High-fluoride catalysts are used in the fore-reform reactor to extend the lifetime and selectivity of the reforming catalyst.

Abstract

This disclosure provides a method for reforming hydrocarbons using a series of adiabatic reactors and catalysts, wherein the catalyst in at least one upstream or front-end catalyst bed or reactor comprises a higher concentration of fluorides, a higher concentration of chlorides, or both than the corresponding halide concentrations in the catalysts of one or more downstream catalyst beds or reactors. It has been unexpectedly found that the method extends the lifespan and / or selectivity of the catalyst system.

Description

[0001] Cross-reference to related applications

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

[0003] This disclosure relates to supported aromatization catalysts and their use in aromatizing aliphatic hydrocarbons into aromatic hydrocarbons. Background Technology

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

[0005] Traditional aromatization reactor systems comprise a series of adiabatic reactors, where the only heat entering the reactors is carried by the input stream. The aromatization catalysts in these reactor systems are typically supported transition metal catalysts that influence a variety of reactions, including dehydrogenation, isomerization, and cyclization of aliphatic hydrocarbons, to produce specific aromatic compounds. However, over time, aromatization catalysts may lose their activity and / or selectivity, which can significantly impact the economics of the process. Given their commercial importance, there is a continued need for improved systems, catalysts, and processes to increase the yield of aromatic hydrocarbons. Summary of the Invention

[0006] This summary is provided to introduce, in a simplified form, various concepts that will be further described in the detailed embodiments described below. This summary is not intended to identify desired or necessary features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter.

[0007] The aromatization or reforming catalysts according to this disclosure may comprise an inorganic support, Group 8-10 metals, and fluorides and / or chlorides. In one aspect, this disclosure provides a process for reforming hydrocarbons using a series of adiabatic reactors and catalysts, wherein the catalyst in at least one upstream or front-end catalyst bed or reactor may comprise 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 found that by using a higher weight percentage of halides in at least one upstream or front-end catalyst bed or reactor compared to one or more downstream catalyst beds or reactors, the lifespan and / or selectivity of the catalyst system can be extended.

[0008] While not intended to be theoretically constrained, it has been found that the concentrations of fluorides and chlorides in aromatization catalysts can decrease over time, and this loss of fluorides and chlorides appears to be associated with a decrease in catalyst selectivity. This decrease in selectivity can become so severe that, despite the catalyst being well maintained within the temperature limits of the process equipment and retaining significant catalytic activity, it is more economically feasible to rotate a commercial unit and replace the catalyst with fresh catalyst. The applicant has found that a higher weight percentage of fluoride, chloride, or both in at least one upstream reactor in series can maintain the selectivity of the catalyst system for a longer period compared to downstream reactors.

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

[0010] a) In a first catalyst bed, under conditions that aromatize aliphatic hydrocarbons, a feedstock containing aliphatic hydrocarbons is contacted with a first catalyst (containing an inorganic support, group 8-10 metals and fluoride at least or about 1.0% by weight relative to the weight of the first catalyst before reduction) to form a first catalyst bed effluent containing aromatic hydrocarbons and aliphatic hydrocarbons.

[0011] b) In one or more tandem intermediate catalyst beds, under conditions that aromatize aliphatic hydrocarbons, the effluent from a first catalyst bed is contacted with one or more independently selected intermediate catalysts (each comprising an inorganic support, a group 8-10 metal, and a fluoride) to form one or more intermediate catalyst bed effluents comprising aromatic hydrocarbons and aliphatic hydrocarbons; and

[0012] c) In the final catalyst bed, under conditions that aromatize aliphatic hydrocarbons, the effluent from one or more intermediate catalyst beds is contacted with the final catalyst (containing an inorganic support, group 8-10 metals and fluoride at least or about 0.7% by weight relative to the weight of the final catalyst prior to reduction) to form a final catalyst bed effluent containing aromatic products.

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

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

[0015] a) In a first catalyst bed, under conditions that aromatize aliphatic hydrocarbons, a feedstock containing aliphatic hydrocarbons is contacted with a first catalyst (containing an inorganic support, group 8-10 metals and chlorides at least or about 1.5% by weight relative to the weight of the first catalyst before reduction) to form a first catalyst bed effluent containing aromatic hydrocarbons and aliphatic hydrocarbons.

[0016] b) In one or more tandem intermediate catalyst beds, under conditions that aromatize aliphatic hydrocarbons, the effluent from a first catalyst bed is contacted with one or more independently selected intermediate catalysts (each comprising an inorganic support, a group 8-10 metal, and a chloride) to form one or more intermediate catalyst bed effluents comprising aromatic hydrocarbons and aliphatic hydrocarbons; and

[0017] c) In the final catalyst bed, under conditions that aromatize aliphatic hydrocarbons, the effluent from one or more intermediate catalyst beds is contacted with the final catalyst (containing an inorganic support, group 8-10 metals and chlorides at least or about 0.5% by weight relative to the weight of the final catalyst prior to reduction) to form a final catalyst bed effluent containing aromatic products.

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

[0019] Generally, and unless otherwise specified, the weight percentage of halides, fluorides, or chlorides in the catalyst is specified prior to the reduction of the catalyst. The use of the terms “fluoride” and “chloride” is not intended to reflect any form of structure or bonding type between fluorine and chlorine atoms and the inorganic support, but only to reflect the frequent use of halide sources in the preparation of these halide catalysts.

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

[0021] a) In a first catalyst bed, under conditions that aromatize aliphatic hydrocarbons, a feedstock containing aliphatic hydrocarbons is contacted with a first catalyst (comprising an inorganic support, group 8-10 metals, and at least or about 1.0% by weight of fluoride relative to the weight of the first catalyst before reduction) to form a first catalyst bed effluent containing aromatic hydrocarbons and aliphatic hydrocarbons; and

[0022] b) In the final catalyst bed, under conditions that aromatize aliphatic hydrocarbons, the first catalyst bed effluent is contacted with the final catalyst to form a final catalyst bed effluent containing an aromatic product, said final catalyst comprising an inorganic support, group 8-10 metals and at least or about 0.7% by weight of fluoride relative to the weight of said final catalyst before reduction.

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

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

[0025] a) In a first catalyst bed, under conditions that aromatize aliphatic hydrocarbons, a feedstock containing aliphatic hydrocarbons is contacted with a first catalyst (comprising an inorganic support, group 8-10 metals, and at least or about 1.5% by weight of chloride relative to the weight of the first catalyst before reduction) to form a first catalyst bed effluent containing aromatic hydrocarbons and aliphatic hydrocarbons; and

[0026] b) In the final catalyst bed, under conditions that aromatize aliphatic hydrocarbons, the first catalyst bed effluent is contacted with the final catalyst to form a final catalyst bed effluent containing an aromatic product, said final catalyst comprising an inorganic support, group 8-10 metals and at least or about 0.5% by weight of chloride relative to the weight of said final catalyst before reduction.

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

[0028] Therefore, in these respects, there are two continuous catalysts or catalyst beds in series, comprising an inorganic support, Group 8-10 metals, and the concentration of the fluoride or chloride in the first upstream catalyst relative to the weight of the upstream catalyst. The immediate downstream catalyst or catalyst bed contains a relatively low weight percentage of fluoride or chloride relative to the weight of the downstream catalyst. Unless otherwise specified, the weight percentages listed are weight percentages in the catalyst prepared prior to reduction.

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

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

[0031] The first catalyst in the first catalyst bed comprises an inorganic support, a group 8-10 metal, and at least or about 1.0% by weight of fluoride relative to the weight of the first catalyst before reduction;

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

[0033] The final catalyst in the final catalyst bed comprises an inorganic support, group 8-10 metals, and at least or about 0.7% by weight of fluoride relative to the weight of the final catalyst prior to reduction;

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

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

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

[0037] The first catalyst in the first catalyst bed comprises an inorganic support, a group 8-10 metal, and at least or about 1.5% by weight of chloride relative to the weight of the first catalyst before reduction;

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

[0039] The final catalyst in the final catalyst bed comprises an inorganic support, group 8-10 metals, and at least or about 0.5% by weight of chloride relative to the weight of the final catalyst prior to reduction;

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

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

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

[0043] The first catalyst in the first catalyst bed comprises an inorganic support, a group 8-10 metal, and a fluoride comprising at least or about 1.0% by weight of the first catalyst prior to reduction; and

[0044] The final catalyst in the final catalyst bed comprises an inorganic support, group 8-10 metals, and at least or about 0.7% by weight of 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 another aspect of this disclosure, a catalytic hydrocarbon reforming system is provided, comprising:

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

[0048] The first catalyst in the first catalyst bed comprises an inorganic support, a group 8-10 metal, and at least or about 1.5% by weight of chloride relative to the weight of the first catalyst before reduction; and

[0049] The final catalyst in the final catalyst bed comprises an inorganic support, group 8-10 metals, and at least or about 0.5% by weight of 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 listed processes and systems, there are practical upper limits to the concentrations of fluorides and chlorides 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% of 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% of fluoride relative to the weight of the final catalyst before reduction. In the chloride-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% of chloride relative to the weight of the last catalyst before reduction, and the last 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% of chloride relative to the weight of the last catalyst before reduction.

[0052] The foregoing description and the following detailed description provide examples and are merely illustrative of the invention. Therefore, the foregoing description and the following detailed description should not be considered limiting. In addition to those set forth herein, other features or variations thereof may be provided, such as various combinations and sub-combinations of features, for example, those described in the detailed description. Attached Figure Description

[0053] Figure 1 A process flow diagram according to one aspect of this disclosure is provided, illustrating a class of aromatization reactor systems for the production of aromatic hydrocarbons.

[0054] Figure 2A An embodiment of this disclosure is illustrated, showing a "baseline" fixed-bed reactor having a standard (STD) aromatization catalyst in both the upper and lower halves of the reactor. The performance of this embodiment is comparable to... Figure 2B The implementation schemes for high-halogenated compounds were compared.

[0055] Figure 2B An embodiment of this disclosure is illustrated, showing a "split bed" fixed-bed reactor, wherein the upper half of the fixed bed has a high-halogen catalyst with a high chloride concentration and the lower half of the fixed bed has a standard (STD) aromatization catalyst arrangement, referred to as a split bed arrangement. This embodiment is similar to... Figure 2A The standard (STD) aromatization catalyst implementation schemes were compared.

[0056] Figure 3 Examples are given for Figure 2A (“baseline”) and Figure 2B The standard in the lower half of the fixed-bed reactor shown in (“stratified bed”) The graph of adjusted catalyst temperature (℉) versus running time (hours) for catalyst II demonstrates that the standard catalyst downstream of the high chloride catalyst exhibits better activity compared to the standard catalyst downstream of the more standard catalyst (i.e., the catalyst with standard chloride concentration).

[0057] Figure 4 Examples are given for Figure 2A (“baseline”) and Figure 2B The standard in the lower half of the fixed-bed reactor shown in (“stratified bed”) The graph of selectivity (mol / mol) versus running time (hours) for catalyst II demonstrates that the standard catalyst downstream of the high chloride catalyst exhibits better selectivity compared to the standard catalyst downstream of a more standard catalyst (i.e., a catalyst with a standard chloride concentration). Detailed Implementation

[0058] definition

[0059] To more clearly define the terms used herein, the following definitions are provided. Unless otherwise indicated, the following definitions apply to this disclosure. If a term is used in this disclosure but is not specifically defined herein, the definition in the IUPAC Compendium of Chemical Terminology, 2nd Edition (1997) may be applied, provided that the definition does not conflict with any other disclosure or definition applied herein, or render any claim to which the definition is applied ambiguous or invalid. If any definition or usage provided by reference to any document incorporated herein conflicts with the definition or usage provided herein, the definition or usage provided herein shall prevail.

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

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

[0062] Unless otherwise specified, the terms “including,” “with,” and “having” as used herein are defined as encompassing (i.e., open-ended language).

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

[0064] This document discloses various numerical ranges. When an applicant discloses or claims protection for any type of range, unless otherwise specified, the applicant intends to individually disclose or claim protection for every possible number that such range can reasonably cover, including the endpoints of the range and any sub-ranges and combinations thereof covered therein. For example, by disclosing weight percentages from 1.0 wt% to 2.0 wt%, the applicant intends to individually 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%, including any sub-ranges and combinations thereof covered therein, and these methods of describing such ranges are interchangeable. Furthermore, unless excluded by attached conditions, all numerical endpoints of the ranges disclosed herein are approximate. As a representative example, if the applicant states that one or more steps in the process disclosed herein can be performed at temperatures ranging from 10°C to 75°C, unless otherwise stated, that range should be interpreted as covering temperatures ranging from “about” 10°C to “about” 75°C.

[0065] Values ​​or ranges herein may be expressed as “about,” from “about” a specific value, and / or to “about” another specific value. When expressing such values ​​or ranges, other disclosed embodiments include the specific value, from one specific value, and / or to another specific value. Similarly, when a value is expressed as an approximation using the antecedent “about,” it should be understood that the specific value forms another embodiment. It should also be 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 a measure smaller than the full scope of this disclosure for any reason (e.g., considering references the applicant might not have known at the time of filing), the applicant reserves the right to exclude or exclude any individual member (including any sub-scopes or combinations of sub-scopes) of any group of such values ​​or ranges that can be claimed based on the scope or in any similar manner. Furthermore, if the applicant chooses to claim a measure smaller than the full scope of the disclosure for any reason (e.g., considering references or prior disclosures the applicant might not have known at the time of filing), the applicant reserves the right to exclude or exclude any individual substituent, analogue, compound, ligand, structure, or group thereof, or any member of the claimed group.

[0067] For any particular compound or group disclosed herein, unless otherwise specified, any name or structure presented (general or specific) is intended to cover all conformational isomers, regio isomers, stereoisomers, and mixtures thereof that can be produced by a particular set of substituents. Unless otherwise specified, the name or structure also covers all enantiomers, diastereomers, and other optical isomers (if present), whether in enantiomeric or racemic form, and mixtures of stereoisomers, as known to those skilled in the art. For example, general references to one or more hexanes include n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, and 2,3-dimethylbutane; and general references to butyl include n-butyl, sec-butyl, isobutyl, and tert-butyl.

[0068] When used to describe a group, such as when referring to a substituted analogue of a particular group, the term "substituted" is intended to describe a compound or group in which any non-hydrogen moiety formally replaces hydrogen in that group or compound, and is intended to be non-limiting. A compound or group 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-limiting and includes inorganic or organic substituents as indicated and understood by those skilled in the art.

[0069] Unless otherwise specified, 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 duration. For example, components can be contacted by blending or mixing. Furthermore, unless otherwise specified, contact of any components can occur in the presence or absence of any other component in the compositions and methods described herein. Additional materials or components can be combined by any suitable method. Additionally, the term "contact product" includes mixtures, blends, solutions, slurries, reaction products, etc., or combinations thereof. Although "contact product" may and often includes reaction products, it does not require that the individual components react with each other. Similarly, "contacting" two or more components can produce reaction products or reaction mixtures. Therefore, depending on the circumstances, a "contact product" can be a mixture, a reaction mixture, or a reaction product.

[0070] "Conditions for aromatizing aliphatic hydrocarbons" means that, upon contact with a catalyst as described herein, at least a portion of the aliphatic hydrocarbons in the feedstock is 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 indicated using the numbering scheme shown in the version of the periodic table published in Chemical and Engineering News, 63(5), 27, 1985. In some cases, element groups may be indicated using the common names 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, and Group 17 elements are halogens or halides, etc.

[0072] In one respect, a chemical “group” can be defined or described according to how the group is formally derived from a reference or “parent” compound, for example, by the number of hydrogen atoms removed from the parent compound to produce the group, even if the group is not literally synthesized in this way. These groups can be used as substituents or coordinated or bonded to metal atoms. For example, an “alkyl” can be formally derived by removing a hydrogen atom from an alkane. The disclosure that substituents, ligands, or other chemical parts can constitute a particular “group” implies that well-known chemical structures and bonding rules are followed when the group is used as described. Unless otherwise specified or required by the context, such terms are used in a formal sense when describing a group as “derived from,” “from,” “formed by,” or “formed from,” and are not intended to reflect any particular synthetic method or procedure.

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

[0074] "Aromatic" compounds or "aromatic hydrocarbons" are compounds containing a cyclic conjugated double bond system that follows Hückel's (4n+2) rule and contains (4n+2) π electrons, where n is an integer from 1 to 5. Aromatic hydrocarbons include "aromatic hydrocarbons" (aromatic compounds, such as benzene, toluene, and xylene) and "heteroaromatic hydrocarbons" (heteroaromatic compounds formally derived from aromatic hydrocarbons by replacing one or more methylene (-C=) carbon atoms in the cyclic conjugated double bond system with trivalent or divalent heteroatoms, thus maintaining the continuous π electron system characteristic of the aromatic system and the number of out-of-plane π electrons corresponding to Hückel's (4n+2) rule). As disclosed herein, unless otherwise specified, the term "substituted" may be used to describe aromatic groups, aromatic hydrocarbons, or heteroaromatic hydrocarbons in which a non-hydrogen portion 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 specific group (if present) in an alkane (e.g., haloalkane indicates the presence of one or more halogen atoms replacing an equal 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 a hydrogen atom from an alkane. Unless otherwise specified, alkanes or alkyl groups may be straight-chain or branched.

[0076] “Cycloalkanes” are 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 a specific group (if present) in a cycloalkane (e.g., halocycloalkanes indicate the presence of one or more halogen atoms replacing an equal 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. In other words, aliphatic compounds are non-aromatic organic compounds.

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

[0079] As used herein, "alkanes" refers to noncyclic, straight-chain, or branched saturated hydrocarbons and includes alkanes. For example, C6 alkanes are noncyclic, straight-chain, or branched hydrocarbons having six carbon atoms per molecule. n-Hexane, methylpentane, and dimethylbutane are examples of C6 alkanes. Alkanes-containing feedstocks include noncyclic saturated hydrocarbons such as n-alkanes, isoalkanes, and mixtures thereof.

[0080] As used herein, “naphthene” and “naphthenic” are terms used to describe cyclic saturated hydrocarbons and include cycloalkanes and their alkyl-substituted analogues. Therefore, “naphthene” is a cyclic saturated hydrocarbon having one or more carbon atoms in its chemical structure and is used herein to mean the same thing as “cycloalkanes.” If such a cyclic structure includes unsaturated carbon-carbon bonds but is not aromatic, such compounds would be aliphatic but not cycloalkanes. In some embodiments, cycloalkanes are cyclic saturated hydrocarbons having 5 to 8 carbon atoms in their cyclic structure, including their substituted (particularly alkyl-substituted) analogues.

[0081] As used herein, "olefin" is an acyclic or cyclic hydrocarbon that has one or more carbon-carbon double bonds in addition to the formal double bonds found in aromatic compounds. Olefins include alkenes, cyclic alkenes, and their corresponding polyolefins.

[0082] As used herein, “naphtha” is a petroleum fraction with a boiling point ranging from 50℉ (10°C) to 550℉ (260°C). In some embodiments, the boiling point of the naphtha is in the range of 70℉ (21°C) to 450℉ (232°C), and more typically in the range of 80℉ (27°C) to 400℉ (204°C), and often in the range of 90℉ (32°C) to 360℉ (182°C). In some embodiments, at least 85% by volume of the naphtha has a boiling point ranging from 50℉ (10°C) to 550℉ (260°C), and more typically in the range of 70℉ (21°C) to 450℉ (232°C). In embodiments, at least 85% by volume of the naphtha is C4 to C6. 12 Within the range, more typically in C5 to C 11 Within the range, and often between C6 and C 10 Within the scope. Naphtha may include, for example, straight-run naphtha, alkane and cycloalkane raffinates from aromatic extraction or adsorption, and naphtha containing C6 to C4. 10 Feedstocks include alkanes and cycloalkanes, 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 terms "convertible hydrocarbon," "convertible C6 substance," or "convertible C7 substance" refer 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. "Highly branched hydrocarbons" are hydrocarbons that are not selectively converted to form aromatic hydrocarbons under conventional aromatization process conditions. For example, "highly branched hydrocarbons" can include highly branched hydrocarbons having six or seven carbon atoms and an internal quaternary carbon, or hydrocarbons having six carbon atoms and two adjacent internal tertiary carbons, or mixtures thereof. Highly branched hydrocarbons can 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 mixtures 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 mixtures thereof. The selectively convertible component readily converts to aromatic hydrocarbons without producing light hydrocarbons.

[0084] As used herein, the terms “primary aromatic hydrocarbon,” “primary aromatic product,” “desired hydrocarbon product,” and “specific aromatic substance” are used interchangeably and refer to an aromatic hydrocarbon that is the desired end product of the reaction and comprises aromatic hydrocarbons generated from a feedstock containing 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] The term "Group 8-10 metals" includes 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. Group 8-10 metals can also be referred to using the earlier nomenclature of Group VIII metals, which also encompasses all of iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, and platinum. Typically, describing a catalyst as a Group 8-10 metal catalyst or containing Group 8-10 metals 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 in this document to name the transition metals in groups 8-10, rows 2 and 3, namely ruthenium, osmium, rhodium, iridium, palladium, and platinum.

[0087] The term "precious metals" is generally used to describe specific metals that are resistant to corrosion, and in this document, the term is used to include certain transition metals in rows 2 and 3, but not those in row 1. Typically, precious metals include ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, and gold. Therefore, the precious metals in groups 8-10 are also platinum metals.

[0088] As used herein, the term "bonded" is intended to describe zeolite-binder combinations or other carrier-binder combinations that form aggregates (such as pills, tablets, extrudates, etc.). As used herein, the term "catalyst matrix" refers to bonded zeolite or bonded carrier.

[0089] The term "catalyst" is used broadly herein and includes both the final catalyst and its precursors. Precursors to the final catalyst include, for example, calcined forms of catalysts containing catalytic metals and catalysts prior to reduction activation. 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 a catalyst, as will be understood by those skilled in the art from the context.

[0090] The term "sulfur-sensitive" describes catalysts that are particularly sensitive to the presence of sulfur in the feedstock. Typically, these catalysts require the sulfur content in the feedstock to be reduced to below 5 ppm through hydrotreatment, adsorbents, or combinations 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 the reactor vessel, reactor interior, and associated process equipment (as context allows), including but not limited to catalysts, inert packing, pits, flow distributors, central tubes, reactor ports, catalyst transport and distribution systems, furnaces and other heating devices, heat transfer equipment, and piping. The aromatization reactor system may comprise a fixed catalyst bed system, a moving catalyst bed system, a fluidized catalyst bed system, or a combination thereof. Such aromatization reactor systems can be batch or continuous. In a fixed-bed system, the feed flow can pass upward, downward, or radially through the reactor. In one aspect, a first catalyst bed, an intermediate catalyst bed, and a final catalyst bed are located in a radial flow reactor.

[0091] The term "catalyst bed," such as first, second, or intermediate catalyst beds, 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 the entirety of an aromatization reactor, or it may occupy a portion of an aromatization reactor, while a "second catalyst bed" occupies the remaining portion of said aromatization reactor. More typically, each catalyst bed may occupy the entirety of an aromatization reactor. Generally, and unless otherwise specified or required by the context, 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 usual meaning and includes halides where the context allows. Therefore, examples of halogens include fluorine, fluorides, chlorine, chlorides, bromine, bromides, iodine, and iodides. Furthermore, the use of the terms "fluoride" and "chloride" when describing catalyst components or catalyst composition (such as weight percentages or molar percentages of these components) does not depend on their presence in the catalyst in any particular molecular or ionic form.

[0093] Mole selectivity is defined as follows:

[0094]

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

[0096]

[0097] In the calculation of selectivity and conversion rate 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 convertible C6, C7, or C6-C8+ compounds remaining in the starting material or feed ("feed") or product ("prod"), as indicated.

[0098] In this article, “ton” is used to refer to a metric ton, which is a unit of mass equal to 1,000 kilograms.

[0099] This abstract is not intended to interpret the scope of the claims or limit the scope of the subject matter disclosed herein, but rather to satisfy the requirements of 37 C. FR § 1.72(b) to enable the U.S. Patent and Trademark Office and the public to quickly determine the nature and essence of the technical disclosure through a cursory examination. Furthermore, any headings used herein are not intended to interpret the scope of the claims or limit the scope of the subject matter disclosed herein. Any use of past tense to describe any instance otherwise indicated as constructive or prophetic is not intended to reflect an instance that has actually been implemented.

[0100] All publications and patents mentioned herein are incorporated herein by reference in their entirety for descriptive and disclosure purposes, such as descriptions and disclosures of constructs and methods described in publications that may be used in conjunction with the present invention. The publications discussed throughout are provided only for their disclosure prior to the filing date of this application. Nothing herein shall be construed as an admission that the inventors have no prior rights to these disclosures due to prior inventions.

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

[0102] This 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 fluorine and chlorine content of the catalyst composition can vary in at least two adjacent catalyst beds. More specifically, this disclosure provides processes and systems for reforming hydrocarbons using a series of adiabatic reactors and catalysts, wherein the catalyst in at least one upstream or foreground catalyst bed comprises 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 lifespan of the catalyst system can be extended by maintaining the selectivity of the catalyst system for a longer period of time than expected.

[0103] This disclosure also demonstrates the distinct roles of fluorides and chlorides in the operation of aromatization catalysts. Fluorides have been observed to act as selectivity enhancers, while chlorides have been observed to improve platinum distribution within the catalyst. Fluorides and chlorides also act synergistically, and catalysts containing both halides outperform those containing only one halide and outperform the additive effect of using a single halide. In this disclosure, we demonstrate that loading the upper portion of a catalyst bed with a high-halide catalyst can increase the overall run length by allowing the released halides to interact with the downstream catalyst. This result is unexpected, as fluorides can slowly evolve into products during the catalyst's run lifetime, potentially leading to reduced selectivity and run length. Chlorides may also be released; however, the observed release of chlorides promotes platinum sintering, which can also reduce selectivity and activity. Therefore, it has been observed that loading a fixed-bed reactor with the upper portion (e.g., the upper half) of a bed containing a high-halide catalyst (high-fluoride catalyst, high-chloride catalyst, or both) followed by a reduction step improves the performance of the catalyst in the lower half of the catalyst bed.

[0104] Overall considerations

[0105] In some embodiments, this disclosure provides two consecutive catalysts or catalyst beds in series, comprising an inorganic support, group 8-10 metals, and the concentration of the fluoride or chloride in the first upstream catalyst relative to the weight of the upstream catalyst prior to 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 prior to reduction.

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

[0107] a) In a first catalyst bed, under conditions that aromatize aliphatic hydrocarbons, a feedstock containing aliphatic hydrocarbons is contacted with a first catalyst (containing an inorganic support, group 8-10 metals and fluoride at least or about 1.0% by weight relative to the weight of the first catalyst before reduction) to form a first catalyst bed effluent containing aromatic hydrocarbons and aliphatic hydrocarbons.

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

[0109] c) In the final catalyst bed, under conditions that aromatize aliphatic hydrocarbons, [1] the first catalyst bed effluent is contacted with the final catalyst or [2] when one or more optional intermediate catalyst beds are present, one or more intermediate catalyst bed effluents are contacted with the final catalyst to form a final catalyst bed effluent containing an aromatic product, wherein the final catalyst comprises an inorganic support, a group 8-10 metal and a fluoride of at least or about 0.7% by weight relative to the weight of the final catalyst prior to reduction;

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

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

[0112] a) In a first catalyst bed, under conditions that aromatize aliphatic hydrocarbons, a feedstock containing aliphatic hydrocarbons is contacted with a first catalyst (containing an inorganic support, group 8-10 metals and chlorides at least or about 1.5% by weight relative to the weight of the first catalyst before reduction) to form a first catalyst bed effluent containing aromatic hydrocarbons and aliphatic hydrocarbons.

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

[0114] c) In the final catalyst bed, under conditions that aromatize aliphatic hydrocarbons, [1] the first catalyst bed effluent is contacted with the final catalyst or [2] when one or more optional intermediate catalyst beds are present, one or more intermediate catalyst bed effluents are contacted with the final catalyst to form a final catalyst bed effluent containing an aromatic product, wherein the final catalyst comprises an inorganic support, a group 8-10 metal and a chloride at least or about 0.5% by weight relative to the weight of the final catalyst prior to reduction;

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

[0116] The process aspects immediately preceding these describe the “first” and “last” catalysts, where two catalyst beds are adjacent to each other. However, these aspects also describe one or more optional intermediate catalyst beds located in series between the upstream (first) and downstream (last) catalyst beds. Therefore, the weight percentages of fluoride or chloride listed in the first and last catalysts apply to adjacent catalysts or to two non-adjacent catalysts characterized by the listed fluoride or chloride concentrations.

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

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

[0119] The first catalyst in the first catalyst bed comprises an inorganic support, a group 8-10 metal, and at least or about 1.0% by weight of fluoride relative to the weight of the first catalyst before reduction;

[0120] Optionally, one or more independently selected intermediate catalysts from 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] The final catalyst in the final catalyst bed downstream of the first catalyst bed and any optional intermediate catalyst bed, the final catalyst comprising an inorganic support, a Group 8-10 metal and at least or about 0.7% by weight of fluoride relative to the weight of the final catalyst prior to reduction;

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

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

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

[0125] The first catalyst in the first catalyst bed comprises an inorganic support, a group 8-10 metal, and at least or about 1.5% by weight of chloride relative to the weight of the first catalyst before reduction;

[0126] Optionally, one or more independently selected intermediate catalysts from 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] The final catalyst in the final catalyst bed downstream of the first catalyst bed and any optional intermediate catalyst bed, the final catalyst comprising an inorganic support, a Group 8-10 metal and a chloride at least or about 0.5% by weight relative to the weight of the final catalyst prior to reduction;

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

[0129] The system aspects immediately preceding those described above are the “first” and “last” catalysts, in which two catalyst beds are adjacent to each other. However, one or more optional intermediate catalyst beds in series between the upstream (first) and downstream (last) catalyst beds in these systems are also described. Therefore, the weight percentages of fluoride or chloride listed in the first and last catalysts apply to adjacent catalysts or to two non-adjacent catalysts characterized by the listed concentrations of fluoride or chloride.

[0130] Fluoride and chloride concentrations

[0131] In each of the listed processes and systems, there are practical upper limits to the concentrations of fluorides and chlorides 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% of 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% of fluoride relative to the weight of the final catalyst before reduction. In the chloride-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% of chloride relative to the weight of the last catalyst before reduction, and the last 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% of chloride relative to the weight of the last 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 final catalyst, or any combination thereof, wherein a fluoride concentration is listed and said fluoride concentration is independent of any other catalyst described in the composition or process, may further comprise any concentration of chloride as disclosed herein. Similarly, in any catalyst compositions or processes disclosed herein, any first catalyst, any one or more intermediate catalysts, any final catalyst, or any combination thereof, wherein a chloride concentration is listed and said chloride concentration is independent of any other catalyst described in the composition or process, may further comprise any concentration of fluoride as disclosed herein.

[0133] Regarding the fluoride concentration, any first catalyst as described herein may also contain fluoride in concentrations ranging from 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 intermediate or final catalyst before reduction. Any one or more intermediate catalysts, final catalysts, or any combination thereof may independently contain fluoride in concentrations ranging from 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 or final catalyst before reduction.

[0134] In another aspect, any fluoride-containing catalyst listed herein, whether a first catalyst, any one or more intermediate catalysts, a final catalyst, or any combination thereof, may independently further comprise a chloride at a concentration ranging from 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 prior to reduction. Alternatively, any fluoride-containing catalyst listed herein, whether a first catalyst, any one or more intermediate catalysts, a final catalyst, or any combination thereof, may independently further comprise a chloride at a concentration ranging from 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 prior to reduction. In these respects, the chloride concentration of these first catalysts may be higher than the chloride concentration of these final catalysts prior to reduction. The chloride concentration of these catalysts can also be higher than the chloride concentration of the adjacent downstream catalyst before reduction.

[0135] Regarding the chloride concentration, any first catalyst as described herein may also contain chloride in concentrations ranging from 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 intermediate catalyst or final catalyst before reduction. Any one or more intermediate catalysts, final catalysts, or any combination thereof may independently contain chloride in concentrations ranging from 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.

[0136] In another aspect, any chloride-containing catalyst listed herein, whether it be a first catalyst, any one or more intermediate catalysts, a final catalyst, or any combination thereof, may independently further comprise a fluoride in a concentration ranging from 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. Alternatively, any chloride-containing catalyst listed herein, whether it be a first catalyst, any one or more intermediate catalysts, a final catalyst, or any combination thereof, may independently further comprise a fluoride in a concentration ranging from 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. In these respects, the fluoride concentration of these first catalysts can be higher than the fluoride concentration of these final 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 first catalysts, intermediate catalysts, and / or final catalysts may independently comprise any chlorine to fluorine (Cl:F) weight ratio disclosed herein, for example, about 1.5:1 to about 8:1, about 2:1 to about 5:1, or about 3:1 to about 4.5:1. Furthermore, any one or more first catalysts, intermediate catalysts, and / or final catalysts may independently comprise 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.

[0138] In one embodiment, the fluoride concentration of the first catalyst may be 10% to 50%, 25% to 65%, or 50% to 90% higher than the fluoride concentration of the final catalyst. In another embodiment, the chloride concentration of the first catalyst may be 10% to 50%, 25% to 65%, 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 catalysts further comprising chlorides listed herein, the first catalyst may further comprise about 0.5 wt% to about 5 wt% chlorides relative to the weight of the first catalyst before reduction, and the final catalyst may further comprise about 0.5 wt% to about 5 wt% chlorides relative to the weight of the final catalyst before reduction. Furthermore, in the processes and systems disclosed herein, for any fluoride-containing catalysts further comprising fluorides listed herein, 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 final catalyst may further comprise about 0.5 wt% to about 5 wt% fluoride relative to the weight of the final catalyst before reduction. Additionally, in embodiments of the processes and systems disclosed herein, any one or more of the first catalyst, intermediate catalyst, and / or final 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] Therefore, in another aspect, the fluoride concentration (wt%) of each of the one or more independently selected intermediate catalysts at startup may be higher than or equal to the fluoride concentration of the final catalyst prior to reduction. Similarly, the chloride concentration (wt%) of each of the one or more independently selected intermediate catalysts at startup may be higher than or equal to the chloride concentration of the final catalyst prior to reduction.

[0141] In other respects, at startup, the fluoride concentration (wt%) of one or more independently selected intermediate catalysts 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 final catalyst before reduction. Similarly, at startup, the chloride concentration (wt%) of one or more independently selected intermediate catalysts may 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 final catalyst before reduction.

[0142] Alternatively, in other respects, the fluoride concentration (wt%) of one or more independently selected intermediate catalysts at start-up 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 final catalyst before reduction. Similarly, the chloride concentration (wt%) of one or more independently selected intermediate catalysts at start-up may be higher than or equal to the chloride concentration of the first catalyst before reduction and higher than or equal to the chloride concentration of the final catalyst before reduction.

[0143] It should be understood that the reduction of the catalyst in the catalyst bed leads to a decrease in the halide concentration, resulting in a decrease in the weight percentage of fluorides and / or chlorides relative to the catalyst weight compared to the weight percentage before reduction. By way of example and not limitation, an upstream catalyst containing 1.5% fluoride before reduction may contain approximately 0.6% to approximately 1.0% fluoride after reduction, depending on the specific catalyst, reduction conditions, etc.

[0144] Typically, the feedstock for aromatization processes is naphtha, a petroleum distillate that can be produced from crude oil, condensate, or other suitable sources. Naphtha feedstocks can contain light hydrocarbons with a boiling range of about 20°C to about 235°C. Naphtha feedstocks can contain aliphatic hydrocarbons, cycloalkanes, or alkanes. While catalytic aromatization usually refers to the conversion of naphtha, other feedstocks can also be used. For example, alkanes, alkenes, acetylenic hydrocarbons, cyclic alkanes, cyclic alkenes, and mixtures thereof, as well as particularly saturated hydrocarbons, can also be reformed to provide aromatic-rich products. The specific aromatic hydrocarbons produced depend on, for example, the composition of the feedstock and the catalyst, as well as 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 feedstock may contain less than 2 to 5 parts per million (ppm) of sulfur by weight, as the presence of sulfur in the feedstock can reduce both the activity and selectivity of the catalyst. Some reforming catalysts are extremely sensitive to sulfur, and even sulfur levels in the feedstock of less than 1 ppm can severely deactivate these catalysts. For sulfur-sensitive catalysts, the feedstock may contain less than 1,000 parts per billion (ppb), less than 600 ppb, less than 300 ppb, less than 100 ppb, or 5 ppb to 50 ppb by weight. Aspects of sulfur removal from 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 zeolites are examples of such sulfur-sensitive catalysts. Examples of Pt-KL zeolite catalysts are described, for example, in 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. U.S. Patent No. 4,456,527 discloses that such catalysts can achieve satisfactory run lengths only when the sulfur content of the feed is significantly reduced, and that patent is incorporated herein by reference. The lower the sulfur content of the feed, the longer the run length of the catalyst.

[0147] In one respect, upstream “high-halogen” reforming catalysts may contain up to 50 wt%, about 50 wt%, or more than about 50 wt% additional halides, whether fluorides or chlorides, compared to the amount of halides in conventional or standard catalyst formulations. For example, if the conventional halide loading in the reforming catalyst is about 1.0 wt%, then in this example, the high-halogen reforming catalyst may have up to about 1.5 wt% halides. In some respects, the upstream high-halide catalyst may have an additional halides of about 10% by weight, about 20% by weight, about 30% by weight, about 40% by weight, about 50% by weight, about 60% by weight, about 70% by weight, about 80% by weight, about 90% by weight, or about 100% by weight more than the amount of halides in the downstream catalyst.

[0148] Catalyst bed and reactor

[0149] As defined herein, the term "catalyst bed" is used 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 the entirety of an aromatization reactor, or it may occupy a portion of an aromatization reactor. Thus, in one aspect, a process or catalytic hydrocarbon reforming system according to this disclosure for reforming hydrocarbons may 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 with different specific catalyst compositions, said catalyst beds may be located in a single reactor. Again, alternatively, more than two adjacent catalyst beds in series may be located in a single reactor. Typically, each different catalyst bed means each different catalyst composition, said catalyst bed being located in a single reactor.

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

[0151] In another aspect, this 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, each of the 1 to 6 intermediate catalyst beds containing 1 to 6 intermediate catalysts, the first catalyst bed, the 1 to 6 intermediate catalyst beds, and the final catalyst bed are all located in different reactors, and the fluoride and chloride concentrations (wt%) of each of the 1 to 6 intermediate catalysts at start-up can be selected independently of the fluoride and chloride concentrations in any other catalyst, such that the fluoride and chloride concentrations in any or all of the first catalyst bed and one or more intermediate catalyst beds are higher than the fluoride and chloride concentrations of the final 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, each of the intermediate catalyst beds containing 1 to 6 or more (e.g., 7, 8, or 9) intermediate catalysts, the intermediate catalyst beds being distributed in fewer than this number of reactors. 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 this disclosure may include four or five intermediate catalyst beds, wherein each of the first catalyst bed, intermediate catalyst beds, and final catalyst bed is located in its own reactor. In another aspect, this disclosure provides a process or a catalytic hydrocarbon reforming system for reforming hydrocarbons, wherein: the process or system includes four or five intermediate catalyst beds, each of the four or five intermediate catalyst beds containing its own corresponding intermediate catalyst; the first catalyst bed, the four or five intermediate catalyst beds, and the final catalyst bed are each located in a different reactor; and the volume of each of the four or five intermediate reactors is greater than or equal to the volume of the first reactor and less than or equal to the volume of the final reactor.

[0153] For example, in an embodiment where the process or system includes four intermediate catalyst beds (each containing its own corresponding intermediate catalyst and located in a different reactor), 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 that reactor. In one aspect, the relative volumes of the first reactor, the four intermediate reactors, and the final reactor may be, for example, 10:10:10:20:20:30. In another aspect, the relative volumes of the first reactor, the four intermediate reactors, and the final reactor may 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 before they enter a subsequent catalyst bed. Therefore, this 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 although not intended to be bound by theory, it has been found that the entire catalyst bed (e.g., in commercial units with six or more reactors in series) can be... Approximately 25% to 50% of the volume of reactors 1, 2, and 3 may encounter low activity in the early stages of operation due to concentrations considered above optimal halide (including fluoride) concentrations. While not intended to be theoretically constrained, and regarding fluoride concentrations, it is believed that as fluoride / fluorine is released from the catalyst, fluoride will be transferred to the downstream catalyst and / or loss from the downstream catalyst will be suppressed by maintaining the vapor pressure of F in the gas phase. Higher fluoride concentrations on the downstream catalyst are believed to slow the rate of selectivity decline and the rate of deactivation of the downstream catalyst. Since the upstream catalyst operates at low reactivity levels, levels above optimal fluoride are not expected to affect the selectivity or run length of the upstream catalyst.

[0156] Aromatization catalysts

[0157] Typically, aromatization catalysts may comprise an inorganic support, a Group 8-10 metal (such as platinum), and one or more halides (such as fluorine, chlorine, iodine, bromine, or combinations thereof). In some embodiments, the catalyst may comprise a Group 8-10 metal on an inorganic support, such as platinum on alumina, Pt / Sn on alumina, and Pt / Re on alumina. In other embodiments, the catalyst may comprise platinum metal on a zeolite support, such as Pt, Pt / Sn, and Pt / Re on a zeolite support, which may comprise a binder and zeolite, such as L-zeolite, X-zeolite, mordenite, mazzite, and ZSM-5. Other catalysts may include platinum metal, fluorine, and chlorine, typically on L-zeolite exchanged with alkali metals and alkaline earth metals. The catalyst may comprise a macroporous zeolite as an inorganic support, on which at least one Group 8-10 metal is supported. For example, the catalyst in the process and system may comprise a low-acid silica-bonded potassium L-type zeolite support, platinum, chloride, and fluoride. In some embodiments, the group 8-10 metals may include platinum, which may be more selective for dehydrogenation cyclization and more stable under reforming conditions than other group 8-10 metals. 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 disclosed herein include, but are not limited to, those available from Chevron Phillips Chemical Company of The Woodlands, Texas. The catalysts described herein can be used, for example, as downstream catalysts with lower halide content in the systems and processes disclosed herein; the catalysts discussed in Fukunaga's U.S. Patent No. 6,812,180 entitled "Method for Preparing Catalyst"; the catalysts disclosed in Wu's U.S. Patent No. 7,153,801 entitled "Aromatization Catalyst and Methods of Making and Using Same"; and catalysts such as halide zeolite catalysts described in Holtermann et al.'s U.S. Patent No. 6,190,539 entitled "Reforming Using a Bound Halided Zeolite Catalyst"; the catalysts disclosed in Khare's U.S. Patent No. 7,902,105 entitled "Aromatization catalyst comprising prolonged silica and methods of making and using same"; and Alvez-Manoli's "Acidic Aromatization Catalyst with Improved Activity and The catalysts disclosed in U.S. Patent Publication No. 2018 / 0065115, entitled “Stability,” are each incorporated herein by reference in their entirety. That is, any catalyst disclosed in these references can be used to prepare an upstream high-halogen reforming catalyst, which may contain up to 50 wt%, about 50 wt%, or more than about 50 wt% of additional halides, such as fluorides, compared to the amount of halides in the downstream catalyst and / or in conventional catalyst formulations.

[0159] In one aspect, the catalyst may comprise a non-acidic zeolite support as an inorganic carrier, 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, iridium, palladium, and / or platinum, i.e., more than one so-called platinum metal.

[0160] Inorganic supports for aromatization catalysts can typically include any inorganic oxide. These inorganic supports include bonded macroporous aluminosilicates (zeolites), amorphous inorganic oxides, and mixtures thereof. Macroporous aluminosilicates include, but are not limited to, L-zeolite, X-zeolite, mordenite, needlestone, ZSM-5, etc. Amorphous inorganic oxides include, but are not limited to, alumina, silica, and titanium dioxide. Suitable binders for inorganic supports include, but are not limited to, silica, alumina, clay, titanium dioxide, magnesium oxide, and combinations thereof.

[0161] The inorganic support can be an aluminosilicate, such as a zeolite. In embodiments, the aromatization catalyst can comprise a zeolite catalyst. Both natural and synthetic zeolite materials can possess suitable catalytic properties for many hydrocarbon processes, including aromatization. Therefore, zeolites can comprise the group of natural or synthetic hydrated aluminosilicate minerals, which typically contain alkali metals and alkaline earth metals. Zeolites are characterized by a framework structure surrounding interconnected cavities occupied by large metal cations (such as potassium) and water molecules capable of ion exchange, thereby achieving reversible dehydration. The actual formula of the zeolite can be varied without altering its 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, which comprises crystalline or amorphous inorganic oxides or combinations thereof. In addition to the first catalyst, the intermediate catalyst, and the final catalyst each independently comprising an inorganic support (containing or selected from zeolites or silica-bonded zeolites), the inorganic support may comprise or be selected from any of clay minerals, silica, alumina, silica-alumina, aluminum phosphate, heteropolytungstates, titanium dioxide, zirconium oxide, magnesium oxide, boron oxide, zinc oxide, mixed oxides thereof, silica-bonded zeolites, or mixtures thereof.

[0163] According to another aspect, the inorganic support for the first catalyst, one or more intermediate catalysts, and / or the final catalyst (such as the zeolite disclosed herein) may each further independently comprise a binder. Any weight percentage of the binder disclosed herein, for example, is independently from about 3% to about 35% or about 5% to about 30% by weight based on the total weight of the first catalyst, intermediate catalyst, and final catalyst. In this regard, for example, the binder for each inorganic support may independently comprise inorganic solid oxides, clays, or combinations thereof, such as alumina, silica, magnesium oxide, boron oxide, titanium dioxide, zirconium oxide, mixed oxides thereof, or mixtures thereof. The term "binder" is used regardless of the extent to which these oxide materials, in addition to the bonded material (such as zeolite), also act as a support for a Group 8 metal catalyst. Examples of binder supports, or simply "inorganic supports," include or comprise L zeolite bonded with silica or alumina, barium ion-exchanged L zeolite, or K / L zeolite.

[0164] The inorganic support disclosed herein can be independently produced by a process comprising the steps described 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. Therefore, the inorganic support for 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 respects, aromatization catalyst supports can comprise macroporous zeolites. The term "macroporous zeolite" can be defined as having approximately... to approximately or about to approximately Zeolites with effective pore sizes. Examples of macroporous crystalline zeolites are L-type zeolites (zeolite L or LTL), X-type zeolites (zeolite X), Y-type zeolites (zeolite Y), Ω-type zeolites, β-type zeolites, 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, macroporous zeolites may comprise isomorphic framework structures. In one embodiment, the aromatization catalyst support may comprise L-type zeolite.

[0166] L-zeolite, its X-ray diffraction pattern, its properties, and its preparation method are described in detail in U.S. Patent No. 3,216,789, the contents of which are incorporated herein by reference. Additional carriers are described as follows: zeolite X is described in U.S. Patent No. 2,882,244; needle zeolite is described in U.S. Patent Nos. 4,503,023 and 4,021,447; mordenite is described in U.S. Patent No. 4,503,023; zeolite Y is described in U.S. Patent No. 3,130,007; and each of U.S. Patent 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 this disclosure.

[0167] In one respect, aromatization catalysts may comprise or be selected from macroporous L-type zeolites. L-type zeolite catalysts are a subclass of zeolite catalysts, and typical L-type zeolites contain an oxide molar ratio that conforms 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, as well as non-metallic cations, such as hydrated hydrogen ions and ammonium ions, which can be replaced by other exchangeable cations without substantially altering 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 potassium L-type zeolite or KL zeolite yields excellent results. As used herein, KL zeolite refers to L-type zeolite in which the major cation M incorporated into the zeolite may contain potassium. KL zeolite can be cation exchanged or impregnated with another metal and one or more halides to produce platinum-impregnated halide zeolite or KL-supported Pt-halide zeolite catalysts. In one embodiment, the zeolite may comprise L-type zeolite. In some aspects, aromatization catalysts may comprise potassium L-type zeolite, hereinafter referred to as KL zeolite, which refers to L-type zeolite in which the major exchangeable cation M of the zeolite is potassium.

[0171] One or more Group 8-10 metals or other suitable metals (such as rhenium) can be added to the catalyst support to form a metallized catalyst support. The metal can be added to the catalyst support using 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 can be added to the zeolite support by any suitable method, such as impregnation with a solution of a platinum-containing compound and one or more halide-containing compounds.

[0172] In one aspect, a metal can be added to a catalyst support by impregnation with a metal-containing solution. The metal in the metal-containing solution may comprise at least one metal from Groups 8-10; alternatively, ruthenium, osmium, rhodium, iridium, palladium, or platinum, or combinations thereof. In one embodiment, the metal may comprise platinum, which can be added to the catalyst support via contact with a metal-containing solution containing 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 complexes in solution, such as, for example, platinum salts, such as chlorides and nitrates; platinum complexes with amines; or combinations thereof. For example, the platinum-containing compound may be any decomposable platinum-containing compound, including but not limited to ammonium tetrachloroplatinate, chloroplatinic acid, diammineplatinum(II) nitrite, bis(ethylenediamine)platinum(II) chloride, platinum(II) acetylacetonate, diammineplatinum(II) dichloroplatinum, platinum(II) chloride, tetraammineplatinum(II) hydroxide, tetraammineplatinum(II) chloride, and tetraammineplatinum(II) nitrate. In one embodiment, the platinum source may comprise tetraammineplatinum(II) chloride (TAPC). The amount of platinum in the metallized catalyst support can range from about 0.1 to about 5% by weight; for example, from about 0.1 to about 3% by weight, for example, from about 0.3 to about 1.8% by weight. In other respects, the concentration of Group 8-10 metals in each of the first catalyst, intermediate catalyst and final catalyst can be independently selected from 0.3% to 1.5% by weight relative to the weight of each respective 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 can be added to the catalyst support by contacting the halide-containing compound to form a halogenated supported catalyst. The halide can be added to the catalyst support alone; alternatively, the halide can be added to the catalyst support simultaneously. Such halides can be incorporated during the addition of a metal, or alternatively, the halides can be incorporated in a separate step, either before or after the addition of a 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 can be introduced, for example, as ammonium halide compounds.

[0174] In one embodiment, the catalyst may comprise a macroporous zeolite support having a platinum-containing compound and at least one ammonium halide compound. The ammonium halide compound may comprise or be selected from one or more compounds having the formula [NR4]X, wherein X may comprise a halide and wherein R represents hydrogen or a substituted or unsubstituted hydrocarbon moiety having 1 to about 20 carbon atoms, and wherein each R may be the same or different, i.e., independently selected. In one embodiment, in formula [NR4]X, R may comprise hydrogen, methyl, ethyl, propyl, butyl, or a combination thereof. Examples of suitable organoammonium compounds of 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 combinations thereof.

[0175] In one aspect, the ammonium halide 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 methyl, ethyl, propyl, butyl, or combinations 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 combinations thereof.

[0176] In another aspect, the ammonium halide compound may comprise (a) 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 carbon atoms, wherein each R may be the same or different, and (b) at least one acidic halide and at least one 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, and wherein each R′ may 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) with the ammonium halide compounds described above. More specifically, ammonium chloride, ammonium fluoride, or both may be used with: (a) a compound represented by formula [NR4]X as described above, wherein X may 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 may be the same or different, and / or (b) at least one acidic halide and at least one organic ammonium hydroxide represented by formula [NR′4]OH as described above, 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, the first fluoride-containing compound or the chloride-containing compound may be introduced as a tetraalkylammonium halide, while the second fluoride-containing compound or the chloride-containing compound may be introduced as an ammonium halide. In some aspects, tetraalkylammonium chloride may be used with ammonium fluoride. In another aspect, ammonium chloride may be used 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 range from about 0.05 wt% to about 6.0 wt% of the total metallized, halogenated supported catalyst. Alternatively, the total amount of halides in any catalyst may independently range from 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 chlorides present in an amount from about 0.05 wt% to about 5 wt% of the catalyst; for example, from about 0.1 wt% to about 3 wt%; for example, from about 0.3 wt% to about 1.8 wt%. Alternatively, the total amount of halides in the catalyst may be independently selected from about 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, 1.2 wt%, 1.4 wt%, 1.6 wt% of the catalyst. %, 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] The process or catalytic reforming system for reforming hydrocarbons according to this disclosure may further include one or more intermediate catalysts in one or more intermediate catalyst beds, wherein the fluoride concentration (wt%) of the one or more intermediate catalysts is higher than or equal to the fluoride concentration of the final catalyst before reduction. In another aspect, the process or catalytic reforming system for reforming hydrocarbons according to this disclosure may further include one or more intermediate catalysts in one or more intermediate catalyst beds, wherein at startup, the chloride concentration (wt%) of the one or more intermediate catalysts 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 final catalyst before reduction. Alternatively, at startup, the fluoride concentration (wt%) of the 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 final catalyst before reduction. Non-limiting examples of weight percentages are set below.

[0180] In one aspect, the aromatization catalyst in any particular catalyst bed may 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 may range from about 0.05 wt% to about 6.0 wt% of the total metallized, halogenated supported catalyst. Alternatively, the total amount of fluoride in any catalyst may independently range from 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 fluoride present in an amount from about 0.05 wt% to about 5 wt% of the catalyst; for example, from about 0.1 wt% to about 3 wt%; for example, from about 0.3 wt% to about 1.8 wt%. Alternatively, the total amount of fluoride in the catalyst may be independently selected from about 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, 1.2 wt%, 1.4 wt%, 1.6 wt% of the catalyst. %, 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 or catalytic hydrocarbon reforming system according to this disclosure may include fluoride concentrations (wt%) in a first catalyst, an intermediate catalyst, and a final catalyst, and said concentrations may 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 final 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 final catalyst.

[0182] Any one or more of the first catalyst, intermediate catalyst, and / or final catalyst may further contain chlorides. Thus, in one aspect, the aromatization catalyst in any particular catalyst bed may contain a metallized, halogenated supported catalyst, wherein the total amount of chlorides in the catalyst is selected independently of the total amount of chlorides in any other catalyst in any other catalyst bed. In this respect, the total amount of chlorides in the catalyst may be selected independently and may range from about 0.05 wt% to about 6.0 wt% of the total metallized, halogenated supported catalyst. Alternatively, the total amount of chlorides in any catalyst may be selected independently from 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 contain chlorides present in an amount from about 0.05 wt% to about 5 wt% of the catalyst; for example, from about 0.1 wt% to about 3 wt%; for example, from about 0.3 wt% to about 1.8 wt%. Alternatively, the total amount of chloride in the catalyst may be independently selected from about 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, 1.2 wt%, 1.4 wt%, 1.6 wt% of the catalyst. %, 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 may comprise both chlorides and fluorides, which may 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 may comprise both chlorides and fluorides, which may 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] Reduction of a catalyst typically reduces its halide content. For example, the first catalyst, any intermediate catalyst, and the final catalyst may contain at least or about 0.5% by weight of chloride relative to the weight of the first catalyst before reduction, and / or the final catalyst may further contain at least or about 0.5% by weight of chloride relative to the weight of the final catalyst before reduction. Furthermore, any one or more of the first catalyst, intermediate catalyst, and / or final catalyst may contain chloride, independently selected from a concentration of up to about 6.0% by weight before reduction. In other aspects, any one or more of the first catalyst, intermediate catalyst, and / or final catalyst may contain chloride at a concentration of 0.5% to 5% by weight relative to the respective first catalyst, intermediate catalyst, and / or final catalyst before reduction. Any one or more of the first catalyst, intermediate catalyst, and / or final catalyst may also contain a combined concentration of up to 5% by weight of fluoride and chloride before reduction.

[0185] One aspect of this disclosure provides a process for reforming hydrocarbons using a series of adiabatic reactors and catalysts, wherein the catalyst in at least one upstream or front-end 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 upstream or front-end catalyst bed or reactor compared to one or more downstream catalyst beds or reactors, the lifespan of the catalyst system can be extended by maintaining selectivity for a longer period compared to cases without a high-halogenated upstream catalyst.

[0186] In the processes and catalytic hydrocarbon reforming systems disclosed herein, the reforming process is typically carried out in a series of more than one adiabatic reactors. Typically, this disclosure describes a first (upstream) catalyst bed, one or more intermediate catalyst beds, and a final or ultimate (downstream) catalyst bed, each of which may be located in a different reactor. Typically, there may be one to six intermediate catalyst beds containing one to six intermediate catalysts; for example, reactor systems comprising four or five intermediate catalyst beds operate well.

[0187] In another respect, the fluoride content (weight percentage, wt%) of each catalyst bed can be selected independently of the fluoride content of any other catalyst bed at start-up, such that the fluoride concentration of any or all of the first catalyst beds and one or more intermediate catalyst beds is higher than the fluoride concentration of the last catalyst bed before reduction.

[0188] In another respect, the fluoride content (weight percentage, 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 start-up, 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 respective catalyst beds have a higher fluoride concentration than the last catalyst in the last catalyst bed before reduction.

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

[0190] For example, in a series of six reactors, each with its own catalyst bed, the upstream reactor, designated 1, 2, and 3 (reactor 1 being the upstream initial reactor), may have a catalyst with a pre-reduction fluoride content (e.g., about 1.5 wt%), while the downstream reactors, 4, 5, and 6 (reactor 6 being the downstream and final reactor), may have a catalyst with a pre-reduction fluoride content (e.g., about 1.0 wt%). Alternatively, reactors 1, 2, 3, and 4 may have a higher pre-reduction fluoride content (e.g., about 1.5 wt%), while the downstream reactors 5 and 6 may have a lower pre-reduction fluoride content (e.g., about 1.0 wt%). Again, alternatively, reactors designated 1 and 2 may have a higher pre-reduction fluoride content (e.g., about 1.5 wt%), while the downstream reactors 3, 4, 5, and 6 may have a lower pre-reduction fluoride content (e.g., about 1.0 wt%). Furthermore, reactor 1 may have a catalyst with a higher fluoride content (e.g., about 1.5 wt%) prior to reduction, while downstream reactors 2, 3, 4, 5, and 6 may have a catalyst with a lower fluoride content (e.g., about 1.0 wt%) prior to reduction. The “higher” fluoride content listed in these aspects or embodiments may be selected, for example, independently of any fluoride concentration disclosed herein, and is higher than the “lower” fluoride content disclosed herein. For example, the “higher” fluoride content may 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 may be any weight percentage lower than the selected higher fluoride content.

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

[0192] In one aspect, when there are fewer than six reactors or more than six reactors in total, a similar choice of higher fluoride content and lower fluoride content downstream, as listed above, is possible. For example, the process or system may include one to six or more (e.g., seven, eight, or nine) intermediate catalyst beds, each containing one to six or more (e.g., seven, eight, or nine) intermediate catalysts, and the upstream “higher” fluoride content may occur in any or all of the first catalyst bed and intermediate catalyst beds, and the “lower” fluoride content may occur in the final catalyst bed and any intermediate catalyst bed downstream of the higher fluoride catalyst bed, wherein the lower fluoride content can be any weight percentage lower than the selected higher fluoride content.

[0193] Conventional catalysts used in the process typically exhibit a decline in catalytic activity, which occurs when the catalyst is used under commercial reaction conditions. A catalyst is generally considered degraded when one or more of its activity, conversion, selectivity, yield, or other operating parameters reach unacceptable levels. Using the process and system of this disclosure, it has been unexpectedly found that the selectivity of an aromatization catalyst in a series of catalyst beds can be maintained for a longer period of use compared to when all aromatization catalysts in a series of catalyst beds have the same fluoride content. The regenerable catalyst is suitable for the process as described, and the catalyst can withstand any regenerative chemistry treatment recognized in the art. For example, transition metal catalysts are typically regenerated by contacting the degraded catalyst with a halogen-containing stream (e.g., chlorine or fluorine) followed by decoking the catalyst in an oxygen stream, wherein the selected upstream catalyst has a higher halide (such as fluoride) content than the downstream catalysts listed herein.

[0194] Aromatization reactions can occur under process conditions that are thermodynamically favorable for dehydrogenation cyclization (aromatization) and limit undesirable hydrocracking reactions. Operating ranges for typical catalytic aromatization processes (such as the aromatization process disclosed herein) can include: reactor inlet temperatures between about 370°C and about 570°C, for example, between about 430°C and about 550°C; system pressures between about 10 pounds per square inch gauge (psig) and about 300 psig, for example, between about 15 psig and about 100 psig; hydrogen rates sufficient to produce a hydrogen-to-hydrocarbon molar ratio of about 0.1 to about 20, for example, between about 3 and about 10, for example, between about 1.5 and about 6; and a liquid hourly space velocity (LHSV) 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 for producing aromatics from naphtha feedstock according to this disclosure are described, for example, in U.S. Patent Nos. 6,548,030, 6,900,365, 7,932,425, 8,912,108, 9,421,530, and 9,718,042, which are incorporated herein by reference in their entirety. In one aspect, a class of catalytic reactor systems comprises six or seven catalytic reforming reactors in series, each reactor having a reactor feed and a reactor effluent. The aromatization reaction is highly endothermic, utilizing more heat than it produces; therefore, the feed to each reactor is heated by a furnace.

[0197] Figure 1 A process diagram is provided for an exemplary catalytic reactor system 100 applicable to aromatization systems and processes as described herein. Figure 1 As shown, the catalytic reactor system 100 includes four aromatization reactors connected 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 connected in series or parallel. Since the aromatization reaction is highly endothermic, a significant temperature drop occurs in reactors 10, 20, 30, and 40. Therefore, each reactor 10, 20, 30, and 40 connected in series may include a corresponding furnace 11, 21, 31, and 41 for reheating the components to a desired temperature to maintain a desired reaction rate. Alternatively, where feasible, one or more reactors 10, 20, 30, and 40 may share a common furnace. Reactors 10, 20, 30, and 40, furnaces 11, 21, 31, and 41, and associated piping, may be referred to herein as reaction zones.

[0198] exist Figure 1 In this process, naphtha or hydrocarbon feed 101 is typically combined with recirculation stream 119 to form combined feed stream 102, which is fed to purification process 80. Purification process 80 employs known processes to purify the hydrocarbon feed, which may include fractionation and / or treatment of the hydrocarbon feed. As used herein, the term "fractionation" includes the removal of heavy metals (e.g., C96) from the hydrocarbon feed. + Hydrocarbons and / or light (e.g., C5) -Hydrocarbons. As used herein, the terms “processing” and “removal” are used interchangeably to refer to the removal of impurities, such as oxygen, sulfur, and / or metals, from a hydrocarbon feed. The resulting purified feed 103 can be combined with dried hydrogen recycle 116 to produce a hydrogen-rich purified feed 104, which can then be combined with oxygen and / or nitrogen 105 to produce reactor feed stream 106. If desired, oxygen and / or nitrogen may be fed to reactor system 100 at one or more locations in addition to or as an alternative to stream 105, as will be described in more detail herein.

[0199] The reactor feed stream 106 is preheated in a 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 reactor 10, where the hydrocarbons are contacted with an aromatizing catalyst under suitable reaction conditions (e.g., temperature and pressure) to increase their aromatic content. The first reactor effluent 108, containing aromatic compounds, unreacted feed, and other hydrocarbon compounds or byproducts, is recovered from the first reactor 10.

[0200] The first reactor effluent 108 is then preheated in a second furnace 21, which heats the hydrocarbons to a desired temperature, thereby producing the second reactor feed 109. The second reactor feed 109 is then fed to 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. The second reactor effluent 110, containing aromatic compounds, unreacted feed, and other hydrocarbon compounds or byproducts, is recovered from the second reactor 20.

[0201] The second reactor effluent 110 is then preheated in a third furnace 31, which heats the hydrocarbons to a desired temperature to produce the third reactor feed 111. The third reactor feed 111 is then fed to 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. The third reactor effluent 112, containing aromatic compounds, unreacted feed, and other hydrocarbon compounds or byproducts, is recovered from the third reactor 30.

[0202] The effluent 112 from the third reactor is then preheated in a fourth furnace 41, which heats the hydrocarbons to a desired temperature, thereby producing the fourth reactor feed 113. The fourth reactor feed 113 is then fed to 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 their aromatic content. If desired, an additional aromatization reactor can be provided downstream of the fourth reactor. Figure 1 (Not shown in the image). The fourth reactor effluent 114, which contains aromatic compounds, unreacted feed, and other hydrocarbon compounds or byproducts, is recovered from the fourth reactor 40.

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

[0204] Hydrogen separation process 50 and purification-extraction process 70 are well known in the art and described in numerous 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 back to feed 101 and sold or otherwise used as needed for the aromatic compound 118. For simplicity, Figure 1Byproduct streams removed from the catalytic reactor system 100 at various points throughout the system are not shown. However, those skilled in the art will understand the composition and location of such byproduct streams. Furthermore, although... Figure 1 The illustration shows the addition of oxygen-containing and / or nitrogen-containing material 105 to a hydrogen-rich purified feed 104, but those skilled in the art will understand that oxygen-containing and / or nitrogen-containing material can be added to any of process streams 101, 102, 103, 104, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 119, or any combination thereof.

[0206] In various aspects, the catalytic reactor systems described herein can include fixed catalyst bed systems, moving catalyst bed systems, fluidized catalyst bed systems, or combinations thereof. Such reactor systems can be batch or continuous. In one aspect, the catalytic reactor system can 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 flow may pass upward, downward, or radially through the reactor. In one aspect, the catalytic reactor systems described herein can operate as either adiabatic or isothermal catalytic reactor systems. As used herein, the terms "catalytic reactor" and "reactor" are used interchangeably to refer to reactor vessel, reactor interior, and associated process equipment, including but not limited to catalyst, inert packing, pits, flow distributors, central tubes, reactor ports, catalyst transfer and distribution systems, furnaces and other heating devices, heat transfer equipment, and piping.

[0207] Other aspects of the process for reforming hydrocarbons according to the invention provide that conditions for aromatizing at least a portion of naphtha or aliphatic hydrocarbons may be included during catalytic reduction at a temperature above about 500℉ for 600 to 1500 hours. -1 The GHSV gas flow rate and heating rate of 10℉ / hr to 25℉ / hr are used for catalyst start-up, wherein the first catalyst, intermediate catalyst and / or final catalyst comprises a fluorinated-chlorinated zeolite platinum catalyst.

[0208] In some aspects, catalytic reactor systems can operate at a rate of approximately 400 to approximately 2000 hours. -1 (e.g. 400hr) -1 Approximately 500 hours -1 Approximately 600 hours -1 Approximately 700 hours -1 Approximately 800 hours -1 Approximately 900 hours -1 Approximately 1000 hours -1 Approximately 1100 hours -1 Approximately 1200 hours-1 Approximately 1300 hours -1 Approximately 1400 hours -1 Approximately 1500 hours -1 Approximately 1600 hours -1 Approximately 1700 hours -1 Approximately 1800 hours -1 Approximately 1900 hours -1 or about 2000hr -1 The catalytic reactor system can be operated during catalyst start-up at a GHSV gas flow rate of approximately 500℉. In other respects, during catalyst reduction at rates above approximately 500℉, the catalytic reactor system can be operated during catalyst start-up at heating rates from 5℉ / hr to 50℉ / hr (e.g., approximately 5℉ / hr, approximately 10℉ / hr, approximately 15℉ / hr, approximately 20℉ / hr, approximately 25℉ / hr, approximately 30℉ / hr, approximately 35℉ / hr, approximately 40℉ / hr, approximately 45℉ / hr, or approximately 50℉ / hr).

[0209] For example, in some embodiments where the catalyst comprises a halide zeolite catalyst, the catalytic reactor system can operate at a catalyst reduction rate above about 500℉ for approximately 2000 hours. -1 (e.g. 400hr) -1 Approximately 500 hours -1 Approximately 600 hours -1 Approximately 700 hours -1 Approximately 800 hours -1 Approximately 900 hours -1 Approximately 1000 hours -1 Approximately 1100 hours -1 Approximately 1200 hours -1 Approximately 1300 hours -1 Approximately 1400 hours -1 Approximately 1500 hours -1 Approximately 1600 hours -1 Approximately 1700 hours -1 Approximately 1800 hours -1 Approximately 1900 hours -1 or about 2000hr -1 The gas flow rate of the GHSV and the heating rate of 5℉ / hr to 50℉ / hr (e.g., about 5℉ / hr, about 10℉ / hr, about 15℉ / hr, about 20℉ / hr, about 25℉ / hr, about 30℉ / hr, about 35℉ / hr, about 40℉ / hr, about 45℉ / hr or about 50℉ / hr) are used to operate during catalyst start-up.

[0210] In aspects where the catalyst includes a fluorinated zeolite platinum catalyst, the catalytic reactor system can operate at catalyst reduction temperatures above approximately 500℉ for approximately 600 to approximately 1500 hours. -1 (for example, about 600hr) -1 Approximately 700 hours -1 Approximately 800 hours -1 Approximately 900 hours -1 Approximately 1000 hours -1 Approximately 1100 hours -1 Approximately 1200 hours -1 Approximately 1300 hours -1 Approximately 1400 hours -1 or about 1500hr -1 The gas flow rate of the GHSV and the heating rate of 10℉ / hr to 30℉ / hr (e.g., about 10℉ / hr, about 15℉ / hr, about 20℉ / hr, about 25℉ / hr or about 30℉ / hr) are used to operate during catalyst start-up.

[0211] In some embodiments where the catalyst includes a fluorinated-chlorinated zeolite platinum catalyst, the catalytic reactor system 100 can operate at a catalyst reduction rate above about 500℉ for approximately 600 to about 1500 hours. -1 (for example, about 600hr) -1 Approximately 700 hours -1 Approximately 800 hours -1 Approximately 900 hours -1 Approximately 1000 hours -1 Approximately 1100 hours -1 Approximately 1200 hours -1 Approximately 1300 hours -1 Approximately 1400 hours -1 or about 1500hr -1 The gas flow rate of the GHSV and the heating rate of 10℉ / hr to 25℉ / hr (e.g., about 10℉ / hr, about 15℉ / hr, about 20℉ / hr or about 25℉ / hr) are used to operate during catalyst start-up.

[0212] Example

[0213] The present invention is further illustrated by the following embodiments, which should not be construed as limiting the scope of the invention in any way. After reading this description, those skilled in the art will conceive of various other aspects, embodiments, modifications, and equivalents without departing from the spirit of the 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 as follows: An impregnation mixture of 0.10 g (g) tetraammineplatinum chloride (TAPC), 0.45 g tetramethylammonium fluoride (TMAF), 0.10 g tetramethylammonium chloride (TMAC), and 2.50 g water was formed and added to 5.0 g of silica-bonded KL zeolite extrudate that had been calcined at 538 °C for 2 hours. The mixture was impregnated into 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 again at 300 °C for 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 as follows: 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-bonded KL zeolite, which was 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 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 catalysts

[0222] Platinum halide L-zeolite catalysts were prepared in a manner similar to Example 4 of EP 498,182A or U.S. Patent No. 5,354,933. 20 parts by weight of a silica binder (SI-350 silica sol, sold by Cat. & Chem. Ind. Inc. [CCIC], Japan) were added to 100 parts by weight of KL-type zeolite (Tosoh, Ltd., Japan) while stirring. The mixture was kneaded and molded, and then calcined in air at 500°C (932℉) for 2 hours (hr) to produce molded, calcined silica-bonded L-zeolite extrudates. An impregnation solution comprising 0.166 g ammonium fluoride, 0.075 g ammonium chloride, 0.171 g tetraammineplatinum chloride, and 4.8 g deionized water was prepared. This solution was slowly added dropwise to 10 g of molded L-zeolite while stirring. The resulting solid was vacuum dried and then treated in dry air at 300°C (572°F) for 3 hours. The resulting catalyst was analyzed and contained approximately 0.7 wt% F and 0.7 wt% Cl. The sodium content was approximately 0.56 wt%, as measured by atomic absorption spectrometry.

[0223] Example 4

[0224] Preparation of high-fluoride platinum L zeolite catalysts

[0225] Platinum halide L zeolite catalysts with higher fluoride content compared to the catalysts of Examples 1-3 were 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, was used relative to the weight of the additional components. This procedure allows for the preparation of platinum halide L zeolite catalysts with a fluoride content of approximately 0.8 wt% and higher, for example, up to approximately 2.0 wt%.

[0226] Example 5

[0227] Weight percentage of fluorides in a series of aromatization reactors

[0228] The table below lists exemplary aromatization reactor configurations having a first and a final reactor, and in the example shown, four intermediate reactors, along with examples of the weight percentage of fluoride in each catalyst bed. Examples are shown where each catalyst bed is located in a separate reactor, and 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, and beds 2 through 6 sequentially constitute intermediate beds. 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 this disclosure illustrate a series of embodiments for fluoride concentrations in aromatization reactors.

[0230]

[0231]

[0232] Example 6

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

[0234] This embodiment demonstrates that loading the upper portion (e.g., the upper half) of a catalyst bed with a high-halogen catalyst increases the overall run length by increasing the interaction of the released halides with the downstream catalyst. Therefore, when a fixed-bed reactor is loaded with the upper half of a bed containing a high-halogen catalyst (whether fluorine or chlorine) and then a reduction step is performed, improved catalyst performance is observed in the lower half of the catalyst bed.

[0235] Figure 2A The description refers to a fixed-bed "baseline" reactor 200, which has a standard (STD) aromatization catalyst arrangement in both the upper and lower halves of the fixed-bed reactor. Catalyst II, the direction of fluid flow 205 and bed sections 210, 215, 220 and 225 is shown in the upstream to downstream direction. Figure 2B The description describes a fixed-bed test reactor 255, which has a high-chlorine catalyst in the (upstream) upper half of the fixed bed and a standard (STD) aromatization in the (downstream) lower half of the fixed bed. The catalyst arrangement, referred to as a "layered bed" arrangement, is shown in the upstream-to-downstream direction of the fluid flow at 255 and the bed sections at 260, 265, 270, and 275. These catalysts are reduced with hydrogen in the process unit reactor, removed, pulverized to 20 / 40 mesh, and then processed in the screening unit.

[0236] For those containing bed sections 220 and 225 Figure 2A The lower half of the fixed catalyst bed (only) and the bed sections 270 and 255. 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 catalysts (bed sections 270 and 255) of the high chloride catalysts in the medium exhibit better activity than those from the standard catalysts (bed sections 270 and 255). Figure 2A The standard catalyst in the lower half of the baseline configuration bed (bed sections 220 and 225) is more selective.

[0237] therefore, Figure 3 Examples are given for Figure 2A (“baseline” relative to) Figure 2B The standard in the lower half of the fixed-bed reactor shown in (“stratified bed”) The graph of adjusted catalyst temperature (℉) versus running time (hours) for catalyst II demonstrates that the standard catalyst downstream of the high chloride catalyst exhibits better activity compared to the standard catalyst downstream of the more standard catalyst (i.e., the catalyst with standard chloride concentration). Figure 4 Examples are given for Figure 2A (“baseline”) and Figure 2B The standard in the lower half of the fixed-bed reactor shown in (“stratified bed”) The graph of selectivity (mol / mol) versus running time (hours) for catalyst II demonstrates that the standard catalyst downstream of the high chloride catalyst exhibits better selectivity compared to the standard catalyst downstream of a more standard catalyst (i.e., a catalyst with a standard chloride concentration).

[0238] The same effect of downstream catalysts was also observed in commercial-scale tandem aromatization reactors. Reactor 3 (reactor 3 of six reactors in series) contained a high-chlorination catalyst, while the remaining five reactors out of a total of six reactors had standard... II. Catalysts. The catalyst activities in different reactors were compared. Reactors 4 and 5, located downstream of reactor 3 (high-chlorination reactor), both showed increased activity compared to the expected levels observed when reactor 3 was not using a high-chlorination reactor. Although not intended to be theoretically rigorous, this observation is attributed to the interaction between the catalysts in those downstream reactors 4 and 5 and the chloride released in reactor 3.

[0239] Therefore, it has been observed that upstream high-halogen reactors (such as high-chloride reactors) can extend the operating life of downstream reactors and improve the selectivity of downstream reactors.

[0240] The invention has been described above with reference to various aspects, features, embodiments, and specific examples. Many variations will occur to those skilled in the art based on the above specific embodiments. All such apparent variations are within the full scope of the appended claims. These and other aspects of this 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 specifically stated otherwise, may “consist substantially of” or “comprise” those components or steps.

[0241] This disclosure

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

[0243] a) In a first catalyst bed, under conditions that cause aromatization of aliphatic hydrocarbons, a feedstock containing aliphatic hydrocarbons is contacted with a first catalyst to form a first catalyst bed effluent containing aromatic hydrocarbons and aliphatic hydrocarbons, wherein the first catalyst comprises an inorganic support, group 8-10 metals and at least or about 1.0% by weight of fluoride relative to the weight of the first catalyst before reduction.

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

[0245] c) In the final catalyst bed, under conditions that aromatize aliphatic hydrocarbons, the one or more intermediate catalyst bed effluents are contacted with the final catalyst to form a final catalyst bed effluent containing an aromatic product, the final catalyst comprising an inorganic support, group 8-10 metals and at least or about 0.7% by weight of fluoride relative to the weight of the final catalyst prior to reduction.

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

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

[0248] a) In a first catalyst bed, under conditions that aromatize aliphatic hydrocarbons, a feedstock containing aliphatic hydrocarbons is contacted with a first catalyst to form a first catalyst bed effluent containing aromatic hydrocarbons and aliphatic hydrocarbons, the first catalyst comprising an inorganic support, group 8-10 metals, and at least or about 1.0% by weight of fluoride relative to the weight of the first catalyst before reduction; and

[0249] b) In the final catalyst bed, under conditions that aromatize aliphatic hydrocarbons, the first catalyst bed effluent is contacted with the final catalyst to form a final catalyst bed effluent containing an aromatic product, said final catalyst comprising an inorganic support, group 8-10 metals and at least or about 0.7% by weight of fluoride relative to the weight of said final catalyst before 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) In a first catalyst bed, under conditions that cause aromatization of aliphatic hydrocarbons, a feedstock containing aliphatic hydrocarbons is contacted with a first catalyst to form a first catalyst bed effluent containing aromatic hydrocarbons and aliphatic hydrocarbons, wherein the first catalyst comprises an inorganic support, group 8-10 metals and at least or about 1.5% by weight of chloride relative to the weight of the first catalyst before reduction.

[0253] b) In one or more tandem intermediate catalyst beds, under conditions that aromatize aliphatic hydrocarbons, the effluent from the first catalyst bed is contacted with one or more independently selected intermediate catalysts to form one or more intermediate catalyst bed effluents comprising aromatic hydrocarbons and aliphatic hydrocarbons, each intermediate catalyst comprising an inorganic support, a group 8-10 metal, and a chloride; and

[0254] c) In the final catalyst bed, under conditions that aromatize aliphatic hydrocarbons, the effluent from one or more intermediate catalyst beds is contacted with the final catalyst to form a final catalyst bed effluent containing an aromatic product, the final catalyst comprising an inorganic support, group 8-10 metals, and at least or about 0.5% by weight of chloride relative to the weight of the final catalyst prior to reduction.

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

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

[0257] a) In a first catalyst bed, under conditions that aromatize aliphatic hydrocarbons, a feedstock containing aliphatic hydrocarbons is contacted with a first catalyst to form a first catalyst bed effluent containing aromatic hydrocarbons and aliphatic hydrocarbons, the first catalyst comprising an inorganic support, group 8-10 metals, and at least or about 1.5% by weight of chloride relative to the weight of the first catalyst before reduction; and

[0258] b) In the final catalyst bed, under conditions that aromatize aliphatic hydrocarbons, the first catalyst bed effluent is contacted with the final catalyst to form a final catalyst bed effluent containing an aromatic product, said final catalyst comprising an inorganic support, group 8-10 metals and at least or about 0.5% by weight of chloride relative to the weight of said final catalyst before 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 in series, the catalyst beds including an upstream first catalyst bed, a downstream last catalyst bed, and one or more intermediate catalyst beds in series between the first catalyst bed and the last catalyst bed;

[0262] The first catalyst in the first catalyst bed comprises an inorganic support, a group 8-10 metal, and at least or about 1.0% by weight of fluoride relative to the weight of the first catalyst before reduction;

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

[0264] The final catalyst in the final catalyst bed comprises an inorganic support, group 8-10 metals, and at least or about 0.7% by weight of fluoride relative to the weight of the final catalyst prior to reduction;

[0265] The fluoride concentration of the first catalyst or at least one of the intermediate catalysts is higher than the fluoride concentration of the final 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] The first catalyst in the first catalyst bed comprises an inorganic support, a group 8-10 metal, and a fluoride comprising at least or about 1.0% by weight of the first catalyst prior to reduction; and

[0269] The final catalyst in the final catalyst bed comprises an inorganic support, group 8-10 metals, and at least or about 0.7% by weight of 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 in series, the catalyst beds including an upstream first catalyst bed, a downstream last catalyst bed, and one or more intermediate catalyst beds in series between the first catalyst bed and the last catalyst bed;

[0273] The first catalyst in the first catalyst bed comprises an inorganic support, a group 8-10 metal, and at least or about 1.5% by weight of chloride relative to the weight of the first catalyst before reduction;

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

[0275] The final catalyst in the final catalyst bed comprises an inorganic support, group 8-10 metals, and at least or about 0.5% by weight of chloride relative to the weight of the final catalyst prior to reduction;

[0276] The chloride concentration of the first catalyst or at least one of the intermediate catalysts is higher than the chloride concentration of the final 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] The first catalyst in the first catalyst bed comprises an inorganic support, a group 8-10 metal, and at least or about 1.5% by weight of chloride relative to the weight of the first catalyst before reduction; and

[0280] The final catalyst in the final catalyst bed comprises an inorganic support, group 8-10 metals, and at least or about 0.5% by weight of 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 or catalytic hydrocarbon reforming system for reforming hydrocarbons according to any one of Aspects 1 to 2 or 5 to 6, wherein the first catalyst comprises at most about 5.0 wt%, at most about 4.0 wt%, at most about 3.5 wt%, at most about 3.0 wt%, or at most about 2.5 wt% of a 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% of fluoride relative to the weight of the final catalyst prior to reduction.

[0284] Aspect 10. A method or catalytic hydrocarbon reforming system for reforming hydrocarbons according to any one of Aspects 3 to 4 or 7 to 8, wherein the first catalyst comprises at most about 5.0 wt%, at most about 4.0 wt%, at most about 3.5 wt%, at most about 3.0 wt%, or at most 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% of fluoride relative to the weight of the final catalyst prior to reduction.

[0286] Aspect 11. A method or catalytic hydrocarbon reforming system for reforming hydrocarbons 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 final catalyst or any combination thereof independently further comprises a chloride.

[0287] Aspect 12. A method or catalytic hydrocarbon reforming system for reforming hydrocarbons 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 final catalyst or any combination thereof independently further comprises a fluoride.

[0288] Aspect 13. A method or catalytic hydrocarbon reforming system for reforming hydrocarbons according to any one of Aspects 1 to 2 or 5 to 6, wherein the first catalyst 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 first catalyst before reduction.

[0289] Aspect 14. A method or catalytic hydrocarbon reforming system for reforming hydrocarbons according to any one of Aspects 1 to 2 or 5 to 6, wherein any one or more of the intermediate catalysts, the final catalysts, or any combination thereof independently comprises a concentration ranging from 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 prior to reduction.

[0290] Aspect 15. A method or catalytic hydrocarbon reforming system for reforming hydrocarbons 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 comprises 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 prior to reduction.

[0291] Aspect 16. A method or catalytic hydrocarbon reforming system for reforming hydrocarbons 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 comprises a chloride in a concentration ranging from 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 prior to reduction.

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

[0293] Aspect 18. A method or catalytic hydrocarbon reforming system for reforming hydrocarbons according to any one of Aspects 3 to 4 or 7 to 8, wherein the first catalyst comprises 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 or catalytic hydrocarbon reforming system for reforming hydrocarbons according to any one of Aspects 3 to 4 or 7 to 8, wherein any one or more of the intermediate catalysts, the final catalysts, or any combination thereof independently comprises a chloride in a concentration ranging from 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 prior to reduction.

[0295] Aspect 20. A method or catalytic hydrocarbon reforming system for reforming hydrocarbons 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 prior to reduction.

[0296] Aspect 21. A method or catalytic hydrocarbon reforming system for reforming hydrocarbons 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 prior to reduction.

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

[0298] Aspect 23. A method or catalytic hydrocarbon reforming system for reforming hydrocarbons 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, about 1.5:1 to about 8:1, about 2:1 to about 5:1 or about 3:1 to about 4.5:1.

[0299] Aspect 24. A method or catalytic hydrocarbon reforming system for reforming hydrocarbons 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 or catalytic hydrocarbon reforming system for reforming hydrocarbons 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%, 25% to 65%, 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, comprising a catalytic hydrocarbon reforming system wherein the chloride concentration of the first catalyst is 10% to 50%, 25% to 65%, or 50% to 90% higher than the chloride concentration of the last catalyst.

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

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

[0304] Aspect 29. A method or catalytic hydrocarbon reforming system for reforming hydrocarbons 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 comprises a combined concentration of fluoride and chloride at a rate of up to about 5% by weight relative to the weight of the catalyst prior to reduction.

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

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

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

[0308] At startup, the fluoride concentration (wt%) of each of the one or more independently selected intermediate catalysts is 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] At startup, the fluoride concentration (wt%) of each of the one or more independently selected intermediate catalysts is 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.

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

[0311] At startup, the chloride concentration (wt%) of each of the one or more independently selected intermediate catalysts is 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] At startup, the chloride concentration (wt%) of each of the one or more independently selected intermediate catalysts is higher 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.

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

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

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

[0316] The method or system includes 1 to 6 intermediate catalyst beds, each of which contains 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. The method or catalytic hydrocarbon reforming system according to any one of Aspects 1 to 33, wherein:

[0319] The method or system includes 1 to 6 intermediate catalyst beds, each containing 1 to 6 intermediate catalysts.

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

[0321] At startup, the fluoride concentration (wt%) in each of the 1 to 6 intermediate catalysts is selected independently of the fluoride concentration in any other catalyst, and is at least or about the same as the fluoride concentration in the final catalyst prior to reduction.

[0322] Aspect 38. A method or catalytic hydrocarbon reforming system for reforming hydrocarbons according to any one of Aspects 1 to 33, wherein the method or system comprises four or five intermediate catalyst beds, and wherein the first catalyst bed, the intermediate catalyst beds and the final catalyst bed are located in their own reactors.

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

[0324] The method or system includes four or five intermediate catalyst beds, each of which contains its own corresponding intermediate catalyst.

[0325] The first catalyst bed, the four or five intermediate catalyst beds, and the final catalyst bed are each located in different reactors; and

[0326] The volume of each of the four or five intermediate reactors is greater than or equal to the volume of the first reactor and less than or equal to the volume of the final reactor.

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

[0328] The method or system includes four intermediate catalyst beds, each 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 that reactor.

[0331] Aspect 41. The method or 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 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 before 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 or catalytic hydrocarbon reforming system for reforming hydrocarbons according to any one of Aspects 1 to 43, wherein the inorganic support for the first catalyst, the one or more intermediate catalysts and / or the final catalyst each independently comprises crystalline or amorphous inorganic oxides or combinations thereof.

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

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

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

[0342] Aspect 49. A method or catalytic hydrocarbon reforming system for reforming hydrocarbons 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 final catalyst each further independently comprises a binder.

[0343] Aspect 50. The method or catalytic hydrocarbon reforming system for reforming hydrocarbons 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 comprises any weight percentage of the binder disclosed herein, for example, about 3% to about 35% or about 5% to about 30% of the total weight of the first catalyst, the intermediate catalyst and the final catalyst.

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

[0345] Aspect 52. A method or catalytic hydrocarbon reforming system for reforming hydrocarbons according to any one of Aspects 49 to 50, wherein the binder of each inorganic support independently comprises alumina, silica, magnesium oxide, boron oxide, titanium dioxide, zirconium oxide, mixed oxides thereof, or mixtures thereof.

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

[0347] Aspect 54. The method or 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 silica or alumina sol to form a mixture, and extruding the mixture to form an extrudate.

[0349] b) Drying and calcining the extrudate to form a bonded carrier; and

[0350] c) Wash, dry and calcine the combined carrier to form the inorganic carrier.

[0351] Aspect 55. A method or catalytic hydrocarbon reforming system for reforming hydrocarbons according to any one of Aspects 1 to 43, wherein the inorganic support for 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 or catalytic hydrocarbon reforming system for reforming hydrocarbons according to any one of Aspects 1 to 43, wherein the group 8-10 metals of the first catalyst, the one or more intermediate catalysts and / or the final catalyst are independently selected from iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum or any combination thereof.

[0353] Aspect 57. A method or catalytic hydrocarbon reforming system for reforming hydrocarbons 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 or catalytic hydrocarbon reforming system for reforming hydrocarbons 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 or catalytic hydrocarbon reforming system for reforming hydrocarbons 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 or catalytic hydrocarbon reforming system for reforming hydrocarbons 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 or catalytic hydrocarbon reforming system for reforming hydrocarbons 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 any weight percentage of the transition metal disclosed herein, such as 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%.

[0358] Aspect 62. A method or catalytic hydrocarbon reforming system for reforming hydrocarbons 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% by weight to about 1.5% by weight relative to the weight of the respective catalyst before reduction.

[0359] Aspect 63. The method for reforming hydrocarbons according to any one of Aspects 1 to 4 and 9 to 62, wherein the conditions for aromatizing the aliphatic hydrocarbons include a catalytic reduction at a rate above about 500℉ for 400 to 2000 hours. -1 The catalyst is started up by a gas flow rate of GHSV and a heating rate of 5℉ / hr to 50℉ / hr, wherein the first catalyst, the intermediate catalyst and / or the final catalyst comprises a fluorinated zeolite platinum catalyst containing group 8-10 metals.

[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 the aliphatic hydrocarbons include a catalytic reduction at a rate above about 500℉ for 600 to 1500 hours. -1 The catalyst is started up by a gas flow rate of GHSV and a heating rate of 10℉ / hr to 30℉ / hr, wherein the first catalyst, the intermediate catalyst and / or the final 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 the aliphatic hydrocarbons include a catalytic reduction at a rate above about 500℉ for 600 to 1500 hours. -1The catalyst is started up by a gas flow rate of GHSV and a heating rate of 10℉ / hr to 25℉ / hr, wherein the first catalyst, the intermediate catalyst and / or the final 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 final catalyst bed are located in a runoff reactor.

[0363] Aspect 67. A method or catalytic hydrocarbon reforming system for reforming hydrocarbons 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℉ to about 800℉, from about 580℉ to about 750℉, from about 600℉ to about 730℉, or from about 600℉ to about 720℉.

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

[0365] Aspect 69. A method or catalytic hydrocarbon reforming system for reforming hydrocarbons 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 that of a catalyst having 0.3% to 1.0% by weight of fluorine.

[0366] Aspect 70. A method or catalytic hydrocarbon reforming system for reforming hydrocarbons 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 that of a catalyst having 0.3% to 1.5% wt% chlorine.

Claims

1. A method for reforming hydrocarbons, comprising: a) In a first catalyst bed, under conditions that cause aliphatic hydrocarbon aromatization, a feedstock containing aliphatic hydrocarbons is contacted with a first catalyst to form a first catalyst bed effluent containing aromatic hydrocarbons and aliphatic hydrocarbons, the first catalyst comprising an inorganic support, group 8-10 metals and fluoride comprising 1.0 wt% to 5.0 wt% of the weight of the first catalyst before reduction. b) In one or more tandem intermediate catalyst beds, under conditions that aromatize aliphatic hydrocarbons, the first catalyst bed effluent is contacted with one or more independently selected intermediate catalysts to form one or more intermediate catalyst bed effluents comprising aromatic hydrocarbons and aliphatic hydrocarbons, each intermediate catalyst comprising an inorganic support, a group 8-10 metal, and a fluoride; and c) In the final catalyst bed, under conditions that aromatize aliphatic hydrocarbons, one or more of the intermediate catalyst bed effluents are contacted with the final catalyst to form a final catalyst bed effluent containing an aromatic product, said final catalyst comprising an inorganic support, group 8-10 metals and fluoride comprising 0.7 wt% to 4.0 wt% of the weight of said final catalyst prior to reduction. The fluoride concentration of the first catalyst or at least one of the intermediate catalysts is higher than the fluoride concentration of the final 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 1.5% to 4.0% by weight 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 at least one of the intermediate catalysts is higher than the chloride concentration of the final catalyst prior to reduction.

3. The method for reforming hydrocarbons according to claim 2, wherein at startup, the chloride concentration (wt%) of one or more of the intermediate catalysts 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 final catalyst before reduction.

4. The method for reforming hydrocarbons according to claim 1, wherein the first catalyst bed, one or more of the 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 includes 1 to 6 intermediate catalyst beds, each containing 1 to 6 different intermediate catalysts. The first catalyst bed, the 1 to 6 intermediate catalyst beds, and the final catalyst bed are all located in different reactors, and At startup, the fluoride concentration (wt%) in each of the 1 to 6 intermediate catalysts is selected independently of the fluoride concentration in any other catalyst, and is at least the same as the fluoride concentration in the final catalyst prior to reduction.

6. The method for reforming hydrocarbons according to claim 1, wherein: The method includes four or five intermediate catalyst beds, each of which contains its own corresponding intermediate catalyst. The first catalyst bed, the four or five intermediate catalyst beds, and the final catalyst bed are each located in a different reactor; and The volume of each of the four or five intermediate catalyst beds is greater than or equal to the volume of the first catalyst bed and less than or equal to the volume of the last catalyst bed.

7. The method for reforming hydrocarbons according to claim 1, wherein the first catalyst bed effluent and / or one or more of the intermediate catalyst bed effluents are heated before entering the final catalyst bed.

8. The method for reforming hydrocarbons according to claim 1, wherein the first catalyst, one or more of the intermediate catalysts and the final catalyst each independently comprises an inorganic support, the inorganic support comprising zeolite, silica-bound zeolite, clay mineral, silica, alumina, silica-alumina, aluminum phosphate, heteropolytungstate, titanium dioxide, 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, one or more of the intermediate catalysts, and the final catalyst each independently comprise an inorganic support, the inorganic support comprising 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, needlestone, octahedralite, or combinations thereof.

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

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

12. The method for reforming hydrocarbons according to claim 1, wherein at startup, the fluoride concentration (wt%) of one or more of the intermediate catalysts is higher than, 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 final 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 a chloride, and the weight ratio of chloride to fluoride is from 1:10 to 10:

1.

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

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

16. The catalytic hydrocarbon reforming system according to claim 15, wherein: The first catalyst, any one or more of the intermediate catalysts, the final catalyst, or any combination thereof independently further comprises 1.5% to 4.0% by weight 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 at least one of the intermediate catalysts is higher than the chloride concentration of the final catalyst prior to reduction.

17. The catalytic hydrocarbon reforming system of claim 15, wherein at startup, the chloride concentration (wt%) of one or more of the intermediate catalysts 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 final catalyst before reduction.

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

19. The catalytic hydrocarbon reforming system according to claim 15, wherein... The system includes 1 to 6 intermediate catalyst beds, each containing 1 to 6 different intermediate catalysts. The first catalyst bed, the 1 to 6 intermediate catalyst beds, and the final catalyst bed are all located in different reactors, and At startup, the fluoride concentration (wt%) in each of the 1 to 6 intermediate catalysts is selected independently of the fluoride concentration in any other catalyst, and is at least the same as the fluoride concentration in the final 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 zeolite, silica-bound zeolite, clay minerals, silica, alumina, silica-alumina, aluminum phosphate, 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 at startup, the fluoride concentration (wt%) of one or more of the intermediate catalysts is higher than, 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 final 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) In a first catalyst bed, under conditions that cause aliphatic hydrocarbon aromatization, a feedstock containing aliphatic hydrocarbons is contacted with a first catalyst to form a first catalyst bed effluent containing aromatic hydrocarbons and aliphatic hydrocarbons, wherein the first catalyst comprises an inorganic support, group 8-10 metals and at least 1.0% by weight of fluoride relative to the weight of the first catalyst before reduction. as well as b) In the final catalyst bed, under conditions that aromatize aliphatic hydrocarbons, the first catalyst bed effluent is contacted with the final catalyst to form a final catalyst bed effluent containing an aromatic product, said final catalyst comprising an inorganic support, group 8-10 metals and at least 0.7% by weight of fluoride relative to the weight of said final catalyst before reduction. The fluoride concentration of the first catalyst is higher than the fluoride concentration of the last catalyst before reduction.

26. The method for reforming hydrocarbons according to claim 25, wherein: The first catalyst and the last catalyst each independently further comprise 1.5% to 4.0% by weight of chloride relative to the respective weight of the first catalyst and the last catalyst before reduction; and The chloride concentration of the first catalyst is higher than the chloride concentration of the last catalyst before 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; The first catalyst in the first catalyst bed comprises an inorganic support, a group 8-10 metal, and a fluoride comprising at least 1.0 wt% of the first catalyst prior to reduction; and The final catalyst in the final catalyst bed comprises an inorganic support, group 8-10 metals, and at least 0.7% by weight of 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 according to claim 27, wherein: The first catalyst and the last catalyst each independently further comprise 1.5% to 4.0% by weight of chloride relative to the respective weight of the first catalyst and the last catalyst before reduction; and The chloride concentration of the first catalyst is higher than the chloride concentration of the last catalyst before reduction.

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