by a BET surface area typically in the range of about 100 m 2 / g to about 300m 2 / g, such as about 100m 2 / g to about 200m 2 / g, or about 110m 2 / g to about 170m 2The surface area is determined using the Brunauer-Emmett-Teller ("BET") method described in Brunauer, Stephen; Emmett, PH; Teller, Edward (1938), "Adsorption of Gases in Multimolecular Layers," Journal of the American Chemical Society, 60(2):309-319, doi:10.1021 / ja01269a023, which is incorporated herein by reference in its entirety.

[0099] The platinum dispersion of the supported catalyst prepared by the methods disclosed herein can generally be in the range of about 40% to about 80%. In one aspect, for example, the platinum dispersion can be in the range of about 50% to about 80%, while in another aspect, the platinum dispersion can be in the range of about 60% to about 80%, and in yet another aspect, the platinum dispersion can be in the range of about 60% to about 75%.

[0100] Although the supported catalysts prepared by the methods disclosed herein can have improved activity, improved selectivity, and lower fouling rates, unexpectedly, these supported catalysts can have a platinum dispersion that is substantially the same as the platinum dispersion of an otherwise identical catalyst prepared under the same catalyst preparation conditions without the alcohol compound. In these cases, "substantially" the same means within + / - 5% of the platinum dispersion, and more typically, within + / - 3%, or within + / - 1% of the platinum dispersion.

[0101] Importantly, the supported catalysts disclosed herein have improved performance in aromatization reactions. Surprisingly, these supported catalysts have higher catalyst activity and stability, as demonstrated by the T SOR (operation start temperature), T EOR (end of run temperature) and FR (fouling rate) metrics. In general, the supported catalysts described herein can have a lower 40 hour T than an otherwise identical catalyst prepared under the same catalyst preparation conditions without the alcohol compound and evaluated under the same 40 hour aromatization reaction conditions. SOR , lower 40 hours T EOR and / or lower 40 hour FR. Therefore, the comparison is to supported catalysts having the same platinum, fluorine, chlorine and other compositional attributes, and prepared in the same manner (except for the use of an alcohol compound in the impregnation step), and tested under the same 40 hour aromatization reaction conditions (see Examples 1-2 below).

[0102] The supported catalysts of the present invention may be characterized by a 40 hour TSOR (Run Start Temperature), which may generally fall within the range of about 910°F (488°C) to about 925°F (496°C) or about 910°F (488°C) to about 920°F (493°C). Additionally or alternatively, these supported catalysts may be characterized by a 40 hour T as described herein. EOR (End of Run Temperature), which may generally fall within the range of about 910°F (488°C) to about 930°F (499°C) or about 910°F (488°C) to about 925°F (496°C).

[0103] Likewise, these supported catalysts may be characterized by a 40 hour aromatics selectivity (or 40 hour benzene + toluene selectivity) of at least about 92 mol%, and in some cases at least about 93 mol% or at least about 94 mol%. Additionally or alternatively, the supported catalysts of the present invention may have a 40 hour aromatics selectivity (or 40 hour benzene + toluene selectivity) that is substantially the same as or greater than the selectivity of an otherwise identical catalyst prepared under the same catalyst preparation conditions without the alcohol compound and evaluated under the same 40 hour aromatization reaction conditions. In these cases, "substantially" the same means within + / -1 mol%, and more typically, within + / -0.5 mol%.

[0104] The supported catalysts disclosed herein also exhibit improved catalytic performance under test conditions longer than 40 hours, as discussed in more detail in the Examples below. In general, the supported catalysts described herein can have a lower 600 hour T value than an otherwise identical catalyst prepared under the same catalyst preparation conditions without the alcohol compound and evaluated under the same 600 hour aromatization reaction conditions. SOR , lower 600 hours T EOR , lower 600-hour FR and / or higher 600-hour H 2 / CH 4 Therefore, the comparison is to supported catalysts having the same platinum, fluorine, chlorine and other compositional attributes, prepared in the same manner (except for the use of an alcohol compound in the impregnation step), and tested under the same 600 hour aromatization reaction conditions (see Example 7 below).

[0105] These supported catalysts may be characterized by a 600 hour T SOR (Run Start Temperature), which may generally fall within the range of about 930°F (499°C) to about 960°F (516°C) or about 940°F (504°C) to about 955°F (513°C). Additionally or alternatively, these supported catalysts may be characterized by a 600 hour T as described herein. EOR(end of run temperature), which may typically fall within the range of about 930°F (499°C) to about 975°F (524°C) or about 940°F (504°C) to about 965°F (518°C). Additionally or alternatively, these supported catalysts may be characterized by a 600 hour FR (fouling rate) as described herein, which may typically be less than about 0.02°F / hour (0.01°C / hour), or less than about 0.01°F / hour (0.006°C / hour). Additionally or alternatively, these supported catalysts may be characterized by a 600 hour FR (fouling rate) as described herein, which may typically be less than about 0.02°F / hour (0.01°C / hour), or less than about 0.01°F / hour (0.006°C / hour). 2 / CH 4 Yield, which may fall within the range of about 30% to about 47%, or about 35% to about 45%.

[0106] The supported catalysts disclosed herein also exhibit improved catalytic performance under testing conditions longer than 600 hours, as discussed in more detail in the Examples below. In general, the supported catalysts described herein can have a lower 2500 hour T value than otherwise identical catalysts prepared under the same catalyst preparation conditions without the alcohol compound and evaluated under the same 2500 hour aromatization reaction conditions. SOR , lower 2500 hours T EOR and / or higher 2500 hour aromatics selectivity (or 2500 hour benzene+toluene selectivity). Therefore, the comparison is to supported catalysts having the same platinum, fluorine, chlorine and other compositional attributes, and prepared in the same manner (except for the use of an alcohol compound in the impregnation step), and tested under the same 2500 hour aromatization reaction conditions (see Example 8 below).

[0107] Aromatization catalyst reforming process

[0108] Various processes for reforming hydrocarbons are also contemplated herein. One such reforming process may comprise (or consist essentially of or consist of) contacting a hydrocarbon feed with a supported aromatization catalyst under reforming conditions in a reactor system to produce an aromatic product. The supported aromatization catalyst used in the reforming process may be any supported catalyst disclosed herein (e.g., a reduced or activated catalyst) and / or may be prepared by any method for preparing a supported catalyst disclosed herein.

[0109] Reactor systems for reforming and corresponding reforming conditions are well known to those skilled in the art and are described, for example, in U.S. Pat. Nos. 4,456,527, 5,389,235, 5,401,386, 5,401,365, 6,207,042, and 7,932,425, the disclosures of which are incorporated herein by reference in their entireties.

[0110] Likewise, typical hydrocarbon feeds are disclosed in these references. Typically, the hydrocarbon feed may be a naphtha stream or a light naphtha stream. In certain aspects, the hydrocarbon feed may contain non-aromatic hydrocarbons, for example, the hydrocarbon feed may contain C 6 -C 9 Alkanes and / or cycloalkanes, or C 6 -C 8 Alkanes and / or cycloalkanes (e.g., hexane, heptane, cyclohexane), and the like.

[0111] Typically, the hydrocarbon feed can be substantially free of sulfur, nitrogen, metals, and other known reforming catalyst poisons. If present, such poisons can be removed using methods known to those skilled in the art. In some aspects, as known to those skilled in the art, the feed can be purified by first using conventional hydrofining techniques and then using an adsorbent to remove the remaining poisons. Such hydrofining techniques and adsorbents can be part of the improved catalytic reforming process described herein.

[0112] As described herein, and unexpectedly, supported catalysts can have improved catalyst activity and stability, and reduced fouling rates in aromatization or reforming reactions compared to an otherwise identical catalyst prepared without using an alcohol compound during the impregnation step.

[0113] Example

[0114] The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the present invention in any way. Various other aspects, modifications and their equivalents may occur to those of ordinary skill in the art after reading the description herein without departing from the spirit of the present invention or the scope of the appended claims.

[0115] Unless otherwise indicated, the weight percentages of Pt, Cl, and F are determined using X-ray fluorescence (XRF) and are based on the total weight of the aromatization catalyst. The platinum dispersion is determined by CO chemisorption.

[0116] Unless otherwise stated, the following general procedure was used to test the performance of supported catalysts in aromatization reactions. The supported aromatization catalyst was ground and sieved to about 20-40 mesh (US), and 2cc of the sieved supported catalyst was placed in a 3 / 8 inch OD stainless steel reactor vessel in a temperature controlled furnace. After reducing the supported catalyst under flowing molecular hydrogen, the feed stream of aliphatic hydrocarbons and molecular hydrogen was heated at a pressure of 65 psig, a hydrogen: hydrocarbon molar ratio of 2:1, and 6 hr. -1 The aliphatic hydrocarbon feed contained approximately 0.61 mole fraction of convertible C 6 species and 0.21 mole fraction of convertible C 7species. The rest are aromatic compounds, C 8 + and unconvertible hydrocarbons. The reactor temperature was then adjusted to maintain a C of the reactor effluent, as determined by gas chromatography. 5 + A target of 75 wt% or 83.5 wt% aromatics in the fractions was also recorded for the selectivity calculations, as were the amounts of a number of feed and product components, including benzene and toluene present.

[0117] Temperature at the start of operation (T SOR ) and fouling rate (abbreviated as FR in °F / hour) of supported catalyst samples were determined by plotting the temperature (yield-adjusted catalyst temperature) required to maintain a total yield of aromatic compounds (such as benzene and toluene) at 75 wt% or 83.5 wt% over time under the standard test conditions provided above. As used herein, the term "yield-adjusted temperature" refers to the catalyst bed temperature in a laboratory scale reactor system that has been adjusted to account for the increase in the temperature of the reactor effluent when the reactor effluent is at a temperature of 100 °C. 5 + The sample was taken when the fraction was free of 75 wt% or 83.5 wt% aromatic compounds. The adjustment factor (e.g., in °F / wt%) was determined from previous experiments using similar supported catalysts. Linear regression analysis of the temperatures collected between 15 and 40 hours yielded the following formula: T adj =FR*t+T SOR , where T adj is the yield regulation temperature, FR is the fouling rate, t is the time, and T SOR is the run start temperature (the temperature required to achieve 75 wt % or 83.5 wt % aromatics yield at an assumed time zero). The total run time was 40 hours, and the run end temperature (abbreviated as T EOR );T EOR is the temperature required to achieve 75 wt% or 83.5 wt% aromatics yield at the end of a 40 hour run. Initial low conversion and catalyst run-in conditions are temperatures prior to 15 hours not included in T SOR and the main reason in the determination of FR.

[0118] In all examples, a standard bound K / L-zeolite matrix consisting of approximately 17% by weight of silica binder was used as starting material. The bound zeolite matrix was prepared by mixing it with a mixture containing tetraammonium platinum chloride (Pt(NH 3 ) 4 Cl 2 ·xH 2A reference supported catalyst was prepared by impregnating a bound zeolite substrate with approximately 1 wt % Pt, 0.85 wt % Cl, and 0.6 wt % F via the incipient wetness technique in contact with an aqueous solution of 20% tantalum (0), ammonium chloride, and ammonium fluoride (water in the absence of alcohol compounds). The impregnated substrate was then dried at 95° C. and calcined at 575° F. (302° C.) to form a supported catalyst.

[0119] Example 1

[0120] In Example 1, a supported catalyst was prepared with a solvent composition containing 70 wt% water and 30 wt% ethanol. Pt, Cl and F precursors were dissolved in a 70 wt% water and 30 wt% ethanol solution, and a bound K / L-zeolite substrate was impregnated with a 70 wt% water and 30 wt% ethanol solution containing Pt, Cl and F precursors (instead of 100% water as a reference supported catalyst). The K / L-zeolite substrate preparation, incipient wetness technique, drying procedure and calcination conditions were identical for both catalysts. After reduction / activation in hydrogen, the catalysts were compared using the 40 hour test procedure described above.

[0121] Figure 1 The yield-adjusted temperature versus reaction time for each supported catalyst was compared and demonstrated higher activity for the catalyst prepared using ethanol compared to the reference catalyst. Unexpectedly, for the catalyst prepared using the water / ethanol solution, the target aromatic yield of 83.5 wt% was achieved at a lower reaction temperature of approximately 8-10°F (4-6°C). In this 40 hour test, the molar selectivity to aromatics was comparable to slightly better for the catalyst prepared using the water / ethanol solution, as shown in Figure 1. Figure 2 shown.

[0122] Example 2

[0123] In Example 2, supported catalysts were prepared as described in Example 1, except that the catalysts were prepared using no ethanol (reference), 10 wt% ethanol, 20 wt% ethanol, or 30 wt% ethanol. The activity (83.5 wt% aromatics yield) and selectivity to aromatics for each catalyst were determined using the 40 hour test procedure described above. Figure 3 to Figure 4 The results are summarized.

[0124] Advantageously, all levels of ethanol (10 wt % to 30 wt %) improve catalyst activity with comparable selectivity performance. As the amount of ethanol increases, the catalyst activity increases accordingly. However, for these supported catalysts and precursors, the maximum amount of ethanol is limited by the solubility of the precursor to approximately 30 wt % ethanol.

[0125] Example 3

[0126] In Example 3, supported catalysts were prepared as described in Examples 1-2, except that the catalysts were prepared using water (reference), 30 wt% ethanol, 30 wt% isopropanol, 30 wt% n-propanol, 30 wt% methanol, 30 wt% acetone, or 30 wt% n-butanol. The activity and selectivity to aromatics for each catalyst except n-butanol were determined using the 40 hour test procedure described above. Useful catalysts could not be synthesized using n-butanol because it is not fully miscible with water and the salt precursors could not be dissolved for impregnation. Figure 5 to Figure 6 The results summarize an 83.5 wt% aromatics yield, while Figures 7 and 8 Results are summarized for 75 wt% aromatics yield.

[0127] The use of isopropanol and methanol during catalyst preparation resulted in the same surprising catalyst activity enhancement as ethanol, while n-propanol did not increase catalyst activity as much as the other alcohol compounds. Unexpectedly, the use of acetone during catalyst preparation significantly reduced catalyst activity - requiring much higher reaction temperatures to produce the same aromatics yields. Regarding selectivity, aromatics selectivity was generally the same for each catalyst.

[0128] Example 4

[0129] In Example 4, supported catalysts were prepared as described in Examples 1-2, except that the catalysts were prepared with water (reference) or with 30 wt% ethanol, the latter in three batches, which were calcined at 575°F (302°C), 750°F (399°C), and 932°F (500°C). This is despite the fact that higher temperature calcinations generally result in lower initial activity. Fig. 9 This indicates that the supported catalysts prepared at all calcination temperatures show better activities than the reference catalyst. Fig.10 The selectivity data in show that the aromatics selectivities of the corresponding catalysts are comparable.

[0130] Example 5

[0131] In Example 5, a supported catalyst was prepared by first impregnating the halogen (F, Cl) in water. For the reference catalyst, the platinum was impregnated in water, while for the experimental catalyst, the platinum was impregnated in a solvent composition containing 60 wt% water and 40 wt% ethanol. The K / L-zeolite matrix preparation, initial wetness technique, drying procedure, and calcination conditions were identical for both catalysts. After reduction / activation in hydrogen, the catalysts were compared using the 40-hour test procedure described above.

[0132] Fig.11The yield-adjusted temperature versus reaction time for each supported catalyst was compared and demonstrated that the catalyst prepared using 40 wt% ethanol was more active than the reference catalyst. Unexpectedly, for the catalyst prepared using the water / ethanol solution, the target aromatic yield of 75 wt% was achieved at a lower reaction temperature of about 5-10°F (3-6°C). In this 40 hour test, the molar selectivity to aromatics was equivalent to slightly better for the catalyst prepared using the water / ethanol solution, as shown in Figure 1. Fig.12 shown.

[0133] Example 6

[0134] In Example 6, a supported catalyst was prepared by first impregnating F in water, followed by drying and calcining. For the reference catalyst, the platinum and Cl were then impregnated in water, while for the experimental catalyst, the platinum and Cl were impregnated in a solvent composition containing 70 wt% water and 30 wt% ethanol. The K / L-zeolite substrate preparation, incipient wetness technique, drying procedure and calcination conditions were identical for both catalysts. After reduction / activation in hydrogen, the catalysts were compared using the 40 hour test procedure described above.

[0135] Fig.13 The yield-regulated temperature and reaction time for each supported catalyst were compared and demonstrated a higher activity for the catalyst prepared using 30 wt% ethanol compared to the reference catalyst. Unexpectedly, the target aromatic yield of 75 wt% was achieved at a lower reaction temperature for the catalyst prepared using the water / ethanol solution. The molar selectivity to aromatics was the same for the catalyst prepared using the water / ethanol solution in this 40 hour test, as shown in Figure 2. Fig.14 shown.

[0136] Example 7

[0137] In Example 7, a supported catalyst was prepared as described in Example 1, but an interim test was run for 600 hours using 5 cc of 20 / 40 mesh catalyst. All other conditions were similar to the 40 hour test procedure described above, and again, the interim test demonstrated a higher activity for the catalyst prepared using 30 wt % ethanol, as shown in FIG. Fig.15 In addition, the catalyst prepared using ethanol had a surprisingly low fouling rate (FR) of 0.0084°F / hr (0.0047°C / hr), which is less than one-third of the fouling rate of the reference catalyst. The lower fouling rate translates into longer run times and consistent stability. The higher long-term selectivity of the catalyst prepared using ethanol is Fig.16 It is shown that it shows a significantly higher H 2 / CH 4Productivity, particularly in the range of 400 hours to 600 hours.

[0138] Example 8

[0139] In Example 8, the long term activity and stability performance of the reference catalyst and the catalyst prepared with 30% ethanol, as well as the catalyst fouling rate, were evaluated. For this 2500 hour test, 80 cc of the supported catalyst (all extrudates) was reduced in nitrogen containing 50 mol% hydrogen, and then a feed stream of aliphatic hydrocarbons and molecular hydrogen was added at a pressure of 65 psig, a 2:1 hydrogen: hydrocarbon ratio, and a LHSV of 1.6 hr. -1 The catalyst was introduced into a 1" reactor containing the catalyst at 40 °C to obtain catalyst performance data over time. By adjusting the temperature to maintain the desired yield as described above for the 40 hour test, the total yield of aromatic compounds was maintained at 83.5 wt% during the 2500 hour run.

[0140] Fig.17 It is shown that the catalyst produced using ethanol achieves an 83.5 wt% aromatics yield at a lower adjusted catalyst temperature of about 10°F (6°C) compared to the reference catalyst, while Fig.18 It is shown that the catalyst prepared using ethanol has a molar selectivity to benzene + toluene that is almost 2 mol% higher than the reference catalyst.

[0141] Example 9

[0142] Example 9 is a drying rate comparison between a reference catalyst and an experimental catalyst prepared as described in Example 1 using 30 wt % ethanol. Fig.19 It was shown that in the first step of drying at a lower temperature of 38° C., up to 50 wt % of the impregnation solvent was removed from the experimental catalyst, while only 14 wt % of the impregnation solvent (water) was removed from the reference catalyst. While not wishing to be bound by theory, it is believed that when ethanol is present, the drying rate is much faster and occurs under milder conditions, which may be beneficial to the distribution of components in the zeolite pores during solvent removal.

[0143] Example 10

[0144] Example 10 compares the platinum dispersion of a reference catalyst and an experimental catalyst prepared using 30 wt % ethanol as described in Example 1 as determined by static CO chemisorption. As shown in Table 1, both catalysts have similar platinum dispersions. Thus, unexpectedly, the experimental catalyst exhibits superior catalyst activity despite no difference in platinum dispersion.

[0145] Table I. Example 10 - Platinum dispersion.

[0146]

[0147] Embodiment 11

[0148] Example 11 is a comparison of drying rates between the reference catalyst and a controlled drying version of the reference catalyst (both using 100% water during impregnation). Fig.19 A controlled drying form of the reference catalyst was dried using a slow heating rate for a milder drying. Fig. 20 Slow drying of the controlled drying form of the reference catalyst is shown, wherein 57 wt. % of the impregnation solvent is removed by a temperature of 50°C.

[0149] The reference catalyst and a controlled dried version of the reference catalyst were compared using the 40 hour test procedure described above, similar to Examples 1 and 2. The activity of each catalyst (83.5 wt.% aromatics yield) was determined, and Fig.21 The results are summarized. Surprisingly, there was no difference in the catalytic activity of the reference catalyst and the controlled dried form of the reference catalyst. Thus, controlled drying with water alone does not provide the beneficial effects observed when using an alcohol compound. Thus, according to Example 9, the premise that the presence of alcohol simply results in milder drying does not seem to fully explain the benefits of alcohol addition.

[0150] Example 12

[0151] In Example 12, supported catalysts were prepared as described in Examples 1-2, except that the catalysts were prepared with water (reference), 10 wt % methanol, or 30 wt % methanol. Another catalyst was prepared with dichloride (1.7 wt % chlorine) and 10 wt % methanol. The activity of each catalyst was determined using the 40 hour test procedure described above, and Fig. 22 The results were summarized for an aromatics yield of 83.5 wt%.

[0152] Advantageously, all levels of methanol (10 wt % to 30 wt %) improve catalyst activity. As the amount of methanol increases, catalyst activity increases accordingly. Unexpectedly, the catalyst prepared using dichloride and 10 wt % methanol has performance comparable to the standard catalyst prepared with 30 wt % ethanol.

[0153] The present invention has been described above with reference to a number of aspects and specific embodiments. A person skilled in the art will appreciate many variations based on the foregoing specific embodiments. All such obvious variations are within the full intended scope of the appended claims. Other aspects of the present invention may include, but are not limited to, the following (each aspect is described as "comprising / including...", but alternatively, may be "essentially composed of..." or "consisting of..."):

[0154] Aspect 1. A method for preparing a supported catalyst, the method comprising:

[0155] (a) impregnating a bound zeolite substrate with the following materials in any order:

[0156] A transition metal precursor in a mixture containing water and about 5 wt % to about 50 wt % of C 1 To C 3 In the solvent composition of the alcohol compound,

[0157] Chlorine precursors, and

[0158] a fluorine precursor to form an impregnated zeolite matrix; and

[0159] (b) drying and then calcining the impregnated zeolite substrate to prepare the supported catalyst, wherein the supported catalyst comprises, based on the total weight of the supported catalyst:

[0160] from about 0.1 wt % to about 10 wt % of a transition metal;

[0161] from about 0.1 wt % to about 5 wt % chlorine; and

[0162] From about 0.1 wt % to about 5 wt % fluorine.

[0163] Aspect 2. The method according to aspect 1, wherein the alcohol compound comprises methanol, ethanol, n-propanol, isopropanol or any combination thereof.

[0164] Aspect 3. The method according to aspect 1, wherein the alcohol compound comprises ethanol.

[0165] Aspect 4. A method as described in any of the preceding aspects, wherein the solvent composition contains any weight percentage of the alcohol compound disclosed herein, for example, about 5 weight % to about 40 weight %, about 10 weight % to about 40 weight %, about 10 weight % to about 35 weight % or about 10 weight % to about 30 weight % of the alcohol compound.

[0166] Aspect 5. The method of any one of aspects 1 to 4, wherein the bound zeolite matrix is ​​impregnated with the chlorine precursor and / or the fluorine precursor prior to the transition metal precursor.

[0167] Aspect 6. The method of any one of aspects 1 to 5, wherein the bound zeolite substrate is impregnated with a solution comprising water and the chlorine precursor and / or the fluorine precursor.

[0168] Aspect 7. The method according to any one of aspects 1 to 6, wherein in a mixture containing water and about 5 wt % to about 50 wt % of the C 1 To C 3The bound zeolite substrate is impregnated with the transition metal precursor and the chlorine precursor (or the fluorine precursor, or both the chlorine precursor and the fluorine precursor) in the solvent composition of the alcohol compound.

[0169] Aspect 8. The method according to any one of the preceding aspects, further comprising the following steps before step (a):

[0170] combining the zeolite with a binder to form a mixture, and extruding the mixture to form an extrudate;

[0171] drying and calcining the extrudate to form a calcined matrix; and

[0172] The calcined matrix is ​​washed, dried and calcined to form the bound zeolite matrix.

[0173] Aspect 9. A method as described in any of the preceding aspects, wherein drying and then calcining the impregnated zeolite matrix comprises any suitable drying conditions or any drying conditions disclosed herein, for example, a drying temperature in the range of about 30°C to about 200°C or about 80°C to about 100°C, and drying at atmospheric or subatmospheric pressure, for example, less than about 150 Torr or less than about 50 Torr.

[0174] Aspect 10. A method as described in any of the preceding aspects, wherein drying and then calcining the impregnated zeolite matrix comprises any suitable calcination conditions or any calcination conditions disclosed herein, such as a peak calcination temperature in the range of about 200°C to about 500°C or about 230°C to about 450°C, and in a calcination gas flow comprising nitrogen, oxygen, air, or any combination thereof.

[0175] Aspect 11. The method of aspect 10, wherein the peak calcination temperature is in the range of about 275°C to about 425°C or about 300°C to about 400°C.

[0176] Aspect 12. A method as described in any of the preceding aspects, wherein the method further comprises a reduction step after drying and calcining the impregnated zeolite substrate, the reduction step comprising contacting the supported catalyst with any suitable reducing gas stream or any reducing gas stream disclosed herein (e.g., containing hydrogen) to produce a reduced (or activated) supported catalyst.

[0177] Aspect 13. The method of aspect 12, wherein the reducing step is performed at any suitable reducing temperature or any reducing temperature disclosed herein, for example in the range of about 100°C to about 700°C or about 200°C to about 600°C.

[0178] Aspect 14. A method as described in any of the preceding aspects, wherein the transition metal precursor comprises any suitable transition metal precursor or any transition metal precursor disclosed herein, such as tetraamine platinum (II) chloride, tetraamine platinum (II) nitrate, platinum (II) acetylacetonate, platinum (II) chloride, ammonium tetrachloroplatinate (II), chloroplatinic acid, platinum (II) nitrate, or a combination thereof.

[0179] Aspect 15. A method as described in any of the preceding aspects, wherein the chlorine precursor comprises any suitable chlorine precursor or any chlorine precursor disclosed herein, such as ammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, methyltriethylammonium chloride, or a combination thereof.

[0180] Aspect 16. A method as described in any of the preceding aspects, wherein the fluorine precursor comprises any suitable fluorine precursor or any fluorine precursor disclosed herein, such as ammonium fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride, methyltriethylammonium fluoride or a combination thereof.

[0181] Aspect 17. A method as described in any of the preceding aspects, wherein the supported catalyst comprises any weight percent of chlorine disclosed herein, such as about 0.3 wt.% to about 4 wt.%, about 0.4 wt.% to about 3.5 wt.%, about 0.5 wt.% to about 3.3 wt.%, about 1.8 wt.% to about 3.2 wt.%, or about 0.5 wt.% to about 1.5 wt.% chlorine.

[0182] Aspect 18. A method as described in any of the preceding aspects, wherein the supported catalyst comprises any weight percent of fluorine disclosed herein, such as about 0.3 wt.% to about 4 wt.%, about 0.4 wt.% to about 3 wt.%, about 0.3 wt.% to about 2 wt.%, or about 0.4 wt.% to about 1.5 wt.% fluorine.

[0183] Aspect 19. The method of any of the preceding aspects, wherein the bound zeolite matrix (or supported catalyst) comprises zeolite and a binder.

[0184] Aspect 20. A method as described in Aspect 19, wherein the bound zeolite matrix (or supported catalyst) contains any weight percentage of the binder disclosed herein, based on the total weight of the bound zeolite matrix (or supported catalyst), for example, about 3 weight % to about 35 weight % or about 5 weight % to about 30 weight % of the binder.

[0185] Aspect 21. The method of aspect 19 or 20, wherein the binder comprises an inorganic solid oxide, clay, or a combination thereof.

[0186] Aspect 22. The method of aspect 19 or 20, wherein the binder comprises alumina, silica, magnesia, boria, titania, zirconia, mixed oxides thereof, or a mixture thereof.

[0187] Aspect 23. The method of aspect 19 or 20, wherein the binder comprises silica.

[0188] Aspect 24. The method of any of the preceding aspects, wherein the bound zeolite matrix (or supported catalyst) comprises bound L-zeolite.

[0189] Aspect 25. The method of any one of aspects 1 to 23, wherein the bound zeolite matrix (or supported catalyst) comprises a bound barium ion-exchanged L-zeolite.

[0190] Aspect 26. The method of any one of aspects 1 to 23, wherein the bound zeolite matrix (or supported catalyst) comprises bound K / L-zeolite.

[0191] Aspect 27. The method of any one of aspects 1 to 23, wherein the bound zeolite matrix (or supported catalyst) comprises silica-bound L-zeolite.

[0192] Aspect 28. The method according to aspect 27, further comprising the following steps before step (a):

[0193] combining K / L-zeolite with silica sol to form a mixture, extruding the mixture to form an extrudate,

[0194] drying and calcining the extrudate to form a calcined matrix; and

[0195] The calcined matrix is ​​washed, dried and calcined to form the bound zeolite matrix.

[0196] Aspect 29. A method as described in any of the preceding aspects, wherein the supported catalyst comprises any weight percent of the transition metal disclosed herein, such as about 0.25 wt. % to about 5 wt. %, about 0.5 wt. % to about 3 wt. %, or about 0.7 wt. % to about 1.5 wt. % transition metal.

[0197] Aspect 30. The method of any of the preceding aspects, wherein the transition metal comprises platinum.

[0198] Aspect 31. A method as described in any of the preceding aspects, wherein the supported catalyst comprises any weight percentage of platinum disclosed herein, such as about 0.25 wt.% to about 5 wt.%, about 0.5 wt.% to about 3 wt.%, or about 0.7 wt.% to about 1.5 wt.% platinum.

[0199] Aspect 32. The method of any of the preceding aspects, wherein the supported catalyst is characterized by a BET surface area within any range disclosed herein, such as about 100 m 2 / g to about 300m 2 / g, about 100m 2 / g to about 200m 2 / g or about 110m 2 / g to about 170m 2 / g.

[0200] Aspect 33. The method of any of the preceding aspects, wherein the supported catalyst has any weight ratio of chlorine:fluorine disclosed herein, for example, from about 1:5 to about 5:1, from about 1:3 to about 3:1, or from about 1:2 to about 2:1.

[0201] Aspect 34. A method as described in any of the preceding aspects, wherein the supported catalyst is characterized by a platinum dispersion in any range disclosed herein, for example, from about 40% to about 80%, from about 50% to about 80%, from about 60% to about 80%, or from about 60% to about 75%.

[0202] Aspect 35. A method as described in any of the preceding aspects, wherein the supported catalyst has a platinum dispersion that is substantially the same as the platinum dispersion of an otherwise identical catalyst prepared under the same catalyst preparation conditions without the alcohol compound (substantially the same means within + / - 5% platinum dispersion, and more typically, the platinum dispersion is within + / - 3%, or within + / - 1%).

[0203] Aspect 36. The method of any of the preceding aspects, wherein the supported catalyst is characterized by a 40 hour Tmax of less than a run end temperature of an otherwise identical catalyst prepared under the same catalyst preparation conditions without the alcohol compound and evaluated under the same 40 hour aromatization reaction conditions. EOR (End of run temperature).

[0204] Aspect 37. The method of any of the preceding aspects, wherein the supported catalyst is characterized by a 40 hour Tmax of less than the run start temperature of an otherwise identical catalyst prepared under the same catalyst preparation conditions without the alcohol compound and evaluated under the same 40 hour aromatization reaction conditions. SOR (Run start temperature).

[0205] Aspect 38. The method of any of the preceding aspects, wherein the supported catalyst is characterized by a 40 hour fouling rate that is less than the fouling rate of an otherwise identical catalyst prepared under the same catalyst preparation conditions without the alcohol compound and evaluated under the same 40 hour aromatization reaction conditions.

[0206] Aspect 39. A method as described in any of the preceding aspects, wherein the supported catalyst is characterized by a 40-hour aromatics selectivity (or 40-hour benzene + toluene selectivity) that is substantially the same as or greater than the selectivity of an otherwise identical catalyst prepared under the same catalyst preparation conditions without the alcohol compound and evaluated under the same 40-hour aromatization reaction conditions.

[0207] Aspect 40. The method of any of the preceding aspects, wherein the supported catalyst is characterized by a 40 hour T in any range disclosed herein. EOR (end of run temperature), such as about 910°F (488°C) to about 930°F (499°C) or about 910°F (488°C) to about 925°F (496°C).

[0208] Aspect 41. The method of any of the preceding aspects, wherein the supported catalyst is characterized by a 40 hour T SOR (operation start temperature), such as about 910°F (488°C) to about 925°F (496°C) or about 910°F (488°C) to about 920°F (493°C).

[0209] Aspect 42. A method as described in any of the preceding aspects, wherein the supported catalyst is characterized by a 40 hour aromatics selectivity (or 40 hour benzene + toluene selectivity) in any range disclosed herein, for example, at least about 92 mol%, at least about 93 mol%, or at least about 94 mol%.

[0210] Aspect 43. The method of any of the preceding aspects, wherein the supported catalyst is characterized by a 600 hour Tmax of less than the run end temperature of an otherwise identical catalyst prepared under the same catalyst preparation conditions without the alcohol compound and evaluated under the same 600 hour aromatization reaction conditions. EOR (End of run temperature).

[0211] Aspect 44. The method of any of the preceding aspects, wherein the supported catalyst is characterized by a 600 hour Tmax of a run start temperature of an otherwise identical catalyst prepared under the same catalyst preparation conditions without the alcohol compound and evaluated under the same 600 hour aromatization reaction conditions. SOR (Run start temperature).

[0212] Aspect 45. The method of any of the preceding aspects, wherein the supported catalyst is characterized by a 600 hour fouling rate that is less than the fouling rate of an otherwise identical catalyst prepared under the same catalyst preparation conditions without the alcohol compound and evaluated under the same 600 hour aromatization reaction conditions.

[0213] Aspect 46. The method of any of the preceding aspects, wherein the supported catalyst is characterized by a 600 hour H yield greater than the yield of an otherwise identical catalyst prepared under the same catalyst preparation conditions without the alcohol compound and evaluated under the same 600 hour aromatization reaction conditions. 2 / CH 4 Yield.

[0214] Aspect 47. The method of any of the preceding aspects, wherein the supported catalyst is characterized by a 600 hour T in any range disclosed herein. EOR (end of run temperature), such as about 930°F (499°C) to about 975°F (524°C) or about 940°F (504°C) to about 965°F (518°C).

[0215] Aspect 48. The method of any of the preceding aspects, wherein the supported catalyst is characterized by a 600 hour T in any range disclosed herein. SOR (operation start temperature), such as about 930°F (499°C) to about 960°F (516°C) or about 940°F (504°C) to about 955°F (513°C).

[0216] Aspect 49. The method of any of the preceding aspects, wherein the supported catalyst is characterized by a 600 hour fouling rate within any range disclosed herein, for example, less than about 0.02°F / hour (0.01°C / hour) or less than about 0.01°F / hour (0.006°C / hour).

[0217] Aspect 50. The method of any of the preceding aspects, wherein the supported catalyst is characterized by a 600 hour H 2 / CH 4 Yield, for example, from about 30% to about 47% or from about 35% to about 45%.

[0218] Aspect 51. The method of any of the preceding aspects, wherein the supported catalyst is characterized by a 2500 hour Tmax of less than the run end temperature of an otherwise identical catalyst prepared under the same catalyst preparation conditions without the alcohol compound and evaluated under the same 2500 hour aromatization reaction conditions. EOR (End of run temperature).

[0219] Aspect 52. The method of any of the preceding aspects, wherein the supported catalyst is characterized by a 2500 hour Tmax of a run start temperature of an otherwise identical catalyst prepared under the same catalyst preparation conditions without the alcohol compound and evaluated under the same 2500 hour aromatization reaction conditions. SOR (Run start temperature).

[0220] Aspect 53. A method as described in any of the preceding aspects, wherein the supported catalyst is characterized by a 2500 hour aromatics selectivity (or a 2500 hour benzene + toluene selectivity) that is greater than the selectivity of an otherwise identical catalyst prepared under the same catalyst preparation conditions without the alcohol compound and evaluated under the same 2500 hour aromatization reaction conditions.

[0221] Aspect 54. A supported catalyst obtained by the method as described in any one of the preceding aspects, such as a supported aromatization catalyst.

[0222] Aspect 55. A reforming process comprising contacting a hydrocarbon feed with a supported aromatization catalyst under reforming conditions in a reactor system to produce an aromatic product, wherein the supported aromatization catalyst is the supported catalyst (or reduced or activated catalyst) as described in any of the preceding aspects.

[0223] Aspect 56. The method according to aspect 55, wherein the hydrocarbon feed is any hydrocarbon feed disclosed herein, for example, comprising non-aromatic hydrocarbons, comprising C 6 -C 9 Alkanes and / or cycloalkanes, or containing C 6 -C 8 Alkanes and / or cycloalkanes.

Claims

1. A method for preparing a supported catalyst, the method comprising: (a) impregnating a bound zeolite substrate with the following materials in any order: a transition metal precursor in a solvent composition containing water and 5 to 50 wt % of a C1 to C3 alcohol compound, Chlorine precursors, and a fluorine precursor to form an impregnated zeolite matrix; and (b) drying and then calcining the impregnated zeolite substrate to prepare the supported catalyst, wherein the supported catalyst comprises, based on the total weight of the supported catalyst: 0.1 to 10 wt % of a transition metal; 0.1 to 5 wt. % chlorine; and 0.1 to 5% by weight of fluorine, Wherein the transition metal comprises platinum.

2. The method of claim 1, wherein the bound zeolite substrate is impregnated with the chlorine precursor and / or the fluorine precursor prior to the transition metal precursor.

3. A method as claimed in claim 1 or 2, wherein the bound zeolite substrate is impregnated with a solution comprising water and the chlorine precursor and / or the fluorine precursor.

4. The method of claim 1, wherein the bound zeolite substrate is impregnated with the transition metal precursor, the chlorine precursor, and the fluorine precursor in the solvent composition comprising water and 5 wt % to 50 wt % of the C1 to C3 alcohol compound.

5. The method of claim 1 or 2, wherein the alcohol compound comprises ethanol.

6. The method of claim 1 or 2, wherein: The solvent composition contains 10 wt % to 40 wt % of the C1 to C3 alcohol compound; and The bound zeolite matrix comprises 5 wt % to 30 wt % of a binder, based on the total weight of the bound zeolite matrix.

7. The method of claim 1 or 2, wherein: The bound zeolite matrix comprises silica bound L-zeolite.

8. The method of claim 1 or 2, wherein the supported catalyst comprises: 0.5 to 3 wt % platinum; 0.4 to 3.5 wt. % chlorine; and 0.3 to 2 wt% fluorine.

9. The method according to claim 1 or 2, further comprising the following steps before step (a): combining the zeolite with a binder to form a mixture, and extruding the mixture to form an extrudate; drying and calcining the extrudate to form a calcined matrix; as well as The calcined matrix is ​​washed, dried and calcined to form the bound zeolite matrix.

10. The method of claim 1 or 2, wherein: The transition metal precursor comprises tetraamine platinum (II) chloride, tetraamine platinum (II) nitrate, platinum (II) acetylacetonate, platinum (II) chloride, ammonium tetrachloroplatinate (II), chloroplatinic acid, platinum (II) nitrate or a combination thereof; The chlorine precursor comprises ammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, methyltriethylammonium chloride or a combination thereof; and The fluorine precursor includes ammonium fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride, methyltriethylammonium fluoride or a combination thereof.

11. The method of claim 1 or 2, wherein: The bound zeolite matrix comprises silica bound L-zeolite; and The supported catalyst comprises: 0.7 to 1.5 wt. % platinum; 0.5 to 3.3 wt % chlorine; and 0.3 to 2 wt% fluorine.

12. The process of claim 1 or 2, wherein the supported catalyst has a platinum dispersion that is substantially the same as the platinum dispersion of an otherwise identical catalyst prepared under the same catalyst preparation conditions without the alcohol compound.

13. The process of claim 1 or 2, wherein the supported catalyst is characterized by a platinum dispersion in the range of 60% to 80%.

14. The method of claim 1 or 2, wherein said method further comprises a reduction step after said drying and calcining said impregnated zeolite substrate, said reduction step comprising contacting said supported catalyst with a reducing gas stream to produce an activated catalyst.

15. The method of claim 14, wherein: The bound zeolite matrix comprises silica bound L-zeolite; and The supported catalyst comprises: 0.5 to 3 wt % platinum; 0.4 to 3.5 wt. % chlorine; and 0.3 to 2 wt% fluorine.

16. The method of claim 14, wherein the solvent composition contains 10 wt% to 40 wt% ethanol.

17. The method of claim 14, wherein the bound zeolite substrate is impregnated with the transition metal precursor, the chlorine precursor, and the fluorine precursor in the solvent composition.

18. An activated aromatization catalyst obtainable by the process according to any one of claims 14 to 17.

19. A reforming method comprising: A hydrocarbon feed is contacted with the activated aromatization catalyst as described in claim 18 under reforming conditions in a reactor system to produce an aromatic product.

20. The process of claim 19, wherein the hydrocarbon feed comprises C6-C8 alkanes and / or cycloalkanes.

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