High fluoride containing catalyst for use in a front reactor for extended life and

Abstract

The present disclosure provides a process for reforming hydrocarbons by using a series of adiabatic reactors and catalysts, wherein the catalyst in the at least one front or upstream catalyst bed or reactor comprises a fluoride concentration higher than the corresponding halide concentration in the catalyst in the one or more downstream catalyst beds or reactors, a chloride concentration higher than the corresponding halide concentration in the catalyst in the one or more downstream catalyst beds or reactors, or both, the process has unexpectedly been found to extend the service life and / or selectivity of the catalyst system.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of and priority to U.S. Provisional Application No. 63 / 353,372, filed on June 17, 2022, which is incorporated by reference in its entirety. Technical Field

[0003] The present disclosure relates to supported aromatization catalysts and their use in aromatizing aliphatic hydrocarbons to aromatic hydrocarbons. Background Art

[0004] The catalytic conversion of aliphatic hydrocarbons to aromatic compounds, commonly referred to as aromatization or reforming, is an important industrial process for producing benzene, toluene and xylenes from naphtha feedstock. These aromatic hydrocarbons are valued as precursors for polymer products, solvents and fuels or fuel additives due to their high octane numbers.

[0005] Conventional aromatization reactor systems include a series of adiabatic reactors in which the only heat entering the reactors is carried by the input streams. The aromatization catalyst in the reactor system is typically a supported transition metal catalyst that effects a variety of reactions, including dehydrogenation, isomerization, and cyclization of aliphatic hydrocarbons, to produce specific aromatic compounds. However, over time, the aromatization catalyst may lose its activity and / or selectivity, which may greatly affect the economics of the process. Given its commercial importance, there is a continuing need for improved systems, catalysts, and processes that can increase the production of aromatic hydrocarbons. Summary of the invention

[0006] This Summary is provided to introduce various concepts in a simplified form that are further described below in the Detailed Description. This Summary is not intended to identify required or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter.

[0007] Aromatization or reforming catalysts according to the present disclosure may comprise an inorganic support, a Group 8-10 metal, and a fluoride and / or chloride. In one aspect, the present disclosure provides a process for reforming hydrocarbons by using a series of adiabatic reactors and catalysts, wherein the catalyst in at least one front or upstream catalyst bed or reactor may include a higher fluoride content (concentration), a higher chloride content, or both a higher fluoride content and a higher chloride content than the catalyst in one or more downstream catalyst beds or reactors. It has been unexpectedly discovered that by using a higher weight percentage of halide in at least one front or upstream catalyst bed or reactor compared to one or more downstream catalyst beds or reactors, the service life and / or selectivity of the catalyst system can be extended.

[0008] While not intending to be bound by theory, it has been found that the fluoride and chloride concentrations of the aromatization catalyst may decrease over time, and that this loss of fluoride and chloride appears to be associated with a decrease in catalyst selectivity. This decrease in selectivity may become so severe that it is more economically feasible to turn around a commercial unit and replace the catalyst with fresh catalyst, even though the catalyst is well maintained within the temperature limits of the process equipment and retains significant catalyst activity. Applicants have found that a higher weight percentage of fluoride, chloride, or both fluoride and chloride in at least one upstream reactor in series can maintain the selectivity of the catalyst system for a longer period of time than in a downstream reactor.

[0009] In one aspect, the present disclosure provides a process for reforming hydrocarbons, the process comprising:

[0010] a) contacting a feedstock containing an aliphatic hydrocarbon with a first catalyst (comprising an inorganic support, a Group 8-10 metal, and at least or about 1.0 weight percent of a fluoride relative to the weight of the first catalyst before reduction) in a first catalyst bed under conditions to aromatize the aliphatic hydrocarbon to form a first catalyst bed effluent comprising aromatic hydrocarbons and aliphatic hydrocarbons;

[0011] b) contacting the first catalyst bed effluent with one or more independently selected intermediate catalysts (each comprising an inorganic support, a Group 8-10 metal, and a fluoride) in one or more intermediate catalyst beds in series under conditions to aromatize aliphatic hydrocarbons to form one or more intermediate catalyst bed effluents comprising aromatic hydrocarbons and aliphatic hydrocarbons; and

[0012] c) contacting the one or more intermediate catalyst bed effluents with a final catalyst (comprising an inorganic support, a Group 8-10 metal, and at least or about 0.7 weight percent fluoride relative to the weight of the final catalyst prior to reduction) in a final catalyst bed under conditions to aromatize aliphatic hydrocarbons to form a final catalyst bed effluent comprising an aromatic product;

[0013] The fluoride concentration of the first catalyst or the fluoride concentration of at least one of the intermediate catalysts is higher than the fluoride concentration of the last catalyst before reduction.

[0014] In another aspect, the present disclosure provides a process for reforming hydrocarbons, the process comprising:

[0015] a) contacting a feedstock containing an aliphatic hydrocarbon with a first catalyst (comprising an inorganic support, a Group 8-10 metal, and at least or about 1.5 weight percent chloride relative to the weight of the first catalyst before reduction) in a first catalyst bed under conditions to aromatize the aliphatic hydrocarbon to form a first catalyst bed effluent comprising aromatic hydrocarbons and aliphatic hydrocarbons;

[0016] b) contacting the first catalyst bed effluent with one or more independently selected intermediate catalysts (each comprising an inorganic support, a Group 8-10 metal, and a chloride) in one or more intermediate catalyst beds in series under conditions to aromatize aliphatic hydrocarbons to form one or more intermediate catalyst bed effluents comprising aromatic hydrocarbons and aliphatic hydrocarbons; and

[0017] c) contacting the one or more intermediate catalyst bed effluents with a final catalyst (comprising an inorganic support, a Group 8-10 metal, and at least or about 0.5 weight percent chloride relative to the weight of the final catalyst prior to reduction) in a final catalyst bed under conditions to aromatize aliphatic hydrocarbons to form a final catalyst bed effluent comprising an aromatic product;

[0018] The chloride concentration of the first catalyst or the chloride concentration of at least one of the intermediate catalysts is higher than the chloride concentration of the last catalyst before reduction.

[0019] Typically and unless otherwise indicated, the weight percentage of halide, fluoride or chloride in the catalyst is indicated prior to reduction of the catalyst. The use of the terms "fluoride" and "chloride" is not intended to reflect any formal structure or type of bonding between the fluorine and chlorine atoms and the inorganic support, but only to reflect that a halide source is often used in the preparation of these halide catalysts.

[0020] According to other aspects, the present disclosure also provides a process for reforming hydrocarbons, the process comprising:

[0021] a) contacting a feedstock containing an aliphatic hydrocarbon with a first catalyst (comprising an inorganic support, a Group 8-10 metal, and at least or about 1.0 weight percent of a fluoride relative to the weight of the first catalyst before reduction) in a first catalyst bed under conditions to aromatize the aliphatic hydrocarbon to form a first catalyst bed effluent comprising aromatic hydrocarbons and aliphatic hydrocarbons; and

[0022] b) contacting the first catalyst bed effluent with a final catalyst in a final catalyst bed under conditions to aromatize aliphatic hydrocarbons to form a final catalyst bed effluent comprising an aromatic product, the final catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 0.7 weight percent fluoride relative to the weight of the final catalyst prior to reduction;

[0023] The fluoride concentration of the first catalyst is higher than the fluoride concentration of the last catalyst before reduction.

[0024] In yet another aspect, the present disclosure also provides a process for reforming hydrocarbons, the process comprising:

[0025] a) contacting a feedstock containing an aliphatic hydrocarbon with a first catalyst (comprising an inorganic support, a Group 8-10 metal, and at least or about 1.5 weight percent chloride relative to the weight of the first catalyst before reduction) in a first catalyst bed under conditions to aromatize the aliphatic hydrocarbon to form a first catalyst bed effluent comprising aromatic hydrocarbons and aliphatic hydrocarbons; and

[0026] b) contacting the first catalyst bed effluent with a final catalyst in a final catalyst bed under conditions to aromatize aliphatic hydrocarbons to form a final catalyst bed effluent comprising an aromatic product, the final catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 0.5 weight percent chloride relative to the weight of the final catalyst prior to reduction;

[0027] The chloride concentration of the first catalyst is higher than the chloride concentration of the last catalyst before reduction.

[0028] Thus, in these aspects, there are two continuous catalysts or catalyst beds in series, comprising an inorganic support, a Group 8-10 metal, and the fluoride or chloride concentration in the first upstream catalyst relative to the weight of the upstream catalyst. The immediately downstream catalyst or catalyst bed comprises a relatively low weight percentage of fluoride or chloride relative to the weight of the downstream catalyst. Unless otherwise indicated, the weight percentages recited are the weight percentages in the catalyst formulated prior to reduction.

[0029] Other aspects of the present disclosure provide a catalytic hydrocarbon reforming system comprising:

[0030] at least three catalyst beds connected in series, the catalyst beds comprising an upstream first catalyst bed, a downstream last catalyst bed, and one or more intermediate catalyst beds connected in series between the first catalyst bed and the last catalyst bed;

[0031] a first catalyst in the first catalyst bed, the first catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 1.0 weight percent fluoride relative to the weight of the first catalyst prior to reduction;

[0032] one or more independently selected intermediate catalysts in the one or more intermediate catalyst beds, each intermediate catalyst comprising an inorganic support, a Group 8-10 metal, and a fluoride; and

[0033] a final catalyst in the final catalyst bed, the final catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 0.7 weight percent fluoride relative to the weight of the final catalyst prior to reduction;

[0034] The fluoride concentration of the first catalyst or the fluoride concentration of at least one of the intermediate catalysts is higher than the fluoride concentration of the last catalyst before reduction.

[0035] Another aspect of the present disclosure provides a catalytic hydrocarbon reforming system comprising:

[0036] at least three catalyst beds connected in series, the catalyst beds comprising an upstream first catalyst bed, a downstream last catalyst bed, and one or more intermediate catalyst beds connected in series between the first catalyst bed and the last catalyst bed;

[0037] a first catalyst in the first catalyst bed, the first catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 1.5 weight percent chloride relative to the weight of the first catalyst prior to reduction;

[0038] one or more independently selected intermediate catalysts in the one or more intermediate catalyst beds, each intermediate catalyst comprising an inorganic support, a Group 8-10 metal, and a chloride; and

[0039] a final catalyst in the final catalyst bed, the final catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 0.5 weight percent chloride relative to the weight of the final catalyst prior to reduction;

[0040] The chloride concentration of the first catalyst or the chloride concentration of at least one of the intermediate catalysts is higher than the chloride concentration of the last catalyst before reduction.

[0041] According to another aspect of the present disclosure, there is provided a catalytic hydrocarbon reforming system comprising:

[0042] Two catalyst beds connected in series, the catalyst beds comprising an upstream first catalyst bed and a downstream last catalyst bed;

[0043] a first catalyst in the first catalyst bed, the first catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 1.0 weight percent fluoride relative to the weight of the first catalyst before reduction; and

[0044] a final catalyst in the final catalyst bed, the final catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 0.7 weight percent fluoride relative to the weight of the final catalyst prior to reduction;

[0045] The fluoride concentration of the first catalyst is higher than the fluoride concentration of the last catalyst before reduction.

[0046] According to yet another aspect of the present disclosure, there is provided a catalytic hydrocarbon reforming system comprising:

[0047] Two catalyst beds connected in series, the catalyst beds comprising an upstream first catalyst bed and a downstream last catalyst bed;

[0048] a first catalyst in the first catalyst bed, the first catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 1.5 weight percent chloride relative to the weight of the first catalyst prior to reduction; and

[0049] a final catalyst in the final catalyst bed, the final catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 0.5 weight percent chloride relative to the weight of the final catalyst prior to reduction;

[0050] The chloride concentration of the first catalyst is higher than the chloride concentration of the last catalyst before reduction.

[0051] In each of the processes and systems listed, there are practical upper limits to the concentrations of fluoride and chloride in the catalyst. For example, in a fluoride-containing catalyst, the first catalyst may contain up to about 5.0 wt. %, up to about 4.0 wt. %, up to about 3.5 wt. %, up to about 3.0 wt. %, or up to about 2.5 wt. % fluoride relative to the weight of the final catalyst before reduction, and the final catalyst may contain up to about 4.0 wt. %, up to about 3.0 wt. %, up to about 2.5 wt. %, up to about 2.0 wt. %, or up to about 1.5 wt. % fluoride relative to the weight of the final catalyst before reduction. In chloride-containing catalysts, the first catalyst may contain up to about 5.0 wt. %, up to about 4.0 wt. %, up to about 3.5 wt. %, up to about 3.0 wt. %, or up to about 2.5 wt. % chloride relative to the weight of the final catalyst before reduction, and the final catalyst may contain up to about 3.0 wt. %, up to about 2.5 wt. %, up to about 2.0 wt. %, or up to about 1.5 wt. % chloride relative to the weight of the final catalyst before reduction.

[0052] Summary of the invention and the following specific embodiments provide examples and are only explanations of the present invention. Therefore, the foregoing summary of the invention and the following specific embodiments should not be considered as restrictive. In addition to those set forth herein, other features or their variations may be provided, such as various feature combinations and sub-combinations of these features described in the detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 A process flow diagram illustrating a type of aromatization reactor system for producing aromatic hydrocarbons according to one aspect of the present disclosure is provided.

[0054] Figure 2A An embodiment of the present disclosure is illustrated showing a "baseline" fixed bed reactor having a standard (STD) aromatization catalyst in both the top and bottom halves of the fixed bed reactor, the performance of which is comparable to Figure 2B A comparison is made with the high halide implementation scheme in FIG.

[0055] Figure 2B One embodiment of the present disclosure is illustrated, showing a "Split Bed" fixed bed reactor having a high halide catalyst with a high chloride concentration in the upper half of the fixed bed and a standard (STD) aromatization catalyst arrangement in the lower half of the fixed bed, referred to as a split bed arrangement, which embodiment is similar to Figure 2A A comparison was made with a standard (STD) aromatization catalyst embodiment in FIG.

[0056] Figure 3 Illustrated for Figure 2A (“baseline”) vs. Figure 2B The standard in the lower half of the fixed bed reactor ("layered bed") is shown in FIG. II Catalyst, a plot of adjusted catalyst temperature (°F) versus run time (hours), demonstrates that the standard catalyst downstream of the high chloride catalyst has better activity than the standard catalyst downstream of the more standard catalyst (i.e., a catalyst with a standard chloride concentration).

[0057] Figure 4 Illustrated for Figure 2A (“baseline”) vs. Figure 2B The standard in the lower half of the fixed bed reactor ("layered bed") is shown in FIG. II catalyst, a plot of selectivity (mol / mol) versus run time (hours), demonstrates that the standard catalyst downstream of the high chloride catalyst has better selectivity than the standard catalyst downstream of the more standard catalyst (ie, a catalyst with a standard chloride concentration). DETAILED DESCRIPTION

[0058] definition

[0059] 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 herein, the definition in the 2nd edition of IUPAC Chemical Terminology (IUPAC Compendium of Chemical Terminology) (1997) can be applied, as long as the definition does not conflict with any other disclosure or definition applied herein, or does not make any claim to which the definition is applied unclear or invalid. If any definition or usage provided by any file incorporated herein by reference conflicts with the definition or usage provided herein, the definition or usage provided herein shall prevail.

[0060] When describing various features of the subject matter of the present disclosure, within a particular aspect, one or more combinations of different features are contemplated. For each aspect of each feature disclosed herein, all combinations that do not adversely affect the design, composition, system, process, or method described herein are contemplated, with or without explicit description of a particular combination. Therefore, unless expressly stated to the contrary, any aspect of the features disclosed herein may be combined to describe and disclose a design, composition, system, process, or method of the present invention consistent with the entire disclosure.

[0061] Although compositions and methods are described as "comprising" various components or steps, unless otherwise stated, the compositions and methods may also "consist essentially of" or "consist of" the various components or steps.

[0062] As used herein, the terms "including," "having," and "having" are defined as comprising (ie, open language) unless otherwise indicated.

[0063] The terms "a / an" and "the" are intended to include plural alternatives, such as at least one. For example, unless otherwise indicated, disclosure of "zeolite", "diluent", "catalyst", etc. is intended to cover a mixture or combination of one or more than one of zeolites, diluents, catalysts, etc.

[0064] Various numerical ranges are disclosed herein. When the applicant discloses or claims any type of range, unless otherwise specified, the applicant intends to disclose or claim individually each possible number that such range can reasonably cover, including the endpoints of the range and any sub-ranges and combinations of sub-ranges covered therein. For example, by disclosing a weight percentage of 1.0 wt % to 2.0 wt %, the applicant's intention is to list 1.0 wt %, 1.1 wt %, 1.2 wt %, 1.3 wt %, 1.4 wt %, 1.5 wt %, 1.6 wt %, 1.7 wt %, 1.8 wt %, 1.9 wt % and 2.0 wt % individually, including any sub-ranges and combinations of sub-ranges covered therein, and these methods of describing such ranges are interchangeable. In addition, unless excluded by proviso, all numerical endpoints of the range disclosed herein are approximate. As a representative example, if the applicant states that one or more steps in the process disclosed herein can be carried out at a temperature in the range of 10 ° C to 75 ° C, unless otherwise specified, the range should be interpreted as covering a temperature in the range of "about" 10 ° C to "about" 75 ° C.

[0065] Values ​​or ranges may be expressed herein as "about", from "about" one particular value, and / or to "about" another particular value. When such values ​​or ranges are expressed, other disclosed embodiments include the specific value, from a specific value, and / or to another specific value. Similarly, when a value is expressed as an approximation by using the antecedent "about", it is understood that the specific value forms another embodiment. It is also understood that multiple values ​​are disclosed herein, and each value is disclosed herein as "about" the specific value in addition to the value itself. In another aspect, each use of the term "about" may independently mean ±20% of the value, ±15% of the value, ±10% of the value, ±5% of the value, or ±3% of the value.

[0066] If the applicant chooses to claim less than the full measure disclosed for any reason (e.g., considering references that the applicant may not have known at the time of filing the application), the applicant reserves the right to exclude or exclude any individual member of the group of any such values ​​or ranges that may be claimed as a range or in any similar manner (including any subranges or combinations of subranges within the group). In addition, if the applicant chooses to claim less than the full measure disclosed for any reason (e.g., considering references or prior publications that the applicant may not have known at the time of filing the application), the applicant reserves the right to exclude or exclude any individual substituent, analog, compound, ligand, structure, or group thereof, or any member of the claimed group.

[0067] For any particular compound or group disclosed herein, unless otherwise indicated, any name or structure presented (general or specific) is intended to encompass all conformational isomers, regioisomers, stereoisomers, and mixtures thereof that may result from a particular set of substituents. Unless otherwise indicated, the name or structure also encompasses all enantiomers, diastereomers, and other optical isomers, if present, in either enantiomeric or racemic form, as well as mixtures of stereoisomers, as known to those skilled in the art. For example, a general reference to one or more hexanes 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.

[0068] When used to describe a group, for example, when referring to a substituted analog of a particular group, the term "substituted" is intended to describe a compound or group in which any non-hydrogen moiety formally replaces a hydrogen in the group or compound, and is intended to be non-restrictive. Compounds or groups may also be referred to herein as "unsubstituted" or by equivalent terms (such as "non-substituted"), which refer to the original group or compound. "Substituted" is intended to be non-restrictive and includes inorganic or organic substituents, as indicated and understood by those of ordinary skill in the art.

[0069] Unless otherwise indicated, the terms "contact product", "contact", etc. are used herein to describe compositions and methods in which components are contacted together in any order, in any manner, and for any length of time. For example, the components can be contacted by blending or mixing. In addition, unless otherwise indicated, the contact of any component can occur in the presence or absence of any other component of the compositions and methods described herein. Additional materials or components can be combined by any suitable method. In addition, the term "contact product" includes mixtures, blends, solutions, slurries, reaction products, etc. or combinations thereof. Although "contact products" can and usually include reaction products, it is not required that the individual components react with each other. Similarly, "contacting" two or more components can produce a reaction product or a reaction mixture. Therefore, depending on the circumstances, a "contact product" can be a mixture, a reaction mixture, or a reaction product.

[0070] "Conditions to aromatize aliphatic hydrocarbons" means conditions under which, when contacted with a catalyst as described herein, at least a portion of the aliphatic hydrocarbons in a feedstock containing aliphatic hydrocarbons are aromatized such that the catalyst bed effluent contains at least some aromatic hydrocarbons. Some unreacted aliphatic hydrocarbons will also be present in the catalyst bed effluent.

[0071] Typically, 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, Group 1 elements are alkali metals, Group 2 elements are alkaline earth metals, Groups 3-12 elements are transition metals, Group 17 elements are halogens or halides, etc.

[0072] In one aspect, 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, "alkyl" can be derived from an alkane by removing a hydrogen atom in form. The disclosure that a substituent, 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. Unless otherwise specified or the context requires otherwise, when describing a group "derived from...", "derived from...", "formed from..." or "formed from...", such terms are used in a formal sense and are not intended to reflect any particular synthesis method or procedure.

[0073] As used herein, the term "hydrocarbon" refers to a compound containing only carbon and hydrogen atoms. Other identifiers can be used to indicate the presence of a specific group (if any) in a hydrocarbon. For example, a halogenated hydrocarbon indicates the presence of one or more halogen atoms replacing an equal number of hydrogen atoms in the hydrocarbon.

[0074] An "aromatic" compound or "aromatic hydrocarbon" 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 hydrocarbons include "arenes" (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 as to maintain 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)). 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.

[0075] As used herein, the term "alkane" refers to a saturated hydrocarbon compound. Other identifiers may be used to indicate the presence of a particular group (if any) in an alkane (e.g., a haloalkane indicates the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the alkane). The term "alkyl" 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 chain.

[0076] "Cycloalkane" is used herein to refer to saturated cyclic hydrocarbons 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., halocycloalkane indicates the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the cycloalkane).

[0077] "Aliphatic" compounds or "aliphatic hydrocarbons" are defined according to the IUPAC recommended definition, meaning acyclic or cyclic, saturated or unsaturated carbon compounds, excluding aromatic compounds. That is, aliphatic compounds are non-aromatic organic compounds.

[0078] The term "hydrocarbyl" is used herein according to the definition specified by IUPAC: a monovalent group formed by removing one hydrogen atom from a hydrocarbon (i.e., a group containing only carbon and hydrogen). Thus, hydrocarbyl includes alkyl (straight or branched chain), cycloalkyl, alkenyl, aryl, and the like. Non-limiting examples of hydrocarbyl include methyl, ethyl, butyl, hexyl, phenyl, tolyl, propenyl, and the like.

[0079] As used herein, "paraffin" refers to a non-cyclic, straight or branched saturated hydrocarbon and includes alkanes. For example, C6 paraffins are non-cyclic, straight or branched hydrocarbons having 6 carbon atoms per molecule. N-hexane, methylpentane, dimethylbutane are examples of C6 paraffins. Paraffin-containing feeds include non-cyclic saturated hydrocarbons such as normal paraffins, isoparaffins, and mixtures thereof.

[0080] As used herein, "naphthene" and "naphthenic" are terms used to describe cyclic saturated hydrocarbons, and include cycloalkanes and alkyl-substituted analogs thereof. Therefore, "cycloalkanes" are cyclic saturated hydrocarbons having one or more carbon atom rings in their chemical structure, and are used herein to mean the same meaning as "cycloalkanes". If this cyclic structure includes unsaturated carbon-carbon bonds but is not aromatic, such compounds will be aliphatic but not cycloalkanes. In some embodiments, cycloalkanes are cyclic saturated hydrocarbons having 5 to 8 carbon atoms in the cyclic structure, including substituted (particularly alkyl-substituted) analogs thereof.

[0081] As used herein, "olefins" are acyclic or cyclic hydrocarbons having one or more carbon-carbon double bonds in addition to the formal double bonds in aromatic compounds. Olefins include alkenes, cycloolefins, and corresponding polyolefins.

[0082] As used herein, "naphtha" is a petroleum fraction with a boiling point in the range of 50°F (10°C) to 550°F (260°C). In some embodiments, the boiling point of naphtha is in the range of 70°F (21°C) to 450°F (232°C), and more typically in the range of 80°F (27°C) to 400°F (204°C), and often in the range of 90°F (32°C) to 360°F (182°C). In some embodiments, at least 85% by volume (volume percent) of the naphtha has a boiling point in the range of 50°F (10°C) to 550°F (260°C), and more typically in the range of 70°F (21°C) to 450°F (232°C). In embodiments, at least 85% by volume of the naphtha is in the range of C4 to C 12 range, more typically between C5 and C 11 range, and often between C6 and C 10 Naphtha can include, for example, straight run naphtha, paraffinic and cycloparaffinic raffinates from aromatic extraction or adsorption, C6 to C 10 Paraffinic and naphthenic feedstocks, bio-derived naphtha, naphtha from hydrocarbon synthesis processes including Fischer-Tropsch and methanol synthesis processes, and naphtha from other refining processes such as hydrocracking or conventional reforming.

[0083] As used herein, the term "convertible hydrocarbons", "convertible C6 materials" or "convertible C7 materials" refers to hydrocarbon compounds that can be selectively converted into aromatic products (such as aromatic hydrocarbons) under aromatization process conditions. In some aspects, the feed stream contains highly branched hydrocarbons that are not selectively converted into aromatic hydrocarbons under conventional aromatization process conditions. And "highly branched hydrocarbons" are hydrocarbons that are not selectively converted to form aromatic hydrocarbons under conventional aromatization process conditions. For example, "highly branched hydrocarbons" may include highly branched hydrocarbons with six or seven carbon atoms and one internal quaternary carbon or hydrocarbons with six carbon atoms and two adjacent internal tertiary carbons or mixtures thereof. Highly branched hydrocarbons may include, but are not limited to, dimethylbutane (e.g., 2,2-dimethylbutane, 2,3-dimethylbutane), dimethylpentane (e.g., 2,2-dimethylpentane, 3,3-dimethylpentane), trimethylbutane (e.g., 2,2,3-trimethylbutane) and mixtures thereof. Highly branched hydrocarbons are not selectively convertible aromatic hydrocarbons, but are converted into light hydrocarbons under aromatization process conditions. The convertible component may include methylpentane, methylhexane, dimethylpentane or a mixture thereof, and / or the selectively convertible component may include at least one of 2-methylpentane, 3-methylpentane, 2,4-dimethylpentane, 2,3-dimethylpentane, n-hexane, 2-methylhexane, 3-methylhexane, n-heptane or a mixture thereof. The selectively convertible component is easily converted into aromatic hydrocarbons without producing light hydrocarbons.

[0084] As used herein, "primary aromatic hydrocarbons," "primary aromatic products," "desired hydrocarbon products," and "specific aromatic species" are used interchangeably and refer to aromatic hydrocarbons that are the desired end product of the reaction and include aromatic hydrocarbons generated from a feedstock that includes a renewable cellulose source. For example, the desired product may be benzene, while toluene and xylene may be byproducts, or the desired product may be xylene, while benzene and toluene may be byproducts.

[0085] "Group 8-10" metals include each of the Group 8 metals iron, ruthenium, and osmium, each of the Group 9 metals cobalt, rhodium, and iridium, and each of the Group 10 metals nickel, palladium, and platinum. The Group 8-10 metals may also be referred to using an earlier nomenclature, i.e., Group VIII metals, which also encompasses all of iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, and platinum. Typically, a catalyst is described as a Group 8-10 metal catalyst or comprising a Group 8-10 metal, and is intended to encompass catalysts comprising at least one Group 8-10 metal and optionally other metals such as Pt / Sn and Pt / Re.

[0086] The term "platinum metal" is used herein to designate the Group 8-10 row 2 and row 3 transition metals, ie, ruthenium, osmium, rhodium, iridium, palladium, and platinum.

[0087] The term "noble metal" is often used to describe a particular metal that is resistant to corrosion, and the term is used herein to include certain 2nd and 3rd row transition metals, but not 1st row transition metals. Typically, noble metals include ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, and gold. Thus, a Group 8-10 noble metal is also a platinum metal.

[0088] As used herein, the term "bound" is intended to describe a zeolite-binder combination or other carrier-binder combination formed into an aggregate such as a pellet, tablet, extrudate, etc. As used herein, the term "catalyst matrix" refers to a bound zeolite or a bound carrier.

[0089] The term "catalyst" is used in a broad sense herein and includes the final catalyst as well as a precursor of the final catalyst. Precursors of the final catalyst include, for example, a calcined form of the catalyst containing the catalytic metal and a catalyst prior to activation by reduction. Thus, the term "catalyst" is used in some contexts herein to refer to an activated catalyst and in other contexts to refer to a precursor form of the catalyst, as will be understood by those skilled in the art from the context.

[0090] The term "sulfur sensitivity" describes a catalyst that is particularly sensitive to the presence of sulfur in the feedstock. Typically, these catalysts require the amount of sulfur in the feedstock to be reduced to less than 5ppm by hydroprocessing, adsorbents, or a combination thereof. As used herein, when referring to an aromatization reactor system, the terms "aromatization reactor system," "aromatization reactor unit," "catalytic reactor system," and "catalytic reactor unit" also refer to reactor vessels, reactor interiors, and associated process equipment (depending on the context), including but not limited to catalysts, inert fillers, pits, flow distributors, center tubes, reactor ports, catalyst transmission and distribution systems, furnaces and other heating devices, heat transfer equipment, and pipelines. The aromatization reactor system may include a fixed catalyst bed system, a mobile catalyst bed system, a fluidized catalyst bed system, or a combination thereof. Such an aromatization reactor system may be intermittent or continuous. In a fixed bed system, the feed stream may pass through the reactor upward, downward, or radially. In one aspect, the first catalyst bed, the intermediate catalyst bed, and the last catalyst bed are located in a radial flow reactor.

[0091] The term "catalyst bed", such as a first, second or intermediate catalyst bed, is used herein to refer to a specific catalyst composition that constitutes at least a portion or all of the catalyst material in a single aromatization reactor. For example, a "first catalyst bed" may occupy all of an aromatization reactor, or it may occupy a portion of an aromatization reactor, while a "second catalyst bed" occupies the remainder of the aromatization reactor. More typically, each catalyst bed may occupy all of an aromatization reactor. Typically, and unless otherwise specified or the context requires otherwise, multiple aromatization reactors are described as having different catalyst beds, regardless of whether their catalysts have the same or different compositions.

[0092] The term "halogen" has its ordinary meaning and includes halides where the context permits. Thus, examples of halogens include fluorine, fluoride, chlorine, chloride, bromine, bromide, iodine and iodide. In addition, when describing catalyst components or catalyst compositions (such as weight percent or molar percent of these components), the use of the terms "fluoride" and "chloride" does not depend on their presence in the catalyst in any particular molecular or ionic form.

[0093] The molar selectivity is defined as follows:

[0094]

[0095] Conversion is defined as the number of moles converted per mole of "convertible" hydrocarbon feed, as follows:

[0096]

[0097] In the selectivity and conversion calculations in Equations 1-7, the following abbreviations are used: Indicates the molar flow rate in a continuous reactor or the number of moles in a batch reactor; "conv" is used to mean "convertible" and represents the convertible C6, C7 or C6-C8+ compounds remaining in the starting material or feed ("feed") or in the product ("prod"), as indicated.

[0098] The term "tonne" is used herein to refer to the metric ton, a unit of mass equal to 1,000 kilograms.

[0099] The abstract of this application is not intended to be used to interpret the scope of the claims or to limit the scope of the subject matter disclosed herein, but is intended to satisfy the requirements of 37 CFR § 1.72 (b) so that the U.S. Patent and Trademark Office and the public can quickly determine the nature and gist of the technical disclosure by a cursory inspection. In addition, any title adopted herein is not intended to be used to interpret the scope of the claims or to limit the scope of the subject matter disclosed herein. Any use of the past tense to describe any example otherwise indicated as constructive or prophetic is not intended to reflect that the constructive or prophetic example has actually been implemented.

[0100] All publications and patents mentioned herein are incorporated herein by reference as a whole for the purpose of description and disclosure, such as describing and disclosing the constructs and methods described in the publications, which can be used in combination with the presently described invention. The publications discussed in full are provided only for their disclosures prior to the filing date of this application. Any content of this article shall not be construed as admitting that the inventor has no right to precede these disclosures due to previous inventions.

[0101] Those skilled in the art will readily appreciate that many modifications may be made to the exemplary embodiments disclosed herein without departing substantially from the novel teachings and advantages of the present disclosure. Therefore, all such modifications and equivalents are intended to be included within the scope of the present disclosure as defined by the following claims. Therefore, it should be understood that, after reading the description herein, those of ordinary skill in the art may conceive of making various other aspects, embodiments, modifications, and their equivalents without departing from the spirit of the present disclosure or the scope of the appended claims.

[0102] The present disclosure generally relates to systems and methods for producing aromatic hydrocarbons from aliphatic hydrocarbons using a series of catalyst beds, wherein the fluorine content, chlorine content, or both the fluorine and chlorine content of the catalyst composition can be varied in at least two adjacent catalyst beds. More specifically, the present disclosure provides a process and system for reforming hydrocarbons by using a series of adiabatic reactors and catalysts, wherein the catalyst in at least one front or upstream catalyst bed includes a higher fluoride content, a higher chloride content, or both a higher fluoride content and a higher chloride content than the catalyst in one or more downstream catalyst beds. It has been unexpectedly discovered that by using a higher weight percentage of fluoride and / or chloride in at least one upstream catalyst bed or reactor compared to one or more downstream catalyst beds or reactors, the service life of the catalyst system can be extended by maintaining the selectivity of the catalyst system for longer than expected.

[0103] The present disclosure also demonstrates the different effects of fluoride and chloride in the operation of aromatization catalyst. It is observed that fluoride can act as a selectivity enhancer, and chloride can improve the distribution of platinum in the catalyst. Both fluoride and chloride also work in a synergistic manner, and the catalyst containing two halides is better than the catalyst containing only one halide and is better than the additive effect of using a single halide. In the present disclosure, we demonstrate that the upper part of the catalyst bed loaded with a high halide catalyst can increase the total run length by interacting with the released halide and downstream catalyst. This result is unexpected, because during the operating life of the catalyst, fluoride may slowly evolve into a product, which may cause a reduction in selectivity and run length. Chloride may also be released, but the release of the observed chloride promotes the sintering of platinum, which may also reduce selectivity and activity. Therefore, it is observed that a fixed bed reactor is loaded with the upper part (such as the upper half) of a bed comprising a high halide catalyst (high fluorine catalyst, high chloride catalyst or both), and then a reduction step is performed, which improves the performance of the catalyst in the lower half of the catalyst bed.

[0104] General considerations

[0105] In some embodiments, the present disclosure provides two consecutive catalysts or catalyst beds in series, comprising an inorganic support, a Group 8-10 metal, and the fluoride or chloride concentration in the first upstream catalyst relative to the weight of the upstream catalyst before reduction. The catalyst or catalyst bed (including the one immediately downstream) may contain a relatively low weight percentage of fluoride or chloride relative to the weight of the downstream catalyst before reduction.

[0106] Thus, in one aspect, the present disclosure provides a process for reforming hydrocarbons, the process comprising:

[0107] a) contacting a feedstock containing an aliphatic hydrocarbon with a first catalyst (comprising an inorganic support, a Group 8-10 metal, and at least or about 1.0 weight percent of a fluoride relative to the weight of the first catalyst before reduction) in a first catalyst bed under conditions to aromatize the aliphatic hydrocarbon to form a first catalyst bed effluent comprising aromatic hydrocarbons and aliphatic hydrocarbons;

[0108] b) optionally, in one or more intermediate catalyst beds in series, contacting the first catalyst bed effluent with one or more independently selected intermediate catalysts (each comprising an inorganic support, a Group 8-10 metal, and a fluoride) under conditions to aromatize aliphatic hydrocarbons to form one or more intermediate catalyst bed effluents comprising aromatic hydrocarbons and aliphatic hydrocarbons; and

[0109] c) in a final catalyst bed, [1] contacting a first catalyst bed effluent with a final catalyst or [2] when one or more optional intermediate catalyst beds are present, contacting one or more intermediate catalyst bed effluents with a final catalyst under conditions for aromatizing aliphatic hydrocarbons to form a final catalyst bed effluent comprising an aromatic product, wherein the final catalyst comprises an inorganic support, a Group 8-10 metal, and at least or about 0.7 weight percent fluoride relative to the weight of the final catalyst prior to reduction;

[0110] wherein the fluoride concentration of the first catalyst or the fluoride concentration of at least one of the intermediate catalysts (when present) is higher than the fluoride concentration of the last catalyst prior to reduction.

[0111] Similarly, in another aspect, the present disclosure provides a process for reforming hydrocarbons, the process comprising:

[0112] a) contacting a feedstock containing an aliphatic hydrocarbon with a first catalyst (comprising an inorganic support, a Group 8-10 metal, and at least or about 1.5 weight percent chloride relative to the weight of the first catalyst before reduction) in a first catalyst bed under conditions to aromatize the aliphatic hydrocarbon to form a first catalyst bed effluent comprising aromatic hydrocarbons and aliphatic hydrocarbons;

[0113] b) optionally, in one or more intermediate catalyst beds in series, contacting the first catalyst bed effluent with one or more independently selected intermediate catalysts (each comprising an inorganic support, a Group 8-10 metal, and a chloride) under conditions to aromatize aliphatic hydrocarbons to form one or more intermediate catalyst bed effluents comprising aromatic hydrocarbons and aliphatic hydrocarbons; and

[0114] c) in a final catalyst bed, [1] contacting the first catalyst bed effluent with a final catalyst or [2] when one or more optional intermediate catalyst beds are present, contacting one or more intermediate catalyst bed effluents with a final catalyst under conditions for aromatizing aliphatic hydrocarbons to form a final catalyst bed effluent comprising an aromatic product, wherein the final catalyst comprises an inorganic support, a Group 8-10 metal, and at least or about 0.5 weight percent chloride relative to the weight of the final catalyst prior to reduction;

[0115] wherein the chloride concentration of the first catalyst or the chloride concentration of at least one of the intermediate catalysts (when present) is higher than the chloride concentration of the last catalyst prior to reduction.

[0116] The process aspects immediately above describe a "first" and a "last" catalyst, wherein two catalyst beds are adjacent to each other. However, these aspects also describe one or more optional intermediate catalyst beds in series located between the upstream (first) and downstream (last) catalyst beds. Thus, the weight percentages of fluoride or chloride recited in the first and last catalysts apply to adjacent catalysts or to two catalysts that are not adjacent but are characterized by the recited fluoride or chloride concentrations.

[0117] The present disclosure also provides a catalytic hydrocarbon reforming system, the system comprising:

[0118] Two or more catalyst beds connected in series, the catalyst beds comprising an upstream first catalyst bed and a downstream last catalyst bed;

[0119] a first catalyst in the first catalyst bed, the first catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 1.0 weight percent fluoride relative to the weight of the first catalyst prior to reduction;

[0120] Optionally, one or more independently selected intermediate catalysts in the one or more intermediate catalyst beds downstream of the first catalyst bed, each intermediate catalyst comprising an inorganic support, a Group 8-10 metal, and a fluoride; and

[0121] a last catalyst in a last catalyst bed downstream of the first catalyst bed and any optional intermediate catalyst beds, the last catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 0.7 weight percent fluoride relative to the weight of the last catalyst prior to reduction;

[0122] wherein the fluoride concentration of the first catalyst or the fluoride concentration of at least one of the intermediate catalysts (when present) is higher than the fluoride concentration of the last catalyst prior to reduction.

[0123] Similarly, in another aspect, the present disclosure also provides a catalytic hydrocarbon reforming system, the system comprising:

[0124] Two or more catalyst beds connected in series, the catalyst beds comprising an upstream first catalyst bed and a downstream last catalyst bed;

[0125] a first catalyst in the first catalyst bed, the first catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 1.5 weight percent chloride relative to the weight of the first catalyst prior to reduction;

[0126] Optionally, one or more independently selected intermediate catalysts in the one or more intermediate catalyst beds downstream of the first catalyst bed, each intermediate catalyst comprising an inorganic support, a Group 8-10 metal, and a chloride; and

[0127] a last catalyst in a last catalyst bed downstream of the first catalyst bed and any optional intermediate catalyst beds, the last catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 0.5 weight percent chloride relative to the weight of the last catalyst prior to reduction;

[0128] wherein the chloride concentration of the first catalyst or the chloride concentration of at least one of the intermediate catalysts (when present) is higher than the chloride concentration of the last catalyst prior to reduction.

[0129] The system aspects immediately above describe a "first" and "last" catalyst, wherein two catalyst beds are adjacent to each other. However, one or more optional intermediate catalyst beds in series located between the upstream (first) and downstream (last) catalyst beds in these systems are also described. Thus, the weight percentages of fluoride or chloride recited in the first and last catalysts apply to adjacent catalysts or to two catalysts that are not adjacent but are characterized by the recited fluoride or chloride concentrations.

[0130] Fluoride and chloride concentrations

[0131] In each of the processes and systems recited, there are practical upper limits to the concentrations of fluoride and chloride in the catalyst. For example, in a fluoride-containing catalyst, the first catalyst may contain up to about 5.0 wt. %, up to about 4.0 wt. %, up to about 3.5 wt. %, up to about 3.0 wt. %, or up to about 2.5 wt. % fluoride relative to the weight of the final catalyst before reduction, and the final catalyst may contain up to about 4.0 wt. %, up to about 3.0 wt. %, up to about 2.5 wt. %, up to about 2.0 wt. %, or up to about 1.5 wt. % fluoride relative to the weight of the final catalyst before reduction. In chloride-containing catalysts, the first catalyst may contain up to about 5.0 wt. %, up to about 4.0 wt. %, up to about 3.5 wt. %, up to about 3.0 wt. %, or up to about 2.5 wt. % chloride relative to the weight of the final catalyst before reduction, and the final catalyst may contain up to about 3.0 wt. %, up to about 2.5 wt. %, up to about 2.0 wt. %, or up to about 1.5 wt. % chloride relative to the weight of the final catalyst before reduction.

[0132] According to one aspect of the catalyst compositions or processes disclosed herein, any first catalyst, any one or more intermediate catalysts, any last catalyst, or any combination thereof, for which a fluoride concentration is listed and which is independent of any other catalyst described in the composition or process, may further comprise a chloride at any concentration as disclosed herein. Similarly, in any catalyst composition or process disclosed herein, any first catalyst, any one or more intermediate catalysts, any last catalyst, or any combination thereof, for which a chloride concentration is listed and which is independent of any other catalyst described in the composition or process, may further comprise a fluoride at any concentration as disclosed herein.

[0133] With respect to fluoride concentration, any first catalyst as described herein may also include a fluoride in a concentration range of about 1.0 wt % to about 4.0 wt %, about 1.2 wt % to about 3.2 wt %, about 1.5 wt % to about 2.8 wt %, about 1.7 wt % to about 2.5 wt %, or about 1.8 wt % to about 2.3 wt % relative to the weight of the first catalyst before reduction. Any one or more intermediate catalysts, the final catalyst, or any combination thereof may independently include a fluoride in a concentration range of about 0.7 wt % to about 2.5 wt %, about 0.8 wt % to about 2.3 wt %, about 0.9 wt % to about 2.0 wt %, about 1.0 wt % to about 2.0 wt %, or about 1.2 wt % to about 1.8 wt % relative to the weight of the corresponding intermediate catalyst or the final catalyst before reduction.

[0134] In another aspect, any fluoride-containing catalyst listed herein, whether it is the first catalyst, any one or more intermediate catalysts, the last catalyst or any combination thereof, can independently further include a chloride in a concentration range of about 1.5 wt % to about 4.0 wt %, about 1.8 wt % to about 3.6 wt %, about 2.2 wt % to about 3.4 wt % or about 2.0 wt % to about 3.3 wt % relative to the weight of the corresponding first catalyst, intermediate catalyst or last catalyst before reduction. Alternatively, any fluoride-containing catalyst listed herein, whether it is the first catalyst, any one or more intermediate catalysts, the last catalyst or any combination thereof, can independently further include a chloride in a concentration range of about 0.5 wt % to about 2.5 wt %, about 0.6 wt % to about 2.3 wt %, about 0.7 wt % to about 2.0 wt % or about 0.8 wt % to about 1.7 wt % relative to the weight of the corresponding first catalyst, intermediate catalyst or last catalyst before reduction. In these aspects, the chloride concentration of these first catalysts can be higher than the chloride concentration of these last catalysts before reduction. These catalysts may also have a higher chloride concentration than the chloride concentration of the adjacent downstream catalyst prior to reduction.

[0135] With regard to chloride concentration, any first catalyst as described herein may also include a chloride in a concentration range of about 1.5 wt % to about 4.0 wt %, about 1.8 wt % to about 3.6 wt %, about 2.2 wt % to about 3.4 wt %, or about 2.0 wt % to about 3.3 wt %, relative to the weight of the first catalyst before reduction. Any one or more intermediate catalysts, the final catalyst, or any combination thereof may independently include a chloride in a concentration range of about 0.5 wt % to about 2.5 wt %, about 0.6 wt % to about 2.3 wt %, about 0.7 wt % to about 2.0 wt %, or about 0.8 wt % to about 1.7 wt %, relative to the weight of the corresponding intermediate catalyst or the final catalyst before reduction.

[0136] In another aspect, any chloride-containing catalyst listed herein, whether the first catalyst, any one or more intermediate catalysts, the last catalyst or any combination thereof, can independently further comprise a fluoride in a concentration range of about 1.0 wt % to about 4.0 wt %, about 1.2 wt % to about 3.2 wt %, about 1.5 wt % to about 2.8 wt %, about 1.7 wt % to about 2.5 wt % or about 1.8 wt % to about 2.3 wt % relative to the weight of the corresponding first catalyst, intermediate catalyst or last catalyst before reduction. Alternatively, any chloride-containing catalyst listed herein, whether the first catalyst, any one or more intermediate catalysts, the last catalyst or any combination thereof, can independently further comprise a fluoride in a concentration range of about 0.7 wt % to about 2.5 wt %, about 0.8 wt % to about 2.3 wt %, about 0.9 wt % to about 2.0 wt %, about 1.0 wt % to about 2.0 wt % or about 1.2 wt % to about 1.8 wt % relative to the weight of the corresponding first catalyst, intermediate catalyst or last catalyst before reduction. In these aspects, the fluoride concentration of the first catalysts can be higher than the fluoride concentration of the last catalysts before reduction. The fluoride concentration of these catalysts can also be higher than the fluoride concentration of the adjacent downstream catalysts before reduction.

[0137] According to another aspect, any one or more of the first catalyst, the intermediate catalyst, and / or the final catalyst can independently comprise any chlorine to fluorine (Cl:F) weight ratio disclosed herein, for example, from about 1.5:1 to about 8:1, from about 2:1 to about 5:1, or from about 3:1 to about 4.5:1. In addition, any one or more of the first catalyst, the intermediate catalyst, and / or the final catalyst can independently comprise a chlorine to fluorine (Cl:F) weight ratio of from about 1:10 to about 10:1, from about 1:5 to about 5:1, or from about 1:2 to about 2:1.

[0138] In embodiments, the fluoride concentration of the first catalyst may be 10% to 50% higher, 25% to 65% higher, or 50% to 90% higher than the fluoride concentration of the final catalyst. In embodiments, the chloride concentration of the first catalyst may be 10% to 50% higher, 25% to 65% higher, or 50% to 90% higher than the chloride concentration of the final catalyst.

[0139] In the processes and systems disclosed herein, for any fluoride-containing catalyst listed herein that further comprises chloride, the first catalyst may further comprise about 0.5 wt % to about 5 wt % chloride relative to the weight of the first catalyst before reduction, and the last catalyst may further comprise about 0.5 wt % to about 5 wt % chloride relative to the weight of the last catalyst before reduction. In addition, in the processes and systems disclosed herein, for any chloride-containing catalyst listed herein that further comprises fluoride, the first catalyst may further comprise about 0.5 wt % to about 5 wt % fluoride relative to the weight of the first catalyst before reduction, and the last catalyst may further comprise about 0.5 wt % to about 5 wt % fluoride relative to the weight of the last catalyst before reduction. In addition, in the embodiments of the processes and systems disclosed herein, any one or more of the first catalyst, the intermediate catalyst, and / or the last catalyst may comprise a combined concentration of up to about 5 wt % fluoride and chloride relative to the weight of the catalyst before reduction.

[0140] Thus, in another aspect, the fluoride concentration (wt%) of each of the one or more independently selected intermediate catalysts at startup can be greater than or equal to the fluoride concentration of the last catalyst before reduction. The chloride concentration (wt%) of each of the one or more independently selected intermediate catalysts at startup can be greater than or equal to the chloride concentration of the last catalyst before reduction.

[0141] In other aspects, the fluoride concentration (wt%) of one or more independently selected intermediate catalysts at startup can be lower than or equal to the fluoride concentration of the first catalyst before reduction and higher than or equal to the fluoride concentration of the last catalyst before reduction. Similarly, the chloride concentration (wt%) of one or more independently selected intermediate catalysts at startup can be lower than or equal to the chloride concentration of the first catalyst before reduction and higher than or equal to the chloride concentration of the last catalyst before reduction.

[0142] Alternatively, in other aspects, the fluoride concentration (wt%) of one or more independently selected intermediate catalysts at startup can be greater than or equal to the fluoride concentration of the first catalyst before reduction and greater than or equal to the fluoride concentration of the last catalyst before reduction. Similarly, the chloride concentration (wt%) of one or more independently selected intermediate catalysts at startup can be greater than or equal to the chloride concentration of the first catalyst before reduction and greater than or equal to the chloride concentration of the last catalyst before reduction.

[0143] It is understood that the reduction of the catalyst in the catalyst bed results in a decrease in the halide concentration, such that the weight percentage of fluoride and / or chloride relative to the weight of the catalyst will decrease relative to the weight percentage prior to reduction. As an example and not limitation, an upstream catalyst containing 1.5 weight percent fluoride prior to reduction may contain approximately from about 0.6 weight percent to about 1.0 weight percent fluoride after reduction, based on the specific catalyst, reduction conditions, etc.

[0144] Typically, the raw material for the aromatization process is naphtha, a petroleum distillate that can be generated from crude oil, condensate or other suitable sources. The naphtha feedstock can contain light hydrocarbons with a boiling range of about 20°C to about 235°C. The naphtha feed can contain aliphatic hydrocarbons, cycloalkanes or paraffins. Although catalytic aromatization generally refers to the conversion of naphtha, other raw materials can also be used. For example, paraffins, olefins, acetylenics, cyclic paraffins, cyclic olefins and mixtures thereof, and particularly saturated hydrocarbons can also be reformed to provide products rich in aromatic hydrocarbons. The specific aromatic hydrocarbons produced depend on, for example, the composition of the raw materials and the composition of the catalyst and the reforming conditions.

[0145] It is generally believed that the sulfur content of the feedstock can be minimized to prevent poisoning of the reforming catalyst. For example, the feed may contain less than 2 to 5 parts per million (ppm) by weight of sulfur, because the presence of sulfur in the feed may reduce both the activity and selectivity of the catalyst. Some reforming catalysts are extremely sensitive to sulfur, and even if the sulfur level in the feed is less than 1ppm, these catalysts may be seriously deactivated. For sulfur-sensitive catalysts, the feed may contain less than 1,000 parts per billion (ppb), less than 600ppb, less than 300ppb, less than 100ppb or 5ppb to 50ppb by weight of the feed. The aspect of removing sulfur from the feedstock can be found in U.S. Patent Nos. 5,059,304, 5,259,946 and 5,518,607, each of which is incorporated herein by reference.

[0146] Non-acidic Pt-L zeolite is an example of such a sulfur-sensitive catalyst. Examples of Pt-KL zeolite catalysts are described in, for example, U.S. Patent Nos. 4,104,320 (Bernard et al.), 4,544,539 (Wortel) and 4,987,109 (Kao et al.), each of which is incorporated herein by reference. Examples of Pt-KL zeolite catalysts are described in U.S. Patent No. 4,517,306 (Buss et al.), which is incorporated herein by reference. It is disclosed in U.S. Patent No. 4,456,527 that such catalysts can achieve satisfactory run lengths only when the sulfur content of the feed is significantly reduced, which is incorporated herein by reference. The lower the sulfur content of the feed, the longer the run length of the catalyst.

[0147] In one aspect, the upstream "high halide" reforming catalyst can contain up to 50 wt%, about 50 wt%, or more than about 50 wt% additional halide, whether fluoride or chloride, than the amount of halide in a conventional or standard catalyst formulation. For example, if the conventional halide loading in the reforming catalyst is about 1.0 wt% halide, in this example, the high halide reforming catalyst can have up to about 1.5 wt% halide. In some aspects, the upstream high halide catalyst can have about 10 wt % additional halide, about 20 wt % additional halide, about 30 wt % additional halide, about 40 wt % additional halide, about 50 wt % additional halide, about 60 wt % additional halide, about 70 wt % additional halide, about 80 wt % additional halide, about 90 wt % additional halide, or about 100 wt % additional halide compared to the amount of halide in the downstream catalyst.

[0148] Catalyst beds and reactors

[0149] As described in the definition section, the term "catalyst bed" is used herein to refer to a specific catalyst composition that constitutes at least a portion or all of the catalyst material in a single aromatization reactor. For example, a "first catalyst bed" can occupy all of an aromatization reactor, or can occupy a portion of an aromatization reactor. Therefore, in one aspect, a process or catalytic hydrocarbon reforming system for reforming hydrocarbons according to the present disclosure can have each of a first catalyst bed, one or more intermediate catalyst beds, and a final catalyst bed in different reactors. Alternatively, two adjacent catalyst beds in series mean two adjacent catalysts having different specific catalyst compositions, and the catalyst beds can be located in a single reactor. Alternatively, more than two adjacent catalyst beds in series can be located in a single reactor. Typically, each different catalyst bed means each different catalyst composition, and the catalyst bed is located in a single reactor.

[0150] According to one aspect, the aromatization reactors in series may include 2, 3, 4, 5, 6, 7, 8, 9, 10 or more reactors in series. In one aspect, a process for reforming hydrocarbons or a catalytic hydrocarbon reforming system is provided, wherein: the process or system includes 1 to 6 intermediate catalyst beds, the 1 to 6 intermediate catalyst beds respectively containing 1 to 6 intermediate catalysts; and the first catalyst bed, the 1 to 6 intermediate catalyst beds and the last catalyst bed are all located in different reactors. In one aspect, the reactor system includes 4 intermediate catalyst beds, or alternatively includes 5 intermediate catalyst beds.

[0151] In another aspect, the present disclosure provides a process for reforming hydrocarbons and further discloses a catalytic hydrocarbon reforming system, wherein: the process or system includes 1 to 6 intermediate catalyst beds, the 1 to 6 intermediate catalyst beds respectively contain 1 to 6 intermediate catalysts, the first catalyst bed, the 1 to 6 intermediate catalyst beds and the last catalyst bed are all located in different reactors, and the fluoride concentration and chloride concentration (weight %) in each of the 1 to 6 intermediate catalysts at startup can be selected independently of the fluoride concentration and chloride concentration in any other catalyst, so that the fluoride concentration and chloride concentration in any or all of the first catalyst bed and one or more intermediate catalyst beds are higher than the fluoride concentration and chloride concentration of the last catalyst bed before reduction. In other aspects, the process or system may include 1 to 6 or more (e.g., 7, 8 or 9) intermediate catalyst beds, the intermediate catalyst beds respectively contain 1 to 6 or more (e.g., 7, 8 or 9) intermediate catalysts, and the intermediate catalyst beds are distributed in reactors less than this number. That is, at least two adjacent catalysts and catalyst beds selected from the first catalyst bed, 1 to 6 intermediate catalyst beds and the last catalyst bed are located in the same reactor.

[0152] For example, in other aspects, the process and / or system of the present disclosure may include 4 or 5 intermediate catalyst beds, wherein each of the first catalyst bed, the intermediate catalyst bed, and the last catalyst bed is located in its own reactor. In one other aspect, the present disclosure provides a process for reforming hydrocarbons or a catalytic hydrocarbon reforming system, wherein: the process or system includes 4 or 5 intermediate catalyst beds, each of the 4 or 5 intermediate catalyst beds contains its own corresponding intermediate catalyst; the first catalyst bed, the 4 or 5 intermediate catalyst beds, and the last catalyst bed are each located in a different reactor; and the volume of each of the 4 or 5 intermediate reactors is greater than or equal to the volume of the first reactor and less than or equal to the volume of the last reactor.

[0153] For example, in an embodiment where the process or system includes 4 intermediate catalyst beds (each of the 4 intermediate catalyst beds contains its own corresponding intermediate catalyst and each is located in a different reactor), the volume of each of the 4 intermediate reactors and the last reactor is greater than or equal to the volume of the reactor immediately upstream of the reactor. In one aspect, the relative volumes of the first reactor, the 4 intermediate reactors, and the last reactor can be, for example, 10:10:10:20:20:30. In another aspect, the relative volumes of the first reactor, the 4 intermediate reactors, and the last reactor can be, for example, 10:10:10:15:20:25; alternatively, 10:10:10:20:30:40; or alternatively, 10:10:15:20:20:30; or alternatively, 10:10:15:20:25:30.

[0154] Typically, processes for reforming hydrocarbons involve heating a first catalyst bed effluent and / or one or more intermediate catalyst bed effluents prior to entering a subsequent catalyst bed. Accordingly, the present disclosure also provides a catalytic hydrocarbon reforming system comprising at least one furnace upstream of a first catalyst bed and / or any one or more intermediate catalyst beds.

[0155] According to one aspect, and while not intending to be bound by theory, it has been found that the overall catalyst bed (e.g., in a commercial plant having 6 or more reactors in series) The first approximately 25% to 50% of the volume of reactors 1, 2 and 3) may experience low activity in the early stages of operation due to what is believed to be higher than optimal halide concentrations (including fluoride concentrations). While not intending to be bound by theory, and with respect to fluoride concentrations, as fluoride / fluorine is released from the catalyst, it is believed that fluoride will be transferred to the downstream catalyst and / or the loss of fluoride from the downstream catalyst is suppressed due to the maintenance of the vapor pressure of F in the gas phase. It is believed that higher fluoride concentrations on the downstream catalyst may slow the rate of selectivity decline and the rate of deactivation of the downstream catalyst. Since the upstream catalyst is operated at a low degree of reaction, levels above the optimal fluoride level are not expected to affect the selectivity or run length of the upstream catalyst.

[0156] Aromatization catalyst

[0157] Typically, the aromatization catalyst may include an inorganic carrier, a Group 8-10 metal (such as platinum), and one or more halides (such as fluorine, chlorine, iodine, bromine, or a combination thereof). In some embodiments, the catalyst may include a Group 8-10 metal on an inorganic carrier, such as platinum on alumina, Pt / Sn on alumina, and Pt / Re on alumina. In other embodiments, the catalyst may include a platinum metal on a zeolite carrier, such as Pt, Pt / Sn, and Pt / Re on a zeolite carrier, and the zeolite carrier may include a binder and a zeolite, such as L zeolite, X zeolite, mordenite, mazzite, and ZSM-5. Other catalysts may include platinum metal, fluorine, and chlorine, typically on an alkali metal and alkaline earth metal exchanged L zeolite. The catalyst may include a macropore zeolite as an inorganic carrier, which carries at least one Group 8-10 metal. For example, the catalyst in the process and system may include a low-acid silica-bound potassium L-type zeolite carrier, platinum, chloride, and fluoride. In an embodiment, the Group 8-10 metal may include platinum, which may be more selective for dehydrocyclization and may be more stable than other Group 8-10 metals under reforming reaction conditions. In other embodiments, the catalyst may include a Group 7 metal such as rhenium or a Group 14 metal or metalloid such as tin.

[0158] Examples of reforming / aromatization catalysts that can be used in the methods and systems of the present disclosure include, but are not limited to, HYDROXY- ... Catalysts of the invention include catalysts of the invention which may be used, for example, as downstream lower halide content catalysts in the systems and processes disclosed herein; catalysts discussed in U.S. Pat. No. 6,812,180 to Fukunaga, entitled “Method for Preparing Catalyst”; catalysts disclosed in U.S. Pat. No. 7,153,801 to Wu, entitled “Aromatization Catalyst and Methods of Making and Using Same”; and catalysts such as halogenated zeolite catalysts described in U.S. Pat. No. 6,190,539 to Holtermann et al., entitled “Reforming Using a Bound Halided Zeolite Catalyst”; catalysts disclosed in U.S. Pat. No. 7,902,105 to Khare, entitled “Aromatization catalyst comprising prolonged silica and methods of making and using same”; catalysts disclosed in U.S. Pat. No. 7,902,105 to Alvez-Manoli, entitled “Acidic Aromatization Catalyst with Improved Activity and The catalysts disclosed in U.S. Patent Publication No. 2018 / 0065115 entitled "Catalyst Stability", each of which is incorporated herein by reference in its entirety. That is, any catalyst disclosed in these references can be used to prepare an upstream high-halide reforming catalyst, which can contain up to 50 wt%, about 50 wt%, or more than about 50 wt% of additional halide, such as fluoride, than the amount of halide in the downstream catalyst and / or the amount of halide in the conventional catalyst formulation.

[0159] In one aspect, the catalyst may comprise a non-acidic zeolite support as an inorganic support, a Group 8-10 metal or other suitable metal and one or more halides. Suitable halides include chlorides, fluorides, bromides, iodides or combinations thereof. Suitable Group 8-10 metals include iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum or combinations thereof. In other aspects, the Group 8-10 metal may comprise or may be selected from rhodium, iridium, rhodium, iridium, palladium and / or platinum, i.e. one of more than one so-called platinum metals.

[0160] The inorganic carrier for aromatization catalyst can generally include any inorganic oxide. These inorganic carriers include combined macroporous aluminosilicates (zeolites), amorphous inorganic oxides and mixtures thereof. Macroporous aluminosilicates include but are not limited to L zeolite, X zeolite, mordenite, needle zeolite, ZSM-5, etc. Amorphous inorganic oxides include but are not limited to aluminum oxide, silicon oxide and titanium dioxide. Suitable binders for inorganic carriers include but are not limited to silicon dioxide, aluminum oxide, clay, titanium dioxide, magnesium oxide and combinations thereof.

[0161] The inorganic carrier can be an aluminosilicate, such as a zeolite. In an embodiment, the aromatization catalyst can comprise a zeolite catalyst. Both natural zeolite materials and synthetic zeolite materials can have suitable catalytic properties for many hydrocarbon processes (including aromatization). Therefore, the zeolite can include a group of natural or synthetic hydrated aluminosilicate minerals, which generally contain alkali metals and alkaline earth metals. The characteristic of zeolites is that the framework structure surrounds interconnected cavities, which are occupied by large metal cations (such as potassium) and water molecules that can be ion-exchanged, thereby achieving reversible dehydration. The actual formula of the zeolite can be changed without changing the crystal structure. In one embodiment, the molar ratio of silicon to aluminum (Si / Al) in the zeolite can vary between about 1.0 and about 3.5.

[0162] Typically, in one aspect, the first catalyst, the intermediate catalyst and the final catalyst each independently comprise an inorganic support, the inorganic support comprising a crystalline or amorphous inorganic oxide or a combination thereof. In addition to the first catalyst, the intermediate catalyst and the final catalyst each independently comprising an inorganic support (comprising or selected from zeolite or silica-bound zeolite), the inorganic support may comprise or be selected from any one of clay minerals, silica, alumina, silica-alumina, aluminum phosphate, heteropolytungstates, titania, zirconium oxide, magnesium oxide, boron oxide, zinc oxide, mixed oxides thereof, zeolites bound to silica or mixtures thereof.

[0163] According to another aspect, the inorganic carrier of the first catalyst, one or more intermediate catalysts and / or the last catalyst (such as zeolite disclosed herein) can each further independently include a binder.Any weight percentage of the binder disclosed herein, for example, is independently about 3 wt % to about 35 wt % or about 5 wt % to about 30 wt % of the gross weight based on the first catalyst, the intermediate catalyst and the last catalyst.In this regard, for example, the binder of each inorganic carrier can independently include inorganic solid oxide, clay or its combination, such as aluminum oxide, silicon dioxide, magnesium oxide, boron oxide, titanium dioxide, zirconium oxide, its mixed oxide or its mixture.No matter these oxide materials, in addition to the material (such as zeolite) combined, also serve as the carrier of the 8th group metal catalyst to what extent, the term "binder" is used.The example of binder carrier or abbreviation "inorganic carrier" includes or includes L zeolite, L zeolite or K / L zeolite of L zeolite, barium ion exchange of L zeolite or L zeolite of L zeolite combined with silicon dioxide or aluminum oxide combined with aluminum oxide.

[0164] The inorganic support of the present disclosure can be independently produced by a process comprising the following steps in this exemplary aspect: a) combining L zeolite, barium ion-exchanged L zeolite or K / L zeolite with silica or alumina sol to form a mixture, extruding the mixture to form an extrudate, b) drying and calcining the extrudate to form a bonded support; and c) washing, drying and calcining the bonded support to form the inorganic support. Thus, the inorganic support of the first catalyst, one or more intermediate catalysts and / or the final catalyst can be described as each independently comprising at least one zeolite and at least one binder.

[0165] In some aspects, the aromatization catalyst support can comprise a large pore zeolite. The term "large pore zeolite" can be defined as a zeolite having a pore size of about to about or about to about The zeolite of effective pore size. Examples of large-pore crystalline zeolites are L-type zeolite (zeolite L or LTL), X zeolite (zeolite X), Y zeolite (zeolite Y), Ω zeolite, beta zeolite, ZSM-4, ZSM-5, ZSM-10, ZSM-12, ZSM-20, REY, USY, RE-USY, LZ-210, LZ-210-A, LZ-210-M, LZ-210-T, SSZ-24, SSZ-26, SSZ-31, SSZ-33, SSZ-35, SSZ-37, SSZ-41, SSZ-42, SSZ-44, MCM-58, mordenite, needle zeolite, faujasite and combinations thereof. In one aspect, the large-pore zeolite may comprise a homologous framework structure. In one embodiment, the aromatization catalyst support may comprise L zeolite.

[0166] L zeolite, its x-ray diffraction pattern, its properties and its method of preparation are described in detail in U.S. Pat. No. 3,216,789, the contents of which are incorporated herein by reference. Additional supports are described as follows: Zeolite X is described in U.S. Pat. No. 2,882,244; zeolite is described in U.S. Pat. Nos. 4,503,023 and 4,021,447; mordenite is described in U.S. Pat. No. 4,503,023; zeolite Y is described in U.S. Pat. No. 3,130,007; and each of U.S. Pat. Nos. 3,216,789, 2,882,244, 4,503,023, 4,021,447 and 3,130,007 is hereby incorporated herein by reference to demonstrate that the zeolite can be used in the aromatization process of the present disclosure.

[0167] In one aspect, the aromatization catalyst may comprise or may be selected from a large pore L zeolite. L-type zeolite catalysts are a subclass of zeolite catalysts, and typical L-type zeolites contain oxide molar ratios that conform to the following formula:

[0168] M 2 / n O·Al2O3·xSiO2·yH2O,

[0169] Wherein "M" represents at least one exchangeable cation, such as barium, calcium, cerium, lithium, magnesium, potassium, sodium, strontium and zinc, and non-metallic cations, such as hydronium ions and ammonium ions, 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 the cation "M", "x" can be 2 or greater; and "y" is the number of water molecules contained in the channels or interconnected voids of the zeolite.

[0170] It has been found that combining with potassium L-type zeolite or KL zeolite works very well. The term KL zeolite as used herein refers to an L-type zeolite, wherein the main cation M incorporated into the zeolite may comprise potassium. The KL zeolite may be cation exchanged or impregnated with another metal and one or more halides to produce a platinum-impregnated halogenated zeolite or a KL supported Pt-halide zeolite catalyst. In one embodiment, the zeolite may comprise an L-type zeolite. In some aspects, the aromatization catalyst may comprise a potassium L-type zeolite, hereinafter referred to as a KL zeolite, which refers to an L-type zeolite in which the main exchangeable cation M of the zeolite is potassium.

[0171] One or more Group 8-10 metals or other suitable metals such as rhenium may be added to the catalyst support to form a metallized catalyst support. The metal may be added to the catalyst support by employing a variety of known and conventional techniques such as ion exchange, incipient wetness, pore filling, impregnation, vapor deposition, etc. In embodiments, platinum and optionally one or more halides may be added to the zeolite support by any suitable method such as by impregnation with a solution of a platinum-containing compound and one or more halide-containing compounds.

[0172] In one aspect, the metal can be added to the catalyst support by impregnation with a metal-containing solution. The metal in the metal-containing solution can include at least one metal from Groups 8-10; alternatively, ruthenium, osmium, rhodium, iridium, palladium or platinum or a combination thereof. In one embodiment, the metal can include platinum that can be added to the catalyst support via contact with a metal-containing solution (which contains at least one platinum-containing compound). Examples of suitable platinum-containing compounds for contact with the catalyst support include, but are not limited to, platinum compounds that form positively charged platinum complex ions in solution, such as, for example, platinum salts, such as chlorides and nitrates; complexes of platinum with amines; or combinations thereof. For example, the platinum-containing compound can be any decomposable platinum-containing compound, including but not limited to ammonium tetrachloroplatinate, chloroplatinic acid, diammine platinum (II) nitrite, bis (ethylenediamine) platinum (II) chloride, acetylacetonato platinum (II), diammine platinum dichloride, platinum (II) chloride, tetraammine platinum (II) hydroxide, tetraammine platinum chloride, and tetraammine platinum (II) nitrate. In one embodiment, the platinum source can include tetraammine platinum chloride (TAPC). The amount of platinum in the metallized catalyst support may be in the range of about 0.1 to about 5 wt %; for example, about 0.1 to about 3 wt %, for example, about 0.3 to about 1.8 wt %. In other aspects, the concentration of the Group 8-10 metal of each of the first catalyst, the intermediate catalyst, and the final catalyst may be independently selected from 0.3 wt % to 1.5 wt % relative to the weight of each corresponding catalyst before reduction.

[0173] In one aspect, the catalyst may comprise a macroporous zeolite support having a platinum-containing compound and at least one halide. One or more halides may be added to the catalyst support by contacting with a halide-containing compound to form a halogenated supported catalyst. The halide may be added to the catalyst support alone; alternatively, the halide may be added to the catalyst support simultaneously. Such halides may be incorporated during the addition of the metal, alternatively, the halide may be incorporated in a separate step that may be before or after the addition of the metal to form a halogenated, metallized catalyst support. Examples of suitable halides include, but are not limited to, fluorides, chlorides, bromides, iodides, or combinations thereof. Such halides may be introduced, for example, as ammonium halide compounds.

[0174] In one embodiment, the catalyst may include a macroporous zeolite support having a platinum-containing compound and at least one ammonium halide compound. The ammonium halide compound may include or be selected from one or more compounds having the formula [NR4]X, wherein X may include a halide and wherein R represents hydrogen or a substituted or unsubstituted hydrocarbon moiety having 1 to about 20 carbons, and wherein each R may be the same or different, i.e., independently selected. In one embodiment, in the formula [NR4]X, R may include hydrogen, methyl, ethyl, propyl, butyl, or may be a combination thereof. Examples of suitable organic ammonium compounds of the formula [NR4]X include, but are not limited to, ammonium chloride, ammonium fluoride, and tetraalkylammonium halides (such as tetramethylammonium chloride (TMAC), tetramethylammonium fluoride (TMAF), tetraethylammonium chloride, tetraethylammonium fluoride, tetrapropylammonium chloride, tetrapropylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium fluoride, methyltriethylammonium chloride, methyltriethylammonium fluoride) or a combination thereof.

[0175] In one aspect, the halogenated ammonium compound may comprise at least one acidic halide and at least one ammonium hydroxide represented by the formula [NR′4]OH, wherein R′ may comprise or be selected from hydrogen or a substituted or unsubstituted hydrocarbon moiety having 1 to about 20 carbon atoms, wherein each R′ may be the same or different, i.e., independently selected. In one embodiment, R′ may comprise a methyl, ethyl, propyl, butyl, or a combination thereof. Examples of suitable ammonium hydroxides represented by the formula [NR′4]OH may include ammonium hydroxide, tetraalkylammonium hydroxides (such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide), and combinations thereof. Examples of suitable acidic halides may include HCl, HF, HBr, HI, or a combination thereof.

[0176] In another aspect, the ammonium halide compound can comprise (a) a compound represented by the formula [NR4]X, wherein X can comprise a halide and wherein R represents hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to about 20 carbon atoms, wherein each R can be the same or different, and (b) at least one acidic halide and at least one ammonium hydroxide represented by the formula [NR′4]OH, wherein R′ can comprise hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to about 20 carbon atoms, and wherein each R′ can be the same or different.

[0177] The halide-containing compound may further comprise various combinations of ammonium halides (such as ammonium chloride, ammonium fluoride or both) and the ammonium halide compounds described above. More specifically, ammonium chloride, ammonium fluoride or both may be used together with the following: (a) as described above, a compound represented by formula [NR4]X, wherein X may comprise a halide and wherein R represents hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to about 20 carbons, wherein each R may be the same or different, and / or (b) as described above, at least one acidic halide and at least one organic ammonium hydroxide represented by formula [NR′4]OH, wherein R′ may comprise hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to about 20 carbon atoms, wherein each R′ may be the same or different. For example, a first fluoride-containing compound or a chloride-containing compound may be introduced as a tetraalkylammonium halide, and a second fluoride-containing compound or a chloride-containing compound may be introduced as an ammonium halide. In some aspects, tetraalkylammonium chloride may be used together with ammonium fluoride. In another aspect, ammonium chloride may be used together with ammonium fluoride.

[0178] Typically, and in one aspect, the aromatization catalyst in any particular catalyst bed may comprise a metallized, halogenated supported catalyst, wherein the total amount of halides in the catalyst is selected independently of the total amount of halides in any other catalyst in any other catalyst bed, and may be in the range of about 0.05% by weight to about 6.0% by weight of the total metallized, halogenated supported catalyst. Alternatively, the total amount of halides in any catalyst may be independently in the range of about 0.1% by weight to about 5.0% by weight, about 0.3% by weight to about 4.0% by weight, or about 0.5% by weight to about 3.5% by weight of the catalyst. In another aspect, any halogenated supported catalyst may comprise chlorides present in an amount of about 0.05% by weight to about 5% by weight of the catalyst; for example, about 0.1% by weight to about 3% by weight; for example, about 0.3% by weight to about 1.8% by weight. Alternatively, the total amount of halide in the catalyst can be independently selected from about 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.2%, 1.4%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5. %, 1.8 wt %, 2.0 wt %, 2.2 wt %, 2.4 wt %, 2.6 wt %, 2.8 wt %, 3.0 wt %, 3.2 wt %, 3.4 wt %, 3.6 wt %, 3.8 wt %, 4.0 wt %, 4.2 wt %, 4.4 wt %, 4.6 wt %, 4.8 wt %, 5.0 wt %, 5.2 wt %, 5.4 wt %, 5.6 wt %, 5.8 wt % or 6.0 wt %.

[0179] According to the process or catalytic hydrocarbon reforming system for reforming hydrocarbons of the present disclosure, one or more intermediate catalysts in one or more intermediate catalyst beds may be further included, wherein the fluoride concentration (weight %) in the one or more intermediate catalysts is higher than or equal to the fluoride concentration of the last catalyst before reduction. In another aspect, according to the process or catalytic hydrocarbon reforming system for reforming hydrocarbons of the present disclosure, one or more intermediate catalysts in one or more intermediate catalyst beds may be further included, wherein the chloride concentration (weight %) of the one or more intermediate catalysts during startup may be lower than or equal to the fluoride concentration of the first catalyst before reduction and higher than or equal to the fluoride concentration of the last catalyst before reduction. Alternatively, during startup, the fluoride concentration (weight %) of one or more intermediate catalysts may be higher than or equal to the fluoride concentration of the first catalyst before reduction and higher than or equal to the fluoride concentration of the last catalyst before reduction. Non-limiting examples of weight percentages are listed below.

[0180] In one aspect, the aromatization catalyst in any particular catalyst bed can comprise a metallized, halogenated supported catalyst, wherein the total amount of fluoride in the catalyst is selected independently of the total amount of fluoride in any other catalyst in any other catalyst bed, and can be in the range of about 0.05% by weight to about 6.0% by weight of the total metallized, halogenated supported catalyst. Alternatively, the total amount of fluoride in any catalyst can be independently in the range of about 0.1% by weight to about 5.0% by weight, about 0.3% by weight to about 4.0% by weight, or about 0.5% by weight to about 3.5% by weight of the catalyst. In another aspect, any halogenated supported catalyst can comprise fluoride present in an amount of about 0.05% by weight to about 5% by weight of the catalyst; for example, about 0.1% by weight to about 3% by weight; for example, about 0.3% by weight to about 1.8% by weight. Alternatively, the total amount of fluoride in the catalyst can be independently selected from about 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.2%, 1.4%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5. %, 1.8 wt %, 2.0 wt %, 2.2 wt %, 2.4 wt %, 2.6 wt %, 2.8 wt %, 3.0 wt %, 3.2 wt %, 3.4 wt %, 3.6 wt %, 3.8 wt %, 4.0 wt %, 4.2 wt %, 4.4 wt %, 4.6 wt %, 4.8 wt %, 5.0 wt %, 5.2 wt %, 5.4 wt %, 5.6 wt %, 5.8 wt % or 6.0 wt %.

[0181] In one aspect, the process for reforming hydrocarbons or catalytic hydrocarbon reforming system according to the present disclosure can include fluoride concentrations (wt%) in the first catalyst, the intermediate catalyst, and the last catalyst, and the concentrations can be independently selected from a concentration of up to 5 wt% or up to 6 wt%. In another aspect, the fluoride concentration (wt%) of the first catalyst is 10% to 50% higher than the fluoride concentration (wt%) of the last catalyst. In yet another aspect, the fluoride concentration (wt%) of the first catalyst is 50% to 90% higher than the fluoride concentration (wt%) of the last catalyst.

[0182] Any one or more of the first catalyst, the intermediate catalyst and / or the last catalyst may further comprise chloride. Therefore, in one aspect, the aromatization catalyst in any particular catalyst bed may comprise a metallized, halogenated supported catalyst, wherein the total amount of chloride in the catalyst is selected independently of the total amount of chloride in any other catalyst in any other catalyst bed. In this regard, the total amount of chloride in the catalyst may be independently selected and may be in the range of about 0.05 wt % to about 6.0 wt % of the total metallized, halogenated supported catalyst. Alternatively, the total amount of chloride in any catalyst may be independently in the range of about 0.1 wt % to about 5.0 wt %, about 0.3 wt % to about 4.0 wt % or about 0.5 wt % to about 3.5 wt % of the catalyst. In another aspect, any halogenated supported catalyst may comprise a chloride present in an amount of about 0.05 wt % to about 5 wt % of the catalyst; for example, about 0.1 wt % to about 3 wt %; for example, about 0.3 wt % to about 1.8 wt %. Alternatively, the total amount of chloride in the catalyst can be independently selected from about 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.2%, 1.4%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5. %, 1.8 wt %, 2.0 wt %, 2.2 wt %, 2.4 wt %, 2.6 wt %, 2.8 wt %, 3.0 wt %, 3.2 wt %, 3.4 wt %, 3.6 wt %, 3.8 wt %, 4.0 wt %, 4.2 wt %, 4.4 wt %, 4.6 wt %, 4.8 wt %, 5.0 wt %, 5.2 wt %, 5.4 wt %, 5.6 wt %, 5.8 wt % or 6.0 wt %.

[0183] In one aspect, the halogenated supported catalyst can comprise both chloride and fluoride, which can be present in a Cl:F weight ratio of about 1:10 to about 10:1; for example, about 1:5 to about 5:1; for example, about 1:2 to about 2:1. In other aspects, the halogenated supported catalyst can comprise both chloride and fluoride, which can be present in a Cl:F molar ratio of about 1:10 to about 10:1; for example, about 1:5 to about 5:1; for example, about 1:2 to about 2:1.

[0184] The reduction of catalyst usually reduces the halide content of catalyst.For example, the first catalyst, any intermediate catalyst and the last catalyst can include at least or about 0.5 weight % chloride relative to the weight of the first catalyst before reduction, and / or the last catalyst can further include at least or about 0.5 weight % chloride relative to the weight of the last catalyst before reduction.In addition, any one or more of the first catalyst, intermediate catalyst and / or the last catalyst can include chloride, and the chloride is independently selected from the concentration of up to about 6.0 weight % before reduction.In other aspects, any one or more of the first catalyst, intermediate catalyst and / or the last catalyst can include chloride of 0.5 weight % to 5 weight % concentration relative to the weight of the corresponding first catalyst, intermediate catalyst and / or the last catalyst before reduction.Any one or more of the first catalyst, intermediate catalyst and / or the last catalyst can also include the combined concentration of fluoride and chloride of up to 5 weight % before reduction.

[0185] One aspect of the present disclosure provides a process for reforming hydrocarbons by using a series of adiabatic reactors and catalysts, wherein the catalyst in at least one front or upstream catalyst bed or reactor may include a higher fluoride content (concentration) than the catalyst in one or more downstream catalyst beds or reactors. It has been unexpectedly discovered that by using a higher weight percentage of fluoride in at least one front or upstream catalyst bed or reactor compared to one or more downstream catalyst beds or reactors, the useful life of the catalyst system can be extended by maintaining selectivity longer than without a high halide upstream catalyst.

[0186] In the process for reforming hydrocarbons disclosed herein and the catalytic hydrocarbon reforming system, the reforming process is usually carried out in more than one series of adiabatic reactors. Typically, the present disclosure describes the first (most upstream) catalyst bed, one or more intermediate catalyst beds and the last or final (most downstream) catalyst bed, each of which can be located in a different reactor. Typically, there can be 1 to about 6 intermediate catalyst beds comprising 1 to 6 intermediate catalysts, for example, a reactor system comprising 4 or 5 intermediate catalyst beds operates well.

[0187] In another aspect, the fluoride content (weight percent, wt %) of each catalyst bed can be selected independently of the fluoride content of any other catalyst bed at startup such that any or all of the first catalyst bed and one or more intermediate catalyst beds have a higher fluoride concentration than the last catalyst bed prior to reduction.

[0188] In another aspect, the fluoride content (weight percent, wt %) of 1, 2, 3, 4 or more upstream catalyst beds can be selected independently of the fluoride content of any other catalyst bed at startup such that the fluoride concentration of any or all of these upstream catalyst beds can be the same or different and wherein one or more first catalysts and / or intermediate catalysts in the corresponding catalyst beds have a higher fluoride concentration than the last catalyst in the last catalyst bed prior to reduction.

[0189] In other aspects, the fluoride content (weight percent, wt %) of any two adjacent catalyst beds can be independently selected at startup such that, prior to reduction, the upstream catalyst bed of both has a higher fluoride concentration than the downstream catalyst bed.

[0190] For example, in a series of 6 reactors, each having its own catalyst bed, the most upstream reactors, designated 1, 2, and 3 (reactor 1 being the most upstream initial reactor), can have a catalyst with a fluoride content (e.g., about 1.5 wt%) before reduction, while the most downstream reactors 4, 5, and 6 (reactor 6 being the most downstream and final reactor) can have a catalyst with a fluoride content (e.g., about 1.0 wt%) before reduction. Alternatively, reactors 1, 2, 3, and 4 can have a higher fluoride content (e.g., about 1.5 wt%) before reduction, while the most downstream reactors 5 and 6 can have a catalyst with a lower fluoride content (e.g., about 1.0 wt%) before reduction. Alternatively again, reactors designated 1 and 2 can have a catalyst with a higher fluoride content (e.g., about 1.5 wt%) before reduction, while the most downstream reactors 3, 4, 5, and 6 can have a catalyst with a lower fluoride content (e.g., about 1.0 wt%) before reduction. In addition, reactor 1 can have a catalyst with a higher fluoride content (e.g., about 1.5 wt %) before reduction, while downstream reactors 2, 3, 4, 5, and 6 can have a catalyst with a lower fluoride content (e.g., about 1.0 wt %) before reduction. The "higher" fluoride content listed in these aspects or embodiments can be selected, for example, independently of any fluoride concentration disclosed herein, which is higher than the "lower" fluoride content disclosed herein. For example, the "higher" fluoride content can be about 0.8 wt %, about 0.9 wt %, about 1.0 wt %, about 1.1 wt %, about 1.2 wt %, about 1.3 wt %, about 1.4 wt %, about 1.5 wt %, about 1.6 wt %, about 1.7 wt %, about 1.8 wt %, about 1.9 wt %, or about 2.0 wt %, while the "lower" fluoride content can be any weight percentage lower than the selected higher fluoride content.

[0191] Examples 1 and 2 set forth exemplary methods for preparing platinum halide L zeolite catalysts, which can be generally used to prepare catalysts with known fluoride content for any single catalyst bed. Example 3 sets forth an exemplary reactor system using a series of 6 reactors, each with its own catalyst bed, the most upstream reactor designated 1 and the most downstream reactor designated 6, and sets forth exemplary fluoride weight percentages according to the present disclosure.

[0192] In one aspect, similar selections of higher fluoride content and lower fluoride content downstream as listed immediately above are possible in the case of fewer than 6 total reactors or more than 6 total reactors. For example, a process or system may include 1 to 6 or more (e.g., 7, 8, or 9) intermediate catalyst beds, each of which contains 1 to 6 or more (e.g., 7, 8, or 9) intermediate catalysts and the upstream "higher" fluoride content may occur in any or all of the first catalyst bed and the intermediate catalyst beds, and the "lower" fluoride content may occur in the last catalyst bed and any intermediate catalyst bed downstream of the higher fluoride catalyst bed, wherein the lower fluoride content may be any weight percentage below the selected higher fluoride content.

[0193] Conventional catalysts used in the process generally experience a decrease in catalytic activity, which occurs when the catalyst is used under commercial reaction conditions. When one or more of the activity, conversion, selectivity, yield, or other operating parameters of the catalyst reach an unacceptable level, the catalyst is generally considered to have failed. Using the process and system of the present disclosure, it was unexpectedly found that the selectivity of the system of the aromatization catalyst in a series of catalyst beds can be maintained for a longer period of time compared to when the fluoride content of all aromatization catalysts in a series of catalyst beds has the same fluoride content. Regenerable catalysts are suitable for processes such as described, and the catalyst can be subjected to any regeneration chemical treatment recognized in the art. For example, transition metal catalysts are generally regenerated in the following manner: the failed catalyst is contacted with a halogen-containing stream (such as chlorine or fluorine), and then the catalyst is decoked in an oxygen stream, wherein the selected upstream catalyst has a higher halide (such as fluoride) content than the downstream catalyst as listed herein.

[0194] The aromatization reaction can occur under process conditions that thermodynamically favor dehydrocyclization (aromatization) reactions and limit undesirable hydrocracking reactions. The operating range for a typical catalytic aromatization process, such as the aromatization process disclosed herein, can include: a reactor inlet temperature between about 370°C and about 570°C, for example, between about 430°C and about 550°C; a system pressure between about 10 pounds per square inch gauge (psig) and about 300 psig, for example, about 15 psig to about 100 psig; a hydrogen rate sufficient to produce a hydrogen to hydrocarbon molar ratio of the feed to the reforming reactor zone between about 0.1 and about 20, for example, about 3 to about 10, for example, about 1.5 to about 6; and a liquid hourly space velocity of the hydrocarbon feed to the aromatization catalyst between about 0.1 and about 10.

[0195] Reactor systems and processes

[0196] Exemplary catalytic reactor systems, reactor vessels, and processes that can be used to produce aromatic hydrocarbons from naphtha feedstocks according to the present disclosure are described, for example, in U.S. Pat. Nos. 6,548,030, 6,900,365, 7,932,425, 8,912,108, 9,421,530, and 9,718,042; the patents are incorporated herein by reference in their entirety. In one aspect, a class of catalytic reactor systems includes six or seven catalytic reforming reactors in series, each having a reactor feed and a reactor effluent. The aromatization reaction is highly endothermic and utilizes more heat than it produces, so the feed to each reactor is heated by a furnace.

[0197] Figure 1 A process diagram of an exemplary catalytic reactor system 100 suitable for use with the aromatization systems and processes described herein is illustrated. Figure 1 As shown, the catalytic reactor system 100 includes four aromatization reactors in series: reactor 10, reactor 20, reactor 30 and reactor 40. In one aspect, the catalytic reactor system 100 may include any suitable number and configuration of aromatization reactors, such as one, two, three, five, six, seven or more reactors in series or in parallel. Since the aromatization reaction is highly endothermic, a large temperature drop occurs in the reactor 10, the reactor 20, the reactor 30 and the reactor 40. Therefore, each reactor 10, the reactor 20, the reactor 30 and the reactor 40 in series may include a corresponding furnace 11, a furnace 21, a furnace 31 and a furnace 41 for reheating the components to the desired temperature to maintain the desired reaction rate. Alternatively, where feasible, one or more reactors 10, reactor 20, reactor 30 and reactor 40 may share a common furnace. Reactors 10, reactors 20, reactors 30 and reactors 40, furnaces 11, furnaces 21, furnaces 31 and furnaces 41 and associated pipelines may be referred to herein as reaction zones.

[0198] exist Figure 1 In the process, naphtha or hydrocarbon feed 101 is typically combined with recycle stream 119 to form a combined feed stream 102, which is fed to purification process 80. Purification process 80 uses known processes to purify the hydrocarbon feed, which may include fractionating and / or treating the hydrocarbon feed. As used herein, the term "fractionation" includes removing heavy (e.g., C9 + ) hydrocarbons and / or light (e.g., C5 -) hydrocarbons. As used herein, the terms "treating" and "removing" interchangeably refer to removing impurities, such as oxygenates, sulfur, and / or metals, from a hydrocarbon feed. The resulting purified feed 103 can be combined with a dry hydrogen recycle 116 to produce a hydrogen-rich purified feed 104, which can then be combined with oxygenates and / or nitrogenates 105 to produce a reactor feed stream 106. If desired, in addition to or as an alternative to stream 105, oxygenates and / or nitrogenates can also be fed to the reactor system 100 at one or more locations, as will be described in more detail herein.

[0199] The reactor feed stream 106 is preheated in the first furnace 11, which heats the hydrocarbons to a desired temperature, thereby producing a first reactor feed 107. The first reactor feed 107 is fed to the reactor 10, where the hydrocarbons are contacted with an aromatization catalyst under suitable reaction conditions (e.g., temperature and pressure) to aromatize one or more components in the feed, thereby increasing its aromatic compound content. A first reactor effluent 108 is recovered from the first reactor 10, which contains aromatic compounds, unreacted feed and other hydrocarbon compounds or by-products.

[0200] The first reactor effluent 108 is then preheated in a second furnace 21, which heats the hydrocarbons to a desired temperature, thereby producing a second reactor feed 109. The second reactor feed 109 is then fed to the reactor 20, where the hydrocarbons are contacted with an aromatization catalyst under suitable reaction conditions for aromatizing one or more components in the feed to increase their aromatic content. A second reactor effluent 110 is recovered from the second reactor 20, which contains aromatic compounds, unreacted feed, and other hydrocarbon compounds or by-products.

[0201] The second reactor effluent 110 is then preheated in the third furnace 31, which heats the hydrocarbons to a desired temperature, thereby producing a third reactor feed 111. The third reactor feed 111 is then fed to the reactor 30, where the hydrocarbons are contacted with an aromatization catalyst under suitable reaction conditions for aromatizing one or more components in the feed to increase their aromatic content. A third reactor effluent 112 is recovered from the third reactor 30, which contains aromatic compounds, unreacted feed, and other hydrocarbon compounds or by-products.

[0202] The third reactor effluent 112 is then preheated in a fourth furnace 41 which heats the hydrocarbons to a desired temperature, thereby producing a fourth reactor feed 113. The fourth reactor feed 113 is then fed to the reactor 40, where the hydrocarbons are contacted with an aromatization catalyst under suitable reaction conditions for aromatizing one or more components in the feed to increase its aromatic content. If desired, an additional aromatization reactor ( Figure 1 A fourth reactor effluent 114 is recovered from the fourth reactor 40 and comprises aromatic compounds, unreacted feed, and other hydrocarbon compounds or by-products.

[0203] The fourth reactor effluent 114 is then fed to a hydrogen separation process 50, which separates a hydrogen recycle 115 from a reformate 117 using a number of known processes. The reformate 117 also includes aromatization reaction products (e.g., aromatic and non-aromatic compounds) from reactor 10, reactor 20, reactor 30, and reactor 40, in addition to any unreacted feed and other hydrocarbon compounds or byproducts. The hydrogen recycle 115 may be dried in a dryer 60 to form a dried hydrogen recycle 116, which may then be recycled to the purified feed 103. The reformate 117 enters a purification-extraction process 70, which separates a raffinate recycle 119 and reactor byproducts (not shown) from aromatic compounds 118.

[0204] The hydrogen separation process 50 and the purification-extraction process 70 are well known in the art and are described in many patents, including: U.S. Patent No. 5,401,386 to Morrison et al., entitled "Reforming Process for Producing High-Purity Benzene"; U.S. Patent No. 5,877,367 to Witte, entitled "Dehydrocyclization Process with Downstream Dimethylbenzene Removal" and U.S. Patent No. 6,004,452 to Ash et al., entitled "Process for Converting Hydrocarbon Feed to High Purity Benzene and High Purity Paraxylene", each of which is incorporated herein by reference as if reproduced in its entirety.

[0205] The raffinate recycle 119 is then recycled to the feed 101 and the aromatic compounds 118 are sold or otherwise used as desired. For simplicity, Figure 1Not shown are byproduct streams removed from the catalytic reactor system 100 at various points throughout the system. However, one of ordinary skill in the art would know the composition and location of such byproduct streams. Figure 1 The oxygenate and / or nitrogenate 105 is shown to be added to the purified hydrogen-rich feed 104, but one of ordinary skill in the art will understand that the oxygenate and / or nitrogenate may be added to any of the process streams 101, 102, 103, 104, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 119, or various combinations thereof.

[0206] In various aspects, the catalytic reactor system described herein may include a fixed catalyst bed system, a mobile catalyst bed system, a fluidized catalyst bed system, or a combination thereof. Such reactor systems may be intermittent or continuous. In one aspect, the catalytic reactor system may be a fixed bed system comprising one or more fixed bed reactors. In a fixed bed system, the feed may be preheated in a furnace tube and enter at least one reactor containing a fixed bed of catalyst. The feed stream may pass through the reactor upward, downward, or radially. In one aspect, the catalytic reactor system described herein may be operated as an adiabatic catalytic reactor system or an isothermal catalytic reactor system. As used herein, the terms "catalytic reactor" and "reactor" interchangeably refer to reactor vessels, reactor interiors, and related process equipment, including but not limited to catalysts, inert fillers, pits, flow distributors, center tubes, reactor ports, catalyst transmission and distribution systems, furnaces and other heating devices, heat transfer equipment, and pipelines.

[0207] Other aspects of the process for reforming hydrocarbons according to the present invention provide that the conditions for aromatizing at least a portion of the naphtha or aliphatic hydrocarbons may include a catalyst reduction period of 600 to 1500 hours at a temperature above about 500°F. -1 Catalyst startup is performed at a gas flow rate of GHSV of 100°F / hr and a heating rate of 10°F / hr to 25°F / hr, wherein the first catalyst, the intermediate catalyst, and / or the last catalyst comprises a fluorinated-chlorinated zeolite platinum catalyst.

[0208] In some aspects, the catalytic reactor system can be operated at a temperature of about 400 to about 2000 hr. -1 (e.g. 400hr -1 , about 500hr -1 , about 600hr -1 , about 700hr -1 , about 800hr -1 , about 900hr -1 , about 1000hr -1 , about 1100hr -1 , about 1200hr-1 , about 1300hr -1 , about 1400hr -1 , about 1500hr -1 , about 1600hr -1 , about 1700hr -1 , about 1800hr -1 , about 1900hr -1 or about 2000hr -1 ). In other aspects, during catalyst reduction above about 500°F, the catalytic reactor system can be operated during catalyst startup at a heating rate of 5°F / hr to 50°F / hr (e.g., about 5°F / hr, about 10°F / hr, about 15°F / hr, about 20°F / hr, about 25°F / hr, about 30°F / hr, about 35°F / hr, about 40°F / hr, about 45°F / hr, or about 50°F / hr).

[0209] For example, in certain embodiments where the catalyst comprises a halogenated zeolite catalyst, the catalytic reactor system may be operated at a temperature comprising about 400 to about 2000 hr during catalyst reduction at temperatures above about 500°F. -1 (e.g. 400hr -1 , about 500hr -1 , about 600hr -1 , about 700hr -1 , about 800hr -1 , about 900hr -1 , about 1000hr -1 , about 1100hr -1 , about 1200hr -1 , about 1300hr -1 , about 1400hr -1 , about 1500hr -1 , about 1600hr -1 , about 1700hr -1 , about 1800hr -1 , about 1900hr -1 or about 2000hr -1 ) and a heating rate of 5°F / hr to 50°F / hr (e.g., about 5°F / hr, about 10°F / hr, about 15°F / hr, about 20°F / hr, about 25°F / hr, about 30°F / hr, about 35°F / hr, about 40°F / hr, about 45°F / hr, or about 50°F / hr) during catalyst startup.

[0210] In aspects where the catalyst comprises a fluorinated zeolite platinum catalyst, the catalytic reactor system may be operated at a temperature of from about 600 to about 1500 hr during catalyst reduction at temperatures above about 500°F. -1 (For example, about 600 hr -1 , about 700hr -1 , about 800hr -1 , about 900hr -1 , about 1000hr -1 , about 1100hr -1 , about 1200hr -1 , about 1300hr -1 , about 1400hr -1 or about 1500hr -1 ) and a heating rate of 10°F / hr to 30°F / hr (e.g., about 10°F / hr, about 15°F / hr, about 20°F / hr, about 25°F / hr, or about 30°F / hr) during catalyst startup.

[0211] In some embodiments where the catalyst comprises a fluorinated-chlorinated zeolite platinum catalyst, the catalytic reactor system 100 may be operated at a temperature of from about 600 to about 1500 hr during catalyst reduction at temperatures above about 500 °F. -1 (For example, about 600 hr -1 , about 700hr -1 , about 800hr -1 , about 900hr -1 , about 1000hr -1 , about 1100hr -1 , about 1200hr -1 , about 1300hr -1 , about 1400hr -1 or about 1500hr -1 ) and a heating rate of 10°F / hr to 25°F / hr (e.g., about 10°F / hr, about 15°F / hr, about 20°F / hr, or about 25°F / hr) during catalyst startup.

[0212] Example

[0213] The present invention is further illustrated by the following examples, which should not be interpreted in any way as limiting the scope of the present invention. After reading the description herein, a person of ordinary skill in the art may think of various other aspects, embodiments, modifications and equivalent schemes without departing from the spirit of the present invention or the scope of the appended claims.

[0214] Example 1

[0215] Preparation of Platinum-Impregnated KL Zeolite Catalyst

[0216] A platinum-impregnated KL zeolite catalyst containing 1.0 wt % platinum was prepared in the following manner. An impregnation mixture of 0.10 grams (g) of tetraammine platinum chloride (TAPC), 0.45 g of tetramethylammonium fluoride (TMAF), 0.10 g of tetramethylammonium chloride (TMAC), and 2.50 g of water was formed and added to 5.0 g of silica-bound KL zeolite extrudates that had been calcined at 538° C. for 2 hours. The mixture was impregnated into the KL zeolite and then allowed to stand at 95° C. for 20 hours. The impregnated KL zeolite was vacuum dried at 170° C. for 2 hours (heating rate of 0.5° C. / min), and then calcined at 300° C. for another 2 hours (heating rate of 0.25° C. / min). The resulting catalyst contained 1.07 wt % Pt, 1.02 wt % Cl, and 1.0 wt % F.

[0217] Example 2

[0218] Alternative preparation of platinum-impregnated KL zeolite catalyst

[0219] A platinum-impregnated KL zeolite catalyst containing 0.5 wt % platinum was prepared in the following manner. An impregnation mixture of 0.05 g TAPC, 0.10 g NH4F and 0.05 g NH4Cl was formed and added to a container containing 5.0 g silica-bound KL zeolite, which had been pre-dried at 538°C for 2 hours. The mixture was impregnated into the KL zeolite and then allowed to stand at 95°C for 20 hours. The impregnated KL zeolite was vacuum dried at 170°C for 2 hours (heating rate of 0.5°C / min) and then calcined at 300°C for another 2 hours (heating rate of 0.25°C / min). The resulting catalyst contained 0.55 wt % Pt, 0.5 wt % Cl and 1.0 wt % F.

[0220] Example 3

[0221] Alternative preparation of platinum halide L zeolite catalyst

[0222] A halogenated platinum L zeolite catalyst was prepared in a manner similar to Example 4 of EP 498,182A or U.S. Pat. No. 5,354,933. 20 parts by weight of a silica binder (SI-350 silica sol, sold by Cat. & Chem. Ind. Inc. [CCIC], Japan) was added with stirring to 100 parts by weight of a KL-type zeolite (Tosoh, Ltd., Japan). The mixture was kneaded and molded, and then air calcined at 500° C. (932° F.) for 2 hours (hr) to produce molded, calcined silica-bound L zeolite extrudates. An impregnation solution containing 0.166 g of ammonium fluoride, 0.075 g of ammonium chloride, 0.171 g (grams) of tetraammine platinum chloride, and 4.8 g of ion-exchanged water was prepared. The liquid was slowly dripped into 10 g of the molded L zeolite under stirring. The solid was vacuum dried and then treated in dry air at 300°C (572°F) for 3 hours. The catalyst was analyzed and contained about 0.7 wt% F and 0.7 wt% Cl. The sodium content was about 0.56 wt% as measured by atomic absorption spectroscopy.

[0223] Example 4

[0224] Preparation of High Fluoride Platinum L Zeolite Catalyst

[0225] Platinum halide L zeolite catalysts having a higher fluoride content than the catalysts of Examples 1-3 are prepared by following the general procedure of Example 1, except that a higher relative amount of a fluoride source compound, such as ammonium fluoride or tetramethylammonium fluoride, relative to the weight of the additional components is used. By this procedure, platinum halide L zeolite catalysts having a fluoride content of about 0.8 wt % and higher, for example up to about 2.0 wt %, can be prepared.

[0226] Example 5

[0227] Weight percent of fluoride in a series of aromatization reactors

[0228] The following table lists exemplary aromatization reactor configurations, having a first and last reactor, and in the example shown, four intermediate reactors, and examples of the weight percentage of fluoride in each catalyst bed. Examples are shown where each catalyst bed is in a separate reactor, as well as some examples where two catalyst beds are in a single reactor. Catalyst bed 1 is the first or most upstream bed, while catalyst bed 6 is the last or most downstream catalyst bed, with beds 2 to 6 constituting intermediate beds in sequence. The procedures of Examples 1 and 2 can be used to prepare these catalysts.

[0229] Table 1. Exemplary aspects of the processes and systems of the present disclosure, illustrating embodiments of fluoride concentrations for a range of aromatization reactors.

[0230]

[0231]

[0232] Example 6

[0233] Layered bed catalyst loading with higher halide loading in the upstream bed

[0234] This example demonstrates that loading the upper portion (e.g., upper half) of the catalyst bed with a high halide catalyst will increase the overall run length through the interaction of the released halide with the downstream catalyst. Thus, when a fixed bed reactor is loaded with the upper half of the bed containing a high halide catalyst (whether fluorine or chlorine) and then subjected to a reduction step, improved performance of the catalyst in the lower half of the catalyst bed is observed.

[0235] Figure 2A A fixed bed "baseline" reactor 200 is illustrated having a standard (STD) aromatization catalyst arrangement in the upper and lower halves of the fixed bed reactor, i.e. II catalyst, the direction of fluid flow 205 and bed portions 210, 215, 220 and 225 are shown in an upstream to downstream direction. Figure 2B A fixed bed test reactor 255 is illustrated having a high chloride catalyst in the upper (upstream) half of the fixed bed and a standard (STD) aromatization catalyst in the lower (downstream) half of the fixed bed. II catalyst arrangement, referred to as a "layered bed" arrangement, with the direction of fluid stream 255 and bed sections 260, 265, 270 and 275 shown in an upstream to downstream direction. These catalysts were reduced with hydrogen in the process unit reactor, removed, crushed to 20 / 40 mesh, and then run through the screening unit.

[0236] For the bed sections 220 and 225 Figure 2A The lower half (only) of the fixed catalyst bed and the Figure 2B The lower half of the fixed catalyst bed was tested for activity and selectivity (only). As indicated by the lower operating temperature, below Figure 2B The standard catalyst (bed sections 270 and 255) with high chloride catalyst in the Figure 2A The standard catalyst in the lower half of the bed (bed sections 220 and 225) of the baseline configuration is more selective.

[0237] therefore, Figure 3 Illustrated for Figure 2A (“baseline”) relative to Figure 2B The standard in the lower half of the fixed bed reactor ("layered bed") is shown in FIG. II Catalyst, a plot of adjusted catalyst temperature (°F) versus run time (hours), demonstrates that the standard catalyst downstream of the high chloride catalyst has better activity than the standard catalyst downstream of the more standard catalyst (i.e., a catalyst with a standard chloride concentration). Figure 4 Illustrated for Figure 2A (“baseline”) vs. Figure 2B The standard in the lower half of the fixed bed reactor ("layered bed") is shown in FIG. II catalyst, a plot of selectivity (mol / mol) versus run time (hours), demonstrates that the standard catalyst downstream of the high chloride catalyst has better selectivity than the standard catalyst downstream of the more standard catalyst (ie, a catalyst with a standard chloride concentration).

[0238] The same effect of downstream catalyst was observed in a commercial scale aromatization reactor series. Reactor No. 3 (reactor No. 3 of six reactors in series) contained a high chloride catalyst, while the remaining five reactors of a total of six had standard II catalyst. The catalyst activities in the different reactors were compared. Both Reactor No. 4 and Reactor No. 5, located downstream of the High Chloride Reactor No. 3, showed an increase in activity compared to the expected level observed when the High Chloride Reactor was not used as Reactor No. 3. Although not intending to be bound by theory, this observation is attributed to the interaction between the catalysts in those downstream Reactors No. 4 and No. 5 and the chloride released in Reactor No. 3.

[0239] Thus, it is observed that an upstream high halide reactor, such as a high chloride reactor, can extend the operating life and improve the selectivity of the reactor downstream of the high halide catalyst.

[0240] The present invention is described above with reference to multiple aspects, features, embodiments and specific examples. According to the above specific embodiments, those skilled in the art will expect many variations. All such obvious variations are within the full expected range of the appended claims. These and other aspects of the present disclosure may further include, but are not limited to, the various embodiments provided below. Many aspects or embodiments are described as "comprising" certain components or steps, but alternatively, unless otherwise specifically stated, can be "essentially composed of" or "consisting of" those components or steps.

[0241] Aspects of the Disclosure

[0242] Aspect 1. A process for reforming hydrocarbons, comprising:

[0243] a) contacting a feedstock containing an aliphatic hydrocarbon with a first catalyst in a first catalyst bed under conditions to aromatize the aliphatic hydrocarbon to form a first catalyst bed effluent comprising aromatic hydrocarbons and aliphatic hydrocarbons, the first catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 1.0 weight percent of a fluoride relative to the weight of the first catalyst before reduction;

[0244] b) contacting the first catalyst bed effluent with one or more independently selected intermediate catalysts in one or more intermediate catalyst beds in series, under conditions to aromatize aliphatic hydrocarbons, to form one or more intermediate catalyst bed effluents comprising aromatic hydrocarbons and aliphatic hydrocarbons, the intermediate catalysts each comprising an inorganic support, a Group 8-10 metal, and a fluoride; and

[0245] c) contacting the one or more intermediate catalyst bed effluents with a final catalyst in a final catalyst bed under conditions to aromatize aliphatic hydrocarbons to form a final catalyst bed effluent comprising an aromatic product, the final catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 0.7 weight percent fluoride relative to the weight of the final catalyst prior to reduction;

[0246] The fluoride concentration of the first catalyst or the fluoride concentration of at least one of the intermediate catalysts is higher than the fluoride concentration of the last catalyst before reduction.

[0247] Aspect 2. A method for reforming hydrocarbons, comprising:

[0248] a) contacting a feedstock containing an aliphatic hydrocarbon with a first catalyst in a first catalyst bed under conditions to aromatize the aliphatic hydrocarbon to form a first catalyst bed effluent comprising aromatic hydrocarbons and aliphatic hydrocarbons, the first catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 1.0 weight percent of a fluoride relative to the weight of the first catalyst before reduction; and

[0249] b) contacting the first catalyst bed effluent with a final catalyst in a final catalyst bed under conditions to aromatize aliphatic hydrocarbons to form a final catalyst bed effluent comprising an aromatic product, the final catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 0.7 weight percent fluoride relative to the weight of the final catalyst prior to reduction;

[0250] The fluoride concentration of the first catalyst is higher than the fluoride concentration of the last catalyst before reduction.

[0251] Aspect 3. A method for reforming hydrocarbons, comprising:

[0252] a) contacting a feedstock containing an aliphatic hydrocarbon with a first catalyst in a first catalyst bed under conditions to aromatize the aliphatic hydrocarbon to form a first catalyst bed effluent comprising aromatic hydrocarbons and aliphatic hydrocarbons, the first catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 1.5 weight percent chloride relative to the weight of the first catalyst before reduction;

[0253] b) contacting the first catalyst bed effluent with one or more independently selected intermediate catalysts in one or more intermediate catalyst beds in series, under conditions to aromatize aliphatic hydrocarbons, to form one or more intermediate catalyst bed effluents comprising aromatic hydrocarbons and aliphatic hydrocarbons, the intermediate catalysts each comprising an inorganic support, a Group 8-10 metal, and a chloride; and

[0254] c) contacting the one or more intermediate catalyst bed effluents with a final catalyst in a final catalyst bed under conditions to aromatize aliphatic hydrocarbons to form a final catalyst bed effluent comprising an aromatic product, the final catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 0.5 weight percent chloride relative to the weight of the final catalyst prior to reduction;

[0255] The chloride concentration of the first catalyst or the chloride concentration of at least one of the intermediate catalysts is higher than the chloride concentration of the last catalyst before reduction.

[0256] Aspect 4. A method for reforming hydrocarbons, comprising:

[0257] a) contacting a feedstock containing an aliphatic hydrocarbon with a first catalyst in a first catalyst bed under conditions to aromatize the aliphatic hydrocarbon to form a first catalyst bed effluent comprising aromatic hydrocarbons and aliphatic hydrocarbons, the first catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 1.5 weight percent chloride relative to the weight of the first catalyst before reduction; and

[0258] b) contacting the first catalyst bed effluent with a final catalyst in a final catalyst bed under conditions to aromatize aliphatic hydrocarbons to form a final catalyst bed effluent comprising an aromatic product, the final catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 0.5 weight percent chloride relative to the weight of the final catalyst prior to reduction;

[0259] The chloride concentration of the first catalyst is higher than the chloride concentration of the last catalyst before reduction.

[0260] Aspect 5. A catalytic hydrocarbon reforming system comprising:

[0261] at least three catalyst beds connected in series, the catalyst beds comprising an upstream first catalyst bed, a downstream last catalyst bed, and one or more intermediate catalyst beds connected in series between the first catalyst bed and the last catalyst bed;

[0262] a first catalyst in the first catalyst bed, the first catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 1.0 weight percent fluoride relative to the weight of the first catalyst prior to reduction;

[0263] one or more independently selected intermediate catalysts in the one or more intermediate catalyst beds, each intermediate catalyst comprising an inorganic support, a Group 8-10 metal, and a fluoride; and

[0264] a final catalyst in the final catalyst bed, the final catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 0.7 weight percent fluoride relative to the weight of the final catalyst prior to reduction;

[0265] The fluoride concentration of the first catalyst or the fluoride concentration of at least one of the intermediate catalysts is higher than the fluoride concentration of the last catalyst before reduction.

[0266] Aspect 6. A catalytic hydrocarbon reforming system comprising:

[0267] Two catalyst beds connected in series, the catalyst beds comprising an upstream first catalyst bed and a downstream last catalyst bed;

[0268] a first catalyst in the first catalyst bed, the first catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 1.0 weight percent fluoride relative to the weight of the first catalyst before reduction; and

[0269] a final catalyst in the final catalyst bed, the final catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 0.7 weight percent fluoride relative to the weight of the final catalyst prior to reduction;

[0270] The fluoride concentration of the first catalyst is higher than the fluoride concentration of the last catalyst before reduction.

[0271] Aspect 7. A catalytic hydrocarbon reforming system comprising:

[0272] at least three catalyst beds connected in series, the catalyst beds comprising an upstream first catalyst bed, a downstream last catalyst bed, and one or more intermediate catalyst beds connected in series between the first catalyst bed and the last catalyst bed;

[0273] a first catalyst in the first catalyst bed, the first catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 1.5 weight percent chloride relative to the weight of the first catalyst prior to reduction;

[0274] one or more independently selected intermediate catalysts in the one or more intermediate catalyst beds, each intermediate catalyst comprising an inorganic support, a Group 8-10 metal, and a chloride; and

[0275] a final catalyst in the final catalyst bed, the final catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 0.5 weight percent chloride relative to the weight of the final catalyst prior to reduction;

[0276] The chloride concentration of the first catalyst or the chloride concentration of at least one of the intermediate catalysts is higher than the chloride concentration of the last catalyst before reduction.

[0277] Aspect 8. A catalytic hydrocarbon reforming system comprising:

[0278] Two catalyst beds connected in series, the catalyst beds comprising an upstream first catalyst bed and a downstream last catalyst bed;

[0279] a first catalyst in the first catalyst bed, the first catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 1.5 weight percent chloride relative to the weight of the first catalyst prior to reduction; and

[0280] a final catalyst in the final catalyst bed, the final catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 0.5 weight percent chloride relative to the weight of the final catalyst prior to reduction;

[0281] The chloride concentration of the first catalyst is higher than the chloride concentration of the last catalyst before reduction.

[0282] Aspect 9. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of aspects 1 to 2 or 5 to 6, wherein the first catalyst comprises up to about 5.0 wt. %, up to about 4.0 wt. %, up to about 3.5 wt. %, up to about 3.0 wt. %, or up to about 2.5 wt. % of fluoride relative to the weight of the first catalyst before reduction, and

[0283] The final catalyst comprises up to about 4.0 wt%, up to about 3.0 wt%, up to about 2.5 wt%, up to about 2.0 wt%, or up to about 1.5 wt% fluoride relative to the weight of the final catalyst before reduction.

[0284] Aspect 10. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of aspects 3 to 4 or 7 to 8, wherein the first catalyst comprises up to about 5.0 wt. %, up to about 4.0 wt. %, up to about 3.5 wt. %, up to about 3.0 wt. % or up to about 2.5 wt. % of chloride relative to the weight of the first catalyst before reduction, and

[0285] The final catalyst comprises up to about 3.0 wt. %, up to about 2.5 wt. %, up to about 2.0 wt. %, or up to about 1.5 wt. % fluoride relative to the weight of the final catalyst before reduction.

[0286] Aspect 11. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 1 to 2, 5 to 6 or 9, wherein the first catalyst, any one or more of the intermediate catalysts, the last catalyst or any combination thereof independently further comprises a chloride.

[0287] Aspect 12. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of aspects 3 to 4, 7 to 8 or 10, wherein the first catalyst, any one or more of the intermediate catalysts, the last catalyst or any combination thereof independently further comprises a fluoride.

[0288] Aspect 13. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 1 to 2 or 5 to 6, wherein the first catalyst contains a fluoride in a concentration range of about 1.0 wt. % to about 4.0 wt. %, about 1.2 wt. % to about 3.2 wt. %, about 1.5 wt. % to about 2.8 wt. %, about 1.7 wt. % to about 2.5 wt. %, or about 1.8 wt. % to about 2.3 wt. % relative to the weight of the first catalyst before reduction.

[0289] Aspect 14. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 1 to 2 or 5 to 6, wherein any one or more of the intermediate catalysts, the final catalyst, or any combination thereof independently contains a fluoride in a concentration range of about 0.7 wt. % to about 2.5 wt. %, about 0.8 wt. % to about 2.3 wt. %, about 0.9 wt. % to about 2.0 wt. %, about 1.0 wt. % to about 2.0 wt. %, or about 1.2 wt. % to about 1.8 wt. % relative to the weight of the corresponding intermediate catalyst or final catalyst before reduction.

[0290] Aspect 15. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 11 or 13 to 14, wherein the first catalyst, any one or more of the intermediate catalysts, the final catalyst or any combination thereof further independently contains a chloride in a concentration range of about 1.5 wt. % to about 4.0 wt. %, about 1.8 wt. % to about 3.6 wt. %, about 2.2 wt. % to about 3.4 wt. % or about 2.0 wt. % to about 3.3 wt. % relative to the weight of the corresponding first catalyst, intermediate catalyst or final catalyst before reduction.

[0291] Aspect 16. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 11 or 13 to 14, wherein the first catalyst, any one or more of the intermediate catalysts, the final catalyst or any combination thereof further independently contains a chloride in a concentration range of about 0.5 wt. % to about 2.5 wt. %, about 0.6 wt. % to about 2.3 wt. %, about 0.7 wt. % to about 2.0 wt. % or about 0.8 wt. % to about 1.7 wt. % relative to the weight of the corresponding first catalyst, intermediate catalyst or final catalyst before reduction.

[0292] Aspect 17. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 11 or 13 to 16, wherein the chloride concentration of the first catalyst or the chloride concentration of at least one of the intermediate catalysts is higher than the chloride concentration of the last catalyst before reduction.

[0293] Aspect 18. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 3 to 4 or 7 to 8, wherein the first catalyst contains a chloride in a concentration range of about 1.5 wt. % to about 4.0 wt. %, about 1.8 wt. % to about 3.6 wt. %, about 2.2 wt. % to about 3.4 wt. % or about 2.0 wt. % to about 3.3 wt. % relative to the weight of the first catalyst before reduction.

[0294] Aspect 19. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 3 to 4 or 7 to 8, wherein any one or more of the intermediate catalysts, the final catalyst, or any combination thereof independently contains a chloride in a concentration range of about 0.5 wt. % to about 2.5 wt. %, about 0.6 wt. % to about 2.3 wt. %, about 0.7 wt. % to about 2.0 wt. % or about 0.8 wt. % to about 1.7 wt. % relative to the weight of the corresponding intermediate catalyst or final catalyst before reduction.

[0295] Aspect 20. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 12 or 18 to 19, wherein the first catalyst, any one or more of the intermediate catalysts, the final catalyst or any combination thereof further independently comprises a fluoride in a concentration range of about 1.0 wt. % to about 4.0 wt. %, about 1.2 wt. % to about 3.2 wt. %, about 1.5 wt. % to about 2.8 wt. %, about 1.7 wt. % to about 2.5 wt. % or about 1.8 wt. % to about 2.3 wt. % relative to the weight of the corresponding first catalyst, intermediate catalyst or final catalyst before reduction.

[0296] Aspect 21. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 12 or 18 to 19, wherein the first catalyst, any one or more of the intermediate catalysts, the final catalyst or any combination thereof further independently comprises a fluoride in a concentration range of about 0.7 wt. % to about 2.5 wt. %, about 0.8 wt. % to about 2.3 wt. %, about 0.9 wt. % to about 2.0 wt. %, about 1.0 wt. % to about 2.0 wt. % or about 1.2 wt. % to about 1.8 wt. % relative to the weight of the corresponding first catalyst, intermediate catalyst or final catalyst before reduction.

[0297] Aspect 22. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 12 or 18 to 21, wherein the fluoride concentration of the first catalyst or the fluoride concentration of at least one of the intermediate catalysts is higher than the fluoride concentration of the last catalyst before reduction.

[0298] Aspect 23. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 11 to 12, 15 to 17 or 20 to 22, wherein any one or more of the first catalyst, the intermediate catalyst and / or the final catalyst independently comprises any chlorine to fluorine (Cl:F) weight ratio disclosed herein, for example, from about 1.5:1 to about 8:1, from about 2:1 to about 5:1 or from about 3:1 to about 4.5:1.

[0299] Aspect 24. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 11 to 12, 15 to 17 or 20 to 22, wherein any one or more of the first catalyst, the intermediate catalyst and / or the final catalyst comprises a chlorine to fluorine (Cl:F) weight ratio of about 1:10 to about 10:1, about 1:5 to about 5:1 or about 1:2 to about 2:1.

[0300] Aspect 25. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 1 to 2, 5 to 6, 9, 11 to 17 or 20 to 22, wherein the fluoride concentration of the first catalyst is 10% to 50% higher, 25% to 65% higher, or 50% to 90% higher than the fluoride concentration of the last catalyst.

[0301] Aspect 26. A method for reforming hydrocarbons according to any one of Aspects 3 to 4, 7 to 8, 10, 12 or 15 to 22, a catalytic hydrocarbon reforming system, wherein the chloride concentration of the first catalyst is 10% to 50% higher, 25% to 65% higher, or 50% to 90% higher than the chloride concentration of the last catalyst.

[0302] Aspect 27. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to Aspect 11, wherein the first catalyst further comprises about 0.5 wt. % to about 5 wt. % chloride relative to the weight of the first catalyst before reduction, and wherein the last catalyst further comprises about 0.5 wt. % to about 5 wt. % chloride relative to the weight of the last catalyst before reduction.

[0303] Aspect 28. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to Aspect 12, wherein the first catalyst further comprises about 0.5 weight % to about 5 weight % fluoride relative to the weight of the first catalyst before reduction, and wherein the last catalyst further comprises about 0.5 weight % to about 5 weight % fluoride relative to the weight of the last catalyst before reduction.

[0304] Aspect 29. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 11 to 28, wherein any one or more of the first catalyst, the intermediate catalyst and / or the final catalyst contains a combined concentration of fluoride and chloride of up to about 5 weight % relative to the weight of the catalyst before reduction.

[0305] Aspect 30. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 1, 5, 9, 11, 13 to 17, 23 to 25, 27 or 29, wherein the fluoride concentration (weight %) of each of the one or more independently selected intermediate catalysts at startup is greater than or equal to the fluoride concentration of the last catalyst before reduction.

[0306] Aspect 31. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 3, 7, 10, 12, 18 to 24, 26 or 28 to 29, wherein the chloride concentration (weight %) of each of the one or more independently selected intermediate catalysts at startup is greater than or equal to the chloride concentration of the last catalyst before reduction.

[0307] Aspect 32. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of aspects 1, 5, 9, 11, 13 to 17, 23 to 25, 27 or 29, wherein:

[0308] each of the one or more independently selected intermediate catalysts at startup has a fluoride concentration (weight %) less than or equal to the fluoride concentration of the first catalyst before reduction and greater than or equal to the fluoride concentration of the last catalyst before reduction; or

[0309] Each of the one or more independently selected intermediate catalysts has a fluoride concentration (wt %) at startup that is greater than or equal to the fluoride concentration of the first catalyst before reduction and greater than or equal to the fluoride concentration of the last catalyst before reduction.

[0310] Aspect 33. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of aspects 3, 7, 10, 12, 18 to 24, 26 or 28 to 29, wherein:

[0311] each of the one or more independently selected intermediate catalysts at startup has a chloride concentration (wt %) less than or equal to the chloride concentration of the first catalyst before reduction and greater than or equal to the chloride concentration of the last catalyst before reduction; or

[0312] The chloride concentration (wt %) of each of the one or more independently selected intermediate catalysts at startup is greater than or equal to the chloride concentration of the first catalyst before reduction and greater than or equal to the chloride concentration of the last catalyst before reduction.

[0313] Aspect 34. The method for reforming hydrocarbons or the catalytic hydrocarbon reforming system according to any one of aspects 1 to 33, wherein the first catalyst bed, the one or more intermediate catalyst beds and the last catalyst bed are each located in a different reactor.

[0314] Aspect 35. The method for reforming hydrocarbons or the catalytic hydrocarbon reforming system according to any one of aspects 1 to 33, wherein two adjacent catalyst beds connected in series are located in a single reactor.

[0315] Aspect 36. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of aspects 1 to 33, wherein:

[0316] The method or system comprises 1 to 6 intermediate catalyst beds, wherein the 1 to 6 intermediate catalyst beds respectively comprise 1 to 6 intermediate catalysts; and

[0317] The first catalyst bed, the 1 to 6 intermediate catalyst beds and the last catalyst bed are all located in different reactors.

[0318] Aspect 37. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of aspects 1 to 33, wherein:

[0319] The method or system comprises 1 to 6 intermediate catalyst beds, wherein the 1 to 6 intermediate catalyst beds respectively comprise 1 to 6 intermediate catalysts,

[0320] The first catalyst bed, the 1 to 6 intermediate catalyst beds and the last catalyst bed are all located in different reactors, and

[0321] The fluoride concentration (wt %) in each of the 1 to 6 intermediate catalysts at start-up is selected independently of the fluoride concentration in any other catalyst and is at least or about the same as the fluoride concentration of the last catalyst prior to reduction.

[0322] Aspect 38. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 1 to 33, wherein the method or system comprises 4 or 5 intermediate catalyst beds, and wherein the first catalyst bed, the intermediate catalyst bed and the last catalyst bed are each located in their own reactor.

[0323] Aspect 39. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of aspects 1 to 33, wherein:

[0324] The method or system includes 4 or 5 intermediate catalyst beds, each of the 4 or 5 intermediate catalyst beds containing its own corresponding intermediate catalyst;

[0325] The first catalyst bed, the 4 or 5 intermediate catalyst beds and the last catalyst bed are each located in a different reactor; and

[0326] The volume of each of the 4 or 5 intermediate reactors is greater than or equal to the volume of the first reactor and less than or equal to the volume of the last reactor.

[0327] Aspect 40. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of aspects 1 to 33, wherein:

[0328] The method or system includes four intermediate catalyst beds, each of the four intermediate catalyst beds containing its own corresponding intermediate catalyst;

[0329] The first catalyst bed, the four intermediate catalyst beds and the final catalyst bed are all located in different reactors; and

[0330] The volume of each of the four intermediate reactors and the final reactor is greater than or equal to the volume of the reactor immediately upstream of the reactor.

[0331] Aspect 41. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of aspects 1 to 33, wherein:

[0332] The method or system includes four intermediate catalyst beds, each of the four intermediate catalyst beds containing its own corresponding intermediate catalyst;

[0333] The first catalyst bed, the four intermediate catalyst beds and the final catalyst bed are all located in different reactors; and

[0334] The relative volumes of the first reactor, the four intermediate reactors and the final reactor are 10:10:10:20:20:30.

[0335] Aspect 42. A method for reforming hydrocarbons according to any one of Aspects 1, 3, 5, 7 or 9 to 33, wherein the first catalyst bed effluent and / or the one or more intermediate catalyst bed effluents are heated prior to entering the subsequent catalyst bed.

[0336] Aspect 43. A catalytic hydrocarbon reforming system according to any one of Aspects 1, 3, 5, 7 or 9 to 33, further comprising at least one furnace upstream of the first catalyst bed and / or any one or more of the intermediate catalyst beds.

[0337] Aspect 44. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 1 to 43, wherein the inorganic support of the first catalyst, the one or more intermediate catalysts and / or the final catalyst each independently comprises a crystalline or amorphous inorganic oxide or a combination thereof.

[0338] Aspect 45. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 1 to 43, wherein the inorganic carrier of the first catalyst, the one or more intermediate catalysts and / or the final catalyst each independently comprises a zeolite, a zeolite bound to silica, a clay mineral, silica, alumina, silica-alumina, aluminum phosphate, a heteropolytungstate, titanium dioxide, zirconium oxide, magnesium oxide, boron oxide, zinc oxide, a mixed oxide thereof or a mixture thereof.

[0339] Aspect 46. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 1 to 43, wherein the inorganic support of the first catalyst, the one or more intermediate catalysts and / or the final catalyst each independently comprises a zeolite.

[0340] Aspect 47. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 1 to 43, wherein the inorganic carrier of the first catalyst, the one or more intermediate catalysts and / or the last catalyst each independently comprises L zeolite, K / L zeolite, X zeolite, Y zeolite, Ω zeolite, β zeolite, ZSM-4, ZSM-5, ZSM-10, ZSM-11, ZSM-12, ZSM-20, REY, USY, RE-USY, LZ-210, LZ-210-A, LZ-210-M, LZ-210-T, SSZ-24, SSZ-26, SSZ-31, SSZ-33, SSZ-35, SSZ-37, SSZ-41, SSZ-42, SSZ-44, MCM-58, mordenite, needle zeolite, faujasite or a combination thereof.

[0341] Aspect 48. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 1 to 43, wherein the inorganic carrier of the first catalyst, the one or more intermediate catalysts and / or the last catalyst each independently comprises L zeolite, K / L zeolite, X zeolite, mordenite, needle zeolite or ZSM-5.

[0342] Aspect 49. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 44 to 48, wherein the inorganic support of the first catalyst, the one or more intermediate catalysts and / or the last catalyst each further independently comprises a binder.

[0343] Aspect 50. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to Aspect 49, wherein the inorganic support of the first catalyst, the one or more intermediate catalysts and / or the final catalyst each independently contains any weight percentage of the binder disclosed herein, for example, from about 3 weight % to about 35 weight % or from about 5 weight % to about 30 weight % of the binder based on the total weight of the first catalyst, the intermediate catalyst and the final catalyst.

[0344] Aspect 51. The method for reforming hydrocarbons or the catalytic hydrocarbon reforming system according to any one of aspects 49 to 50, wherein the binder of each inorganic support independently comprises an inorganic solid oxide, a clay, or a combination thereof.

[0345] Aspect 52. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 49 to 50, wherein the binder of each inorganic support independently comprises alumina, silica, magnesia, boria, titania, zirconia, mixed oxides thereof, or a mixture thereof.

[0346] Aspect 53. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of aspects 49 to 50, wherein each inorganic support independently comprises a silica-bound or alumina-bound L zeolite, a barium ion-exchanged L zeolite, or a K / L zeolite.

[0347] Aspect 54. The method for reforming hydrocarbons or the catalytic hydrocarbon reforming system according to aspect 53, wherein each inorganic support is independently produced by a method comprising:

[0348] a) combining the L zeolite, barium ion-exchanged L zeolite or K / L zeolite with a silica or alumina sol to form a mixture, extruding the mixture to form an extrudate,

[0349] b) drying and calcining the extrudates to form a bonded support; and

[0350] c) washing, drying and calcining the combined support to form the inorganic support.

[0351] Aspect 55. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 1 to 43, wherein the inorganic support of the first catalyst, the one or more intermediate catalysts and / or the final catalyst each independently comprises a zeolite and a binder.

[0352] Aspect 56. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 1 to 43, wherein the Group 8-10 metal of the first catalyst, the one or more intermediate catalysts and / or the final catalyst is independently selected from iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum or any combination thereof.

[0353] Aspect 57. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 1 to 43, wherein the first catalyst, the one or more intermediate catalysts and / or the final catalyst each independently comprises a Group 8 metal independently selected from iron, ruthenium or osmium.

[0354] Aspect 58. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 1 to 43, wherein the first catalyst, the one or more intermediate catalysts and / or the final catalyst each independently comprises a Group 9 metal independently selected from cobalt, rhodium or iridium.

[0355] Aspect 59. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 1 to 43, wherein the first catalyst, the one or more intermediate catalysts and / or the final catalyst each independently comprises a Group 10 metal independently selected from nickel, palladium or platinum.

[0356] Aspect 60. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 1 to 43, wherein the first catalyst, the one or more intermediate catalysts and / or the final catalyst each independently comprises platinum and L zeolite.

[0357] Aspect 61. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 1 to 43, wherein the first catalyst, the one or more intermediate catalysts and / or the final catalyst each independently contains any weight percentage of the transition metal disclosed herein, for example, about 0.5 wt. % to about 2.5 wt. %, about 0.5 wt. % to about 2 wt. %, or about 0.7 wt. % to about 1.5 wt. % of the transition metal.

[0358] Aspect 62. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 1 to 43, wherein the Group 8-10 metal of each of the first catalyst, the one or more intermediate catalysts and / or the final catalyst is platinum and the platinum concentration of each catalyst is independently selected from about 0.3 weight % to about 1.5 weight % relative to the weight of the respective corresponding catalyst before reduction.

[0359] Aspect 63. A method for reforming hydrocarbons according to any one of aspects 1 to 4 and 9 to 62, wherein the conditions for aromatizing aliphatic hydrocarbons include a catalyst temperature of 400 to 2000 hr during reduction at a temperature above about 500 °F. -1 Catalyst startup is performed at a gas flow rate of GHSV of 1.35°C / hr and a heating rate of 5°F / hr to 50°F / hr, wherein the first catalyst, the intermediate catalyst and / or the last catalyst comprises a fluorinated zeolite platinum catalyst containing a Group 8-10 metal.

[0360] Aspect 64. A method for reforming hydrocarbons according to any one of aspects 1 to 4 and 9 to 62, wherein the conditions for aromatizing aliphatic hydrocarbons include a catalyst temperature of 600 to 1500 hr during reduction at a temperature above about 500 °F. -1 Catalyst startup is performed at a gas flow rate of GHSV of 10°C / hr to 30°C / hr and a heating rate of 10°C / hr to 30°C / hr, wherein the first catalyst, the intermediate catalyst, and / or the last catalyst comprises a fluorinated zeolite platinum catalyst.

[0361] Aspect 65. A method for reforming hydrocarbons according to any one of aspects 1 to 4 and 9 to 62, wherein the conditions for aromatizing aliphatic hydrocarbons include a catalyst temperature of 600 to 1500 hr during reduction at a temperature above about 500 °F. -1Catalyst startup is performed at a gas flow rate of GHSV of 10°C / hr to 25°C / hr and a heating rate of 10°C / hr to 25°C / hr, wherein the first catalyst, the intermediate catalyst, and / or the last catalyst comprises a fluorinated-chlorinated zeolite platinum catalyst.

[0362] Aspect 66. The method for reforming hydrocarbons according to any one of aspects 1 to 4 and 9 to 62, wherein the first catalyst bed, the intermediate catalyst bed and / or the last catalyst bed are located in a radial flow reactor.

[0363] Aspect 67. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 1 to 4 and 9 to 62, wherein the first catalyst is characterized by a peak temperature on a temperature programmed reduction (TPR) curve within any range disclosed herein, for example, from about 580°F to about 800°F, from about 580°F to about 750°F, from about 600°F to about 730°F, or from about 600°F to about 720°F.

[0364] Aspect 68. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 1 to 4 and 9 to 62, wherein the first catalyst is characterized by a peak temperature on a programmed temperature reduction (TPR) curve comprising a lower temperature peak and a higher temperature peak, and wherein the height of the higher temperature peak is higher than the lower temperature peak.

[0365] Aspect 69. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 1 to 2, 5 to 6, or 9 to 62, wherein the first catalyst is characterized in that under the same catalyst preparation conditions, the temperature-programmed reduction (TPR) curve of the first catalyst is about 120°F to about 300°F higher than the temperature-programmed reduction curve of a catalyst having 0.3 wt% to 1.0 wt% fluorine.

[0366] Aspect 70. A method for reforming hydrocarbons or a catalytic hydrocarbon reforming system according to any one of Aspects 3 to 4, 7 to 8 or 9 to 62, wherein the first catalyst is characterized in that under the same catalyst preparation conditions, the temperature-programmed reduction (TPR) curve of the first catalyst is about 120°F to about 300°F higher than the temperature-programmed reduction curve of a catalyst having 0.3 wt% to 1.5 wt% chlorine.

Claims

1. A method for reforming hydrocarbons, comprising: a) contacting a feedstock containing an aliphatic hydrocarbon with a first catalyst in a first catalyst bed under conditions to aromatize the aliphatic hydrocarbon to form a first catalyst bed effluent comprising aromatic hydrocarbons and aliphatic hydrocarbons, the first catalyst comprising an inorganic support, a Group 8-10 metal, and from about 1.0 wt % to about 5.0 wt % of a fluoride relative to the weight of the first catalyst before reduction; b) contacting the first catalyst bed effluent with one or more independently selected intermediate catalysts in one or more intermediate catalyst beds in series, under conditions to aromatize aliphatic hydrocarbons, to form one or more intermediate catalyst bed effluents comprising aromatic hydrocarbons and aliphatic hydrocarbons, the intermediate catalysts each comprising an inorganic support, a Group 8-10 metal, and a fluoride; and c) contacting the one or more intermediate catalyst bed effluents with a final catalyst in a final catalyst bed under conditions to aromatize aliphatic hydrocarbons to form a final catalyst bed effluent comprising an aromatic product, the final catalyst comprising an inorganic support, a Group 8-10 metal, and from about 0.7 wt % to about 4.0 wt % fluoride relative to the weight of the final catalyst prior to reduction; The fluoride concentration of the first catalyst or the fluoride concentration of at least one of the intermediate catalysts is higher than the fluoride concentration of the last catalyst before reduction.

2. The method for reforming hydrocarbons according to claim 1, wherein: The first catalyst, any one or more of the intermediate catalysts, the final catalyst, or any combination thereof independently further comprises from about 1.5 wt % to about 4.0 wt % of chloride relative to the weight of the corresponding first catalyst, intermediate catalyst, or final catalyst prior to reduction; and The chloride concentration of the first catalyst or the chloride concentration of at least one of the intermediate catalysts is higher than the chloride concentration of the last catalyst before reduction.

3. A method for reforming hydrocarbons according to claim 2, wherein the chloride concentration (weight %) of the one or more intermediate catalysts at startup is higher, lower or equal to the chloride concentration of the first catalyst before reduction and higher than or equal to the chloride concentration of the last catalyst before reduction.

4. The process for reforming hydrocarbons according to claim 1, wherein the first catalyst bed, the one or more intermediate catalyst beds and the final catalyst bed are each located in a different reactor.

5. The method for reforming hydrocarbons according to claim 1, wherein: The method comprises 1 to 6 intermediate catalyst beds, wherein the 1 to 6 intermediate catalyst beds respectively contain 1 to 6 intermediate catalysts, The first catalyst bed, the 1 to 6 intermediate catalyst beds and the last catalyst bed are all located in different reactors, and The fluoride concentration (wt %) in each of the 1 to 6 intermediate catalysts at start-up is selected independently of the fluoride concentration in any other catalyst and is at least or about the same as the fluoride concentration of the last catalyst prior to reduction.

6. The method for reforming hydrocarbons according to claim 1, wherein: The process comprises 4 or 5 intermediate catalyst beds, each of the 4 or 5 intermediate catalyst beds comprising its own corresponding intermediate catalyst; The first catalyst bed, the 4 or 5 intermediate catalyst beds and the last catalyst bed are each located in a different reactor; and The volume of each of the 4 or 5 intermediate reactors is greater than or equal to the volume of the first reactor and less than or equal to the volume of the last reactor.

7. The process for reforming hydrocarbons according to claim 1, wherein the first catalyst bed effluent and / or the one or more intermediate catalyst bed effluents are heated prior to entering the subsequent catalyst bed.

8. The process for reforming hydrocarbons according to claim 1, wherein the first catalyst, the one or more intermediate catalysts and the final catalyst each independently comprise an inorganic support, the inorganic support comprising a zeolite, a zeolite bound to silica, a clay mineral, silica, alumina, silica-alumina, aluminum phosphate, a heteropolytungstate, titania, zirconium oxide, magnesium oxide, boron oxide, zinc oxide, mixed oxides thereof or mixtures thereof.

9. The method for reforming hydrocarbons according to claim 1, wherein the first catalyst, the one or more intermediate catalysts and the final catalyst each independently comprise an inorganic support, and the inorganic support includes L zeolite, X zeolite, Y zeolite, omega zeolite, beta zeolite, ZSM-4, ZSM-5, ZSM-10, ZSM-11, ZSM-12, ZSM-20, REY, USY, RE-USY, LZ-210, LZ-210-A, LZ-210-M, LZ-210-T, SSZ-24, SSZ-26, SSZ-31, SSZ-33, SSZ-35, SSZ-37, SSZ-41, SSZ-42, SSZ-44, MCM-58, mordenite, phillipsite, faujasite or a combination thereof.

10. The process for reforming hydrocarbons according to claim 1, wherein the first catalyst, the one or more intermediate catalysts, and the final catalyst each comprise a Group 10 metal independently selected from nickel, palladium, or platinum.

11. The process for reforming hydrocarbons according to claim 1, wherein the first catalyst, the one or more intermediate catalysts and / or the final catalyst comprises platinum and L zeolite.

12. The method for reforming hydrocarbons according to claim 1, wherein the fluoride concentration (weight %) of the one or more intermediate catalysts at startup is higher, lower or equal to the fluoride concentration of the first catalyst before reduction and higher than or equal to the fluoride concentration of the last catalyst before reduction.

13. The method for reforming hydrocarbons according to claim 1, wherein any one or more of the first catalyst, the intermediate catalyst and / or the final catalyst further comprises chloride, and a weight ratio of chloride to fluoride is from 1:10 to 10:

1.

14. The process for reforming hydrocarbons according to claim 1, wherein the Group 8-10 metal of each of the first catalyst, the one or more intermediate catalysts and the final catalyst is platinum and the platinum concentration of each catalyst is independently selected from 0.3 wt.% to 1.5 wt.% relative to the weight of each corresponding catalyst before reduction.

15. A catalytic hydrocarbon reforming system comprising: at least three catalyst beds connected in series, the catalyst beds comprising an upstream first catalyst bed, a downstream last catalyst bed, and one or more intermediate catalyst beds connected in series between the first catalyst bed and the last catalyst bed; a first catalyst in the first catalyst bed, the first catalyst comprising an inorganic support, a Group 8-10 metal, and from about 1.0 wt % to about 5.0 wt % fluoride relative to the weight of the first catalyst prior to reduction; one or more independently selected intermediate catalysts in the one or more intermediate catalyst beds, each intermediate catalyst comprising an inorganic support, a Group 8-10 metal, and a fluoride; and a final catalyst in the final catalyst bed, the final catalyst comprising an inorganic support, a Group 8-10 metal, and from about 0.7 wt % to about 4.0 wt % fluoride relative to the weight of the final catalyst prior to reduction; The fluoride concentration of the first catalyst or the fluoride concentration of at least one of the intermediate catalysts is higher than the fluoride concentration of the last catalyst before reduction.

16. The catalytic hydrocarbon reforming system of claim 15, wherein: The first catalyst, any one or more of the intermediate catalysts, the final catalyst, or any combination thereof independently further comprises from about 1.5 wt % to about 4.0 wt % of chloride relative to the weight of the corresponding first catalyst, intermediate catalyst, or final catalyst prior to reduction; and The chloride concentration of the first catalyst or the chloride concentration of at least one of the intermediate catalysts is higher than the chloride concentration of the last catalyst before reduction.

17. A catalytic hydrocarbon reforming system according to claim 15, wherein the chloride concentration (weight %) of the one or more intermediate catalysts at startup is higher than, lower than or equal to the chloride concentration of the first catalyst before reduction and higher than or equal to the chloride concentration of the last catalyst before reduction.

18. The catalytic hydrocarbon reforming system of claim 15, wherein the first catalyst bed, the one or more intermediate catalyst beds, and the final catalyst bed are each located in a different reactor.

19. The catalytic hydrocarbon reforming system of claim 15, wherein The system comprises 1 to 6 intermediate catalyst beds, wherein the 1 to 6 intermediate catalyst beds respectively comprise 1 to 6 intermediate catalysts, The first catalyst bed, the 1 to 6 intermediate catalyst beds and the last catalyst bed are all located in different reactors, and The fluoride concentration (wt %) in each of the 1 to 6 intermediate catalysts at start-up is selected independently of the fluoride concentration in any other catalyst and is at least or about the same as the fluoride concentration of the last catalyst prior to reduction.

20. The catalytic hydrocarbon reforming system of claim 15, wherein the first catalyst, the intermediate catalyst, and the final catalyst each independently comprise an inorganic support, the inorganic support comprising a zeolite, a silica-bound zeolite, a clay mineral, silica, alumina, silica-alumina, aluminum phosphate, a heteropolytungstate, titanium dioxide, zirconium oxide, magnesium oxide, boron oxide, zinc oxide, mixed oxides thereof, or mixtures thereof.

21. The catalytic hydrocarbon reforming system of claim 15, wherein the first catalyst, the intermediate catalyst, and the final catalyst each comprise a Group 10 metal independently selected from nickel, palladium, or platinum.

22. The catalytic hydrocarbon reforming system of claim 15, wherein the first catalyst, the intermediate catalyst, and / or the final catalyst comprises platinum and L zeolite.

23. The catalytic hydrocarbon reforming system of claim 15, wherein the fluoride concentration (wt %) of the one or more intermediate catalysts at startup is higher, lower, or equal to the fluoride concentration of the first catalyst before reduction and higher than or equal to the fluoride concentration of the last catalyst before reduction.

24. The catalytic hydrocarbon reforming system of claim 15, wherein any one or more of the first catalyst, the intermediate catalyst, and / or the final catalyst further comprises a chloride, and the weight ratio of chloride to fluoride is from 1:10 to 10:

1.

25. A method for reforming hydrocarbons, comprising: a) contacting a feedstock containing an aliphatic hydrocarbon with a first catalyst in a first catalyst bed under conditions to aromatize the aliphatic hydrocarbon to form a first catalyst bed effluent comprising aromatic hydrocarbons and aliphatic hydrocarbons, the first catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 1.0 weight percent of a fluoride relative to the weight of the first catalyst before reduction; as well as b) contacting the first catalyst bed effluent with a final catalyst in a final catalyst bed under conditions to aromatize aliphatic hydrocarbons to form a final catalyst bed effluent comprising an aromatic product, the final catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 0.7 weight percent fluoride relative to the weight of the final catalyst prior to reduction; The fluoride concentration of the first catalyst is higher than the fluoride concentration of the last catalyst before reduction.

26. A process for reforming hydrocarbons according to claim 26, wherein: The first catalyst and the last catalyst independently further comprise from about 1.5 wt % to about 4.0 wt % chloride relative to the weight of the respective first catalyst and last catalyst prior to reduction; and The first catalyst has a chloride concentration that is higher than the chloride concentration of the last catalyst prior to reduction.

27. A catalytic hydrocarbon reforming system comprising: Two catalyst beds connected in series, the catalyst beds comprising an upstream first catalyst bed and a downstream last catalyst bed; a first catalyst in the first catalyst bed, the first catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 1.0 weight percent fluoride relative to the weight of the first catalyst before reduction; and a final catalyst in the final catalyst bed, the final catalyst comprising an inorganic support, a Group 8-10 metal, and at least or about 0.7 weight percent fluoride relative to the weight of the final catalyst prior to reduction; The fluoride concentration of the first catalyst is higher than the fluoride concentration of the last catalyst before reduction.

28. The catalytic hydrocarbon reforming system of claim 27, wherein: The first catalyst and the last catalyst independently further comprise from about 1.5 wt % to about 4.0 wt % chloride relative to the weight of the respective first catalyst and last catalyst prior to reduction; and The first catalyst has a chloride concentration that is higher than the chloride concentration of the last catalyst prior to reduction.

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