Method for regenerating aromatic catalysts

Abstract

A method for regenerating spent catalysts, such as spent aromatic catalysts, which may contain transition metals and catalyst supports. The method may include contacting the catalyst with a fluorine-containing stream containing a fluorine-containing compound. The fluorine-containing compound may include hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), fluorocarbons (FCs), or combinations thereof.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to U.S. Provisional Patent Application No. 63 / 568,189 filed on 21 March 2024, U.S. Provisional Patent Application No. 63 / 493,418 filed on 31 March 2023, and U.S. Provisional Patent Application No. 63 / 491,703 filed on 22 March 2023, which are incorporated herein by reference.

[0002] This disclosure relates to a method for regenerating used aromatization catalysts and their use in the aromatization of aliphatic hydrocarbons to aromatic hydrocarbons. [Background technology]

[0003] Aromatic catalysts can be regenerated through processes including chlorination, oxidation, and fluorination. Fluorination is typically carried out using a fluorination source containing fluorine gas in nitrogen, which can be unfavorable, particularly with respect to the distribution of fluorine on the catalyst bed. Fluorine can react with the catalyst upon contact, and therefore the leading edge of the catalyst bed may have a higher fluorine concentration than the rest of the bed. In some cases, most, but not all, of the fluorine can be adsorbed by the catalyst with little to no breakthrough of fluorine on the bed.

[0004] There is still a need for improved methods for regenerating aromatization catalysts, including methods for overcoming one or more of the aforementioned drawbacks of using fluorine in the fluorination step. [Overview of the Initiative]

[0005] This summary is provided to briefly introduce various concepts that are further described later in the modes for carrying out the invention. This summary is not intended to define any required or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter.

[0006] This specification provides a method for regenerating an aromatization catalyst, which may include using a fluorine-containing compound instead of fluorine in the fluorination step. The use of a fluorine-containing compound as described herein may improve the fluorine distribution throughout the catalyst bed.

[0007] In one embodiment, a method is provided for regenerating catalysts such as spent aromatization catalysts. The spent catalyst may contain a transition metal and a catalyst support in a metal reactor. In some embodiments, the method comprises any two or more of steps (A) to (H): (A) contacting an aromatization catalyst containing a transition metal and a catalyst support with a hydrocarbon feed in a metal reactor system under reforming conditions to produce aromatic products; (B) performing step (A) for a sufficient time to form spent catalyst; (C) contacting the spent catalyst with hydrogen gas to produce stripped spent catalyst; and (D) stripping spent catalyst for a time effective to remove at least a portion of the hydrocarbon feed, at least a portion of the aromatic products, or a combination thereof from the spent catalyst. (E) subjecting the spent catalyst to carbon combustion at a temperature not exceeding approximately 500°F to form a treated spent catalyst; (F) contacting the treated spent catalyst with a chlorine-containing stream containing a chlorine-containing compound to produce a chlorinated spent catalyst; (G) subjecting the chlorinated spent catalyst to carbon combustion at a temperature not exceeding 900°F for a time effective in improving the dispersion of transition metals in the chlorinated spent catalyst to form a redispersed spent catalyst; (H) contacting the redispersed spent catalyst with a fluorine-containing stream containing a fluorine-containing compound to form a regenerated catalyst; and (H) reducing the regenerated catalyst.

[0008] In some embodiments, the method includes contacting a spent catalyst with a chlorine-containing stream containing a chlorine-containing compound to produce a chlorinated spent catalyst; contacting the chlorinated spent catalyst with a coke-removing gas stream containing oxygen to produce a coke-removed catalyst; and contacting the coke-removed catalyst with a fluorine-containing stream containing a fluorine-containing compound to produce a regenerated catalyst. In some embodiments, the fluorine-containing compound includes hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), fluorocarbons (FCs), or combinations thereof.

[0009] In another embodiment, reactivated catalysts and regenerated catalysts are provided, such as those produced by any of the methods described herein.

[0010] In a further embodiment, a method is provided for producing a product by contacting a reactivated or regenerated catalyst with a hydrocarbon.

[0011] In yet another embodiment, a method is provided for contacting a spent catalyst with a fluorine-containing stream. In some embodiments, the method includes (a) providing two or more reactors that are in fluid communication with each other, the two or more reactors being connected in series, so that a fluorine-containing stream is (i) injected at an injection point selected from one or more injection points, (ii) continuously circulated to each of the two or more reactors downstream of the injection point, (iii) returned to a first reactor of the two or more reactors, and optionally (iv) continuously recirculated to each of the two or more reactors, each of the two or more reactors including a storage container for storing spent catalyst, (b) heating one of the two or more reactors to a temperature above the fluorination temperature effective for at least partially decomposing the fluorine-containing compounds in the fluorine-containing stream, and maintaining each of the remaining reactors of the two or more reactors below the fluorination temperature, and (c) injecting the fluorine-containing stream and circulating or recirculating the fluorine-containing stream at a temperature above the fluorination temperature for a time effective for achieving a desired level of fluorination of the spent catalyst in one of the two or more reactors. The method may also include (d) heating one of two or more reactors to a temperature above the fluorination temperature and maintaining each of the remaining reactors of the two or more reactors below the fluorination temperature, and (e) injecting a fluorine-containing stream and circulating or recirculating the fluorine-containing stream at a temperature above the fluorination temperature for a time effective to achieve a desired level of fluorination of the spent catalyst in one of the two or more reactors.

[0012] In further embodiments, a system for fluorinating spent catalysts is provided. In some embodiments, the system includes (a) two or more reactors and (b) two or more heating devices. The two or more reactors may be in fluid communication with each other or connected in series. This configuration may allow a fluid flow, for example, a fluorine-containing flow, to be (i) injected at an injection point selected from one or more injection points, (ii) continuously circulated to each of the two or more reactors downstream of the injection point, (iii) returned to the first of the two or more reactors, and optionally (iv) continuously recirculated to each of the two or more reactors. The two or more heating devices may be configured to heat each of the two or more reactors to the same or different temperatures. For example, the reactors and devices may be connected such that one reactor is connected to one heating device.

[0013] Further embodiments may be partially shown in the following description, partially revealed therefrom, or recognized by carrying out the embodiments described herein. The advantages described herein may be realized and achieved in combination with the elements specifically shown in the appended claims. It should be understood that both the general description above and the detailed description below are illustrative and descriptive only, and not limiting. [Brief explanation of the drawing]

[0014] [Figure 1] Embodiments of the system provided herein may be used to carry out one or more embodiments of contacting a spent catalyst with a fluorine-containing stream. [Figure 2] The following shows a plot of catalyst adjustment temperature against time relating to an embodiment of a catalyst according to the method described herein. [Figure 3] A plot of aromatic compound selectivity against time is shown for an embodiment of the catalyst according to the method described herein. [Figure 4]The following plots show the catalyst adjustment temperature against time for (1) an embodiment of a new aromatization catalyst, (2) an embodiment of a used aromatization catalyst, and (3) an embodiment of a used aromatization catalyst in Example 1C that follows an embodiment of the reactivation procedure described herein. [Figure 5] The following plots show the selectivity of aromatic compounds against time for (1) an embodiment of a new aromaticization catalyst, (2) an embodiment of a used aromaticization catalyst, and (3) an embodiment of a used aromaticization catalyst following an embodiment of the reactivation procedure described herein in Example 1C. [Figure 6] (1) an embodiment of a new aromatization catalyst, (2) an embodiment of a used aromatization catalyst, and (3) a plot of catalyst adjustment temperature against time for a used aromatization catalyst following an embodiment of the reactivation procedure described herein in Example 1D are shown. [Figure 7] The following plots show the selectivity of aromatic compounds against time for (1) an embodiment of a new aromatization catalyst, (2) an embodiment of a used aromatization catalyst, and (3) a used aromatization catalyst following an embodiment of the reactivation procedure shown in Example 1D.

[0015] definition

[0016] To more clearly define the terms used herein, the following definitions are provided. Unless otherwise specified, the following definitions apply to this disclosure. If a term is used in this disclosure but is not specifically defined herein, then the IUPAC Compendium of Chemical Terminology, 2 nd The definitions in Ed(1997) may be applied, provided that such definitions do not conflict with any other disclosures or definitions applicable herein, or that any claim to which such definitions apply becomes uncertain or invalid. To the extent that any definition or use provided by any document incorporated herein by reference conflicts with any definition or use provided herein, the definition or use provided herein shall prevail.

[0017] When various features of the subject matter of this disclosure are described, within a particular aspect, combinations of different features may be contemplated. For all aspects and for all features disclosed herein, any combination that does not adversely affect the designs, compositions, systems, processes or methods described herein is contemplated, whether or not there is an explicit description of that specific combination. Thus, unless the contrary is explicitly stated, any combination of aspects of the features disclosed herein can be used to describe and disclose designs, compositions, systems, processes or methods of the invention that are consistent with the overall disclosure herein.

[0018] The compositions and methods are described in terms of "comprising" various components or steps, but the compositions and methods can also "consist essentially of" or "consist of" those various components or steps, unless otherwise stated.

[0019] The terms "including", "and" and "having" are defined as "comprising" (i.e., open terms) when used herein, unless otherwise defined.

[0020] The terms "a", "an" and "the" are intended to include plural alternatives, such as at least one. For example, the disclosure of "a fluorine-containing compound", "a catalyst", etc. is intended to include, unless otherwise stated, one fluorine-containing compound, catalyst, etc., or a mixture or combination of two or more fluorine-containing compounds, catalysts, etc.

[0021] Various numerical ranges are disclosed herein. When the applicant discloses or claims any kind of range, the applicant intends, unless otherwise stated, to disclose or claim each conceivable number that can reasonably be included in such range, including the endpoint values ​​of that range, as well as any sub-ranges and combinations of sub-ranges that fall within that range. For example, the applicant intends to individually represent 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 of sub-ranges that fall within that range, by disclosing weight percentages of 1.0 wt% to 2.0 wt% or 1 wt% to 2 wt%, and these methods of describing such ranges are interchangeable. Furthermore, all endpoint values ​​within the range disclosed herein are approximations unless otherwise specified. For example, where the applicant indicates that one or more steps in a process disclosed herein can be performed at temperatures in the range of 10°C to 75°C, this range should be interpreted as including temperatures in the range of "approximately" 10°C to "approximately" 75°C, unless otherwise indicated.

[0022] Values ​​or ranges may be expressed herein as values ​​“approximately,” from a value “approximately” a particular value, and / or from a value “approximately” a different particular value. When such values ​​or ranges are expressed, other embodiments disclosed include the specific values ​​shown, from a particular value, and / or other specific values. Similarly, the use of the preposition “approximately” indicates that when a value is expressed as an approximation, that particular value forms a different embodiment. It will be further noted that a considerable number of values ​​are disclosed herein, and that each value is disclosed herein not only as the value itself but also as a value “approximately” a particular value. In other embodiments, the use of the term “approximately” can independently mean ±20% of the shown value, ±15% of the shown value, ±10% of the shown value, ±5% of the shown value, or ±3% of the shown value.

[0023] If, for any reason, the applicant chooses to claim means that are less than the complete means of the Disclosure, the applicant reserves the right to exclude any of the individual components of any of the values ​​or ranges of any of the groups described above (including any partial range or combination of partial ranges within that group) that can be claimed in accordance with the range or in any similar form, for example, to take into account references that the applicant may not have known at the time of filing. Furthermore, if, for any reason, the applicant chooses to claim means that are less than the complete means of the Disclosure, the applicant reserves the right to exclude any of the individual substituents, analogs, compounds, ligands, structures or any of the groups thereof, or any of the components of the claimed group, for example, to take into account references or prior disclosures that the applicant may not have known at the time of filing.

[0024] In any particular compound or group disclosed herein, any name or structure shown (general or specific) is intended to include, unless otherwise stated, all conformational isomers, positional isomers, stereoisomers, and mixtures thereof that may result from a particular group of substituents. Unless otherwise stated, the name or structure also includes, as a person skilled in the art would recognize, all enantiomers, diastereomers, and other optical isomers (if any exist) (whether in enantiomer or racemic form), as well as mixtures of stereoisomers. For example, when hexane is generally referred to, it includes n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, and 2,3-dimethylbutane; and when butyl is generally referred to, it includes n-butyl, sec-butyl, isobutyl, and t-butyl.

[0025] The term “substituted” is intended to be non-limiting when used to describe a group, for example, when referring to a substituted analog of a particular group, to describe a compound or group in which any part other than hydrogen in that group or compound is formally replaced by hydrogen. Compounds or groups may also be referred to herein as “unsubstituted” or equivalent terms, e.g., “not substituted,” and refer to the original group or compound. “Substituted” is intended to be non-limiting and includes inorganic substituents or organic substituents, as defined and as understood by those skilled in the art.

[0026] Terms such as “contact product” and “contact” are used herein to describe compositions and methods in which components are brought into contact together in any order, in any form and for any length of time, unless otherwise specified. For example, the components can be brought into contact by blending or mixing. Furthermore, unless otherwise stated, contact of any component can be carried out in the presence or absence of any of the other components of the compositions and methods described herein. The addition of additional materials or components can be carried out by any suitable method. Furthermore, the term “contact product” includes mixtures, blends, solutions, slurries, reaction products, or combinations thereof. “Contact products” can and often include reaction products, but the components do not need to react with each other. Similarly, reaction products or reaction mixtures can be obtained by “contacting” two or more components. Thus, “contact products” can be mixtures, reaction mixtures, or reaction products, depending on the context.

[0027] "Conditions for aromatizing aliphatic hydrocarbons" means conditions under which, when contacted with a catalyst as described herein, at least a portion of the aliphatic hydrocarbons in a raw material containing aliphatic hydrocarbons are aromatized, and as a result the catalyst bed effluent contains at least some aromatic hydrocarbons. Some unreacted aliphatic hydrocarbons will also be present in the catalyst bed effluent.

[0028] Generally, element groups are indicated using the numbering system shown in the version of the periodic table published in Chemical and Engineering News, 63(5), 27, 1985. In some cases, element groups are also indicated by the common names assigned to them, such as alkali metals for Group 1 elements, alkaline earth metals for Group 2 elements, transition metals for Groups 3-12 elements, and halogens or halides for Group 17 elements.

[0029] In one embodiment, a chemical “group” may be defined or described by the number of hydrogen atoms removed from a parent compound to produce the group, in accordance with the manner in which the group is formally derived from a reference compound or “parent” compound, for example, even if the group is not synthesized by literally removing hydrogen atoms. These groups may be used as substituents or coordinate-bonded to or bonded to metal atoms. As an example, an “alkyl group” may be formally derived by removing one hydrogen atom from an alkane. Depending on the disclosure that substituents, ligands or other chemical parts may constitute a particular “group,” it is implied that when the group is used as described, it conforms to well-known rules of chemical structure and bonding. When a group is described as “derived by,” “derived from,” “formed by,” or “formed from,” such terms are used in a formal sense and are not intended to reflect any specific method or procedure of synthesis, unless otherwise specified or otherwise required by the context.

[0030] As used herein, the term "hydrocarbon" refers to a compound containing only carbon and hydrogen atoms. Where applicable, other identifying names may be used to indicate the presence of specific groups in a hydrocarbon. For example, halogenated hydrocarbons indicate that the hydrocarbon contains one or more halogen atoms in which an equal number of hydrogen atoms are replaced.

[0031] An “aromatic” compound or “aromatic hydrocarbon” is a compound that obeys Hückel’s rule (4n+2) and contains a cyclic conjugated double bond system with (4n+2) π electrons (wherein n is an integer from 1 to 5). Examples of aromatic hydrocarbons include “arenes” (aromatic compounds, e.g., benzene, toluene, and xylene) and “heterearnes” (heteroaromatic compounds formally derived from arenes by replacing one or more methine (-C=) carbon atoms in a cyclic conjugated double bond system with trivalent or divalent heteroatoms in a manner that preserves the continuous π electron system and a substantial number of out-of-planar π electrons characteristic of aromatic systems, corresponding to Hückel’s rule (4n+2)). As disclosed herein, the term “substituted” can be used to describe an aromatic group, arene, or heteroarene in which a non-hydrogen portion formally replaces a hydrogen atom in the compound, and is intended to be non-limiting unless otherwise specified.

[0032] As used herein, the term "alkane" refers to a saturated hydrocarbon compound. Other identifying names may be used to indicate, where applicable, the presence of a specific group in the alkane (for example, a halide alkane indicates that the alkane contains one or more halogen atoms in which an equal number of hydrogen atoms are replaced). The term "alkyl group" is used herein according to the definition set forth by IUPAC and refers to a monovalent group formed by removing a hydrogen atom from an alkane. Unless otherwise stated, the alkane group or alkyl group may be linear or branched.

[0033] In this specification, "cycloalkane" is used to refer to saturated cyclic hydrocarbons, with or without side chains, such as cyclobutane, cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane. Other identifying names may be used to indicate, where applicable, the presence of a specific group in the cycloalkane (for example, halogenated cycloalkane indicates that the cycloalkane contains one or more halogen atoms that replace an equal number of hydrogen atoms).

[0034] "Aliphatic" compounds or "aliphatic hydrocarbons" are defined according to the IUPAC recommended definition and mean acyclic or cyclic saturated or unsaturated carbon compounds, excluding aromatic compounds. In other words, aliphatic compounds are non-aromatic organic compounds.

[0035] The term "hydrocarbyl group" is used herein according to the definition set forth by IUPAC and refers to a monovalent group formed by removing a hydrogen atom from a hydrocarbon (i.e., a group containing only carbon and hydrogen). Therefore, examples of hydrocarbyl groups include alkyl groups (linear or branched), cycloalkyl groups, alkenyl groups, and aryl groups. Non-limiting examples of hydrocarbyl groups include methyl, ethyl, butyl, hexyl, phenyl, tolyl, and propenyl.

[0036] As used herein, “paraffin” refers to acyclic, linear or branched saturated hydrocarbons, and examples of paraffins include alkanes. For example, C6 paraffins are acyclic, linear or branched hydrocarbons having six carbon atoms per molecule. n-hexane, methylpentane, and dimethylbutane are examples of C6 paraffins. Paraffin-containing raw materials include acyclic saturated hydrocarbons, such as n-paraffins, isoparaffins, and mixtures thereof.

[0037] As used herein, “naphthene” and “naphthenic” are terms used to describe cyclic saturated hydrocarbons, including cycloalkanes and their alkyl-substituted analogs. That is, “naphthene” is a cyclic saturated hydrocarbon having one or more carbon-carbon rings in its chemical structure, and is used herein to mean the same as “cycloalkane.” If such a cyclic structure contains unsaturated carbon-carbon bonds but is not aromatic, then such a compound is aliphatic but not naphthenic. In some embodiments, naphthenes, including their substituted analogs (particularly alkyl-substituted analogs), are cyclic saturated hydrocarbons having 5 to 8 carbon atoms in their cyclic structure.

[0038] As used herein, "olefin" refers to acyclic or cyclic hydrocarbons having one or more carbon-carbon double bonds, distinct from the formal hydrocarbons of aromatic compounds. Olefins include alkenes, cycloalkenes, and their corresponding polyenes.

[0039] As used herein, “naphtha” is a petroleum fraction that boils in the range of 50°F (10°C) to 550°F (260°C). In some embodiments, naphtha boils in the range of 70°F (21°C) to 450°F (232°C), more typically in the range of 80°F (27°C) to 400°F (204°C), and often in the range of 90°F (32°C) to 360°F (182°C). In some embodiments, at least 85 vol.% (volume percent) of naphtha boils in the range of 50°F (10°C) to 550°F (260°C), more typically in the range of 70°F (21°C) to 450°F (232°C). In various embodiments, at least 85 vol.% of naphtha boils in the range of C4 to C 12 This range is C5 to C 11 This range is C6~C 10 This range includes, for example, straight-run naphtha, paraffinic and naphthenic raffinates derived from aromatic extraction or adsorption, and C6-C6. 10Examples include naphtha derived from paraffin and naphthene-containing raw materials, naphtha derived from bio-based raw materials, naphtha derived from hydrocarbon synthesis processes (including the Fischer-Tropsch process and methanol synthesis process), and naphtha derived from other refining processes, such as hydrocracking or conventional reforming.

[0040] As used herein, the terms “convertible hydrocarbon,” “convertible C6 species,” or “convertible C7 species” refer to hydrocarbon compounds that can be selectively converted to aromatic products, such as aromatic hydrocarbons, under the conditions of an aromatization process. In some embodiments, the feed stream includes highly branched hydrocarbons that are not selectively converted to aromatic hydrocarbons under the conditions of a conventional aromatization process. A “highly branched hydrocarbon” is a hydrocarbon that is not selectively convertible to form an aromatic hydrocarbon under the conditions of a conventional aromatization process. For example, a “highly branched hydrocarbon” may include a highly branched hydrocarbon having 6 to 7 carbon atoms and an internal quaternary carbon, or a hydrocarbon having 6 carbon atoms and 2 adjacent internal tertiary carbons, or a mixture thereof. Examples of highly branched hydrocarbons 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 rather converted to light hydrocarbons under the conditions of an aromatization process. The convertible components may include methylpentane, methylhexane, dimethylpentane, or mixtures thereof, and / or the selectively convertible components 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 components are readily converted to aromatic hydrocarbons without the production of light hydrocarbons.

[0041] As used herein, “primary aromatic hydrocarbon,” “primary aromatic product,” “desired hydrocarbon product,” and “specific aromatic chemical species” are used synonymously and refer to the desired final product of the reaction, including aromatic hydrocarbons produced from raw materials containing a renewable cellulose source. For example, the desired product may be benzene, with toluene and xylene as by-products, or the desired product may be xylene, with benzene and toluene as by-products.

[0042] The metals of Groups 8-10 include the metals of Group 8, iron, ruthenium, and osmium; the metals of Group 9, cobalt, rhodium, and iridium; and the metals of Group 10, nickel, palladium, and platinum. The metals of Groups 8-10 may also be referred to using the earlier nomenclature, Group VIII metals, which include all of iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, and platinum. Generally, describing a catalyst as a catalyst for Groups 8-10 metals, or as containing Groups 8-10 metals, is intended to include catalysts containing at least one Group 8-10 metal and optionally other metals, such as Pt / Sn and Pt / Re.

[0043] In this specification, the term "platinum group metals" is used to refer to the transition metals of the second and third periods of groups 8 through 10, namely ruthenium, osmium, rhodium, iridium, palladium, and platinum.

[0044] The term "precious metal" is generally used to describe certain metals that are corrosion-resistant, and in this specification, this term is used to mean: 第2 Period and 第3 It is used to include certain transition metals of a period but exclude the transition metals of the first period. Generally, precious metals include ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, and gold. Therefore, the precious metals of groups 8 through 10 are also platinum group metals.

[0045] As used herein, the term “bound” is intended to describe a combination of zeolite and binder, or a combination of other carrier and binder, that forms aggregates, such as pellets, pills, extruded bodies, etc. The term “catalytic substrate” as used herein refers to bound zeolite or bound carrier.

[0046] The term "catalyst" is used herein in a broad sense and includes both the final catalyst and its precursors. Examples of precursors to the final catalyst include the calcined form of the catalyst containing the catalyst metal, which is also the catalyst before activation by reduction. Therefore, as will be apparent to those skilled in the art from the context, the term "catalyst" is used in some contexts to refer to the activated catalyst, and in other contexts to refer to the precursor form of the catalyst.

[0047] The term “sulfur-sensitive” describes catalysts that are particularly sensitive to the presence of sulfur in the feedstock. Generally, these catalysts require the amount of sulfur in the feedstock to be reduced to less than 5 ppm by hydrogenation, adsorbent, or a combination thereof. As used herein, when referring to an aromatization reactor system, the terms “aromatization reactor system,” “aromatization reactor unit,” “catalytic reactor system,” and “catalytic reactor unit” also refer to the reaction vessel, the inside of the reactor, and associated processing equipment, to the extent permitted by the context, including, but not limited to, catalysts, inert packing materials, scallops, flow dividers, center pipes, reactor ports, catalyst transfer and distribution systems, furnaces and other heating equipment, heat transfer equipment, and piping. The aromatization reactor systems described may include fixed-bed catalyst systems, mobile-bed catalyst systems, fluid-bed catalyst systems, or a combination thereof. Such aromatization reactor systems may be batch or continuous. In fixed-bed systems, the feed flow can pass through the reactor upward, downward, or radially. In one embodiment, the first catalyst bed, the intermediate catalyst bed, and the final catalyst bed may be located within a radial flow reactor.

[0048] The term “catalyst bed,” for example, a first catalyst bed, a second catalyst bed, or an intermediate catalyst bed, is used herein to refer to a given catalyst composition comprising at least some or all of the catalyst material in an aromatization reactor. For example, a “first catalyst bed” may occupy the entirety of an aromatization reactor, or a “first catalyst bed” may occupy part of an aromatization reactor while a “second catalyst bed” occupies the remainder of that reactor. More typically, each catalyst bed may occupy the entirety of an aromatization reactor. Generally, and unless otherwise specified or required by context, multiple aromatization reactors are described as having different catalyst beds, regardless of whether their catalysts are identical or different in composition.

[0049] The term "halogen" has its usual meaning and includes halides to the extent permitted by the context. Examples of halogens include fluorine, fluorides, chlorine, chlorides, bromine, bromides, iodine, and iodides. Furthermore, the use of the terms "fluoride" and "chloride" is not dependent on whether they exist in any particular molecular or ionic form when describing catalytic components or catalytic compositions, such as their weight percentages or molar percentages.

[0050] Molar selectivity is defined as follows:

number

[0051] The conversion rate is defined as the number of moles converted per mole of "convertible" hydrocarbon supplied, as follows:

number

[0052]

number

[0053] In this specification, "ton" refers to the metric ton, that is, a unit of mass equivalent to 1,000 kilograms.

[0054] This abstract is not intended to be used to interpret the claims or to limit the scope of the subject matter disclosed herein, but rather to satisfy the requirements of Section 1.72(b) of the U.S. Patent Law Enforcement Rules, so that the United States Patent and Trademark Office and the public can generally quickly grasp the nature and essence of the technical disclosures by brief reading. Furthermore, none of the titles used herein are intended to interpret the claims or to limit the scope of the subject matter disclosed herein. Any use of the past tense to describe any example otherwise presented as an interpretive or hypothetical example is not intended to reflect that such an interpretive or hypothetical example was actually performed.

[0055] All publications and patents referenced herein, for example, constructs and methodologies described in publications, are incorporated herein by reference in their entirety for the purpose of describing and disclosing constructs and methodologies that may be used in connection with the present invention. Publications discussed throughout this text are shown simply because they were disclosed prior to the filing date of this application. Nothing in this specification should be construed as granting the inventors no prior rights to such disclosures by prior art.

[0056] Those skilled in the art will readily see that many modifications are possible in the exemplary embodiments disclosed herein without significantly 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. That is, one can rely on various other aspects, embodiments, modifications and equivalents of the invention, which those skilled in the art will understand, after reading the description herein, may be shown without departing from the spirit of this disclosure or the scope of the appended claims. [Modes for carrying out the invention]

[0057] This disclosure relates, in general terms, to a method for regenerating and / or reactivating spent catalysts, such as spent aromatization catalysts. By using a fluorine-containing compound instead of fluorine gas during the fluorination step, it has been unexpectedly found that the method herein can achieve improved fluorine distribution throughout the catalyst bed with little to no effect on the performance of the regenerated and / or reactivated catalyst.

[0058] Any used catalyst can be used in the methods described herein. In some embodiments, the used catalyst includes a transition metal and a catalyst support. The catalyst, such as the used catalyst, may be present in the metal reactor for some or all of the steps of the methods provided herein. In some embodiments, the metal reactor includes stainless steel, for example, 347SS or 321SS.

[0059] method

[0060] This specification provides a reforming method which may comprise any two or more of the following steps (e.g., any two, any three, any four, any five, any six, any seven, or all eight): (A) contacting a hydrocarbon feed with an aromatizing catalyst comprising a transition metal and a catalyst support in a metal reactor system under reforming conditions to produce an aromatic product; (B) carrying out step (A) for a time sufficient to form a spent catalyst; (C) contacting the spent catalyst with hydrogen gas to produce a stripped spent catalyst; (D) removing at least a portion of the hydrocarbon feed, at least a portion of the aromatic product, or a combination thereof from the spent catalyst. (E) subjecting the stripped spent catalyst to carbon combustion at a temperature not exceeding approximately 500°F for a time effective to improve the dispersion of transition metals in the chlorinated spent catalyst to form a treated spent catalyst; (F) contacting the treated spent catalyst with a chlorine-containing stream containing a chlorine-containing compound to produce a chlorinated spent catalyst; (G) subjecting the chlorinated spent catalyst to carbon combustion at a temperature not exceeding 900°F for a time effective to improve the dispersion of transition metals in the chlorinated spent catalyst to form a redispersed spent catalyst; (G) contacting the redispersed spent catalyst with a fluorine-containing stream containing a fluorine-containing compound to form a regenerated catalyst; and (H) reducing the regenerated catalyst. The method herein may also include a step of reactivating the catalyst after step (H), for example. In some embodiments, the reforming method herein is an in situ process. Thus, in some embodiments, steps (A) to (H) (or two or more selected steps (A) to (H)) are performed in the same reactor system. In some embodiments, steps (C) to (H) are performed outside the reactor system in which steps (A) to (B) are carried out. For example, steps (C) to (H) may be carried out in a metal reactor that is not located within the reforming reactor system.

[0061] In some embodiments, the method includes: (1) contacting the spent catalyst with hydrogen gas to produce a stripped spent catalyst; (2) subjecting the stripped spent catalyst to carbon combustion at a temperature not exceeding about 500°F for a time effective in removing at least a portion of the hydrocarbon feed, at least a portion of the aromatic products, or a combination thereof, from the spent catalyst to form a treated spent catalyst; (3) contacting the treated spent catalyst with a chlorine-containing stream containing a chlorine-containing compound to produce a chlorinated spent catalyst; (4) subjecting the chlorinated spent catalyst to carbon combustion at a temperature not exceeding 900°F for a time effective in improving the dispersion of transition metals in the chlorinated spent catalyst to form a redispersed spent catalyst; (5) contacting the redispersed spent catalyst with a fluorine-containing stream containing a fluorine-containing compound to form a regenerated catalyst; and (6) reducing the regenerated catalyst.

[0062] In some embodiments, the method includes (A) contacting a hydrocarbon feed with an aromatizing catalyst comprising a transition metal and a catalyst support under reforming conditions in a metal reactor system to produce an aromatic product; (B) performing step (A) for a sufficient time to form spent catalyst; (C) contacting the spent catalyst with a chlorine-containing stream comprising a chlorine-containing compound to produce a chlorinated spent catalyst, wherein optionally the chlorine-containing compound comprises chlorine, chlorinated hydrocarbons, chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), or a combination thereof; (D) contacting the chlorinated spent catalyst with a coke-removing gas stream comprising oxygen to produce a coke-removed catalyst; and (E) contacting the coke-removed catalyst with a fluorine-containing stream comprising a fluorine-containing compound, wherein the fluorine-containing compound comprises hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), fluorocarbons (FCs), or a combination thereof. In some embodiments, the method is an in situ process. For example, steps (A) to (E) may be performed in the same reactor system. In some embodiments, steps (C) to (E) are performed outside the reactor system of steps (A) to (B). For example, steps (C) to (E) may be performed in a metal reactor that is not in the reforming reactor system. In some embodiments, the method includes reactivating the catalyst after step (E).

[0063] In some embodiments, the method includes regenerating a spent catalyst, which comprises a transition metal and a catalyst support, in a metal reactor. The method includes (1) contacting the spent catalyst with a chlorine-containing stream containing a chlorine-containing compound to produce a chlorinated spent catalyst; (2) contacting the chlorinated spent catalyst with a coke-removing gas stream containing oxygen to produce a coke-removed catalyst; and (3) contacting the coke-removed catalyst with a fluorine-containing stream containing a fluorine-containing compound to produce a regenerated catalyst, wherein the fluorine-containing compound includes hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), fluorocarbons (FCs), or combinations thereof.

[0064] The steps of the methods provided herein can generally be carried out for any effective time, temperature, pressure, etc.

[0065] hydrogen gas

[0066] Contact between the spent catalyst and hydrogen gas can occur at any effective temperature. In some embodiments, contact between the spent catalyst and hydrogen gas occurs at least partially at temperatures above 25°F, above 100°F, above 200°F, above 300°F, above 400°F, or above 500°F. In some embodiments, contact between the spent catalyst and hydrogen gas occurs at least partially at temperatures between approximately 300°F and approximately 800°F, approximately 400°F and approximately 800°F, or approximately 500°F and approximately 800°F.

[0067] Contact between the spent catalyst and hydrogen gas can occur at any effective time. In some embodiments, contact between the spent catalyst and hydrogen gas occurs over a period of time of approximately 1 minute to 24 hours, approximately 1 minute to 18 hours, approximately 1 minute to 12 hours, approximately 1 minute to 6 hours, or approximately 1 minute to 2 hours.

[0068] Fluorine-containing compounds and fluorine-containing fluids

[0069] The fluorine-containing compounds used in the methods described herein can include any compound in any phase that contains one or more fluorine atoms in its structure. For example, the fluorine-containing compounds can include hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), fluorocarbons (FCs), or combinations thereof. In some embodiments, the fluorine-containing compound is a compound of formula (I),

[0070] C a H b Cl c F d Formula (I),

[0071] where a is from 1 to 6, b is from 0 to 14, c is from 0 to 14, d is from 1 to 14, optionally, b and / or c is not 0, and b + c + d = 2a + 2, and optionally, the compound of formula (I) is substituted. In some embodiments, the fluorine-containing compound is 1,1,1,2-tetrafluoroethane. In some embodiments, the fluorine-containing compound is difluoromethane. In some embodiments, the fluorine-containing compound is dichlorodifluoromethane.

[0072] The fluorine-containing compound can be a component of a fluorine-containing stream. The fluorine-containing stream can consist of one or more fluorine-containing compounds, for example, one, two, three, etc. fluorine-containing compounds. The fluorine-containing stream can include at least one component other than one or more fluorine-containing compounds. The at least one component other than one or more fluorine-containing compounds can be a fluid such as an inert gas, air, oxygen gas, etc. In some embodiments, the fluorine-containing stream includes (i) a fluorine-containing compound and any inert gas disclosed herein, for example, nitrogen, (ii) a fluorine-containing compound, any inert gas disclosed herein, and air, (iii) a fluorine-containing compound and air, or (iv) a fluorine-containing compound, oxygen (O2), and any inert gas disclosed herein (e.g., nitrogen).

[0073] One or more fluorine-containing compounds may be present in a fluorine-containing stream at any concentration and / or ratio. If two or more components other than fluorine-containing compounds are present in the fluorine-containing stream, these two or more components may be present at any concentration and / or ratio (volume ratio or weight ratio). For example, a fluorine-containing stream may contain an inert gas and air, and the inert gas and air may be present in volume ratios of about 3:1 to about 30:1, about 3:1 to about 20:1, about 3:1 to about 10:1, about 3:1 to about 5:1, or about 4:1. As a further example, the volume ratio of inert gas to oxygen (O2) in a fluorine-containing stream is about 90:10 to about 99.9:0.1, about 95:5 to about 99:1, or about 97:3 (inert gas:oxygen (O2)). In some embodiments, the fluorine-containing stream contains about 0.01 mol% to about 40 mol%, about 0.01 mol% to about 30 mol%, about 0.01 mol% to about 20 mol%, about 0.01 mol% to about 10 mol%, or about 0.01 mol% to about 5 mol% of oxygen. Oxygen (O2) can be a component of air.

[0074] Fluorine-containing streams can be formed using any known apparatus, and the components of the fluorine-containing stream can be combined in any way and / or order, such as simultaneously or sequentially. In some embodiments, contacting a redispersed spent catalyst with a fluorine-containing stream involves circulating a fluid, such as an inert gas, and injecting a fluorine-containing compound into the circulating fluid. In some embodiments, the injection of the fluorine-containing compound is achieved at least partially using a spraying device configured to disperse the fluorine-containing compound into a circulating fluid, such as an inert gas, oxygen, or a combination thereof. For example, contacting a redispersed spent catalyst with a fluorine-containing stream may involve circulating a stream containing an inert gas and oxygen (O2), and injecting a fluorine-containing compound into the circulating stream. The circulating stream may contain oxygen (O2) at any concentration. In some embodiments, oxygen (O2) is present in the circulating flow at concentrations of approximately 0.01% to 10% by volume, approximately 0.01% to 8% by volume, approximately 0.01% to 6% by volume, approximately 0.01% to 4% by volume, approximately 1% to 4% by volume, approximately 2% to 4% by volume, approximately 2.5% to 3.5% by volume, or approximately 3% by volume.

[0075] A catalyst, such as a redispersed spent catalyst, can be brought into contact with a fluorine-containing compound or fluorine-containing flow in any way and under any conditions that is effective in placing a desired weight percentage of fluorine (e.g., up to 3%, up to 2%, or up to 1% by weight) on the catalyst.

[0076] In some embodiments, a method for contacting spent catalyst, such as a redispersed spent catalyst, with a fluorine-containing flow is to (a) provide two or more reactors that are in fluid communication with each other, the two or more reactors connected in series, so that the fluorine-containing flow is (i) injected at an injection point selected from one or more injection points, (ii) continuously circulated to each of the two or more reactors downstream of the injection point, (iii) returned to the first reactor of the two or more reactors, and optionally (iv) continuously recirculated to each of the two or more reactors, and to the two or more reactors The invention provides, each comprising: (b) heating one of two or more reactors to a temperature above the fluorination temperature effective for at least partially decomposing the fluorine-containing compounds in the fluorine-containing stream, and maintaining each of the remaining reactors of the two or more reactors below the fluorination temperature; and (c) injecting the fluorine-containing stream and circulating or recirculating the fluorine-containing stream at a temperature above the fluorination temperature for a time effective for achieving a desired level of fluorination of the spent catalyst in one of the two or more reactors.

[0077] Where a system or method described herein includes a group of components (e.g., reactors) connected in series, the component optionally referred to as “first” is the upstream component, and the remaining components are numbered sequentially thereafter, with the largest number optionally assigned to the component downstream of all other components in the group. For example, if a system includes three reactors, the “first” reactor is upstream of the “second” and “third” reactors, and the “third” reactor is downstream of the “first” and “second” reactors. Thus, where a limitation of this specification states that a flow “returns to the first reactor of two or more reactors,” this limitation indicates that the flow passes through a reactor upstream of the other “two or more reactors.”

[0078] The method may also include heating one of two or more reactors to a temperature above the fluorination temperature, maintaining each of the remaining reactors below the fluorination temperature, and injecting a fluorine-containing stream and circulating or recirculating the fluorine-containing stream at a temperature above the fluorination temperature for a time effective to achieve the desired level of fluorination of the spent catalyst in one of the two or more reactors. These elements may be repeated until the spent catalyst in each of the reactors is fluorinated to the desired level.

[0079] The fluorine-containing stream may be circulated once through two or more reactors, or it may be recirculated any number of times through two or more reactors. Recirculation may be continued until a desired concentration of fluorine is present in the catalyst.

[0080] The fluorination temperature may include any temperature at which the fluorine-containing compound decomposes at least partially. In some embodiments, temperatures above the fluorination temperature are at least 700°F. In some embodiments, temperatures above the fluorination temperature are about 650°F to about 850°F, about 700°F to about 850°F, about 700°F to about 800°F, about 700°F to about 775°F, or about 700°F to about 750°F. In some embodiments, temperatures below the fluorination temperature are about 600°F or less. In some embodiments, temperatures below the fluorination temperature are about 300°F to about 600°F, about 400°F to about 600°F, or about 500°F to about 600°F.

[0081] The fluorine-containing stream can be introduced into two or more reactors in any manner. In some embodiments, the fluorine-containing stream is injected. Injection of the fluorine-containing stream may include (1) selecting an injection point from one or more injection points, and (2) injecting the fluorine-containing stream into the injection junction selected from one or more injection points. The selected injection point may be any of the injection points present in the system provided herein. In some embodiments, the selected injection point is (i) upstream of one reactor (or different reactors) heated to a temperature above the fluorination temperature, (ii) downstream of all other reactors that are upstream of a reactor (or different reactors) heated to a temperature above the fluorination temperature, or (iii) a combination thereof.

[0082] The amount of fluorine-containing compound or fluorine-containing flow injected and circulated / recirculated may be effective in placing any amount of fluorine, e.g., about 0.1 wt% to about 1.5 wt%, about 0.5 wt% to about 1.5 wt%, or about 0.15 wt% to about 1.2 wt%, onto the spent catalyst. The method may include analyzing the fluorine-containing flow during circulation or recirculation to determine the amount or concentration of fluorine-containing compound and / or fluorine in the fluorine-containing flow. The method may include stopping the circulation / recirculation of the fluorine-containing flow when the amount or concentration of fluorine-containing compound and / or fluorine is below a threshold concentration or amount indicating that fluorine deposition on the spent catalyst is achieved. Monitoring of the fluorine-containing flow can be achieved using any known technique or apparatus, such as spectroscopy.

[0083] This specification also provides a system for fluorinating spent catalysts. The system may include (a) two or more reactors in fluid communication with each other, the two or more reactors connected in series, so that a fluid flow, for example, a fluorine-containing flow, can be (i) injected at an injection point selected from one or more injection points, (ii) continuously circulated to each of the two or more reactors downstream of the injection point, (iii) returned to the first of the two or more reactors, and optionally (iv) continuously recirculated to each of the two or more reactors; and (b) two or more heating devices configured to heat each of the two or more reactors to the same or different temperatures.

[0084] An embodiment of the system is shown in Figure 1. System 100 includes a first furnace 110 configured to heat a first reactor 120, a second furnace 111 configured to heat a second reactor 121, and a third furnace 112 configured to heat a third reactor 122. These components are connected in series via piping 101, which includes a “feedback loop” 102 that allows the circulating flow to be recirculated from the third reactor 122 to the first reactor 110. Three reactor / furnace pairs (110 / 120, 111 / 121, 112 / 122) are shown in Figure 1, but the system may include two, three, four, five, six, seven, eight, nine, ten, or more reactors. The system 100 in Figure 1 includes three possible injection points (130, 131, 132), which are upstream of the first reactor 120, the second reactor 121, and the third reactor 122, respectively. Furnaces with configurations other than those shown in Figure 1, such as tubular furnaces or others, may be used.

[0085] The system 100 in Figure 1 may be used to carry out embodiments of the methods provided herein. For example, in some embodiments, the method includes (i) heating reactor 120 to a temperature of about 700°F to about 850°F in furnace 110, (ii) maintaining the temperatures of the second reactor 121 and the third reactor 122 below about 600°F, and (iii) injecting a fluorine-containing stream at a first injection point 130 and circulating or recirculating the fluorine-containing stream through the first reactor 120, the second reactor 121, and the third reactor 122 for a time effective in depositing a desired level of fluorine onto the spent catalyst 140 of the first reactor 120. The method may also include (i) lowering the temperature of the first reactor 120 to a temperature of about 600°F or less, (ii) raising the temperature of the second reactor 121 to a temperature of about 700°F to about 850°F using the furnace 111, (iii) maintaining the temperatures of the first reactor 120 and the third reactor 122 at or below about 600°F, and (iv) injecting a fluorine-containing stream at a second injection point 131 and circulating or recirculating the fluorine-containing stream through the second reactor 121, the third reactor 122, and the first reactor 120 for a time effective in depositing a desired level of fluorine onto the spent catalyst 141 of the second reactor 121. The method may also include (i) lowering the temperature of the second reactor 121 to a temperature of about 600°F or less, (ii) raising the temperature of the third reactor 122 to a temperature of about 700°F to about 850°F using the furnace 112, (iii) maintaining the temperatures of the first reactor 120 and the second reactor 121 at about 600°F or less, and (iv) injecting a fluorine-containing stream at a third injection point 132 and circulating or recirculating the fluorine-containing stream through the third reactor 122, the first reactor 120, and the second reactor 121 for a time effective in depositing a desired level of fluorine onto the spent catalyst 142 of the second reactor 122.

[0086] In some embodiments, (i) the amount of fluorine-containing compound in the fluorine-containing stream, (ii) the duration of contact between the spent catalyst and the fluorine-containing stream, or (iii) a combination thereof, is selected so that about 0.1 wt% to about 2 wt%, about 0.15 wt% to about 1.5 wt%, about 0.2 wt% to about 1.5 wt%, about 0.2 wt% to about 1 wt%, about 0.5 wt% to about 1.5 wt%, about 0.5 wt% to about 1 wt%, or about 0.8 wt% to about 1 wt% of fluorine is distributed on the redispersed spent catalyst. In some embodiments, contact between a catalyst, such as a spent catalyst, and a fluorine-containing stream occurs, at least partially, at temperatures of about 500°F to about 1,000°F, about 600°F to about 1,000°F, about 600°F to about 900°F, about 700°F to about 900°F, or about 700°F to about 850°F. In some embodiments, the amount of fluorine-containing compound in the fluorine-containing stream is controlled to ensure a desired concentration of fluorine [F] on the catalyst, for example, less than any maximum amount disclosed herein or within any range of concentrations, for example, less than about 10 wt%, less than about 8 wt%, less than about 6 wt%, less than about 4 wt%, less than about 2 wt%, less than 1.5 wt%, about 0.1 wt% to about 3 wt%, about 1 wt% to about 2 wt%, about 1.25 wt% to about 1.75 wt%, about 0.1 wt% to about 1.5 wt%, about 0.15 wt% to about 1.3 wt%, about 0.1 wt% The range obtained is approximately 1.0 wt%, 3 wt%, 2 wt%, 1.75 wt%, 1.5 wt%, 1.3 wt%, 1.0 wt%, 1.0 wt%, 1.5 wt%, or 1.8 wt%. In some embodiments, the fluorination step is carried out (i) at a fluorination temperature within any fluorination temperature range disclosed herein, for example, about 0°C to about 600°C, about 10°C to about 550°C, about 20°C to about 450°C, about 0°C to about 300°C, about 20°C to about 250°C, or about 15°C to about 50°C, or (ii) at a fluorination pressure of atmospheric pressure to about 15 bar, atmospheric pressure to about 10 bar, atmospheric pressure to about 7 bar, about 2 bar to about 10 bar, about 2 bar to about 5 bar, or about 2 bar.In some embodiments, the fluorination step is carried out for a time within any range of the fluorination times disclosed herein, for example, about 0.1 hours to about 96 hours, about 0.1 hours to about 72 hours, about 0.1 to about 48 hours, about 0.1 to about 12 hours, or about 0.1 to about 8 hours.

[0087] In some embodiments, the amount of fluorine-containing compound in the fluorine-containing stream is controlled to be less than any maximum amount disclosed herein or within any range of concentrations of fluorine [F] or fluorine-containing compound in the fluorine-containing stream, for example, less than about 50,000 ppmv, in the range of about 5 to about 25,000 ppmv, in the range of about 10 to about 25,000 ppmv, in the range of about 50 to about 25,000 ppmv, and in the range of about 5,000 to about 25,000 ppmv. Obtain a range of ppmv, approximately 50 to approximately 20,000 ppmv, approximately 50 to approximately 15,000 ppmv, approximately 50 to approximately 10,000 ppmv, approximately 50 to approximately 5,000 ppmv, approximately 50 to approximately 2,500 ppmv, approximately 50 to approximately 1,000 ppmv, approximately 500 to approximately 1,000 ppmv, approximately 600 to approximately 900 ppmv, approximately 700 to approximately 800 ppmv, or approximately 750 ppmv.

[0088] In some embodiments, the fluorine concentration in the regenerated catalyst is approximately 0.15 wt% to approximately 1.2 wt%, or approximately 0.2 wt% to approximately 1.2 wt%. In some embodiments, the fluorine concentration gradient in the regenerated catalyst is 60% or less, 50% or less, 40% or less, 30% or less, 20% or less, or 10% or less.

[0089] In general, a fluorine-containing stream may contain any of the compounds, gases, etc., described herein, and one or more of the compounds, gases, etc., described herein may be excluded from the fluorine-containing stream. For example, a fluorine-containing stream may substantially not contain oxygen-containing compounds and / or chlorine-containing compounds that do not contain fluorine atoms. A fluorine-containing stream is considered "substantially free" of a compound if that compound is present in the fluorine-containing stream at a concentration of less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw.

[0090] The methods provided herein may also include recovering at least a portion of the fluorine-containing flow to produce a recovered fluorine-containing flow. Recovery of at least a portion of the fluorine-containing flow may be performed after contact between the coked catalyst and the fluorine-containing flow. The methods may also include contacting the coked catalyst with the recovered fluorine-containing flow.

[0091] Chlorine-containing compounds and chlorine-containing flows

[0092] The chlorine-containing compounds used in the methods described herein may include any compound of any phase containing one or more chlorine atoms in its structure. In some embodiments, the chlorine-containing compound includes chlorine gas (Cl2). The chlorine-containing stream may include one or more compounds other than the chlorine-containing compound (e.g., an inert gas). In some embodiments, the chlorine-containing stream includes chlorine gas (Cl2) and an inert gas, such as nitrogen (N2). In some embodiments, the chlorine-containing compound includes hydrochloric acid, chlorine gas (Cl2), carbon tetrachloride, tetrachloroethylene, chlorobenzene, methyl chloride, methylene chloride, chloroform, allyl chloride, trichloroethylene, chloramine, chlorine oxide, chlorine acid, chlorine dioxide, dichlorine monoxide, dichlorine heptoxide, chloric acid, perchloric acid, ammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, methyltriethylammonium chloride, or any combination thereof.

[0093] A chlorine-containing stream can be formed using any known apparatus, and the components of the chlorine-containing stream can be combined in any way and / or order, such as simultaneously or sequentially. For example, the method described herein involves circulating a fluid, such as an inert gas, and injecting a chlorine-containing compound into the circulating fluid. The injection of the chlorine-containing compound can be achieved, at least partially, by a spraying device configured to disperse the chlorine-containing compound in the circulating inert gas.

[0094] In some embodiments, the amount of chlorine-containing compound in the chlorine-containing stream is controlled to achieve a desired concentration of chlorine (Cl) or chlorine-containing compound, for example, less than any maximum amount disclosed herein or within any range of concentrations, for example, less than about 50,000 ppmv, in the range of about 5 to about 25,000 ppmv, in the range of about 10 to about 25,000 ppmv, in the range of about 50 to about 25,000 ppmv, and in the range of about 50 to about 20,000 ppmv. Obtain a range of 0 ppmv, approximately 50 to approximately 15,000 ppmv, approximately 50 to approximately 10,000 ppmv, approximately 50 to approximately 5,000 ppmv, approximately 50 to approximately 2,500 ppmv, approximately 50 to approximately 1,000 ppmv, approximately 50 to approximately 500 ppmv, approximately 50 to approximately 100 ppmv, approximately 100 to approximately 750 ppmv, or approximately 500 to approximately 600 ppmv.

[0095] The catalyst can be brought into contact with a chlorine-containing compound or chlorine-containing stream in any way and under any conditions that is effective in placing a desired weight percentage of chlorine or chlorine-containing compound (e.g., up to 3%, up to 2%, or up to 1% by weight) on the catalyst. In some embodiments, (i) the amount of chlorine-containing compound in the chlorine-containing stream, (ii) the duration of contact between the treated spent catalyst and the chlorine-containing stream, or (iii) a combination thereof, is controlled so that about 0.1 wt% to about 2 wt%, about 0.5 wt% to about 1.5 wt%, about 0.5 wt% to about 1 wt%, or about 0.6 wt% to about 1 wt% of chlorine or chlorine-containing compound is placed on the treated spent catalyst.

[0096] In general, a chlorine-containing stream may contain any of the compounds, gases, etc., described herein, and one or more of the compounds, gases, etc., described herein may be excluded from the chlorine-containing stream. For example, a chlorine-containing stream may be substantially free of oxygen-containing compounds and / or fluorine-containing compounds. A chlorine-containing stream is considered "substantially free" of a compound if that compound is present in the chlorine-containing stream at a concentration of less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw.

[0097] The catalyst can be brought into contact with a chlorine-containing compound or chlorine-containing stream in any way and under any conditions (e.g., temperature, pressure, etc.). In some embodiments, the chlorination step is carried out at a chlorination temperature within any chlorination temperature range disclosed herein, for example, about 0°F to about 600°F, about 100°F to about 600°F, about 200°F to about 600°F, about 300°F to about 600°F, about 400°F to about 600°F, about 400°F to about 500°F, or about 400°F to about 450°F. In some embodiments, the chlorination step is carried out for a time within any chlorination time range disclosed herein, for example, about 0.5 hours to about 72 hours, about 0.75 hours to about 60 hours, about 1 to about 48 hours, about 1 to about 12 hours, or about 2 to about 8 hours. In some embodiments, the chlorination step is carried out at chlorination temperatures of about 0°F to about 600°F, about 100°F to about 600°F, about 200°F to about 600°F, about 300°F to about 600°F, about 300°F to about 500°F, about 350°F to about 500°F, or about 350°F to about 450°F. In some embodiments, the chlorination step is carried out for a time within any range of chlorination times disclosed herein, for example, about 0.10 hours to about 72 hours, about 0.50 hours to about 60 hours, about 0.5 to about 48 hours, about 0.5 to about 12 hours, or about 1 to about 8 hours.

[0098] Coke removal gas flow

[0099] The coke removal gas stream may include any known in the art. In some embodiments, the coke removal gas stream includes any combination of one or more inert gases disclosed herein and oxygen, for example, a mixture of nitrogen and oxygen, air, or a mixture of air and nitrogen.

[0100] The concentration of oxygen in the coke removal gas stream can be limited. In some embodiments, the coke removal gas stream contains oxygen in a mol% range less than any maximum amount disclosed herein or within any range, for example, less than about 5 mol%, in the range of about 0.1 to about 10 mol%, in the range of about 0.1 to about 8 mol%, in the range of about 0.1 to about 5 mol%, in the range of about 0.5 to about 3 mol%, or in the range of about 0.5 to about 6 mol%.

[0101] The coke removal gas stream may contain any one or more of the compounds disclosed herein, or any one or more of the compounds disclosed herein may be excluded from the coke removal gas stream. In some embodiments, the coke removal gas stream is substantially free of halogen-containing compounds, such as added halogen-containing compounds (e.g., substantially halogen-free, substantially chlorine-free). The coke removal gas stream is "substantially free" of halogen-containing compounds if halogen-containing compounds are present at concentrations of less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw. In some embodiments, the coke removal gas stream is substantially free of water (e.g., added water). The coke removal gas stream is "substantially free" of water if water is present at concentrations of less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw.

[0102] Monocombustion

[0103] The carbon combustion step of the method provided herein can be carried out under any effective conditions (e.g., temperature, time, etc.). In some embodiments, the carbon combustion temperature of a catalyst, such as a stripped spent catalyst, is about 300°F to about 600°F, about 350°F to about 550°F, about 350°F to about 500°F, or about 400°F to about 475°F. In some embodiments, the carbon combustion temperature of a catalyst, such as a chlorinated spent catalyst, is about 500°F to about 1,200°F, about 500°F to about 1,100°F, about 500°F to about 1,000°F, about 600°F to about 1,000°F, about 700°F to about 1,000°F, about 700°F to about 900°F, about 800°F to about 900°F, or about 850°F. In some embodiments, the carbon combustion step is carried out at a peak coke removal temperature within any of the peak coke removal temperature ranges disclosed herein, for example, about 100°C (about 212°F) to about 700°C (about 1,292°F), about 125°C (about 257°F) to about 650°C (about 1,202°F), about 150°C (302°F) to about 600°C (about 1,112°F), about 200°C (about 392°F) to about 500°C (about 932°F), or about 350°C (about 662°F) to about 450°C (about 842°F). In some embodiments, the carbon combustion step is initiated at an initial coke removal temperature that is the same as any chlorine purge temperature disclosed herein, for example, about 0°C (about 32°F) to about 300°C (about 572°F), about 20°C (about 68°F) to about 275°C (about 527°F), about 20°C (about 68°F) to about 250°C (about 482°F), or about 50°C (about 122°F) to about 200°C (about 392°F).

[0104] Carbon combustion of stripped spent catalyst can occur over a period of time of about 1 minute to about 24 hours, about 1 minute to about 18 hours, about 1 minute to about 12 hours, about 1 minute to about 6 hours, or about 1 minute to about 2 hours. In some embodiments, carbon combustion of catalysts such as chlorinated spent catalyst occurs over a period of time of about 1 minute to about 24 hours, about 1 minute to about 18 hours, about 1 minute to about 12 hours, about 1 minute to about 6 hours, or about 1 minute to about 2 hours. In some embodiments, the carbon combustion step is carried out over a period of time within any range of coke removal times disclosed herein, for example, about 0.5 hours to about 120 hours, about 0.75 hours to about 108 hours, about 1 hour to about 96 hours, about 1 to about 72 hours, about 12 to about 48 hours, or about 1 to about 6 hours.

[0105] The carbon combustion step can remove any desired amount of hydrocarbon feed and / or aromatic feed from the catalyst. For example, carbon combustion of a catalyst, such as a stripped spent catalyst, can remove at least 90 wt%, at least 95 wt%, at least 99 wt%, or 100 wt% of the hydrocarbon feed from the spent catalyst. Carbon combustion of a catalyst, such as a stripped spent catalyst, can remove at least 90 wt%, at least 95 wt%, at least 99 wt%, or 100 wt% of the aromatic products from the spent catalyst. A certain amount of soft coke may be absorbed and / or adsorbed by the catalyst, such as a spent catalyst, and carbon combustion of the catalyst can reduce the amount of soft coke absorbed and / or adsorbed by the spent catalyst. In some embodiments, the carbon combustion step is performed for a time sufficient to reduce the wt% of carbon on the catalyst, such as a chlorinated spent catalyst, to less than any maximum weight percentage of carbon disclosed herein, for example, less than about 1 wt%, less than about 0.5 wt%, or less than about 0.2 wt%.

[0106] Carbon combustion of catalysts, such as chlorinated catalysts, can improve the dispersion of transition metals in the catalyst. For example, carbon combustion can improve the dispersion of group VIII metals in the catalyst by at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, or at least 90%.

[0107] Partial coke removal step

[0108] The methods provided herein may include a partial coking step. The partial coking step may be carried out at any effective point in the method, such as before the chlorination step. The partial coking step may include contacting a catalyst, such as a spent catalyst, with a partial coking gas stream that may contain oxygen.

[0109] The partial coke removal gas stream includes any combination of one or more inert gases disclosed herein and oxygen, for example, a mixture of nitrogen and oxygen, or air. The partial coke removal gas stream may include mol% in amounts less than any maximum amount disclosed herein or within any range, for example, less than about 5 mol%, or in the range of about 0.1 to about 4 mol%, about 0.1 to about 3 mol%, about 0.5 to about 3 mol%, or about 1 to about 3 mol% of oxygen.

[0110] A partial coke removal gas stream may contain any of the compounds disclosed herein, and any of the compounds disclosed herein may be excluded from the partial coke removal gas stream. For example, a partial coke removal gas stream may be substantially halogen-free (e.g., substantially halogen-free). A partial coke removal gas stream is "substantially halogen-free" if halogen-containing compounds are present at concentrations of less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw. As a further example, a coke removal gas stream may be substantially water-free. A coke removal gas stream is "substantially water-free" if water is present at concentrations of less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw.

[0111] The partial coke removal step can be carried out under any effective conditions (e.g., time, temperature, etc.). The partial coke removal step can be carried out at a partial coke removal temperature within any partial coke removal temperature range disclosed herein, for example, about 150°C (about 302°F) to about 600°C (about 1,112°F) or about 150°C (about 302°F) to about 250°C (about 482°F). The partial coke removal step can be carried out for a time within any range of partial coke removal times disclosed herein, for example, about 1 hour to about 48 hours or about 2 to about 24 hours. The partial coke removal step can be carried out for a sufficient amount of time to reduce the wt% of carbon on the spent catalyst to any range of the weight percentages of carbon disclosed herein, for example, about 0.05 wt% to about 10 wt%, about 0.1 wt% to about 10 wt%, about 0.05 wt% to about 5 wt%, about 0.1 wt% to about 5 wt%, about 1 wt% to 10 wt%, or about 4 wt% to about 5 wt%.

[0112] Pre-drying step

[0113] The methods provided herein may include a pre-drying step. The pre-drying step can be performed at any valid point in the process. In some embodiments, the method includes performing the pre-drying step before the chlorination step.

[0114] The pre-drying step may include contacting the spent catalyst with a pre-drying gas stream. The pre-drying gas stream may include any inert gas disclosed herein, for example, nitrogen. The pre-drying gas stream may contain any of the compounds disclosed herein, and any of the compounds disclosed herein may be removed from the pre-drying gas. For example, the pre-drying gas stream may be substantially free of oxygen-containing compounds. The pre-drying gas stream is "substantially free" of oxygen-containing compounds if they are present at concentrations of less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw.

[0115] The pre-drying step can be carried out under any effective conditions (e.g., time, temperature, pressure, etc.). The pre-drying step can be carried out at a pre-drying temperature within any pre-drying temperature range disclosed herein, for example, about 75°C to about 500°C, about 100°C to about 500°C, about 0°C to about 400°C, about 100°C to about 400°C, about 125°C to about 300°C, or about 180°C to about 280°C. The pre-drying step can be carried out for a time within any range of pre-drying times disclosed herein, for example, about 1 hour to about 96 hours, or about 1 to about 48 hours. In some embodiments, the pre-drying step is carried out for a time sufficient to reduce the moisture content of the catalyst, such as a spent catalyst, to a desired level, for example, to a concentration below any maximum moisture content of a spent catalyst disclosed herein, for example, less than about 4 wt%, or less than about 1 wt%.

[0116] Chlorine purging step

[0117] The methods provided herein may include a chlorine purging step. The chlorine purging step can be performed at any point in the methods provided herein, such as before the carbon combustion step.

[0118] The chlorine purging step may include contacting a catalyst, such as a chlorinated spent catalyst, with a chlorine purging stream. The chlorine purging stream may contain any inert gas disclosed herein, for example, nitrogen. The chlorine purging stream may contain any of the compounds disclosed herein, and any of the compounds disclosed herein may be removed from the chlorine purging stream. For example, the chlorine purging stream may be substantially free of oxygen-containing compounds, for example, oxygen-containing compounds may be present at concentrations of less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw. As a further example, the chlorine purging stream may be substantially free of halogen-containing compounds (substantially halogen-free), for example, halogen-containing compounds may be present at concentrations of less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw.

[0119] The chlorine purging step can be carried out under any effective conditions (e.g., time, temperature, pressure, etc.). In some embodiments, the chlorine purging step is carried out at a chlorine purging temperature within any chlorine purging temperature range disclosed herein, for example, about 0°C to about 400°C, about 15°C to about 350°C, about 15°C to about 300°C, or about 25°C to about 250°C. The chlorine purging step can be carried out for a time within any range of chlorine purging times disclosed herein, for example, about 1 hour to about 96 hours, or about 1 to about 48 hours. The chlorine purging step can be carried out for a time sufficient to reduce the chlorine content of the chlorine purging effluent after contact with a catalyst such as a chlorinated spent catalyst to a chlorine-containing compound below any maximum chlorine content described herein, for example, less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw.

[0120] Fluorine purging step

[0121] The method herein may also include a fluorine purging step. The fluorine purging step can be performed at any point in the method herein, such as after the fluorination step. The fluorine purging step may include contacting a catalyst, such as a coke removal and fluorinated catalyst, with a fluorine purging stream. The fluorine purging stream may include any inert gas disclosed herein, such as nitrogen.

[0122] The fluorine-purging stream may contain any of the compounds disclosed herein, and any of the compounds disclosed herein may be excluded from the fluorine-purging stream. In some embodiments, the fluorine-purging stream is substantially free of oxygen-containing compounds. The fluorine-purging stream is "substantially free" of oxygen-containing compounds if they are present at concentrations of less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw. The fluorine-purging stream may be substantially free of halogen-containing compounds (substantially halogen-free). The fluorine-purging stream is "substantially free" of halogen-containing compounds if they are present at concentrations of less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw.

[0123] The fluorine purging step can be carried out under any effective conditions (e.g., time, temperature, pressure, etc.). In some embodiments, the fluorine purging step is carried out at a fluorine purging temperature within any of the fluorine purging temperature ranges disclosed herein, for example, about 0°C to about 500°C, about 0°C to about 400°C, about 15°C to about 475°C, about 15°C to about 300°C, or about 25°C to about 250°C, or about 25°C to about 450°C, for example, about 450°C. The fluorine purging step can be carried out for a time within any of the fluorine purging time ranges disclosed herein, for example, about 0.25 hours to about 72 hours, or about 1 to about 48 hours. The fluorine purging step can be carried out for a sufficient amount of time after coke removal and contact with the fluorinated catalyst to reduce the fluorine content of the fluorine purging effluent to less than any of the maximum fluorine content described herein, for example, less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw of fluorine-containing compounds.

[0124] Oxygen purge step

[0125] The methods provided herein may include an oxygen purging step. The oxygen purging step can be performed at any point in the methods provided herein, such as after a carbon combustion step or a fluorine purging step.

[0126] The oxygen purging step may include contacting the catalyst with an oxygen purging stream. The oxygen purging stream may contain any inert gas disclosed herein, for example, nitrogen. The oxygen purging stream may contain any of the compounds disclosed herein, and any of the compounds disclosed herein may be removed from the oxygen purging stream. The oxygen purging stream may be substantially free of oxygen-containing compounds, for example, oxygen-containing compounds may be present at concentrations of less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw. The oxygen purging stream may be substantially free of halogen-containing compounds (substantially halogen-free), for example, halogen-containing compounds may be present at concentrations of less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw.

[0127] The oxygen purging step can be carried out under any effective conditions (e.g., time, temperature, pressure, etc.). For example, the oxygen purging step can be carried out at an oxygen purging temperature within any of the oxygen purging temperature ranges disclosed herein, for example, about 0°C to about 400°C, about 15°C to about 350°C, about 25°C to about 325°C, about 25°C to about 300°C, about 15°C to about 300°C, about 25°C to about 260°C, about 25°C to about 250°C, about 0°C to about 600°C, about 15°C to about 550°C, about 25°C to about 500°C, or about 25°C to about 450°C. The oxygen purging step can be carried out for a time within any of the oxygen purging time ranges disclosed herein, for example, about 0.5 hours to about 96 hours, or about 1 to about 48 hours. The oxygen purging step can be carried out for a sufficient amount of time after contacting the catalyst to reduce the oxygen content of the effluent oxygen purge stream to less than any of the maximum oxygen content described herein, for example, less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw of oxygen-containing compound.

[0128] Hydrocarbon treatment step

[0129] The methods provided herein may include a hydrocarbon treatment step. The hydrocarbon treatment step can be carried out at any point in the methods herein, such as before the carbon combustion step, and the hydrocarbon treatment step includes contacting a chlorinated spent catalyst with a hydrocarbon treatment stream containing a hydrocarbon feed.

[0130] The hydrocarbon feed may contain one or more alkanes and / or one or more cycloalkanes, for example, C6-C8 alkanes and / or cycloalkanes.

[0131] The hydrocarbon treatment step can be carried out under any effective conditions (e.g., time, temperature, pressure, etc.). In some embodiments, the hydrocarbon treatment step is carried out at a hydrocarbon treatment temperature within any hydrocarbon treatment temperature range disclosed herein, for example, about 400°C (about 752°F) to about 600°C (about 1,112°F). The hydrocarbon treatment step can be carried out for a time within any range of hydrocarbon treatment times disclosed herein, for example, about 1 to about 48 hours.

[0132] Reduction step

[0133] The methods provided herein may include a reduction step. The reduction step may be carried out at any point in the methods provided herein, such as after the fluorination step. The reduction step may include contacting a regenerated catalyst or a catalyst, such as a coke-removed and fluorinated catalyst, with a reducing gas stream. The reducing gas stream may contain molecular hydrogen. The reducing gas stream may contain more than or within any range of mole percent than any minimum amount disclosed herein, for example, more than about 25 mol% or more than about 75 mol% of molecular hydrogen.

[0134] The reduction step can be carried out under any effective conditions (e.g., time, temperature, pressure, etc.). The reduction of a catalyst, such as a regenerated catalyst, may be carried out at approximately 600°F to approximately 1,200°F, approximately 700°F to approximately 1,100°F, approximately 800°F to approximately 1,000°F, approximately 900°F to approximately 1,000°F, or approximately 950°F to approximately 1,000°F. The reduction of a catalyst, such as a regenerated catalyst, may be carried out in an atmosphere containing at least partially an inert gas (such as nitrogen), hydrogen (H2), or a combination thereof. The reduction step may be carried out at a peak reduction temperature within any peak reduction temperature range disclosed herein, for example, approximately 200°F to approximately 600°C, or approximately 400°F to approximately 600°C. The reduction step may be initiated at an initial reduction temperature that is the same as any oxygen purge temperature disclosed herein, for example, in the range of about 0°C to about 600°C, about 15°C to about 550°C, about 25°C to about 500°C, about 25°C to about 450°C, about 0°C to about 500°C, about 0°C to about 300°C, about 20°C to about 250°C, or about 15°C to about 50°C. The reduction step may be carried out for a time within any range of reduction step times disclosed herein, for example, about 0.5 hours to about 48 hours, about 10 to about 30 hours.

[0135] catalyst

[0136] Catalysts according to the methods provided herein may include any known catalyst, which may include any known catalyst support. The catalyst support may include zeolites, amorphous inorganic oxides, or any combination thereof.

[0137] The catalyst support may include L-zeolite, Y-zeolite, mordenite, omega-zeolite, and / or beta-zeolite. The catalyst support may also include potassium L-zeolite or barium ion-exchange L-zeolite.

[0138] The catalyst may include a binder such as alumina, silica, mixed oxides thereof, or mixtures thereof.

[0139] The catalyst may contain metals such as transition metals. The transition metals may include transition metals from groups 8 to 11. The transition metals may include platinum. The catalyst may contain transition metals in any weight percentage range, for example, about 0.1 wt% to about 10 wt%, or about 0.3 wt% to about 5 wt%.

[0140] The spent catalyst may contain transition metals such as platinum in any weight percentage range. For example, the spent catalyst may contain any amount of transition metal, platinum, ranging from about 0.1 wt% to about 10 wt%, or from about 0.5 wt% to about 2 wt%.

[0141] In some embodiments, the catalyst comprises platinum on KL zeolite. The catalyst may also contain chlorine and fluorine. For example, the catalyst may contain chlorine and / or fluorine in any weight percentage range disclosed herein, e.g., about 0.01 wt% to about 5 wt%, or about 0.3 to about 1.3 wt%, and / or about 0.01 wt% to about 5 wt%, about 0.3 to about 3 wt%, or about 0.3 to about 1.3 wt%, of chlorine. When chlorine and fluorine are present, they may be present in any ratio. For example, the catalyst may have a chlorine:fluorine molar ratio of about 0.5:1 to about 4:1.

[0142] Regenerated / reactivated catalyst

[0143] Similarly, provided herein are catalysts subjected to methods provided herein, for example, reactivated or regenerated catalysts produced by methods herein. In some embodiments, the reactivated or regenerated catalyst contains any amount of iron disclosed herein, for example, less than about 400 ppmw, less than about 300 ppmw, less than about 250 ppmw, about 5 ppmw to about 400 ppmw, about 50 ppmw to about 300 ppmw, or about 50 ppmw to about 250 ppmw of iron. In some embodiments, the reactivated or regenerated catalyst contains any amount of iron disclosed herein, for example, the difference in iron concentration between the reactivated catalyst and the spent catalyst is less than about 1,000 ppmw, less than about 600 ppmw, less than about 400 ppmw, about 5 ppmw to about 600 ppmw, about 5 ppmw to about 500 ppmw, or about 5 ppmw to about 300 ppmw of iron.

[0144] In some embodiments, the reactivated or regenerated catalyst contains any amount of carbon disclosed herein, for example, less than about 1 wt%, less than about 0.5 wt%, about 0.01 wt% to about 1 wt%, about 0.01 wt% to about 0.75 wt%, about 0.01 wt% to about 0.5 wt%, or about 0.02 wt% to about 0.5 wt%.

[0145] In some embodiments, the reactivated or regenerated catalyst contains any amount of chlorine disclosed herein, for example, about 0.01 wt% to about 5 wt%, about 0.05 wt% to about 3 wt%, about 0.05 wt% to about 2.0 wt%, or about 0.3 wt% to about 1.3 wt%.

[0146] In some embodiments, the reactivated or regenerated catalyst contains any amount of fluorine disclosed herein, for example, about 0.01 wt% to about 5 wt%, about 0.05 wt% to about 3 wt%, about 0.01 wt% to about 3 wt%, about 0.1 wt% to about 1.3 wt%, or about 0.15 wt% to about 1.3 wt%.

[0147] In some embodiments, the reactivated or regenerated catalyst contains any amount of fluorine disclosed herein, for example, about 0.01 wt% to about 5 wt%, about 0.05 wt% to about 3 wt%, about 0.01 wt% to about 3 wt%, about 0.1 wt% to about 1.3 wt%, or about 0.15 wt% to about 1.3 wt%.

[0148] In some embodiments, the reactivated or regenerated catalyst is characterized by a TEOR of the fresh reference catalyst within approximately 50°F, within approximately 40°F, within approximately 30°F, or within approximately 20°F. The reactivated or regenerated catalyst may be characterized by a TSOR of the fresh reference catalyst within approximately 50°F, within approximately 40°F, within approximately 30°F, or within approximately 20°F. The reactivated or regenerated catalyst may be characterized by a fouling rate (FR) within any range disclosed herein, for example, approximately 0.01°F / hr to approximately 0.25°F / hr, approximately 0.02°F / hr to approximately 0.2°F / hr, approximately 0.03°F / hr to approximately 0.2°F / hr, or approximately 0.03°F / hr to approximately 0.15°F / hr. The reactivated or regenerated catalyst may be characterized by benzene + toluene selectivity within any selectivity range disclosed herein, for example, about 0.88 to about 0.95, or about 0.89 to about 0.94. The reactivated or regenerated catalyst may be characterized by benzene + toluene selectivity within any selectivity range disclosed herein, for example, from about 0.88, or from about 0.90.

[0149] The methods provided herein also include methods using reactivated and / or regenerated catalysts. In some embodiments, the methods include providing a catalyst to which any one or more of the regeneration / reactivation methods provided herein have been applied, and contacting the catalyst with reactants such as hydrocarbons to produce products such as aromatic products. [Examples]

[0150] The present disclosure is further illustrated by the following embodiments, which should not be construed as limiting the scope of the Art in any way. After reading the description herein, various other aspects, embodiments, modifications and equivalents thereof can be suggested to those skilled in the art without departing from the spirit of the disclosure or the appended claims.

[0151] The weight percentages of Pt, Cl, F, and Fe were determined using X-ray fluorescence (XRF) and are based on the total weight of the aromatization catalyst unless otherwise specified. Carbon (wt%) was determined by a CHNS analyzer (Carlo Erba). Platinum dispersions were determined by CO pulsed chemiadsorption.

[0152] In some of the following examples, the regenerated catalysts were tested for their respective fouling rates (abbreviated as FR, in °F. / hr), which were correlated with their activity by the formula y = FR*t + TSOR, where y is temperature, FR is the fouling rate, t is time, and TSOR is the initial operating start temperature. The FR of the regenerated catalyst samples was determined by plotting the temperature required to maintain a total aromatic yield of 75 wt% over time under standard test conditions, as described later herein. The FR was then determined from the calculated slope fitted to the obtained data. The total flow time was typically 40 hours, and the operating end temperature (abbreviated as TEOR) was also determined.

[0153] In each example, the following standard test procedure was used: The catalyst was crushed and sieved through approximately 20-40 meshes, and 2 cc of the sieved catalyst was placed in a 1 / 4-inch OD stainless steel reaction vessel in a temperature-controlled furnace. After reducing the catalyst under a molecular hydrogen stream, feed streams of aliphatic hydrocarbons (approximately 12 mL / hour) and molecular hydrogen (approximately 65 mL / min) were introduced into the reaction vessel (pressure approximately 65 psig, H2:hydrocarbon molar ratio 2.0:1, liquid-space velocity (LHSV) 6 hr). -1), and catalytic performance data over time were obtained. The aliphatic hydrocarbon feed consisted of approximately 22-32 wt% n-hexane, approximately 4-8 wt% n-heptane, approximately 33-37 wt% C6 isoparaffin, approximately 15-21 wt% C7 isoparaffin, and approximately 6-10 wt% C8 isoparaffin, with the remainder consisting of C6 and C7 olefins, naphthenes, and aromatic compounds. The composition of the reactor effluent was analyzed by gas chromatography to determine the total aromatic compounds and benzene + toluene selectivity.

[0154] In the examples, experiments were conducted using the performance of a fresh aromatization catalyst as a target baseline to demonstrate the effectiveness of various processes and steps in regenerating a spent catalyst. The fresh aromatization catalyst was a Pt / KL-zeolite containing approximately 1 wt% platinum, 0.85 wt% Cl, and 0.70 wt% F, with a BET surface area of ​​approximately 177.5 m². 2 The mercury intrusion pore volume was approximately 0.19 cc / g, and the micropore volume was approximately 0.0615 cc / g. The source of the spent catalyst was fresh catalyst, but it had been deactivated by prolonged use in the aromatization process. Before use in these examples, the spent catalyst was subjected to a mild partial coke removal treatment to remove unreacted hydrocarbons and light carbonaceous deposits from the catalyst.

[0155] Example 1A - Preparation of a regenerating catalyst using fluorine

[0156] For comparison purposes, the following regeneration procedure, including the use of fluorine gas, was performed. Unless otherwise noted, approximately 42 g of spent catalyst was placed in a new metal fixed-bed reactor (including 347 stainless steel), then contacted with a nitrogen gas stream (approximately 1500 mL / min) at approximately 400°F (approximately 204.4°C) for 12 hours, then contacted with a chlorine-containing gas stream containing nitrogen (approximately 1463 mL / min) and chlorine gas (e.g., a blend of 2% Cl2 in N2) (approximately 37 mL / min) at approximately 300°F (approximately 148.9°C) for approximately 3 hours, then contacted with a nitrogen gas stream (1463 mL / min or 1500 mL / min) at approximately 400°F (approximately 204.4°C) for approximately 3 hours, or approximately 12 hours to approximately The samples were then exposed to a coke removal gas stream containing a mixture of air (75 mL / min) and nitrogen (1425 mL / min) at approximately 850°F (approximately 454.4°C) for approximately 44 hours, then exposed to a fluorine-containing gas stream containing nitrogen (approximately 1350 mL / min) and fluorine gas (e.g., a blend of F2 gas in N2) (approximately 147 mL / min) at approximately 300°F (approximately 148.9°C) for approximately 3 hours, and then exposed to a nitrogen gas stream (approximately 1353 mL / min or approximately 1500 mL / min) at approximately 400°F (approximately 204.4°C) for approximately 3 hours, or approximately 12 to 16 hours.

[0157] Example 1B - Preparation of a regenerative catalyst using hydrofluorocarbons in two reactors

[0158] Unless otherwise stated, a certain amount of spent catalyst was introduced into a new metal fixed-bed reactor (containing stainless steel 347) (for example, in some tests, fluorine gas was placed in a container containing stainless steel 347, and hydrofluorocarbons were placed in a container containing stainless steel 321). Next, the spent catalyst was brought into contact with a nitrogen gas stream (approximately 1500 mL / min) at approximately 400°F (approximately 204.4°C) for approximately 12 hours, then into contact with a chlorine-containing gas stream containing nitrogen (approximately 1463 mL / min) and chlorine gas (e.g., 2% Cl2 in N2) (approximately 37 mL / min) at approximately 300°F (approximately 148.9°C) for approximately 3 hours, then into contact with a nitrogen gas stream (approximately 1463 mL / min) at approximately 400°F (approximately 204.4°C) for approximately 3 hours, or approximately 12 to 16 hours, and then into contact with a coke-removing gas stream containing air (approximately 500 mL / min) at approximately 850°F (approximately 454.4°C) for approximately 2 hours to produce a coke-removed catalyst. The temperature was then lowered to 700°F and the air stream was reduced to 200 mL / min. This process was repeated several times to produce a large batch of catalyst from which the chlorided coke had been removed.

[0159] Approximately 45 g of chloride coke removal catalyst was transferred to a reactor (stainless steel 347) with an outer diameter of 1 inch. A flow of 1,1,1,2-tetrafluoroethane (20%) in N2 at a flow rate of approximately 17 mL / min was mixed with a second flow of air at 200 mL / min to create a mixed flow. The coke-removed catalyst was brought into contact with the mixed flow at a pressure of 50 psi for approximately 60 minutes. At the end of the 60-minute contact time, the flow of FREON® fluorinated organic compound / N2 was stopped. A purge with 200 mL / min of air at 730°F and 50 psi was continued for 30 minutes. The temperature was lowered to 500°F, and when it fell below 500°F, the air was stopped and 200 mL / min of N2 was started. The catalyst was cooled to room temperature in the N2 flow.

[0160] Example 1C - Preparation of a regenerative catalyst using hydrofluorocarbons in a single reactor

[0161] Unless otherwise specified, approximately 60 g of spent catalyst was placed in a new metal fixed-bed reactor (including 321 stainless steel), then exposed to a nitrogen gas stream (approximately 1700 mL / min) at approximately 400°F (approximately 204.4°C) for 12 hours, then exposed to a chlorine-containing gas stream containing nitrogen (approximately 1640 mL / min) and chlorine gas (e.g., a blend of 2% Cl2 in N2) (approximately 40 mL / min) at approximately 300°F (approximately 148.9°C) for approximately 3 hours, then exposed to a nitrogen gas stream (approximately 1640 mL / min) at approximately 400°F (approximately 204.4°C) for approximately 3 hours, or approximately 12 to 16 hours, and then exposed to a coke-removing air gas stream (680 mL / min) at approximately 850°F (approximately 454.4°C) for approximately 2 hours.

[0162] The airflow was reduced (approximately 280 mL / min), and a flow of 1,1,1,2-tetrafluoroethane (20%) in N2 at a flow rate of approximately 22 mL / min was mixed with air to create a mixed flow. The coke-removed catalyst was brought into contact with the mixed flow at a pressure of 50 psi for approximately 60 minutes. At the end of the 60-minute contact time, the flow of FREON® fluorinated organic compound / N2 was stopped. A purging with 200 mL / min of air at 730°F and 50 psi was continued for 30 minutes. The temperature was lowered to 500°F, and the air was stopped when the temperature fell below 500°F, and the catalyst was cooled to room temperature in an N2 flow (approximately 500 mL / min).

[0163] Example 1D - Preparation of a regenerative catalyst using hydrofluorocarbons in a single reactor

[0164] Unless otherwise specified, approximately 30 g of used catalyst is placed in a new metal fixed-bed reactor (including 321 stainless steel), then contacted with a nitrogen gas stream (approximately 2363 mL / min) at approximately 400°F (approximately 204.4°C) for 12 hours, then contacted with a chlorine-containing gas stream containing nitrogen (approximately 2333 mL / min) and chlorine gas (e.g., a blend of 2% Cl2 in N2) (approximately 30 mL / min) at approximately 400°F (approximately 148.9°C) for approximately 3 hours, then The material was then exposed to a nitrogen gas stream (approximately 2333 mL / min) at approximately 400°F (approximately 204.4°C) for approximately 3 hours, or approximately 12 to 16 hours. Subsequently, it was exposed to a coke removal gas stream of air (112 mL / min) and nitrogen (2258 mL / min) at approximately 400°F (approximately 204.4°C) for approximately 30 minutes. Subsequently, it was exposed to a coke removal gas stream of air (336 mL / min) and nitrogen (2025 mL / min) at approximately 850°F (approximately 454.4°C) for approximately 3 hours.

[0165] The airflow was continued (approximately 336 mL / min), the nitrogen flow was reduced (approximately 2000 mL / min), and a flow of 1,1,1,2-tetrafluoroethane (5%) in N2 at a flow rate of approximately 25 mL / min was mixed with air to create a mixed flow. The coke-removed catalyst was brought into contact with the mixed flow at a pressure of 50 psi for approximately 60 minutes. At the end of the 60-minute contact time, the flow of FREON® fluorinated organic compound / N2 was stopped. Purge with air (approximately 336 mL / min) and nitrogen (approximately 2000 mL / min) flows was continued for 30 minutes at 700°F and 50 psi. The temperature was lowered to 500°F, and when it fell below 500°F, the air was stopped and the catalyst was cooled to room temperature in the N2 flow.

[0166] Next, the regenerated catalyst was tested to determine its fluorine concentration. Two samples of the regenerated catalyst were collected from a vertically oriented reactor for testing. Specifically, the first sample was collected from the "upper" half of the reactor, and the second sample from the "lower" half. The results of these tests are shown in the table below. [Table 1]

[0167] The results in this table show that the distribution of fluorine in the regenerated catalyst was improved by 1,1,1,2-tetrafluoroethane. In Example 1B, 1,1,1,2-tetrafluoroethane achieved a better distribution than fluorine gas, but it should be noted that the aforementioned treatment with 1,1,1,2-tetrafluoroethane was carried out on spent catalyst that had been treated with the aforementioned chlorine-containing gas stream and coke-removing gas stream and then transferred to a different reactor for treatment with 1,1,1,2-tetrafluoroethane. The transfer between reactors may have exposed the catalyst to moisture, which may have improved the fluorine distribution. If this possibility of moisture exposure had been avoided (for example, by performing each of the three steps described above in a single reactor), the fluorine distribution may not have matched the results described above, but would still likely have surprisingly exceeded the results achieved with fluorine gas. The same trend in fluorine distribution was observed in Examples 1C and 1D. The reactivation process in those examples was carried out in a single reactor and therefore there was no possibility of exposure to moisture.

[0168] Next, a series of aromatization reactions were carried out to test and compare the catalyst adjustment temperature and the selectivity of the reactivated catalyst. Figure 2 shows a plot of catalyst adjustment temperature against time, and Figure 3 shows a plot of aromatic compound selectivity against time for (1) a fresh aromatization catalyst, (2) a used aromatization catalyst, (3) a used aromatization catalyst treated with Cl2 and O2 for 8 hours according to the procedure described above, (4) a used aromatization catalyst treated with Cl2, O2 and fluorine gas as described in Example 1A, and (5) a used aromatization catalyst subjected to the reactivation procedure of Example 1B, which includes treating the catalyst with 1,1,1,2-tetrafluoroethane.

[0169] Figure 4 shows a plot of catalyst adjustment temperature against time, and Figure 5 shows a plot of aromatic compound selectivity against time for (1) an embodiment of a fresh aromatization catalyst, (2) an embodiment of a used aromatization catalyst, and (3) a used aromatization catalyst subjected to the reactivation procedure shown in Example 1C, which includes treating the catalyst with 1,1,1,2-tetrafluoroethane.

[0170] Figure 6 shows a plot of catalyst adjustment temperature against time, and Figure 7 shows a plot of aromatic compound selectivity against time for (1) an embodiment of a fresh aromatic catalyst, (2) an embodiment of a used aromatic catalyst, and (3) a used aromatic catalyst subjected to the reactivation procedure shown in Example 1D, which includes treating the catalyst with 1,1,1,2-tetrafluoroethane.

[0171] The data in Figures 2 to 7 demonstrate that activity substantially equivalent to that of a fresh catalyst can be restored using fluorine gas or FREON® fluorinated organic compounds as the fluoride source.

[0172] Example 2 - Preparation of a regenerative catalyst using hydrofluorocarbons in a downstream reactor

[0173] FREON® fluorinated organic compounds can be used as a fluorinating agent. When using FREON® fluorinated organic compounds, the temperature at which the spent catalyst is brought into contact with the FREON® fluorinated organic compound may be between 700°F and 850°F in order to decompose the FREON® fluorinated organic compound and thereby deposit fluorine on the spent catalyst.

[0174] Laboratory-scale tests included fluoridation using FREON® fluorinated organic compounds in nitrogen containing up to 3% oxygen, with a single pass through the spent catalyst. It was observed that with a single pass, a temperature of at least 850°F was required to decompose the desired portion of the FREON® fluorinated organic compound to deposit fluorine on the catalyst.

[0175] However, the distribution of fluorine across the catalyst bed was generally poor in these laboratory-scale tests, raising concerns regarding furnace / reactor smelting.

[0176] Therefore, lower decomposition temperatures were tested. At lower decomposition temperatures, only a small portion of the FREON® fluorinated organic compound decomposed in a single pass, but the fluorine distribution across the catalyst bed improved. Thus, lower temperatures were advantageous in several respects.

[0177] If this procedure were performed in a commercial unit where all furnaces / reactors are maintained at decomposition temperature, only a portion of the FREON® fluorinated organic compound would decompose, and subsequent contact with each subsequent catalyst bed would deposit a similar portion of Freon in the feed (less than the previous bed). This was thought to cause uneven loading and potentially other problems. There was also concern that the decomposition of the FREON® fluorinated organic compound in the furnace would generate hydrogen fluoride, which could damage the furnace metal or other components of the system. Therefore, proper fluorine loading onto the catalyst would be ensured by keeping the reactor in question at a temperature suitable for decomposing Freon, while maintaining the rest of the plant below the decomposition temperature of the FREON® fluorinated organic compound, and recycling the reactor effluent back into the reactor in question. To demonstrate that Freon or decomposition products in the reactor effluent in question do not affect downstream smelting, the following tests were performed, and the results of one of these tests are shown in the table below. In this test, a fluorine-containing stream (containing FREON® fluorinated organic compounds) was sequentially circulated through reactor 1, furnace tubes, and reactor 2. Reactors 1 and 2 were filled with spent catalyst that had been pre-dried, chlorided, purged, and oxidized as described in Example 1D. The furnace tubes were filled with support balls, which were added to assist in heat transfer.

[0178] [Table 2]

[0179] To mitigate one or more of these concerns, fluorination was performed by maintaining only one furnace / reactor at the decomposition temperature, i.e., the fluorination temperature. By keeping the temperatures of the other furnaces / reactors below the decomposition temperature, the decomposition of the FREON® fluorinated organic compounds was reduced or minimized in the lower-temperature furnaces / reactors, and as a result, a significant portion of the FREON® fluorinated organic compounds would not accumulate in those reactors, if present at all.

[0180] Example 3 - Preparation of a regenerated catalyst using recycled hydrofluorocarbons

[0181] Unless otherwise specified, approximately 61 g of spent catalyst is placed in a metal fixed-bed reactor (including 321 stainless steel), then contacted with a nitrogen gas stream (approximately 9291 mL / min) at approximately 400°F (approximately 204.4°C) for approximately 12 hours, then contacted with a chlorine-containing gas stream containing nitrogen (approximately 9236 mL / min) and chlorine gas (e.g., a blend of 2% Cl2 in N2) (approximately 55 mL / min) at approximately 400°F (approximately 148.9°C) for approximately 3 hours, and then, The material was exposed to a nitrogen gas stream (approximately 9236 mL / min) at approximately 400°F (approximately 204.4°C) for approximately 3 hours, or approximately 12 to 16 hours. Then, it was exposed to a coke removal gas stream of air (444 mL / min) and nitrogen (8847 mL / min) at approximately 400°F (approximately 204.4°C) for approximately 30 minutes. Then, it was exposed to a coke removal gas stream of air (1325 mL / min) and nitrogen (7966 mL / min) at approximately 850°F (approximately 454.4°C) for approximately 3 hours.

[0182] Air (approximately 258 mL / min) and nitrogen (approximately 1522 mL / min) were continuously supplied to the reactor. While the air-nitrogen mixture was flowing into the reactor, the compressor was set to return a total flow rate of 1800 sccm to the reactor. The recycle flow was checked using a flow measurement system installed in the recycle loop (or, in other words, a "feedback loop" such as "feedback loop" 102 shown in Figure 1). Once the recycle flow rate was confirmed, the air-nitrogen mixture feed was stopped, and the reactor system was shut off by the recycle loop. This allowed the system to operate in 100% recycle mode while maintaining a reactor pressure of 50 psig without introducing fresh gas into the reactor. The recycle loop was operated for 10 minutes, and then a flow of 1,1,1,2-tetrafluoroethane (5%) in N2 at a flow rate of 20 mL / min was mixed with the recycle flow at the reactor inlet to generate a mixed flow. The coke-removed catalyst was brought into contact with a mixed flow at 730°F and a pressure of 50 psig. After 10 minutes, a gas bag sample of the reactor effluent was collected as shown in Figure 1. The flow of the FREON® fluorinated organic compound was stopped at 60 minutes, and the compressor was kept running in a recycle loop for 120 minutes. A second sample bag was taken at 180 minutes. The compressor was stopped, and the reactor was purged for 30 minutes with a mixed flow of air (approximately 286 mL / min) and nitrogen (approximately 1714 mL / min) at 730°F and 50 psi. The reactor was cooled to room temperature in a flow of air and nitrogen. [Table 3]

[0183] During reactivation, the FREON® fluorinated organic compound was then transferred back to the target furnace / reactor, i.e., the furnace / reactor maintained at decomposition temperature, along the recycling loop. This procedure may have required passing the FREON® fluorinated organic compound through the recycling loop multiple times, but this procedure is thought to maximize the amount of fluorine that comes into contact with and is placed in the target reactor, i.e., the reactor maintained at decomposition temperature.

[0184] manner

[0185] The following is a list of non-restrictive embodiments.

[0186] Embodiment 1. A modification method comprising, essentially comprising, or consisting of two or more of the following steps:

[0187] (A) A hydrocarbon feed is brought into contact with an aromatization catalyst containing a transition metal and a catalyst support in a metal reactor system under reforming conditions to produce an aromatic product.

[0188] (B) Perform step (A) for a sufficient amount of time to form the spent catalyst.

[0189] (C) Contacting the used catalyst with hydrogen gas to produce a stripped used catalyst,

[0190] (D) The stripped spent catalyst is subjected to carbon combustion at a temperature not exceeding approximately 500°F for a time effective in removing at least a portion of the hydrogen-carbon feed, at least a portion of the aromatic products, or a combination thereof, from the spent catalyst to form a treated spent catalyst.

[0191] (E) The treated spent catalyst is brought into contact with a chlorine-containing stream containing a chlorine-containing compound to produce a chlorinated spent catalyst.

[0192] (F) The chlorinated spent catalyst is subjected to carbon combustion at a temperature not exceeding 900°F for a time effective in improving the dispersion of the transition metal in the chlorinated spent catalyst, thereby forming a redispersed spent catalyst, and

[0193] (G) Contacting the redispersed spent catalyst with a fluorine-containing stream containing a fluorine-containing compound to form a regenerated catalyst, and

[0194] (H) Reducing the regenerated catalyst.

[0195] Embodiment 2. The method as defined in Embodiment 1, wherein the modification method is an in situ process, and for example, steps (A) to (H) are performed in the same reactor system.

[0196] Embodiment 3. The method as defined in Embodiment 1, wherein steps (C) to (H) are performed outside the reactor system of steps (A) to (B), for example, steps (C) to (H) are performed in a metal reactor not located within the reforming reactor system.

[0197] Embodiment 4. A method as defined in any one of Embodiments 1 to 3, further comprising the step of reactivating the catalyst after step (H).

[0198] Embodiment 5. A method for regenerating a spent catalyst, including a transition metal and a catalyst support, in a metal reactor, comprising, or consisting of, any two or more of the following steps:

[0199] (1) The used catalyst is brought into contact with hydrogen gas to produce a stripped used catalyst.

[0200] (2) The stripped spent catalyst is subjected to carbon combustion at a temperature such as not exceeding approximately 500°F for a time effective in removing at least a portion of the hydrogen-carbon feed, at least a portion of the aromatic products, or a combination thereof, from the spent catalyst to form a treated spent catalyst.

[0201] (3) The treated spent catalyst is brought into contact with a chlorine-containing stream containing a chlorine-containing compound to produce a chlorinated spent catalyst.

[0202] (4) The chlorinated spent catalyst is subjected to carbon combustion at a temperature not exceeding 900°F for a time effective in improving the dispersion of the transition metal in the chlorinated spent catalyst, thereby forming a redispersed spent catalyst.

[0203] (5) Contacting the redispersed spent catalyst with a fluorine-containing stream containing a fluorine-containing compound to form a regenerated catalyst, and

[0204] (6) Reducing the regenerated catalyst.

[0205] Embodiment 6. A modification method comprising, essentially comprising, or consisting of two or more of the following steps:

[0206] (A) A hydrocarbon feed is brought into contact with an aromatization catalyst containing a transition metal and a catalyst support in a metal reactor system under reforming conditions to produce an aromatic product.

[0207] (B) Perform step (A) for a sufficient amount of time to form the spent catalyst.

[0208] (C) Contacting the spent catalyst with a chlorine-containing stream containing a chlorine-containing compound to produce a chlorinated spent catalyst, wherein the chlorine-containing compound optionally includes chlorine, chlorinated hydrocarbons, chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), or a combination thereof,

[0209] (D) Contacting the chlorinated spent catalyst with a coke removal gas stream containing oxygen to produce a coke-removed catalyst,

[0210] (E) Contacting the coke-removed catalyst with a fluorine-containing stream containing a fluorine-containing compound, wherein the fluorine-containing compound includes hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), fluorocarbons (FCs), or combinations thereof.

[0211] Embodiment 7. The modification method as defined in Embodiment 6, wherein the modification method is an in situ process, and for example, steps (A) to (E) are performed in the same reactor system.

[0212] Embodiment 8. The method as defined in Embodiment 6, wherein steps (C) to (E) are performed outside the reactor system of steps (A) to (B), for example, steps (C) to (E) are performed in a metal reactor not located within the reforming reactor system.

[0213] Embodiment 9. A method as defined in any of Embodiments 6 to 8, further comprising the step of reactivating the catalyst after step (E).

[0214] Embodiment 10. A method for regenerating a spent catalyst, which includes a transition metal and a catalyst support, in a metal reactor,

[0215] (1) The spent catalyst is brought into contact with a chlorine-containing stream containing a chlorine-containing compound to produce a chlorinated spent catalyst.

[0216] (2) The chlorinated spent catalyst is brought into contact with a coke removal gas stream containing oxygen to produce a coke-removed catalyst, and

[0217] (3) The method comprising or comprising contacting the coke-removed catalyst with a fluorine-containing stream containing a fluorine-containing compound to produce a regenerated catalyst, wherein the fluorine-containing compound includes hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), fluorocarbons (FCs), or combinations thereof, and comprising the contact.

[0218] Embodiment 11. The contact between the spent catalyst and hydrogen gas occurs, at least partially, at a temperature above 25°F, above 100°F, above 200°F, above 300°F, above 400°F, or above 500°F, as defined in any of the preceding embodiments.

[0219] Embodiment 12. The contact between the spent catalyst and hydrogen gas occurs, at least partially, at a temperature of about 300°F to about 800°F, about 400°F to about 800°F, or about 500°F to about 800°F, as defined in any of the preceding embodiments.

[0220] Embodiment 13. The contact between the spent catalyst and hydrogen gas occurs over a period of time of approximately 1 minute to approximately 24 hours, approximately 1 minute to approximately 18 hours, approximately 1 minute to approximately 12 hours, approximately 1 minute to approximately 6 hours, or approximately 1 minute to approximately 2 hours, as defined in any of the preceding embodiments.

[0221] Embodiment 14. A method as defined in any of the prior embodiments, wherein the fluorine-containing compound essentially comprises or consists of hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), fluorocarbons (FCs), or combinations thereof.

[0222] Appearance 15. The method as defined in any of the prior arts, wherein the fluorine-containing stream comprises (i) the fluorine-containing compound and any inert gas disclosed herein, e.g., nitrogen; (ii) the fluorine-containing compound, any inert gas disclosed herein, and air; (iii) the fluorine-containing compound and air; or (iv) the fluorine-containing compound, oxygen (O2), and any inert gas disclosed herein, e.g., nitrogen, and if the fluorine-containing stream comprises the inert gas and air, the inert gas and air may be present in a volume ratio of about 3:1 to about 30:1, about 3:1 to about 20:1, about 3:1 to about 10:1, about 3:1 to about 5:1, or about 4:1; or the volume ratio of the inert gas to oxygen (O2) in the fluorine-containing stream is about 90:10 to about 99.9:0.1, about 95:5 to about 99:1, or about 97:3 (inert gas:oxygen (O2)).

[0223] Embodiment 16. A method as defined in any of the prior embodiments, wherein the contact between the redispersed spent catalyst and the fluorine-containing stream comprises (essentially comprising) circulating the inert gas and injecting the fluorine-containing compound into the circulating inert gas.

[0224] Embodiment 17. The injection of the fluorine-containing compound is achieved, at least partially, by a spraying device configured to disperse the fluorine-containing compound in the circulating inert gas, as defined in any of the preceding embodiments.

[0225] Embodiment 18. A method as defined in any of the preceding embodiments, wherein the contact between the redispersed spent catalyst and the fluorine-containing flow comprises (essentially comprising) circulating the flow containing the inert gas and oxygen (O2), and injecting the fluorine-containing compound into the circulating flow.

[0226] Embodiment 19. A method as defined in any of the preceding embodiments, wherein the oxygen (O2) is present in the circulating flow at a concentration of approximately 0.01 vol% to approximately 10 vol%, approximately 0.01 vol% to approximately 8 vol%, approximately 0.01 vol% to approximately 6 vol%, approximately 0.01 vol% to approximately 4 vol%, approximately 1 vol% to approximately 4 vol%, approximately 2 vol% to approximately 4 vol%, approximately 2.5 vol% to approximately 3.5 vol%, or approximately 3 vol%.

[0227] Embodiment 20. A method as defined in any of the preceding embodiments, wherein (i) the amount of fluorine-containing compound in the fluorine-containing stream, (ii) the duration of contact between the spent catalyst and the fluorine-containing stream, or (iii) a combination thereof, is selected such that about 0.1 wt% to about 2 wt%, about 0.5 wt% to about 1.5 wt%, about 0.5 wt% to about 1 wt%, or about 0.8 wt% to about 1 wt% of fluorine is distributed on the redispersed spent catalyst.

[0228] Embodiment 21. The contact between the spent catalyst and the fluorine-containing stream occurs, at least partially, at a temperature of about 500°F to about 1,000°F, about 600°F to about 1,000°F, about 600°F to about 900°F, about 700°F to about 900°F, or about 700°F to about 850°F, as defined in any of the preceding embodiments.

[0229] Embodiment 22. A method defined in any of the prior embodiments, wherein the fluorine-containing compound includes (or is essentially derived from, or consists of):

[0230] (i) Compounds of formula (I)

[0231] C a H b Cl c F d Equation (I)

[0232] During the ceremony,

[0233] a is 1 to 6,

[0234] b is between 0 and 14.

[0235] c is between 0 and 14.

[0236] d is 1 to 14,

[0237] Optionally, b and / or c are not 0.

[0238] b+c+d=2a+2,

[0239] The compound of formula (I) is optionally substituted;

[0240] (ii) 1,1,1,2-tetrafluoroethane,

[0241] (iii) difluoromethane, or

[0242] (iv) Dichlorodifluoromethane.

[0243] Embodiment 23. A method as defined in any of the preceding embodiments, wherein the fluorine-containing compound comprises 1,1,1,2-tetrafluoroethane.

[0244] Embodiment 24. A method defined in any of the preceding embodiments, for controlling the amount of a fluorine-containing compound in the fluorine-containing stream to obtain a concentration of fluorine [F] on the catalyst that is less than any maximum amount disclosed herein or within any range, for example, less than about 10 wt%, less than about 8 wt%, less than about 6 wt%, less than about 4 wt%, less than about 2 wt%, less than 1.5 wt%, about 0.1 wt% to about 3 wt%, about 1 wt% to about 2 wt%, about 1.25 wt% to about 1.75 wt%, about 0.1 wt% to about 1.0 wt%, about 0.5 wt% to about 1 wt%, or about 0.3 wt% to about 0.8 wt%.

[0245] Embodiment 25. A method as defined in any of the prior embodiments, wherein the fluorine-containing stream is substantially free of oxygen-containing compounds and / or chlorine-containing compounds that do not contain fluorine atoms, and is, for example, less than about 100 ppmw, about 50 ppmw, or less than about 25 ppmw.

[0246] Embodiment 26. Controlling the amount of fluorine-containing compound in the fluorine-containing stream to a concentration below any maximum amount or within any range disclosed herein, for example, less than about 50,000 ppmv, in the range of about 5 to about 25,000 ppmv, in the range of about 10 to about 25,000 ppmv, in the range of about 50 to about 25,000 ppmv, in the range of about 5,000 to about 25,000 ppmv, in the range of about 50 to about 20,000 ppmv, and in the range of about 50 to about 15,000 ppmv. A method, as defined in any of the preceding embodiments, for obtaining fluorine (F) or a fluorine-containing compound in the range of pmv, approximately 50 to approximately 10,000 ppmv, approximately 50 to approximately 5,000 ppmv, approximately 50 to approximately 2,500 ppmv, approximately 50 to approximately 1,000 ppmv, approximately 500 to approximately 1,000 ppmv, approximately 600 to approximately 900 ppmv, approximately 700 to approximately 800 ppmv, or approximately 750 ppmv.

[0247] Embodiment 27. A method as defined in any of the preceding embodiments, wherein the fluorination step is carried out at (i) a fluorination temperature within any fluorination temperature range disclosed herein, for example, about 0°C to about 600°C, about 10°C to about 550°C, about 20°C to about 450°C, about 0°C to about 300°C, about 20°C to about 250°C, or about 15°C to about 50°C, and (ii) a fluorination pressure of atmospheric pressure to about 15 bar, atmospheric pressure to about 10 bar, atmospheric pressure to about 7 bar, about 0.5 bar to about 10 bar, about 0.5 bar to about 5 bar, about 0.5 bar to about 1.5 bar, about 1 bar, about 2 bar to about 10 bar, about 2 bar to about 5 bar, or about 2 bar.

[0248] Embodiment 28. A method as defined in any of the prior embodiments, wherein the fluorination step is carried out for a time within any range of fluorination times disclosed herein, for example, about 0.5 hours to about 96 hours, about 0.5 hours to about 72 hours, about 0.5 hours to about 48 hours, about 0.5 hours to about 12 hours, about 0.5 hours to about 8 hours, about 0.1 hours to about 96 hours, about 0.1 hours to about 72 hours, about 0.1 hours to about 48 hours, about 0.1 hours to about 12 hours, or about 0.1 hours to about 8 hours.

[0249] Embodiment 29. A method as defined in any of the prior embodiments, wherein the chlorine-containing stream comprises (or essentially consists of) the chlorine-containing compound and any inert gas disclosed herein, such as nitrogen.

[0250] Embodiment 30. A method as defined in any of the prior embodiments, further comprising circulating the inert gas and injecting the chlorine-containing compound into the circulating inert gas.

[0251] Embodiment 31. The injection of the chlorine-containing compound is achieved, at least partially, by a spraying device configured to disperse the chlorine-containing compound in the circulating inert gas, as defined in any of the preceding embodiments.

[0252] Embodiment 32. A method as defined in any of the preceding embodiments, wherein the chlorine-containing stream contains (or is essentially composed of) chlorine gas (Cl2) and nitrogen.

[0253] Embodiment 33. Controlling the amount of chlorine-containing compound in the chlorine-containing stream to a concentration less than any maximum amount or within any range disclosed herein, for example, less than about 50,000 ppmv, in the range of about 5 to about 25,000 ppmv, in the range of about 10 to about 25,000 ppmv, in the range of about 50 to about 25,000 ppmv, in the range of about 50 to about 20,000 ppmv, in the range of about 50 to about 15,000 ppmv, and about 50 to about 10 A method, as defined in any of the preceding embodiments, for obtaining chlorine (Cl) or a chlorine-containing compound in the range of 1,000 ppmv, about 50 to about 5,000 ppmv, about 50 to about 2,500 ppmv, about 50 to about 1,000 ppmv, about 50 to about 500 ppmv, about 50 to about 100 ppmv, about 100 to about 750 ppmv, or about 500 to about 600 ppmv.

[0254] Embodiment 34. A method as defined in any of the preceding embodiments, wherein (i) the amount of chlorine or chlorine-containing compound in the chlorine-containing stream, (ii) the duration of contact between the treated spent catalyst and the chlorine-containing stream, or (iii) a combination thereof, is controlled so that about 0.1 wt% to about 2 wt%, about 0.5 wt% to about 1.5 wt%, about 0.5 wt% to about 1 wt%, or about 0.6 wt% to about 1 wt% of chlorine or the chlorine-containing compound is distributed on the treated spent catalyst.

[0255] Embodiment 35. A method as defined in any of the preceding embodiments, wherein the chlorine-containing stream is substantially free of oxygen-containing compounds and / or fluorine-containing compounds, for example, less than about 100 ppmw.

[0256] Embodiment 36. A method as defined in any of the preceding embodiments, wherein the chlorination step is performed at a chlorination temperature within any chlorination temperature range disclosed herein, for example, about 0°F to about 600°F, about 100°F to about 600°F, about 200°F to about 600°F, about 3000°F to about 600°F, about 400°F to about 600°F, about 400°F to about 500°F, about 400°F to about 450°F, about 300°F to about 500°F, about 350°F to about 500°F, or about 350°F to about 450°F.

[0257] Embodiment 37. A method as defined in any of the prior embodiments, wherein the chlorination step is carried out for a time within any range of chlorination times disclosed herein, for example, about 0.5 hours to about 72 hours, about 0.75 hours to about 60 hours, about 1 to about 48 hours, about 1 to about 12 hours, about 2 to about 8 hours, about 0.10 hours to about 72 hours, about 0.50 hours to about 60 hours, about 0.5 to about 48 hours, about 0.5 to about 12 hours, or about 1 to about 8 hours.

[0258] Embodiment 38. A method as defined in any of the prior embodiments, wherein the coke removal gas flow includes (or essentially consists of, or comprises) any combination of one or more inert gases disclosed herein and oxygen, for example, a mixture of nitrogen and oxygen, air, or a mixture of air and nitrogen.

[0259] Embodiment 39. A method as defined in any of the preceding embodiments, wherein the coke removal gas flow contains oxygen in a mol% amount less than any maximum amount disclosed herein or within any range, for example, less than about 5 mol%, in the range of about 0.1 to about 10 mol%, in the range of about 0.1 to about 8 mol%, in the range of about 0.1 to about 5 mol%, in the range of about 0.5 to about 3 mol%, or in the range of about 0.5 to about 6 mol%.

[0260] Embodiment 40. A method as defined in any of the preceding embodiments, wherein the coke removal gas flow is substantially free of halogen-containing compounds such as added halogen-containing compounds (e.g., substantially halogen-free, substantially chlorine-free), and for example, less than about 100 ppmw.

[0261] Embodiment 41. A method as defined in any of the preceding embodiments, wherein the coke removal gas flow is substantially free of water (e.g., added water) and, for example, less than about 100 ppmw.

[0262] Embodiment 42. A method as defined in any of the preceding embodiments, wherein the carbon combustion temperature of the stripped spent catalyst is approximately 300°F to approximately 600°F, approximately 350°F to approximately 550°F, approximately 350°F to approximately 500°F, or approximately 400°F to approximately 475°F.

[0263] Embodiment 43. A method as defined in any of the preceding embodiments, wherein the carbon combustion of the stripped spent catalyst occurs over a period of time of about 1 minute to about 24 hours, about 1 minute to about 18 hours, about 1 minute to about 12 hours, about 1 minute to about 6 hours, or about 1 minute to about 2 hours.

[0264] Embodiment 44. A method as defined in any of the preceding embodiments, wherein the carbon combustion of the stripped spent catalyst removes at least 90 wt%, at least 95 wt%, at least 99 wt%, or 100 wt% of the hydrocarbon feed from the spent catalyst.

[0265] Embodiment 45. A method as defined in any of the preceding embodiments, wherein the carbon combustion of the stripped spent catalyst removes at least 90 wt%, at least 95 wt%, at least 99 wt%, or 100 wt% of the aromatic products from the spent catalyst.

[0266] Embodiment 46. A method as defined in any of the preceding embodiments, wherein a certain amount of soft coke is absorbed and / or adsorbed by the spent catalyst, and the carbon combustion of the stripped spent catalyst reduces the amount of soft coke absorbed and / or adsorbed by the spent catalyst.

[0267] Embodiment 47. A method as defined in any of the preceding embodiments, wherein the carbon combustion temperature of the chlorinated spent catalyst is approximately 500°F to approximately 1,200°F, approximately 500°F to approximately 1,100°F, approximately 500°F to approximately 1,000°F, approximately 600°F to approximately 1,000°F, approximately 700°F to approximately 1,000°F, approximately 700°F to approximately 900°F, approximately 800°F to approximately 900°F, or approximately 850°F.

[0268] Embodiment 48. A method as defined in any of the preceding embodiments, wherein the carbon combustion of the chlorinated spent catalyst occurs over a period of time of approximately 1 minute to approximately 24 hours, approximately 1 minute to approximately 18 hours, approximately 1 minute to approximately 12 hours, approximately 1 minute to approximately 6 hours, or approximately 1 minute to approximately 2 hours.

[0269] Embodiment 49. A method as defined in any of the prior embodiments, wherein the carbon combustion of the chlorinated catalyst improves the dispersion of the transition metal in the chlorinated spent catalyst by at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, or at least 90%.

[0270] Embodiment 50. A method as defined in any of the preceding embodiments, wherein the carbon combustion temperature of the chlorinated spent catalyst is approximately 500°F to approximately 1,200°F, approximately 500°F to approximately 1,100°F, approximately 500°F to approximately 1,000°F, approximately 600°F to approximately 1,000°F, approximately 700°F to approximately 1,000°F, approximately 700°F to approximately 900°F, approximately 800°F to approximately 900°F, or approximately 850°F.

[0271] Embodiment 51. A method as defined in any of the preceding embodiments, wherein the carbon combustion of the chlorinated spent catalyst occurs over a period of time of approximately 1 minute to approximately 24 hours, approximately 1 minute to approximately 18 hours, approximately 1 minute to approximately 12 hours, approximately 1 minute to approximately 6 hours, or approximately 1 minute to approximately 2 hours.

[0272] Embodiment 52. A method as defined in any of the prior embodiments, wherein the carbon combustion of the chlorinated catalyst improves the dispersion of the transition metal in the chlorinated spent catalyst by at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, or at least 90%.

[0273] Embodiment 53. A method as defined in any of the preceding embodiments, wherein the carbon combustion step is carried out at a peak coke removal temperature within any peak coke removal temperature range disclosed herein, for example, about 100°C to about 700°C, about 125°C to about 650°C, about 150°C to about 600°C, about 200°C to about 500°C, or about 350°C to about 450°C.

[0274] Embodiment 54. A method as defined in any of the preceding embodiments, wherein the carbon combustion step is initiated at an initial coke removal temperature that is the same as any chlorine purge temperature disclosed herein, for example, about 0°C to about 300°C, about 20°C to about 275°C, about 20°C to about 250°C, or about 50°C to about 200°C.

[0275] Aspect 55. The carbon combustion step is carried out for a time within any range of the coke removal times disclosed herein, for example, from about 0.5 hours to about 120 hours, from about 0.75 hours to about 108 hours, from about 1 hour to about 96 hours, from about 1 to about 72 hours, from about 12 to about 48 hours, or from about 1 to about 6 hours, in the method defined in any of the preceding aspects.

[0276] Aspect 56. The carbon combustion step is carried out for a time sufficient to reduce the wt% of carbon on the chlorinated used catalyst to less than any maximum weight percentage of carbon disclosed herein, for example, less than about 1 wt%, less than about 0.5 wt%, or less than about 0.2 wt%, in the method defined in any of the preceding aspects.

[0277] Aspect 57. The method further includes a partial coke removal step prior to the chlorination step, the partial coke removal step including contacting the used catalyst with a partial coke removal gas stream containing oxygen, in the method defined in any of the preceding aspects.

[0278] Aspect 58. The partial coke removal gas stream contains (or consists essentially of, or consists of) any combination of inert gas(es) and oxygen disclosed herein, for example, a mixture of nitrogen and oxygen, or air, in the method defined in any of the preceding aspects.

[0279] Aspect 59. The partial coke removal gas stream contains oxygen less than any maximum amount or within any range of mol% disclosed herein, for example, less than about 5 mol%, or in the range of about 0.5 to about 3 mol%, about 1 to about 3 mol%, about 0.1 to about 4 mol%, or about 0.1 to about 3 mol%, in the method defined in any of the preceding aspects.

[0280] Aspect 60. The partial coke removal gas stream is substantially free of halogen-containing compounds (e.g., substantially halogen-free), for example, less than about 100 ppmw, in the method defined in any of the preceding aspects.

[0281] Embodiment 61. A method as defined in any of the preceding embodiments, wherein the coke removal gas flow is substantially water-free, for example, less than about 100 ppmw.

[0282] Embodiment 62. A method as defined in any of the preceding embodiments, wherein the partial coke removal step is performed at a partial coke removal temperature within any partial coke removal temperature range disclosed herein, for example, about 150°C to about 600°C, or about 150°C to about 250°C.

[0283] Embodiment 63. A method as defined in any of the prior embodiments, wherein the partial coke removal step is performed for a time within any range of the partial coke removal times disclosed herein, for example, about 1 hour to about 48 hours, or about 2 to about 24 hours.

[0284] Embodiment 64. A method as defined in any of the preceding embodiments, wherein the partial coke removal step is performed for a time sufficient to reduce the wt% of carbon on the spent catalyst to any range of the weight percentages of carbon disclosed herein, for example, about 0.05 wt% to about 10 wt%, about 0.1 wt% to about 10 wt%, about 0.05 wt% to about 5 wt%, about 0.1 wt% to about 5 wt%, about 1 wt% to 10 wt%, or about 4 wt% to about 5 wt%.

[0285] Embodiment 65. The method as defined in any of the prior embodiments, further comprising a pre-drying step prior to the chlorination step, wherein the pre-drying step comprises contacting the spent catalyst with a pre-drying gas stream containing (or essentially consisting of) any inert gas disclosed herein, such as nitrogen.

[0286] Embodiment 66. A method as defined in any of the preceding embodiments, wherein the pre-drying gas stream is substantially free of oxygen-containing compounds, for example, less than about 100 ppmw.

[0287] Embodiment 67. A method as defined in any of the preceding embodiments, wherein the pre-drying step is performed at a pre-drying temperature within any pre-drying temperature range disclosed herein, for example, about 75°C to about 500°C, about 100°C to about 500°C, about 0°C to about 400°C, about 100°C to about 400°C, about 125°C to about 300°C, or about 180°C to about 280°C.

[0288] Embodiment 68. A method as defined in any of the prior embodiments, wherein the pre-drying step is performed for a time within any range of pre-drying times disclosed herein, for example, about 1 hour to about 96 hours, or about 1 to about 48 hours.

[0289] Embodiment 69. A method as defined in any of the prior embodiments, wherein the pre-drying step is performed for a time sufficient to reduce the moisture content of the spent catalyst to less than any maximum moisture content of the spent catalyst disclosed herein, for example, less than about 4 wt% or less than about 1 wt%.

[0290] Embodiment 70. The method as defined in any of the prior embodiments, further comprising a chlorine purging step prior to the carbon combustion step, wherein the chlorine purging step comprises contacting the chlorinated spent catalyst with a chlorine purging stream containing (or essentially consisting of) any inert gas disclosed herein, such as nitrogen.

[0291] Embodiment 71. A method as defined in any of the prior embodiments, wherein the chlorine purge stream is substantially free of oxygen-containing compounds, for example, less than about 100 ppmw.

[0292] Embodiment 72. A method as defined in any of the preceding embodiments, wherein the chlorine purge stream is substantially free of halogen-containing compounds (substantially halogen-free), for example, less than about 100 ppmw.

[0293] Embodiment 73. A method as defined in any of the prior embodiments, wherein the chlorine purging step is performed at a chlorine purging temperature within any chlorine purging temperature range disclosed herein, for example, about 0°C to about 400°C, about 15°C to about 350°C, about 15°C to about 300°C, or about 25°C to about 250°C.

[0294] Embodiment 74. A method as defined in any of the prior embodiments, wherein the chlorine purging step is performed for a time within any range of the chlorine purging times disclosed herein, for example, about 1 hour to about 96 hours, or about 1 to about 48 hours.

[0295] Embodiment 75. A method as defined in any of the preceding embodiments, wherein the chlorine purging step is performed for a sufficient amount of time after contact with the chlorinated spent catalyst to reduce the chlorine content of the chlorine purging effluent to less than any maximum chlorine content described herein, for example, less than about 100 ppmw of chlorine-containing compounds.

[0296] Embodiment 76. The method as defined in any of the prior embodiments, further comprising a fluorine purging step after the fluorination step, wherein the fluorine purging step comprises contacting the coke removal and fluorinated catalyst with a fluorine purging stream containing (or essentially consisting of) any inert gas disclosed herein, such as nitrogen.

[0297] Embodiment 77. A method as defined in any of the prior embodiments, wherein the fluorine purging stream is substantially free of oxygen-containing compounds, for example, less than about 100 ppmw.

[0298] Embodiment 78. A method as defined in any of the prior embodiments, wherein the fluorine purging stream is substantially free of halogen-containing compounds (substantially halogen-free), for example, less than about 100 ppmw.

[0299] Aspect 79. The method according to any of the preceding aspects, wherein the fluorine purge step is carried out at a fluorine purge temperature within any of the fluorine purge temperature ranges disclosed herein, for example, about 0 °C to about 500 °C, about 0 °C to about 400 °C, about 15 °C to about 475 °C, about 15 °C to about 300 °C, or about 25 °C to about 250 °C, or about 25 °C to about 450 °C, for example about 450 °C.

[0300] Aspect 80. The method according to any of the preceding aspects, wherein the fluorine purge step is carried out for a time within any of the ranges of fluorine purge times disclosed herein, for example, about 0.25 hours to about 72 hours, or about 1 to about 48 hours.

[0301] Aspect 81. The method according to any of the preceding aspects, wherein the fluorine purge step is carried out for a time sufficient to reduce the fluorine content of the effluent fluorine purge effluent stream to less than any of the maximum fluorine contents described herein, for example, less than about 100 ppmw of fluorine-containing compounds, after contacting the coked catalyst with the fluorinated catalyst.

[0302] Aspect 82. The method according to any of the preceding aspects, further comprising an oxygen purge step after the carbon combustion step or the fluorine purge step, the oxygen purge step comprising contacting the catalyst with an oxygen purge stream comprising (or consisting essentially of, or consisting of) any of the inert gases disclosed herein, for example nitrogen.

[0303] Aspect 83. The method according to any of the preceding aspects, wherein the oxygen purge stream is substantially free of oxygen-containing compounds, for example, less than about 100 ppmw.

[0304] Aspect 84. The method according to any of the preceding aspects, wherein the oxygen purge stream is substantially free of halogen-containing compounds (substantially halogen-free), for example, less than about 100 ppmw.

[0305] Embodiment 85. A method as defined in any of the preceding embodiments, wherein the oxygen purging step is performed at an oxygen purging temperature within any of the oxygen purging temperature ranges disclosed herein, for example, about 0°C to about 400°C, about 15°C to about 350°C, about 25°C to about 325°C, about 25°C to about 300°C, about 15°C to about 300°C, about 25°C to about 260°C, about 25°C to about 250°C, about 0°C to about 600°C, about 15°C to about 550°C, about 25°C to about 500°C, or about 25°C to about 450°C.

[0306] Embodiment 86. A method as defined in any of the prior embodiments, wherein the oxygen purging step is performed for a time within any range of the oxygen purging times disclosed herein, for example, about 0.5 hours to about 96 hours, or about 1 to about 48 hours.

[0307] Embodiment 87. A method as defined in any of the prior embodiments, wherein the oxygen purging step is performed for a sufficient amount of time to reduce the oxygen content of the oxygen purging effluent flowing out after contact with the catalyst to less than any maximum oxygen content described herein, for example, less than about 100 ppmw of the oxygen-containing compound.

[0308] Embodiment 88. A method as defined in any of the preceding embodiments, wherein the method further comprises a hydrocarbon treatment step prior to the carbon combustion step, the hydrocarbon treatment step comprising contacting the chlorinated spent catalyst with a hydrocarbon treatment stream containing a hydrocarbon feed.

[0309] Embodiment 89. A method as defined in any of the preceding embodiments, wherein the hydrocarbon feed comprises (or essentially consists of) C6-C8 alkanes and / or cycloalkanes.

[0310] Embodiment 90. A method as defined in any of the prior embodiments, wherein the hydrocarbon treatment step is performed at a hydrocarbon treatment temperature within any hydrocarbon treatment temperature range disclosed herein, for example, about 400°C to about 600°C.

[0311] Embodiment 91. A method as defined in any of the prior embodiments, wherein the hydrocarbon treatment step is performed for a time within any range of hydrocarbon treatment times disclosed herein, for example, about 1 to about 48 hours.

[0312] Embodiment 92. A method as defined in any of the preceding embodiments, further comprising a reduction step after the fluorination step.

[0313] Embodiment 93. A method as defined in any of the preceding embodiments, wherein the reduction step comprises contacting the regenerated catalyst, the fluorinated spent catalyst, or the coke removal and fluorinated catalyst with a reducing gas stream containing (or essentially consisting of) molecular hydrogen.

[0314] Embodiment 94. A method as defined in any of the preceding embodiments, wherein the reduction of the fluorinated spent catalyst or the regenerated catalyst occurs at a temperature of about 600°F to about 1,200°F, about 700°F to about 1,100°F, about 800°F to about 1,000°F, about 900°F to about 1,000°F, or about 950°F to about 1,000°F.

[0315] Embodiment 95. A method as defined in any of the preceding embodiments, wherein the reduction of the fluorinated spent catalyst or the regenerated catalyst is carried out in an atmosphere containing (essentially consisting of or comprising) at least partially an inert gas (such as nitrogen), hydrogen (H2), or a combination thereof, and optionally the volume ratio of the inert gas to the hydrogen (H2) is about 10:90 to about 90:10, about 20:80 to about 80:20, or about 40:60 to about 60:40.

[0316] Embodiment 96. A method as defined in any of the prior embodiments, wherein the reducing gas stream contains more than any minimum amount disclosed herein or within any range of mole percent, for example, more than about 25 mol% or more than about 75 mol% of molecular hydrogen.

[0317] Embodiment 97. A method as defined in any of the prior embodiments, wherein the reduction step is performed at a peak reduction temperature within any peak reduction temperature range disclosed herein, for example, about 200°C to about 600°C, or about 400°C to about 600°C.

[0318] Embodiment 98. A method as defined in any of the preceding embodiments, wherein the reduction step is initiated at an initial reduction temperature that is the same as any oxygen purging temperature disclosed herein, for example, in the range of about 0°C to about 600°C, about 15°C to about 550°C, about 25°C to about 500°C, about 25°C to about 450°C, about 0°C to about 500°C, about 0°C to about 300°C, about 20°C to about 250°C, or about 15°C to about 50°C.

[0319] Embodiment 99. A method as defined in any of the prior embodiments, wherein the reduction step is performed for a time within any range of the reduction step times disclosed herein, for example, about 0.5 hours to about 48 hours, or about 10 hours to about 30 hours.

[0320] Embodiment 100. A method as defined in any of the prior embodiments, wherein the catalyst support comprises (or essentially consists of) a zeolite, an amorphous inorganic oxide, or any combination thereof.

[0321] Embodiment 101. A method as defined in any of the prior embodiments, wherein the catalyst support comprises (or is essentially derived from, or consists of) L-zeolite, Y-zeolite, mordenite, omega-zeolite, and / or beta-zeolite.

[0322] Embodiment 102. A method as defined in any of the prior embodiments, wherein the catalyst support comprises (or is essentially derived from, or consists of) potassium L-zeolite or barium ion-exchange L-zeolite.

[0323] Embodiment 103. A method as defined in any of the prior embodiments, wherein the catalyst support comprises (or essentially consists of, or comprises) a binder comprising alumina, silica, mixed oxides thereof, or mixtures thereof.

[0324] Embodiment 104. A method defined in any of the preceding embodiments, wherein the transition metal includes transition metals of groups 8 to 11.

[0325] Embodiment 105. A method as defined in any of the prior embodiments, wherein the transition metal includes (or is essentially made from or consists of) platinum.

[0326] Embodiment 106. A method as defined in any of the preceding embodiments, wherein the catalyst comprises a transition metal in any weight percent range disclosed herein, for example, about 0.1 wt% to about 10 wt%, or about 0.3 wt% to about 5 wt%.

[0327] Embodiment 107. A method as defined in any of the prior embodiments, wherein the spent catalyst comprises platinum in any weight percentage range disclosed herein, for example, about 0.1 wt% to about 10 wt%, or about 0.5 wt% to about 2 wt%.

[0328] Embodiment 108. A method as defined in any of the prior embodiments, wherein the catalyst comprises (or essentially consists of or comprises) platinum on a KL zeolite.

[0329] Embodiment 109. A method as defined in any of the prior embodiments, wherein the catalyst further comprises chlorine and fluorine.

[0330] Embodiment 110. A method as defined in any of the preceding embodiments, wherein the catalyst comprises chlorine in any weight percentage range disclosed herein and / or fluorine in any weight percentage range, for example, about 0.01 wt% to about 5 wt%, or about 0.3 to about 1.3 wt%, and / or about 0.01 wt% to about 5 wt%, about 0.3 wt% to about 3 wt%, or about 0.3 to about 1.3 wt%, of chlorine.

[0331] Embodiment 111. A method as defined in any of the prior embodiments, wherein the catalyst comprises any molar ratio disclosed herein, for example, chlorine:fluorine in a ratio of about 0.5:1 to about 4:1.

[0332] Embodiment 112. A method as defined in any of the preceding embodiments, wherein the chlorine-containing compound includes (or is essentially made from or consists of) hydrochloric acid, chlorine gas (Cl2), carbon tetrachloride, tetrachloroethylene, chlorobenzene, methyl chloride, methylene chloride, chloroform, allyl chloride, trichloroethylene, chloramine, chlorine oxide, chlorine acid, chlorine dioxide, dichlorine monoxide, dichlorine heptoxide, chloric acid, perchloric acid, ammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, methyltriethylammonium chloride, or any combination thereof.

[0333] Embodiment 113. A method as defined in any of the prior embodiments, wherein the chlorine-containing compound contains (or is essentially derived from or consists of) chlorine gas (Cl2).

[0334] Embodiment 114. A reactivated or regenerated catalyst produced by a method defined in any one of the preceding embodiments.

[0335] Embodiment 115. A reactivated or regenerated catalyst as defined in any of the preceding embodiments, wherein the reactivated or regenerated catalyst comprises any amount of iron disclosed herein, for example, less than about 400 ppmw, less than about 300 ppmw, less than about 250 ppmw, about 5 ppmw to about 400 ppmw, about 50 ppmw to about 300 ppmw, or about 50 ppmw to about 250 ppmw of iron.

[0336] Embodiment 116. A reactivated or regenerated catalyst as defined in any of the preceding embodiments, wherein the reactivated or regenerated catalyst contains any amount of carbon disclosed herein, for example, less than about 1 wt%, less than about 0.5 wt%, about 0.01 wt% to about 1 wt%, about 0.01 wt% to about 0.75 wt%, about 0.01 wt% to about 0.5 wt%, or about 0.02 wt% to about 0.5 wt%.

[0337] Embodiment 117. A reactivated or regenerated catalyst as defined in any one of the preceding embodiments, wherein the reactivated or regenerated catalyst contains any amount of chlorine disclosed herein, for example, about 0.01 wt% to about 5 wt%, about 0.05 wt% to about 3 wt%, about 0.05 wt% to about 2.0 wt%, or about 0.3 wt% to about 1.3 wt% of chlorine.

[0338] Embodiment 118. A reactivated or regenerated catalyst as defined in any one of the preceding embodiments, wherein the reactivated or regenerated catalyst contains any amount of fluorine disclosed herein, for example, about 0.01 wt% to about 5 wt%, about 0.05 wt% to about 3 wt%, about 0.01 wt% to about 3 wt%, about 0.1 wt% to about 1.3 wt%, or about 0.15 wt% to about 1.3 wt% of fluorine.

[0339] Embodiment 119. A reactivated or regenerated catalyst as defined in any one of the preceding embodiments, characterized by a TEOR of a fresh reference catalyst within approximately 50°F, within approximately 40°F, within approximately 30°F, or within approximately 20°F.

[0340] Embodiment 120. A reactivated or regenerated catalyst as defined in any one of the preceding embodiments, wherein the reactivated or regenerated catalyst is characterized by the TSOR of a fresh reference catalyst at a temperature of about 50°F, about 40°F, about 30°F, or about 20°F.

[0341] Embodiment 121. A reactivated or regenerated catalyst as defined in any one of the preceding embodiments, characterized by a fouling rate (FR) within any range disclosed herein, for example, about 0.01°F / hr to about 0.25°F / hr, about 0.02°F / hr to about 0.2°F / hr, about 0.03°F / hr to about 0.2°F / hr, or about 0.03°F / hr to about 0.15°F / hr.

[0342] Embodiment 122. A reactivated or regenerated catalyst as defined in any one of the prior embodiments, characterized by a benzene + toluene selectivity within any selectivity range disclosed herein, for example, about 0.88 to about 0.95, or about 0.89 to about 0.94, or greater than 0.88, or greater than 0.90.

[0343] Embodiment 123. A method or catalyst as defined in any of the prior embodiments, wherein the metal reactor (or metal reactor system) includes (or is essentially made from, or consists of) stainless steel, for example, 347SS or 321SS.

[0344] Embodiment 124. A method or catalyst as defined in any of the prior embodiments, comprising, or comprising, recovering at least a portion of the fluorine-containing flow in order to generate a recovered fluorine-containing flow, wherein the recovery is optionally performed after the contact between the coked catalyst and the fluorine-containing flow, and the recovery includes contacting the coked catalyst with the recovered fluorine-containing flow.

[0345] Embodiment 125. A method or catalyst as defined in any of the preceding embodiments, wherein the concentration of fluorine in the regenerated catalyst is about 0.15 wt% to about 1.2 wt%, or about 0.2 wt% to about 1.2 wt%.

[0346] Embodiment 126. A method or catalyst as defined in any of the preceding embodiments, wherein the fluorine concentration gradient in the regenerated catalyst is 60% or less, 50% or less, 40% or less, 30% or less, 20% or less, or 10% or less.

[0347] Embodiment 127. A method for producing a product, comprising, or comprising, (A) providing a reactivated or regenerated catalyst, for example, one of the prior embodiments, and (B) contacting a hydrocarbon with the reactivated / regenerated catalyst to produce a product such as an aromatic product.

[0348] Embodiment 128. A method as defined in any of the prior embodiments, wherein the contact between the hydrocarbon and the reactivated / regenerated catalyst is carried out for a time sufficient to produce a second spent catalyst, and the method further comprises subjecting the second spent catalyst to a method as defined in any of the prior embodiments.

[0349] Embodiment 129. (I) A method of contacting a spent catalyst with a fluorine-containing flow, or (II) A method defined in either of the preceding embodiments, wherein the contact between the spent catalyst, such as the redispersed spent catalyst, and the fluorine-containing flow essentially comprises, or consists of:

[0350] (a) To provide two or more reactors that are in fluid communication with each other, the two or more reactors (e.g., 2 to 10 or more reactors) connected in series, so that a fluorine-containing flow can be (i) injected at an injection point selected from one or more injection points, (ii) continuously circulated to each of the two or more reactors downstream of the injection point, (iii) returned to a first reactor of the two or more reactors, and optionally (iv) continuously recirculated to each of the two or more reactors, each of the two or more reactors including a storage container for the spent catalyst,

[0351] (b) Heating one of the two or more reactors to a temperature above the fluorination temperature which is effective in at least partially decomposing the fluorine-containing compound in the fluorine-containing stream, and maintaining each of the remaining reactors of the two or more reactors at a temperature below the fluorination temperature,

[0352] (c) Injecting the fluorine-containing stream and circulating or recirculating the fluorine-containing stream at a temperature above the fluorination temperature for a time effective in achieving the desired level of fluorination of the spent catalyst in one of the two or more reactors.

[0353] Embodiment 130. A method defined in any of the prior embodiments, which further includes, essentially consists of, or comprises:

[0354] (d) Heating one of the two or more reactors to a temperature above the fluorination temperature, and maintaining each of the remaining reactors below the fluorination temperature,

[0355] (e) Injecting the fluorine-containing stream and circulating or recirculating the fluorine-containing stream at a temperature above the fluorination temperature for a time effective in achieving the desired level of fluorination of the spent catalyst in one of the two or more reactors.

[0356] Embodiment 131. A method as defined in any of the prior embodiments, further comprising repeating steps (d) and (e) until the spent catalyst in each of the one or more reactors is fluorinated to a desired level.

[0357] Embodiment 132. A method as defined in any of the prior embodiments, wherein the temperature above the fluorination temperature is at least 650°F or at least 700°F.

[0358] Embodiment 133. A method as defined in any of the preceding embodiments, wherein the temperature above the fluorination temperature is approximately 650°F to approximately 850°F, approximately 700°F to approximately 850°F, approximately 700°F to approximately 800°F, approximately 700°F to approximately 775°F, or approximately 700°F to approximately 750°F.

[0359] Embodiment 134. A method as defined in any of the preceding embodiments, wherein the temperature below the fluorination temperature is approximately 600°F or less.

[0360] Embodiment 135. A method as defined in any of the preceding embodiments, wherein the temperature below the fluorination temperature is approximately 300°F to approximately 600°F, approximately 400°F to approximately 600°F, or approximately 500°F to approximately 600°F.

[0361] Embodiment 136. The injection of the fluorine-containing stream is a method defined in any of the preceding embodiments, comprising, essentially, or consisting of:

[0362] (1) Selecting an injection point from one or more injection points, wherein the selected injection point is located upstream of one reactor (or a different reactor) that is heated to a temperature equal to or greater than the fluorination temperature, and,

[0363] (2) Inject the fluorine-containing flow into the injection junction selected from the one or more injection points.

[0364] Embodiment 137. A method as defined in any of the preceding embodiments, wherein the amount of the fluorine-containing compound or the fluorine-containing flow injected and circulated / recirculated is effective in distributing about 0.1 wt% to about 1.5 wt%, about 0.5 wt% to about 1.5 wt% of fluorine, or about 0.15 wt% to about 1.2 wt% of fluorine to the spent catalyst.

[0365] Embodiment 138. A method defined in any of the prior embodiments, which further comprises, or comprises, analyzing the fluorine-containing flow during the circulation or recirculation of the fluorine-containing flow to determine the amount or concentration of the fluorine-containing compound and / or fluorine in the fluorine-containing flow.

[0366] Embodiment 139. A method defined in any of the prior embodiments, comprising, or comprising, stopping the circulation / recirculation of the fluorine-containing flow when the amount or concentration of the fluorine-containing compound and / or fluorine is below a threshold concentration or amount indicating that fluorine deposition on the spent catalyst is achieved.

[0367] Embodiment 140. A system for fluorinating a spent catalyst, comprising, essentially comprising, or including the following:

[0368] (a) Two or more reactors that are in fluid communication with each other, the two or more reactors are connected in series, so that a fluid flow, for example, a fluorine-containing flow, can be (i) injected at an injection point selected from one or more injection points, (ii) continuously circulated to each of the two or more reactors downstream of the injection point, (iii) returned to the first reactor of the two or more reactors, and optionally (iv) continuously recirculated to each of the two or more reactors, and

[0369] (b) Two or more heating devices configured to heat each of the two or more reactors to the same or different temperatures.

[0370] Embodiment 141. The system according to Embodiment 140, wherein the system includes at least one injection point for all reactors.

[0371] Embodiment 142. The system according to Embodiment 141, wherein the at least one injection point is positioned to inject a fluorine-containing stream immediately upstream of any one of the two or more reactors.

Claims

1. A method for regenerating a spent catalyst, including a transition metal and a catalyst support, in a metal reactor, (1) The used catalyst is brought into contact with hydrogen gas to produce a stripped used catalyst. (2) The stripped spent catalyst is subjected to carbon combustion at a temperature not exceeding approximately 500°F to produce a treated spent catalyst. (3) The treated spent catalyst is brought into contact with a chlorine-containing stream containing a chlorine-containing compound to produce a chlorinated spent catalyst. (4) The chlorinated spent catalyst is subjected to carbon combustion at a temperature not exceeding 900°F for a time effective in improving the dispersion of the transition metal in the chlorinated spent catalyst to form a redispersed spent catalyst, and (5) Contacting the redispersed spent catalyst with a fluorine-containing stream containing a fluorine-containing compound to form a regenerated catalyst, and (6) Reducing the regenerated catalyst, The method, including the method described above.

2. The fluorine-containing compound includes the compound of formula (I), C ａ H ｂ Cl ｃ F ｄ Formula (I) During the ceremony, a is 1 to 6, b is between 0 and 14. c is between 0 and 14. d is 1 to 14, By choice, (i) b is not 0, (ii) c is not 0, or (iii) a combination of the above. The method according to claim 1, wherein b + c + d = 2a + 2.

3. The method according to claim 1, wherein the fluorine-containing compound comprises 1,1,1,2-tetrafluoroethane.

4. The method according to claim 1, wherein the fluorine-containing compound is difluoromethane.

5. The method according to claim 1, wherein the fluorine-containing compound is dichlorodifluoromethane.

6. The fluorine-containing stream contains an inert gas and oxygen (O ２ The method according to claim 1, further comprising ), or a combination thereof.

7. The oxygen (O) of the inert gas in the fluorine-containing stream ２ The volume ratio to ) is approximately 95:5 to approximately 99:1 (inert gas: oxygen (O) ２ The method according to claim 6, wherein the method is as follows:

8. The method according to claim 1, wherein (i) the amount of the fluorine-containing compound in the fluorine-containing stream, (ii) the duration of contact between the redispersed spent catalyst and the fluorine-containing stream, or (iii) a combination thereof, is selected so that about 0.15 wt% to about 1.2 wt% of fluorine is distributed on the redispersed spent catalyst.

9. The method according to claim 1, wherein the fluorine-containing stream substantially does not contain (i) an oxygen-containing compound, (ii) a chlorine-containing compound that does not contain a fluorine atom, or (iii) an oxygen-containing compound and a chlorine-containing compound that does not contain a fluorine atom.

10. The method according to claim 1, wherein the temperature of the carbon combustion of the stripped spent catalyst is about 400°F to about 500°F, and the carbon combustion of the stripped catalyst occurs in a time period of about 1 minute to about 24 hours.

11. The method according to claim 1, wherein an initial amount of hydrocarbon feed and an initial amount of aromatic products are present on the spent catalyst, and the carbon combustion of the stripped spent catalyst removes at least 90 wt% of the initial amount of hydrocarbon feed and at least 90 wt% of the initial amount of aromatic products from the stripped spent catalyst.

12. The method according to claim 1, wherein a certain amount of soft coke is absorbed and / or adsorbed by the spent catalyst, and the carbon combustion of the stripped spent catalyst reduces the amount of soft coke absorbed and / or adsorbed by the spent catalyst.

13. The method according to claim 1, wherein the temperature of the carbon combustion of the chlorinated spent catalyst is about 700°F to about 1,000°F, and the carbon combustion of the chlorinated spent catalyst occurs in a time period of about 1 minute to about 24 hours.

14. The method according to claim 1, wherein the carbon combustion of the chlorinated catalyst improves the dispersion of the transition metal in the chlorinated spent catalyst by at least 70%.

15. The method according to claim 1, wherein the reduction of the regenerated catalyst occurs at a temperature of about 800°F to about 1,000°F.

16. The reduction of the regenerated catalyst is at least partially carried out by an inert gas, hydrogen (H ２ The method according to claim 1, which occurs in an atmosphere containing, or a combination thereof.

17. The volume ratio of the inert gas to the hydrogen (H ２ ), is from about 20:80 to about 80:20, the method according to claim 16.

18. The method according to claim 1, further comprising contacting a hydrocarbon feed with an aromatizing catalyst under modifying conditions to produce an aromatic product, wherein the contact between the hydrocarbon feed and the aromatizing catalyst occurs for a time sufficient to form the spent catalyst.

19. The method according to claim 1, wherein each of steps (1) to (6) is carried out in the metal reactor.

20. The method according to claim 19, wherein the metal reactor is made of stainless steel.

21. A method for contacting a used catalyst with a fluorine-containing stream, (a) To provide two or more reactors that are in fluid communication with each other, the two or more reactors being connected in series, so that a fluorine-containing flow can be (i) injected at an injection point selected from one or more injection points, (ii) continuously circulated to each of the two or more reactors downstream of the injection point, (iii) returned to a first reactor of the two or more reactors, and optionally (iv) continuously recirculated to each of the two or more reactors, each of the two or more reactors including a storage container for the spent catalyst, (b) Heating one of the two or more reactors to a temperature above the fluorination temperature which is effective in at least partially decomposing the fluorine-containing compound in the fluorine-containing stream, and maintaining each of the remaining reactors of the two or more reactors at a temperature below the fluorination temperature, (c) Inject the fluorine-containing stream and circulate or recirculate the fluorine-containing stream at a temperature above the fluorination temperature for a time effective in achieving the desired level of fluorination of the spent catalyst in one of the two or more reactors. The method, including the method described above.

22. moreover, (d) Heating one of the two or more reactors to a temperature above the fluorination temperature, and maintaining each of the remaining reactors below the fluorination temperature, (e) Injecting the fluorine-containing stream and circulating or recirculating the fluorine-containing stream at a temperature above the fluorination temperature for a time effective in achieving the desired level of fluorination of the spent catalyst in one of the two or more reactors. The method according to claim 21, including the method described in claim 21.

23. The method according to claim 22, further comprising repeating steps (d) and (e) until the spent catalyst in each of the one or more reactors is fluorinated to a desired level.

24. The method according to any one of claims 21 to 23, wherein the temperature above the fluorination temperature is at least 650°F, and the temperature below the fluorination temperature is about 600°F or less.

25. The method according to any one of claims 21 to 23, wherein the temperature above the fluorination temperature is approximately 650°F to approximately 850°F.

26. The method according to any one of claims 21 to 23, wherein the temperature above the fluorination temperature is approximately 700°F to approximately 850°F.

27. The method according to any one of claims 21 to 23, wherein the temperature below the fluorination temperature is approximately 300°F to approximately 600°F.

28. The injection of the fluorine-containing stream is (1) Selecting the injection point from the one or more injection points, (2) Inject the fluorine-containing flow into the injection junction selected from the one or more injection points, The method according to any one of claims 21 to 23, including the method described in any one of claims 21 to 23.

29. The method according to claim 28, wherein the selected injection point is located upstream of one reactor or one of the different reactors that is heated to a temperature equal to or greater than the fluorination temperature.

30. The method according to any one of claims 21 to 23, wherein the amount of the fluorine-containing compound or the fluorine-containing flow injected and circulated / recirculated is effective in distributing about 0.1 wt% to about 1.5 wt% of fluorine to the spent catalyst.

31. The method according to any one of claims 21 to 23, wherein the amount of the fluorine-containing compound or the fluorine-containing flow injected and circulated / recirculated is effective in distributing fluorine in an amount of about 0.15 wt% to about 1.2 wt% to the spent catalyst.

32. The method according to any one of claims 21 to 23, further comprising analyzing the fluorine-containing flow during the circulation or recirculation of the fluorine-containing flow to determine the amount or concentration of the fluorine-containing compound and / or fluorine in the fluorine-containing flow.

33. The method according to any one of claims 21 to 23, further comprising stopping the circulation / recirculation of the fluorine-containing flow when the amount or concentration of the fluorine-containing compound and / or fluorine is below a threshold concentration or amount indicating that fluorine deposition on the spent catalyst is achieved.

34. A system for fluorinating used catalysts, (a) Two or more reactors that are in fluid communication with each other, the two or more reactors are connected in series, so that a fluid flow, for example, a fluorine-containing flow, can be (i) injected at an injection point selected from one or more injection points, (ii) continuously circulated to each of the two or more reactors downstream of the injection point, (iii) returned to the first reactor of the two or more reactors, and optionally (iv) continuously recirculated to each of the two or more reactors, and (b) Two or more heating devices configured to heat each of the two or more reactors to the same or different temperatures, The system including the above.

35. The system according to claim 34, wherein the system comprises exactly two reactors, three reactors, four reactors, five reactors, six reactors, seven reactors, eight reactors, nine reactors, or ten reactors.

36. The system according to claim 34, wherein the two or more heating devices include two or more tubular furnaces.

37. The system according to claim 34, wherein the one or more injection points include at least one injection point for each of the two or more reactors.

38. The system according to claim 37, wherein the system comprises strictly 2, 3, 4, 5, 6, 7, 8, 9, or 10 reactors and at least 2, 3, 4, 5, 6, 7, 8, 9, or 10 injection points.

39. The system according to claim 34, further comprising the spent catalyst, wherein the spent catalyst is placed in at least one of the two or more reactors, and the spent catalyst comprises a transition metal and a catalyst support.

40. The system according to claim 34, wherein the two or more reactors include two or more metal reactors.

41. A method for regenerating a spent catalyst, including a transition metal and a catalyst support, in a metal reactor, (1) The spent catalyst is brought into contact with a chlorine-containing stream containing a chlorine-containing compound to produce a chlorinated spent catalyst. (2) The chlorinated spent catalyst is brought into contact with a coke removal gas stream containing oxygen to produce a coke-removed catalyst, and (3) The process of contacting the coke-removed catalyst with a fluorine-containing stream containing a fluorine-containing compound to produce a regenerated catalyst, wherein the fluorine-containing compound includes hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), or combinations thereof, The method, including the method described above.

42. The fluorine-containing compound includes the compound of formula (I), C ａ H ｂ Cl ｃ F ｄ Formula (I) During the ceremony, a is 1 to 6, b is between 0 and 14. c is between 0 and 14. d is 1 to 14, By choice, (i) b is not 0, (ii) c is not 0, or (iii) a combination of the above. The method according to claim 41, wherein b + c + d = 2a + 2.

43. The method according to claim 42, wherein b is not 0.

44. The method according to claim 42, wherein c is not 0.

45. The method according to claim 41, wherein the fluorine-containing compound includes 1,1,1,2-tetrafluoroethane.

46. The method according to claim 41, wherein the fluorine-containing compound includes dichlorodifluoromethane, difluoromethane, or a combination thereof.

47. The method according to claim 41, wherein the fluorine-containing stream further comprises an inert gas, air, or a combination thereof.

48. The method according to claim 41, wherein the fluorine-containing stream further contains an inert gas and air in a volume ratio of about 3:1 to about 5:1 (inert gas:air).

49. The method according to claim 41, wherein the fluorine-containing compound is present in the fluorine-containing stream in an amount effective in giving the fluorine-containing stream a concentration of about 0.05 wt% to about 3 wt% of fluorine [F].

50. The method according to claim 41, wherein the fluorine-containing stream substantially does not contain an oxygen-containing compound, a chlorine-containing compound that does not contain a fluorine atom, or an oxygen-containing compound and a chlorine-containing compound that does not contain a fluorine atom.

51. The method according to claim 41, wherein the contact of the coke-removed catalyst with the fluorine-containing stream occurs at a temperature of about 0°C to about 500°C.

52. The method according to claim 41, wherein the contact of the coke-removed catalyst with the fluorine-containing stream occurs at a pressure of about 0.5 bar to about 7 bar.

53. The method according to claim 41, wherein the contact of the coke-removed catalyst with the fluorine-containing stream occurs over a period of time of about 0.5 to about 96 hours.

54. moreover, To generate a recovered fluorine-containing flow, the recovery involves recovering at least a portion of the fluorine-containing flow, wherein the recovery is performed after the contact between the coke-removed catalyst and the fluorine-containing flow, and The catalyst from which the coke has been removed is brought into contact with the recovered fluorine-containing stream. The method according to claim 41, including the method described in claim 41.

55. The method according to claim 41, wherein the concentration of fluorine in the regenerated catalyst is about 0.03 wt% to about 1.3 wt%.

56. The method according to claim 41, wherein the fluorine concentration gradient in the regenerated catalyst is 60% or less.

57. The method according to claim 41, wherein the fluorine concentration gradient in the regenerated catalyst is 40% or less.

58. The method according to claim 41, wherein the chlorine-containing stream substantially does not contain oxygen-containing compounds and fluorine-containing compounds.

59. The method according to claim 41, wherein the coke removal gas substantially contains no water.

60. The chlorine-containing stream contains chlorine gas (Cl ２ ) and nitrogen (N ２ The method according to claim 41, including )

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