Regeneration method of aromatization catalyst

Abstract

A method of regenerating a spent catalyst, such as a spent aromatization catalyst, which may include a transition metal and a catalyst support. The method may include contacting a catalyst with a fluorine-containing stream including a fluorine-containing compound. The fluorine-containing compound may include a hydrofluorocarbon (HFC), a chlorofluorocarbon (CFC), a hydrochlorofluorocarbon (HCFC), a fluorocarbon (FC), or a combination thereof.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 568,189, filed March 21, 2024; U.S. Provisional Patent Application No. 63 / 493,418, filed March 31, 2023; and U.S. Provisional Patent Application No. 63 / 491,703, filed March 22, 2023, which are incorporated herein by reference. Technical Field

[0003] This disclosure relates to a method for regenerating spent aromatization catalysts and their use in the aromatization of aliphatic hydrocarbons into aromatic hydrocarbons. Background Technology

[0004] Aromatization catalysts can be regenerated through methods including chlorination, oxidation, and fluorination. Fluorination typically uses a fluorination source containing fluorine in nitrogen, which can be disadvantageous, particularly regarding the distribution of fluorine within the catalyst bed. Fluorine can react with the catalyst upon contact, thus the front edge of the catalyst bed can have a higher fluorine concentration than the rest of the bed. In some cases, most (if not all) of the fluorine can be adsorbed by the catalyst, with little or no fluorine permeation through the bed.

[0005] There is still a need for improved methods for regenerating aromatization catalysts, including methods that overcome one or more of the aforementioned drawbacks associated with the use of fluorine in the fluorination step. Summary of the Invention

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

[0007] This article provides a method for regenerating aromatization catalysts, which may include using fluorinated compounds instead of fluorine in the fluorination step. The fluorinated compounds used in this article can improve the distribution of fluorine in the catalyst bed.

[0008] In one aspect, a method for regenerating catalysts, such as spent aromatization catalysts, is provided. The spent catalyst may comprise a transition metal and a catalyst support in a metal reactor. In some embodiments, the method includes any two or more of steps (A)-(H): (A) contacting a hydrocarbon feedstock with an aromatization catalyst comprising a transition metal and a catalyst support under reforming conditions in a metal reactor system to generate an aromatic product; (B) performing step (A) for a period sufficient to form a spent catalyst; (C) contacting the spent catalyst with hydrogen to generate stripped spent catalyst; and (D) subjecting the stripped spent catalyst to carbon combustion at a temperature, for example, not exceeding about 500℉, for a period of time to effectively remove at least a portion of the hydrogen from the spent catalyst. (E) A carbon feedstock, at least a portion of an aromatic product, or a combination thereof, is used to form a treated spent catalyst; (F) The treated spent catalyst is contacted with a chlorinated stream containing chlorine compounds to generate a chlorinated spent catalyst; (G) The chlorinated spent catalyst is subjected to carbon combustion at a temperature not exceeding 900℉ for a period of time to effectively improve the dispersibility of transition metals in the chlorinated spent catalyst to form a redistributed spent catalyst; (H) The redistributed spent catalyst is contacted with a fluorinated stream containing fluorine compounds to form a regenerated catalyst; and (X) The regenerated catalyst is reduced.

[0009] In some embodiments, the method includes contacting the spent catalyst with a chlorinated stream containing a chlorinated compound to generate a chlorinated spent catalyst; contacting the chlorinated spent catalyst with a decoking stream containing oxygen to generate a decoking catalyst; and contacting the decoked catalyst with a fluorinated stream containing a fluorinated compound to generate a regenerated catalyst. In some embodiments, the fluorinated compound includes hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), fluorocarbons (FCs), or combinations thereof.

[0010] On the other hand, reactivation catalysts and regenerated catalysts are provided, such as catalysts generated by any of the methods described herein.

[0011] In another aspect, a method is provided for contacting a reactivated or regenerated catalyst with hydrocarbons to generate products.

[0012] In another aspect, a method is provided for contacting spent catalyst with a fluorinated stream. In some embodiments, the method includes (a) providing two or more reactors in fluid communication with each other, wherein the two or more reactors are connected in series, thereby allowing the fluorinated stream to (i) be injected at an injection point selected from one or more injection points, (ii) be circulated sequentially through each of the two or more reactors downstream of the injection point, (iii) be returned to the first of the two or more reactors, and optionally (iv) be circulated sequentially through each of the two or more reactors, wherein each of the two or more reactors includes a reservoir in which the spent catalyst is disposed; (b) heating one of the two or more reactors to a temperature equal to or above the fluorination temperature, and holding the remaining reactors of the two or more reactors at a temperature below the fluorination temperature, wherein the fluorination temperature effectively at least partially decomposes the fluorinated compounds in the fluorinated stream; and (c) injecting the fluorinated stream and circulating or recirculating the fluorinated stream for a period of time to effectively achieve the desired level of fluorination of the spent catalyst in one of the two or more reactors at a temperature equal to or above the fluorination temperature. The method may further include: (d) heating one of the two or more reactors to a temperature equal to or above the fluorination temperature, and holding the remaining reactors at a temperature below the fluorination temperature; and (e) injecting a fluorinated stream and circulating or recirculating the fluorinated stream for a period of time to effectively achieve the desired level of fluorination of the spent catalyst in one of the two or more reactors at a temperature equal to or above the fluorination temperature.

[0013] On the other hand, 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 and connected in series. This configuration allows a fluid flow (e.g., a fluorinated flow) to (i) be injected at an injection point selected from one or more injection points, (ii) circulate sequentially through each of the two or more reactors downstream of the injection point, (iii) return to the first of the two or more reactors, and optionally (iv) recirculate sequentially through 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, reactors and devices may be connected such that one reactor is connected to one heating device.

[0014] Additional aspects will be set forth in part in the description which follows, and in part will be apparent from the description, or may be learned by practicing the aspects described herein. The advantages described herein can be realized and obtained by the elements and combinations particularly pointed out in the appended claims. It should be understood that the foregoing general description and the following detailed description are exemplary and explanatory only, and not restrictive. Attached Figure Description

[0015] Figure 1 An implementation scheme of the system provided herein is described, which can be used to carry out one or more implementation schemes that contact waste catalyst with a fluorine-containing stream.

[0016] Figure 2 A graph depicting catalyst conditioning temperature versus time for an embodiment of the method described herein is presented.

[0017] Figure 3 A graph depicting the selectivity of aromatic compounds versus time for an embodiment of the catalyst according to the method described herein is presented.

[0018] Figure 4 The following are plots of catalyst conditioning temperature versus time: (1) an embodiment of a fresh aromatization catalyst, (2) an embodiment of a spent aromatization catalyst, and (3) an embodiment of a spent aromatization catalyst subjected to the reactivation procedure described herein in Example 1C.

[0019] Figure 5 The following are plots of the selectivity of aromatic compounds versus time: (1) embodiments of fresh aromatization catalysts, (2) embodiments of spent aromatization catalysts, and (3) embodiments of spent aromatization catalysts subjected to the reactivation procedure described herein in Example 1C.

[0020] Figure 6 The following are plots of catalyst conditioning temperature versus time: (1) an embodiment of a fresh aromatization catalyst, (2) an embodiment of a spent aromatization catalyst, and (3) an embodiment of a spent aromatization catalyst subjected to the reactivation procedure described herein in Example 1D.

[0021] Figure 7 The following are plots of the selectivity of aromatic compounds versus time: (1) embodiments of fresh aromatization catalysts, (2) embodiments of spent aromatization catalysts, and (3) embodiments of spent aromatization catalysts subjected to the reactivation procedure described herein in Example 1D.

[0022] definition

[0023] 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, the definition in the IUPAC Compendium of Chemical Terminology, 2nd Edition (1997) may be applied, provided that the definition does not conflict with any other disclosure or definition applied herein, or render any claim to which the definition is applied ambiguous or invalid. If any definition or usage provided by reference to any document incorporated herein conflicts with the definition or usage provided herein, the definition or usage provided herein shall prevail.

[0024] Because various features of the subject matter of this disclosure have been described, one or more combinations of different features may be contemplated within a particular aspect. For each aspect of each feature disclosed herein, all combinations are considered, whether or not a particular combination is explicitly described, provided they do not adversely affect the design, composition, system, process, or method described herein. Therefore, unless expressly stated to the contrary, any aspect of the features disclosed herein can be combined to describe and disclose an inventive design, composition, system, process, or method consistent with the entire disclosure.

[0025] Although compositions and methods are described as “comprising” various components or steps, they may also be described as “consisting substantially of various components or steps” or “component of various components or steps” unless otherwise stated.

[0026] Unless otherwise specified, the terms “including,” “with,” and “having” as used herein are defined as encompassing (i.e., open-ended language).

[0027] The terms “a / an” and “described” are intended to include plural alternatives, such as at least one / an. For example, unless otherwise stated, the disclosure of “fluorinated compound,” “catalyst,” etc., is intended to cover mixtures or combinations of one or more fluorinated compounds, catalysts, etc.

[0028] This document discloses various numerical ranges. When an applicant discloses or claims protection for any type of range, unless otherwise indicated, the applicant intends to individually disclose or claim protection for every possible number that such range can reasonably cover, including the endpoints of the range and any subranges and combinations thereof covered therein. For example, by disclosing weight percentages of 1.0 wt% to 2.0 wt% or 1 wt% to 2 wt%, the applicant intends to express 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%, respectively, including any subranges and combinations thereof contained therein, and these methods of describing such ranges are interchangeable. Furthermore, all numerical endpoints of the ranges disclosed herein are approximate unless excluded by attached conditions. As a representative example, if the applicant states that one or more steps in the process disclosed herein can be performed at temperatures ranging from 10°C to 75°C, unless otherwise stated, this range shall be interpreted as covering temperatures ranging from “about” 10°C to “about” 75°C.

[0029] Values ​​or ranges herein may be expressed as “about,” from “about” a specific value, and / or to “about” another specific value. When expressing such values ​​or ranges, other disclosed embodiments include the specific value, from one specific value, and / or to another specific value. Similarly, when a value is expressed as an approximation using the antecedent “about,” it should be understood that the specific value forms another embodiment. It should be further understood that numerous values ​​are disclosed herein, and each value, in addition to being stated as the value itself, is also disclosed herein as “about” the specific value. On the other hand, each use of the term “about” may independently represent ±20% of the value, ±15% of the value, ±10% of the value, ±5% of the value, or ±3% of the value.

[0030] Therefore, if the applicant chooses to claim protection for less than the full extent of the disclosure for any reason, such as considering references that the applicant might not have been aware of at the time of filing the application, the applicant reserves the right to specify or exclude any individual member of any such group of values ​​or ranges (including any subranges or combinations of subranges within that group) that can be claimed based on the scope or in any similar manner. Furthermore, if the applicant chooses to claim protection for less than the full extent of the disclosure for any reason, such as considering references or prior disclosures that the applicant might not have been aware of at the time of filing the application, the applicant reserves the right to specify or exclude any individual substituent, analogue, compound, ligand, structure, or group thereof, or any member of the claimed group.

[0031] For any particular compound or group disclosed herein, unless otherwise stated, any name or structure presented (general or specific) is intended to cover all conformational isomers, regio isomers, stereoisomers, and mixtures thereof that can be produced by a particular set of substituents. Unless otherwise specified, the name or structure also covers all enantiomers, diastereomers, and other optical isomers (if any), whether enantiomers or racemic forms, and mixtures of stereoisomers, as known to those skilled in the art. For example, general references to hexane or hexanes include n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, and 2,3-dimethylbutane; general references to butyl include n-butyl, sec-butyl, isobutyl, and tert-butyl.

[0032] When used to describe a group, such as when referring to a substituted analogue of a particular group, the term "substituted" is intended to describe a compound or group in which any non-hydrogen moiety formally replaces hydrogen in the group or compound, and is intended to be non-limiting. A compound or group may also be referred to herein as "unsubstituted" or equivalent terms such as "non-substituted," referring to the original group or compound. "Substituted" is intended to be non-limiting and includes inorganic or organic substituents as specified and understood by one of ordinary skill in the art.

[0033] Unless otherwise stated, the terms “contact product,” “contact,” etc., are used herein to describe compositions and methods in which components are contacted together in any order, in any manner, and for any duration. For example, components may be contacted by blending or mixing. Furthermore, unless otherwise stated, contact of any components may occur with or without any other components of the compositions and methods described herein. Additional materials or components may be combined by any suitable method. Additionally, the term “contact product” includes mixtures, blends, solutions, slurries, reaction products, etc., or combinations thereof. Although “contact product” may and often includes reaction products, it does not require that the individual components react with each other. Similarly, “contacting” two or more components can produce reaction products or reaction mixtures. Thus, depending on the specific circumstances, a “contact product” can be a mixture, a reaction mixture, or a reaction product.

[0034] "Conditions for the aromatization of aliphatic hydrocarbons" refers to the conditions under which at least a portion of the aliphatic hydrocarbons in the feedstock are aromatized upon contact with the catalyst described herein, such that the catalyst bed effluent contains at least some aromatic hydrocarbons. Some unreacted aliphatic hydrocarbons will also be present in the catalyst bed effluent.

[0035] Typically, element groups are indicated using the numbering scheme indicated in the version of the periodic table published in Chemical and Engineering News, 63(5), 27, 1985. In some cases, element groups may be indicated using the common names assigned to the group; for example, alkali metals of Group 1, alkaline earth metals of Group 2, transition metals of Groups 3-12, halogens or halogens of Group 17, etc.

[0036] In one respect, a chemical “group” can be defined or described according to how the group is formally derived from a reference or “parent” compound, for example by the number of hydrogen atoms removed from the parent compound to produce the group, even if the group is not literally synthesized in this way. These groups can be used as substituents or coordinated or bonded to metal atoms. For example, an “alkyl group” can be formally obtained by removing a hydrogen atom from an alkane. The disclosure that substituents, ligands, or other chemical parts can constitute a particular “group” means that well-known chemical structures and bonding rules are followed when the group is used as described. When a group is described as “derived from,” “from,” “formed from,” or “formed from,” these terms are used in a formal sense and are not intended to reflect any particular synthetic method or procedure unless otherwise specified or required by the context.

[0037] As used herein, the term "hydrocarbon" refers to a compound containing only carbon and hydrogen atoms. Other identifiers may be used to indicate the presence of specific groups (if any) in a hydrocarbon. For example, a halohydrocarbon indicates the presence of one or more halogen atoms replacing an equal amount of hydrogen atoms in the hydrocarbon.

[0038] "Aromatic" compounds or "aromatic hydrocarbons" are compounds containing a cyclic conjugated double bond system that follows Hückel's (4n+2) rule and contains (4n+2) π electrons, where n is an integer from 1 to 5. Aromatic hydrocarbons include "aromatic hydrocarbons" (aromatic compounds, such as benzene, toluene, and xylene) and "heteroaromatic hydrocarbons" (heteroaromatic compounds formally derived from aromatic hydrocarbons by substituting one or more methylene (-C=) carbon atoms in the cyclic conjugated double bond system with trivalent or divalent heteroatoms, thereby preserving the continuous π electron system characteristic of the aromatic system and the number of out-of-plane π electrons corresponding to Hückel's (4n+2) rule). As disclosed herein, unless otherwise specified, the term "substituted" may be used to describe aromatic groups, aromatic hydrocarbons, or heteroaromatic hydrocarbons in which non-hydrogen portions formally replace hydrogen atoms in the compound, and is intended to be non-limiting.

[0039] As used herein, the term "alkane" refers to a saturated hydrocarbon compound. Other identifiers may be used to indicate the presence of a specific group (if any) in an alkane (e.g., haloalkanes indicate the presence of one or more halogen atoms that have substituted an equal number of hydrogen atoms in the alkane). The term "alkyl" is used herein according to the definition given by IUPAC: a monovalent group formed by removing a hydrogen atom from an alkane. Unless otherwise specified, alkane or alkyl groups may be straight-chain or branched.

[0040] As used herein, “cycloalkanes” refers to saturated cyclic hydrocarbons with or without side chains, such as cyclobutane, cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane. Other identifiers may be used to indicate the presence of a specific group (if any) in a cycloalkane (e.g., halocycloalkanes indicate the presence of one or more halogen atoms that replace an equal amount of hydrogen atoms in the cycloalkane).

[0041] According to the IUPAC recommended definition, "aliphatic" compounds or "aliphatic hydrocarbons" are defined as acyclic or cyclic, saturated or unsaturated carbon compounds, excluding aromatic compounds. In other words, aliphatic compounds are non-aromatic organic compounds.

[0042] The term "hydrocarbon group" is used herein according to the definition prescribed by IUPAC: a monovalent group (i.e., a group containing only carbon and hydrogen) formed by removing a hydrogen atom from a hydrocarbon. Therefore, hydrocarbon groups include alkyl (straight-chain or branched), cycloalkyl, alkenyl, aryl, etc. Non-limiting examples of hydrocarbon groups include methyl, ethyl, butyl, hexyl, phenyl, tolyl, propenyl, etc.

[0043] As used herein, "alkanes" refers to acyclic, straight-chain, or branched saturated hydrocarbons, including alkanes. For example, C6 alkanes are acyclic, straight-chain, or branched hydrocarbons with six carbon atoms per molecule. n-Hexane, methylpentane, and dimethylbutane are examples of C6 alkanes. Feeds containing alkanes include acyclic saturated hydrocarbons such as n-alkanes, isoalkanes, and mixtures thereof.

[0044] As used herein, “cycloalkane” and “cycloalkane” are terms used to describe cyclic saturated hydrocarbons, including cycloalkanes and their alkyl-substituted analogues. Therefore, “cycloalkane” is a cyclic saturated hydrocarbon having one or more carbon atom rings in its chemical structure, and its meaning herein is the same as “cycloalkane.” If such a cyclic structure contains unsaturated carbon-carbon bonds but is not aromatic, the compound will be aliphatic, not cycloalkane. In some embodiments, cycloalkane is a cyclic saturated hydrocarbon having 5 to 8 carbon atoms in its cyclic structure, including its substituted (especially alkyl-substituted) analogues.

[0045] As used herein, "olefin" is an acyclic or cyclic hydrocarbon having one or more carbon-carbon double bonds, excluding formal double bonds in aromatic compounds. Olefins include alkenes, cycloolefins, and corresponding polyolefins.

[0046] As used herein, "naphtha" refers to a petroleum fraction with a boiling point ranging from 50℉ (10°C) to 550℉ (260°C). In some embodiments, the boiling point of the naphtha is in the range of 70℉ (21°C) to 450℉ (232°C), more typically in the range of 80℉ (27°C) to 400℉ (204°C), and often in the range of 90℉ (32°C) to 360℉ (182°C). In some embodiments, at least 85 vol.% (volume percentage) of the naphtha has a boiling point ranging from 50℉ (10°C) to 550℉ (260°C), more typically in the range of 70℉ (21°C) to 450℉ (232°C). In embodiments, at least 85 vol.% of the naphtha is C4 to C5. 12 Within the range, more typically in C5 to C 11 Within the range, and often between C6 and C 10 Within the scope. Naphtha may include, for example, straight-run naphtha, raffinates of alkanes and cycloalkanes derived from aromatic extraction or adsorption, and substances containing C6 to C4 hydrocarbons. 10 Feedstocks of alkanes and cycloalkanes, bio-derived naphtha, naphtha from hydrocarbon synthesis processes (including Fischer-Tropsch and methanol synthesis processes), and naphtha from other refining processes (such as hydrocracking or conventional reforming).

[0047] As used herein, the terms "convertible hydrocarbon," "convertible C6 substance," or "convertible C7 substance" refer to hydrocarbon compounds that can be selectively converted into aromatic products such as aromatics under aromatization process conditions. In some aspects, the feed stream contains highly branched hydrocarbons that cannot be selectively converted into aromatics under conventional aromatization process conditions. "Highly branched hydrocarbons" refers to hydrocarbons that cannot be selectively converted into aromatics under conventional aromatization process conditions. For example, "highly branched hydrocarbons" can include highly branched hydrocarbons having six or seven carbon atoms and an internal quaternary carbon, or hydrocarbons having six carbon atoms and two adjacent internal tertiary carbons, or mixtures thereof. Highly branched hydrocarbons can include, but are not limited to, dimethylbutane (e.g., 2,2-dimethylbutane, 2,3-dimethylbutane), dimethylpentane (e.g., 2,2-dimethylpentane, 3,3-dimethylpentane), trimethylbutane (e.g., 2,2,3-trimethylbutane), and mixtures thereof. Highly branched hydrocarbons are not selectively convertible aromatics but are converted into light hydrocarbons under aromatization process conditions. The convertible component may include methylpentane, methylhexane, dimethylpentane, or mixtures thereof, and / or the selectively convertible component may include at least one of 2-methylpentane, 3-methylpentane, 2,4-dimethylpentane, 2,3-dimethylpentane, n-hexane, 2-methylhexane, 3-methylhexane, n-heptane, or mixtures thereof. The selectively convertible component readily converts to aromatics without producing light hydrocarbons.

[0048] The terms “primary aromatic hydrocarbons,” “primary aromatic products,” “desired hydrocarbon products,” and “specific aromatic substances” used in this article are interchangeable and refer to aromatic hydrocarbons that are the desired final products of the reaction, including aromatic hydrocarbons produced from feedstocks containing renewable cellulose sources. For example, the desired product may be benzene, while toluene and xylene may be byproducts, or the desired product may be xylene, while benzene and toluene may be byproducts.

[0049] The term "Group 8-10 metals" includes each of the Group 8 metals iron, ruthenium, and osmium; each of the Group 9 metals cobalt, rhodium, and iridium; and each of the Group 10 metals nickel, palladium, and platinum. Group 8-10 metals may also be referred to using the earlier nomenclature of Group VIII metals, which also includes all of iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, and platinum. Generally, describing a catalyst as a Group 8-10 metal catalyst or containing Group 8-10 metals is intended to encompass catalysts containing at least one Group 8-10 metal and optionally other metals (e.g., Pt / Sn and Pt / Re).

[0050] The term "platinum metal" as used in this article refers to the transition metals in Groups 8-10, Rows 2 and 3, namely ruthenium, osmium, rhodium, iridium, palladium, and platinum.

[0051] The term "precious metals" is generally used to describe specific metals that are resistant to corrosion, and this term includes certain transition metals in the second and third rows, but not those in the first row. Typically, precious metals include ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, and gold. Therefore, Groups 8-10 precious metals are also platinum group metals.

[0052] As used herein, the term "bonded" is intended to describe zeolite-binder combinations or other carrier-binder combinations that form aggregates such as particles, pellets, and extrudates. The term "catalyst matrix" as used herein refers to bound zeolite or bound carrier.

[0053] As used herein, the term "catalyst" has a broad meaning, encompassing both the final catalyst and its precursors. Precursors to the final catalyst include, for example, calcined forms of catalysts containing catalytic metals and catalysts prior to reduction activation. Therefore, the term "catalyst" is used in some contexts herein to refer to an activated catalyst, and in other contexts to refer to a precursor form of a catalyst, as understood by those skilled in the art from the context.

[0054] The term "sulfur-sensitive" describes a catalyst that is particularly sensitive to the presence of sulfur in the feedstock. Typically, these catalysts require the sulfur content in the feedstock to be reduced to less than 5 ppm through hydrotreating, adsorbents, or a combination of both. As used herein, the terms "aromatization reactor system," "aromatization reactor unit," "catalytic reactor system," and "catalytic reactor unit" also refer to the reactor vessel, internal reactor components, and associated processing equipment (as the context permits) when referring to an aromatization reactor system, including but not limited to catalysts, inert packing, scalloped containers, flow distributors, central tubes, reactor ports, catalyst delivery and distribution systems, furnaces and other heating devices, heat transfer equipment, and piping. An aromatization reactor system may include a fixed catalyst bed system, a moving catalyst bed system, a fluidized catalyst bed system, or a combination thereof. Such aromatization reactor systems can be batch or continuous. In a fixed-bed system, the feed flow can pass upward, downward, or radially through the reactor. In one aspect, a first catalyst bed, an intermediate catalyst bed, and a final catalyst bed are located in a radial flow reactor.

[0055] The term "catalyst bed," such as first, second, or intermediate catalyst beds, is used herein to refer to a specific catalyst composition that constitutes at least a portion or all of the catalyst material in a single aromatization reactor. For example, a "first catalyst bed" may occupy the entirety of an aromatization reactor, or it may occupy a portion of an aromatization reactor, while a "second catalyst bed" occupies the remaining portion. More typically, each catalyst bed may occupy the entirety of an aromatization reactor. Generally, unless otherwise specified or required by context, multiple aromatization reactors are described as having different catalyst beds, regardless of whether their catalysts have the same or different compositions.

[0056] The term "halogen" has its usual meaning and, depending on the context, includes halides. Therefore, examples of halogens include fluorine, fluorides, chlorine, chlorides, bromine, bromides, iodine, and iodides. Furthermore, the use of the terms "fluoride" and "chloride" in describing catalyst components or catalyst composition (e.g., weight percentage or molar percentage of these components) does not depend on their presence in the catalyst in any particular molecular or ionic form.

[0057] Molar selectivity is defined as:

[0058] Benzene selectivity:

[0059] Toluene selectivity:

[0060] Benzene + Toluene selectivity:

[0061] Selectivity of aromatic compounds:

[0062] Conversion rate is defined as the number of moles of "convertible" hydrocarbons converted per mole of feed, as follows:

[0063] C6 conversion rate:

[0064] C7 conversion rate:

[0065]

[0066] In these equations, This indicates the molar flow rate in a continuous reactor or the number of moles in a batch reactor.

[0067] The term "ton" as used in this article refers to a metric ton, which is a unit of mass equal to 1,000 kilograms.

[0068] This abstract is not intended to interpret the scope of the claims or limit the scope of the subject matter disclosed herein, but rather to satisfy the requirements of 37 C. FR § 1.72(b) to enable the U.S. Patent and Trademark Office and the public to quickly determine the nature and purpose of the technical disclosure through a cursory examination. Furthermore, any headings adopted herein are not intended to interpret the scope of the claims or limit the scope of the subject matter disclosed herein. Any use of past tense to describe instances otherwise indicated as constructive or prophetic is not intended to reflect instances that have actually been implemented.

[0069] All disclosures mentioned herein are incorporated herein by reference for the purpose of describing and disclosing, for example, the constructs and methods described in the disclosures, which can be used in conjunction with the present invention. The publications discussed throughout are provided solely for their disclosure prior to the filing date of this application. Nothing herein shall be construed as an admission that the inventor has no right to any prior disclosure due to a prior invention.

[0070] Those skilled in the art will readily recognize that various modifications can be made to the exemplary embodiments disclosed herein without substantially departing from the novel teachings and advantages of this disclosure. Therefore, all such modifications and equivalents are intended to be included within the scope of this disclosure as defined in the following claims. Accordingly, it should be understood that various other aspects, embodiments, modifications, and equivalents will arise in those skilled in the art upon reading the description herein without departing from the spirit of this disclosure or the scope of the appended claims. Detailed Implementation

[0071] This disclosure generally relates to methods for regenerating and / or reactivating spent catalysts, such as spent aromatization catalysts. It has been unexpectedly found that by using a fluorinated compound instead of fluorine gas in the fluorination step, the methods described herein can achieve improved fluorine distribution on the catalyst bed with little or no impact on the performance of the regenerated and / or reactivated catalyst.

[0072] Any spent catalyst can be subjected to the methods described herein. In some embodiments, the spent catalyst comprises a transition metal and a catalyst support. In some or all steps of the methods provided herein, the catalyst, such as the spent catalyst, may be present in a metal reactor. In some embodiments, the metal reactor comprises stainless steel, such as 347SS or 321SS.

[0073] method

[0074] This document provides a reforming method that may include 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 feedstock with an aromatization catalyst comprising a transition metal and a catalyst support under reforming conditions in a metal reactor system to generate an aromatic product; (B) performing step (A) for a period of time sufficient to form spent catalyst; (C) contacting the spent catalyst with hydrogen to generate stripped spent catalyst; and (D) subjecting the stripped spent catalyst to carbon combustion at a temperature, for example, not exceeding about 500℉, for a period of time. The reforming process involves: (A) effectively removing at least a portion of the hydrogen-carbon feedstock, at least a portion of the aromatic products, or combinations thereof from the spent catalyst to form a treated spent catalyst; (E) contacting the treated spent catalyst with a chlorinated stream containing chlorine compounds to generate a chlorinated spent catalyst; (F) subjecting the chlorinated spent catalyst to carbon combustion at a temperature not exceeding 900℉ for a period of time to effectively improve the dispersion of transition metals in the chlorinated spent catalyst to form a redistributed spent catalyst; (G) contacting the redistributed spent catalyst with a fluorinated stream containing fluorine compounds to form a regenerated catalyst; and (H) reducing the regenerated catalyst. The method may also include a step of reactivating the catalyst, for example, after step (H). In some embodiments, the reforming method described herein is an in-situ process. Therefore, in some embodiments, steps (A)-(H) (or two or more selected from steps (A)-(H)) are carried out in the same reactor system. In some embodiments, steps (C)-(H) are carried out outside the reactor system in which steps (A)-(B) are performed. For example, steps (C)-(H) may be carried out in a metal reactor that is not part of the reforming reactor system.

[0075] In some embodiments, the method includes: (1) contacting the spent catalyst with hydrogen to generate stripped spent catalyst; (2) subjecting the stripped spent catalyst to carbon combustion at a temperature not exceeding about 500℉ for a period of time to effectively remove at least a portion of the hydrogen-carbon feedstock, at least a portion of the aromatic products, or combinations thereof from the spent catalyst to form a treated spent catalyst; (3) contacting the treated spent catalyst with a chlorinated stream including chlorinated compounds to generate chlorinated spent catalyst; (4) subjecting the chlorinated spent catalyst to carbon combustion at a temperature not exceeding 900℉ for a period of time to effectively improve the dispersion of transition metals in the chlorinated spent catalyst to form a redistributed spent catalyst; (5) contacting the redistributed spent catalyst with a fluorinated stream including fluorinated compounds to form a regenerated catalyst; and (6) reducing the regenerated catalyst.

[0076] In some embodiments, the method includes: (A) contacting a hydrocarbon feedstock with an aromatization catalyst comprising a transition metal and a catalyst support under reforming conditions in a metal reactor system to generate an aromatic product; (B) performing step (A) for a period of time sufficient to form spent catalyst; (C) contacting the spent catalyst with a chlorinated stream containing a chlorinated compound to generate a chlorinated spent catalyst, wherein the chlorinated compound optionally includes chlorine, chlorinated hydrocarbons, chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), or combinations thereof; (D) contacting the chlorinated spent catalyst with a decoking stream containing oxygen to generate a decoking catalyst; and (E) contacting the decoking catalyst with a fluorinated stream containing a fluorinated compound, wherein the fluorinated compound includes hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), fluorocarbons (FCs), or combinations thereof. In some embodiments, the method is an in-situ process. For example, steps (A)-(E) can be carried out in the same reactor system. In some embodiments, steps (C)-(E) are carried out outside the reactor system of steps (A)-(B). For example, steps (C)-(E) can be carried out in a metal reactor outside the reforming reactor system. In some embodiments, the method includes reactivating the catalyst after step (E).

[0077] In some embodiments, the method includes regenerating a spent catalyst comprising a transition metal and a catalyst support in a metal reactor. The method may include: (1) contacting the spent catalyst with a chlorinated stream containing a chlorinated compound to generate a chlorinated spent catalyst; (2) contacting the chlorinated spent catalyst with a decoking stream containing oxygen to generate a decoking catalyst; and (3) contacting the decoking catalyst with a fluorinated stream containing a fluorinated compound to generate a regenerated catalyst, wherein the fluorinated compound includes hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), fluorocarbons (FCs), or combinations thereof.

[0078] The steps of the methods described in this article can generally be performed at any effective time period, temperature, pressure, etc.

[0079] hydrogen

[0080] Contact between the spent catalyst and hydrogen can be carried out at any effective temperature. In some embodiments, the contact between the spent catalyst and hydrogen is at least partially carried out at temperatures above 25℉, above 100℉, above 200℉, above 300℉, above 400℉, or above 500℉. In some embodiments, the contact between the spent catalyst and hydrogen is at least partially carried out at temperatures from about 300℉ to about 800℉, from about 400℉ to about 800℉, or from about 500℉ to about 800℉.

[0081] The contact between the spent catalyst and hydrogen can last for any effective time. In some embodiments, the contact between the spent catalyst and hydrogen can last for 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.

[0082] Fluorine compounds and flow

[0083] The fluorinated compounds used in the methods described herein can include any compound of any phase containing one or more fluorine atoms in its structure. For example, fluorinated compounds can include hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), fluorocarbons (FCs), or combinations thereof. In some embodiments, the fluorinated compound is a compound of formula (I) –

[0084] C a H b Cl c F d Formula (I),

[0085] Wherein a is 1 to 6, b is 0 to 14, c is 0 to 14, and d is 1 to 14, wherein optionally b and / or c are not 0, wherein b + c + d = 2a + 2, and wherein optionally the compound of formula (I) is substituted. In some embodiments, the fluorinated compound is 1,1,1,2-tetrafluoroethane. In some embodiments, the fluorinated compound is difluoromethane. In some embodiments, the fluorinated compound is dichlorodifluoromethane.

[0086] Fluorinated compounds can be components of a fluorinated stream. A fluorinated stream can consist of one or more fluorinated compounds, such as monofluorinated, difluorinated, trifluorinated, etc. A fluorinated stream may contain at least one component other than one or more fluorinated compounds. At least one component other than one or more fluorinated compounds can be a fluid, such as an inert gas, air, oxygen, etc. In some embodiments, a fluorinated stream includes (i) a fluorinated compound and any inert gas disclosed herein, such as nitrogen; (ii) a fluorinated compound, any inert gas disclosed herein, and air; (iii) a fluorinated compound and air; or (iv) a fluorinated compound, oxygen (O2), and any inert gas disclosed herein, such as nitrogen.

[0087] One or more fluorinated compounds may be present in the fluorinated stream at any concentration and / or ratio. When two or more components other than fluorinated compounds are present in the fluorinated stream, these two or more components may be present at any concentration and / or ratio (volume ratio or weight ratio). For example, the fluorinated stream may include an inert gas and air, which 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. As another example, the volume ratio of inert gas to oxygen (O2) in the fluorinated stream may be 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 fluorinated stream includes 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) may be a component of air.

[0088] The fluorinated stream can be formed using any known equipment, and the components of the fluorinated stream can be combined in any manner and / or sequence, such as simultaneously, sequentially, etc. In some embodiments, contact between the redistributed spent catalyst and the fluorinated stream includes a circulating fluid (e.g., an inert gas) and the injection of a fluorinated compound into the circulating fluid. In some embodiments, the injection of the fluorinated compound is achieved at least in part using a spraying apparatus, such as a spraying apparatus configured to disperse the fluorinated compound in the circulating fluid (e.g., an inert gas, oxygen, or a combination thereof). For example, contact between the redistributed spent catalyst and the fluorinated stream may include circulating a stream containing an inert gas and oxygen (O2) and injecting the fluorinated compound into the circulating stream. The circulating stream may contain any concentration of oxygen (O2). In some embodiments, the concentration of oxygen (O2) present in the circulating stream is, by volume, about 0.01% to about 10%, about 0.01% to about 8%, about 0.01% to about 6%, about 0.01% to about 4%, about 1% to about 4%, about 2% to about 4%, about 2.5% to about 3.5%, or about 3%.

[0089] Catalysts (e.g., redistributed spent catalysts) can be contacted with fluorinated compounds or fluorinated streams in any manner and under any conditions to effectively place the desired weight percentage of fluorine (e.g., up to 3%, up to 2%, or up to 1% by weight) onto the catalyst.

[0090] In some embodiments, contacting the spent catalyst (e.g., redistributed spent catalyst) with the fluorinated stream includes (a) providing two or more reactors in fluid communication with each other, wherein the two or more reactors are connected in series, thereby allowing the fluorinated stream to (i) be injected at an injection point selected from one or more injection points, (ii) be circulated sequentially through each of the two or more reactors downstream of the injection point, (iii) return to the first of the two or more reactors, and optionally (iv) be circulated sequentially through each of the two or more reactors, wherein each of the two or more reactors includes a reservoir in which the spent catalyst is disposed; (b) heating one of the two or more reactors to a temperature equal to or above the fluorination temperature, and holding each of the remaining two or more reactors at a temperature below the fluorination temperature, wherein the fluorination temperature is capable of at least partially decomposing the fluorinated compounds in the fluorinated stream; and (c) injecting the fluorinated stream and circulating or recirculating the fluorinated stream for a period of time to bring the spent catalyst in one of the two or more reactors to the desired fluorination level at a temperature equal to or above the fluorination temperature.

[0091] When the systems and methods of this paper comprise a set of components connected in series (e.g., reactors), any component referred to as “first” is the most upstream component, with the remaining components subsequently numbered sequentially, where the highest number is assigned to any component downstream of all other components in the group. For example, if a system comprises three reactors, the “first” reactor is upstream of the “second” and “third” reactors, while the “third” reactor is downstream of the “first” and “second” reactors. Therefore, if the limitation of this paper states that the stream “returns to the first of two or more reactors,” then that limitation indicates that the stream is conveyed to a reactor upstream of the other “two or more reactors.”

[0092] The method may further include heating one of two or more reactors to a temperature equal to or above the fluorination temperature, and maintaining each of the remaining reactors at a temperature below the fluorination temperature; and injecting a fluorinated stream and circulating or recirculating the fluorinated stream for a period of time to bring the spent catalyst in one of the two or more reactors to the desired fluorination level at a temperature equal to or above the fluorination temperature. These steps may be repeated until the spent catalyst in each of the one or more reactors is fluorinated to the desired level.

[0093] The fluorinated stream can be circulated through two or more reactors once, or it can be recirculated through two or more reactors any number of times. Recirculation can continue until the desired fluorine concentration is achieved on the catalyst.

[0094] The fluorination temperature can include any temperature at which the fluorinated compound at least partially decomposes. In some embodiments, the temperature equal to or above the fluorination temperature is at least 700℉. In some embodiments, the temperature equal to or above the fluorination temperature is about 650℉ to about 850℉, about 700℉ to about 850℉, about 700℉ to about 800℉, about 700℉ to about 775℉, or about 700℉ to about 750℉. In some embodiments, the temperature below the fluorination temperature is about 600℉ or lower. In some embodiments, the temperature below the fluorination temperature is about 300℉ to about 600℉, about 400℉ to about 600℉, or about 500℉ to about 600℉.

[0095] The fluorinated stream can be introduced into two or more reactors in any manner. In some embodiments, the fluorinated stream is injected. The injection of the fluorinated stream may include: (1) selecting an injection point from one or more injection points, and (2) injecting the fluorinated stream into an injection connector selected from said one or more injection points. The selected injection point can be any of the systems provided herein. In some embodiments, the selected injection point is (i) upstream of a reactor (or different reactors) heated to a temperature equal to or above the fluorination temperature, (ii) downstream of all other reactors upstream of a reactor (or different reactors) heated to a temperature equal to or above the fluorination temperature, or (iii) a combination thereof.

[0096] The amount of fluorinated compound or fluorinated stream injected and recycled / recycled can effectively place any amount of fluorine, such as about 0.1 wt% to about 1.5 wt% fluorine, about 0.5 wt% to about 1.5 wt% fluorine, or about 0.15 wt% to about 1.2 wt% fluorine, on the spent catalyst. This method may include analyzing the fluorinated stream during recycling or recycling to determine the amount or concentration of fluorinated compound and / or fluorine in the fluorinated stream. This method may include stopping the recycling / recycling of the fluorinated stream when the amount or concentration of fluorinated compound and / or fluorine is equal to or below a threshold concentration or amount indicating successful deposition of fluorine on the spent catalyst. Monitoring of the fluorinated stream can be achieved using any known technique or equipment (e.g., spectrometry).

[0097] This document also provides a system for fluorinating spent catalysts. The system may include: (a) two or more reactors in fluid communication with each other, wherein the two or more reactors are connected in series, thereby allowing a fluid flow (e.g., a fluorinated flow) to (i) be injected at an injection point selected from one or more injection points, (ii) circulate sequentially through each of the two or more reactors downstream of the injection point, (iii) return to the first of the two or more reactors, and optionally (iv) recirculate sequentially through 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.

[0098] Figure 1 An embodiment of the system is shown. 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, wherein these components are connected in series via a pipe 101, which includes a "feedback loop" 102 that recirculates the circulating flow from the third reactor 122 back to the first reactor 110. Although Figure 1Three pairs of reactor / heater furnaces (110 / 120, 111 / 121, 112 / 122) are depicted, but the system may include two, three, four, five, six, seven, eight, nine, ten or more reactors. Figure 1 The system 100 includes three possible injection points (130, 131, 132), located upstream of the first reactor 120, the second reactor 121, and the third reactor 122, respectively. A system with [specific features] can be used. Figure 1 The diagram shows furnaces with different configurations, such as tube furnaces or other configurations.

[0099] Figure 1 System 100 can be used to perform embodiments of the methods provided herein. For example, in some embodiments, the method includes: (i) heating reactor 120 to a temperature of about 700℉ to about 850℉ using furnace 110; (ii) maintaining the temperatures of second reactor 121 and third reactor 122 at or below about 600℉; and (iii) injecting a fluorinated stream at a first injection point 130 and circulating or recirculating the fluorinated stream through the first reactor 120, second reactor 121, and third reactor 122 for a period of time to effectively deposit the desired level of fluorine on the spent catalyst 140 of the first reactor 120. The method may further include: (i) reducing the temperature of the first reactor 120 to about 600℉ or lower; (ii) raising the temperature of the second reactor 121 to about 700℉ to about 850℉ using furnace 111; (iii) maintaining the temperatures of the first reactor 120 and the third reactor 122 at or below about 600℉; and (iv) injecting a fluorinated stream at the second injection point 131 and circulating or recirculating the fluorinated stream through the second reactor 121, the third reactor 122 and the first reactor 120 for an effective duration to allow the desired level of fluorine to be deposited on the spent catalyst 141 of the second reactor 121. The method may further include: (i) reducing the temperature of the second reactor 121 to about 600℉ or lower; (ii) using furnace 112 to raise the temperature of the third reactor 122 to about 700℉ to about 850℉; (iii) maintaining the temperature of the first reactor 120 and the second reactor 121 at or below about 600℉; and (iv) injecting a fluorinated stream at a third injection point 132 and circulating or recirculating the fluorinated stream through the third reactor 122, the first reactor 120 and the second reactor 121 for an effective duration to allow the desired level of fluorine to be deposited on the spent catalyst 142 of the second reactor 122.

[0100] In some embodiments, the selection of (i) the amount of fluorinated compound in the fluorinated stream, (ii) the duration of contact between the spent catalyst and the fluorinated stream, or (iii) a combination thereof, is such 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 placed on the redistributed spent catalyst. In some embodiments, the contact between the catalyst (e.g., the spent catalyst) and the fluorinated stream is at least partially carried out at temperatures of about 500℉ to about 1,000℉, about 600℉ to about 1,000℉, about 600℉ to about 900℉, about 700℉ to about 900℉, or about 700℉ to about 850℉. In some embodiments, the amount of fluorinated compound in the fluorinated stream is controlled to obtain the desired fluorine [F] concentration on the catalyst, for example, less than any maximum amount or within any range disclosed herein, such as 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%, from about 0.1 wt% to about 3 wt%, from about 1 wt% to about 2 wt%, from about 1.25 wt% to about 1.75 wt%, from about 0.1 wt% to About 1.5 wt%, about 0.15 wt% to about 1.3 wt%, about 0.1 wt% to about 1.0 wt%, about 0.25 wt% to about 3 wt%, about 0.25 wt% to about 2 wt%, about 0.25 wt% to about 1.75 wt%, about 0.25 wt% to about 1.5 wt%, about 0.25 wt% to about 1.3 wt%, about 0.25 wt% to about 1.0 wt%, about 0.5 wt% to about 1 wt%, or about 0.3 wt% to about 0.8 wt%. In some embodiments, the fluorination step is performed under the following conditions: (i) a fluorination temperature within any of the fluorination temperature ranges disclosed herein, such as 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 about 15 bar at atmospheric pressure, about 10 bar at atmospheric pressure, about 7 bar at atmospheric pressure, 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 performed for a period of time within any of the fluorination time periods disclosed herein, such as 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.

[0101] In some embodiments, the amount of fluorinated compound in the fluorinated stream is controlled such that the concentration of fluorine [F] or the fluorinated compound (e.g., the concentration in the fluorinated stream) is less than any maximum amount disclosed herein or within any range, such as 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 The range is approximately 50 to 15,000 ppmv, approximately 50 to 10,000 ppmv, approximately 50 to 5,000 ppmv, approximately 50 to 2,500 ppmv, approximately 50 to 1,000 ppmv, approximately 500 to 1,000 ppmv, approximately 600 to 900 ppmv, approximately 700 to 800 ppmv, or approximately 750 ppmv.

[0102] In some embodiments, the fluorine concentration in the regenerated catalyst is from about 0.15 wt% to about 1.2 wt%, or from about 0.2 wt% to about 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.

[0103] Generally, a fluorinated stream may include any compounds, gases, etc. described herein, and any one or more compounds, gases, etc. described herein may be excluded from a fluorinated stream. For example, a fluorinated stream may be substantially free of oxygen-containing compounds and / or chlorine-containing compounds that do not contain fluorine atoms. A fluorinated stream is considered "substantially free" of a compound when the concentration of the compound in the stream is less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw.

[0104] The method provided herein may also include recovering at least a portion of the fluorinated stream to generate a recovered fluorinated stream. At least a portion of the fluorinated stream can be recovered after the decoking catalyst has been contacted with the fluorinated stream. The method may also include contacting the decoked catalyst with the recovered fluorinated stream.

[0105] Chlorine-containing compounds and flow

[0106] The chlorine-containing compounds used in the methods described herein can 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 contain one or more compounds other than chlorine-containing compounds (e.g., inert gases). In some embodiments, the chlorine-containing stream includes chlorine gas (Cl2) and an inert gas, such as nitrogen gas (N2). In some embodiments, the chlorine-containing compound includes hydrochloric acid, chlorine gas (Cl2), carbon tetrachloride, tetrachloroethylene, chlorobenzene, chloromethane, dichloromethane, chloroform, allyl chloride, trichloroethylene, chloramine, chlorine oxide, chloric acid, chlorine dioxide, dichloride, dichloride heptaoxide, chloric acid, perchloric acid, ammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, methyltriethylammonium chloride, or any combination thereof.

[0107] The chlorine-containing stream can be formed using any known device, and the components of the chlorine-containing stream can be combined in any manner and / or sequence, such as simultaneously, sequentially, etc. For example, the method described herein may include a circulating fluid, such as an inert gas, and the injection of a chlorine-containing compound into the circulating fluid. The injection of the chlorine-containing compound may be achieved, at least in part, using a spray device configured to disperse the chlorine-containing compound in the circulating inert gas.

[0108] In some embodiments, the amount of chlorinated compound in the chlorinated stream is controlled to obtain the desired concentration of chlorine (Cl) or chlorinated compound, for example less than any maximum amount disclosed herein or in any range, such as 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, in the range of about 50 to about 10,000 ppmv, in the range of about 50 to about 5,000 ppmv, in the range of about 50 to about 2,500 ppmv, in the range of about 50 to about 1,000 ppmv, in the range of about 50 to about 500 ppmv, in the range of about 50 to about 100 ppmv, in the range of about 100 to about 750 ppmv, or in the range of about 500 to about 600 ppmv.

[0109] The catalyst can be contacted with a chlorinated compound or a chlorinated stream in any manner and under any conditions to effectively place a desired weight percentage of chlorine or a chlorinated compound (e.g., up to 3%, up to 2%, or up to 1% by weight) onto the catalyst. In some embodiments, (i) the amount of chlorinated compound in the chlorinated stream, (ii) the duration of contact between the treated spent catalyst and the chlorinated stream, or (iii) a combination thereof, are controlled to place 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 0.6 wt% to about 1 wt% of chlorine or a chlorinated compound onto the treated spent catalyst.

[0110] Generally, a chlorinated stream may include any compounds, gases, etc. described herein, and any one or more compounds, gases, etc. described herein may be excluded from a chlorinated stream. For example, a chlorinated stream may be substantially free of oxygen-containing compounds and / or fluorine-containing compounds. A chlorinated stream is considered "substantially free" of a compound when the concentration of the compound present in the chlorinated stream is less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw.

[0111] The catalyst can be contacted with a chlorinated compound or a chlorinated stream in any manner and under any conditions (e.g., temperature, pressure, etc.). In some embodiments, the chlorination step is carried out at a chlorination temperature within any of the chlorination temperature ranges disclosed herein, such as about 0℉ to about 600℉, about 100℉ to about 600℉, about 200℉ to about 600℉, about 300℉ to about 600℉, about 400℉ to about 600℉, about 400℉ to about 500℉, or about 400℉ to about 450℉. In some embodiments, the chlorination step is carried out for a period of time within any of the chlorination time ranges disclosed herein, such as about 0.5 hours to about 72 hours, about 0.75 hours to about 60 hours, about 1 hour to about 48 hours, about 1 hour to about 12 hours, or about 2 hours to about 8 hours. In some embodiments, the chlorination step is carried out at chlorination temperatures of about 0℉ to about 600℉, about 100℉ to about 600℉, about 200℉ to about 600℉, about 300℉ to about 600℉, about 300℉ to about 500℉, about 350℉ to about 500℉, or about 350℉ to about 450℉. In some embodiments, the chlorination step is carried out for a period of time within any of the chlorination time periods disclosed herein, such as about 0.10 hours to about 72 hours, about 0.50 hours to about 60 hours, about 0.5 hours to about 48 hours, about 0.5 hours to about 12 hours, or about 1 hour to about 8 hours.

[0112] Decoking airflow

[0113] The decoking gas flow can include any of those known in the art. In some embodiments, the decoking gas flow includes any combination of inert gas (one or more) and oxygen disclosed herein, such as a mixture of nitrogen and oxygen, air, or a mixture of air and nitrogen.

[0114] The oxygen concentration in the decoking gas stream may be limited. In some embodiments, the decoking gas stream includes less than any maximum amount or in any range of mol% disclosed herein, 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%.

[0115] The decoking gas stream may include any one or more compounds disclosed herein, or any one or more compounds disclosed herein may be excluded from the decoking gas stream. In some embodiments, the decoking gas stream is substantially free of halogen-containing compounds, such as added halogen-containing compounds (e.g., substantially halogen-free, substantially chlorine-free). The decoking gas stream is "substantially free" of halogen-containing compounds when the concentration of the halogen-containing compound is less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw. In some embodiments, the decoking gas stream is substantially free of water (e.g., added water). The decoking gas stream is "substantially free" of water when the concentration of water is less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw.

[0116] carbon combustion

[0117] 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 the catalyst (e.g., stripped spent catalyst) is about 300℉ to about 600℉, about 350℉ to about 550℉, about 350℉ to about 500℉, or about 400℉ to about 475℉. In some embodiments, the carbon combustion temperature of the catalyst (e.g., chlorinated spent catalyst) is about 500℉ to about 1,200℉, about 500℉ to about 1,100℉, about 500℉ to about 1,000℉, about 600℉ to about 1,000℉, about 700℉ to about 1,000℉, about 700℉ to about 900℉, about 800℉ to about 900℉, or about 850℉. In some embodiments, the carbon combustion step is carried out at a peak decoking temperature within any of the peak decoking temperature ranges disclosed herein, such as 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 begins at an initial decoking temperature that is the same as any chlorine purging temperature disclosed herein, such as 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).

[0118] The carbon combustion of stripped spent catalyst can take place for 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 of the catalyst (e.g., chlorinated spent catalyst) takes place for 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 performed within any of the decoking time ranges disclosed herein, such as 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 hour to about 72 hours, about 12 hours to about 48 hours, or about 1 hour to about 6 hours.

[0119] 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 (e.g., stripped spent catalyst) can remove at least 90 wt%, at least 95 wt%, at least 99 wt%, or 100 wt% of hydrocarbon feed from the spent catalyst. Carbon combustion of a catalyst (e.g., stripped spent catalyst) can remove at least 90 wt%, at least 95 wt%, at least 99 wt%, or 100 wt% of aromatic products from the spent catalyst. A certain amount of soft coke can be absorbed and / or adsorbed onto the catalyst (e.g., spent catalyst), and carbon combustion of the catalyst can reduce the amount of soft coke absorbed and / or adsorbed onto the spent catalyst. In some embodiments, the carbon combustion step is carried out for a period of time sufficient to reduce the weight percentage of carbon on the catalyst (e.g., chlorinated spent catalyst) to less than any maximum carbon weight percentage disclosed herein (e.g., less than about 1 wt%, less than about 0.5 wt%, or less than about 0.2 wt%).

[0120] Carbon combustion of a catalyst (e.g., a chlorination catalyst) can improve the dispersion of transition metals within 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%.

[0121] Partial defocusing steps

[0122] The methods provided herein may include a partial decoking step. The partial decoking step can be performed at any effective point in the method, such as before the chlorination step. The partial decoking step may include contacting a catalyst (e.g., spent catalyst) with a partially decoking gas stream that may include oxygen.

[0123] The partial decoking gas stream may include any combination of the inert gas (one or more) disclosed herein and oxygen, such as a mixture of nitrogen and oxygen, or air. The partial decoking gas stream may contain less than any maximum amount or within any range disclosed herein in mol%, 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%.

[0124] The partial decoking gas stream may include any compounds disclosed herein, and any compounds disclosed herein may be present outside the partial decoking gas stream. For example, the partial decoking gas stream may be substantially free of halogen-containing compounds (e.g., substantially free of halogens). The partial decoking gas stream is “substantially free” of halogen-containing compounds when the concentration of the halogen-containing compound is less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw. As a further example, the decoking gas stream may be substantially free of water. The decoking gas stream is “substantially free” of water when the concentration of water is less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw.

[0125] The partial decoking step can be carried out under any effective conditions (e.g., time, temperature, etc.). The partial decoking step can be carried out at partial decoking temperatures within any of the partial decoking temperature ranges disclosed herein, such as from about 150°C (about 302°F) to about 600°C (about 1,112°F), or from about 150°C (about 302°F) to about 250°C (about 482°F). The partial decoking step can be carried out for a period of time within any of the partial decoking time ranges disclosed herein, such as from about 1 hour to about 48 hours, or from about 2 hours to about 24 hours. The partial decoking step can be carried out for a period of time sufficient to reduce the carbon weight percentage on the spent catalyst to any range of carbon weight percentages disclosed herein, such as from about 0.05 wt% to about 10 wt%, from about 0.1 wt% to about 10 wt%, from about 0.05 wt% to about 5 wt%, from about 0.1 wt% to about 5 wt%, from about 1 wt% to 10 wt%, or from about 4 wt% to about 5 wt%.

[0126] Pre-drying step

[0127] The methods provided herein may include a pre-drying step. The pre-drying step can be performed at any effective point in the process. In some embodiments, the method includes performing a pre-drying step prior to the chlorination step.

[0128] 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, such as nitrogen. The pre-drying gas stream may include any compounds disclosed herein, and any compounds disclosed herein may be excluded from the pre-drying gas. For example, the pre-drying gas stream may be substantially free of oxygen-containing compounds. A pre-drying gas stream is considered "substantially free" of oxygen-containing compounds when the concentration of oxygen-containing compounds is less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw.

[0129] 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 pre-drying temperatures within any of the pre-drying temperature ranges disclosed herein, such as 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 period of time within any of the pre-drying time ranges disclosed herein, such as 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 period of time sufficient to reduce the moisture content of the catalyst (e.g., spent catalyst) to a desired level, such as to a concentration less than any maximum moisture content of the spent catalyst disclosed herein, for example, less than about 4% by weight or less than about 1% by weight.

[0130] Chlorine purging procedure

[0131] The methods provided herein may include a chlorine purging step. The chlorine purging step may be performed at any point in the methods provided herein, for example, before the carbon combustion step.

[0132] The chlorine purging step may include contacting a catalyst (e.g., a chlorinated spent catalyst) with a chlorine purge stream. The chlorine purge stream may include any inert gas disclosed herein, such as nitrogen. The chlorine purge stream may include any compounds disclosed herein, and any compounds disclosed herein may be excluded from the chlorine purge stream. For example, the chlorine purge stream may be substantially free of oxygen-containing compounds, for example, at a concentration of less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw. As a further example, the chlorine purge stream may be substantially free of halogen-containing compounds (substantially halogen-free), for example, halogen-containing compounds are present at a concentration of less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw.

[0133] The chlorine purging step can be performed under any effective conditions (e.g., time, temperature, pressure, etc.). In some embodiments, the chlorine purging step is performed at a chlorine purging temperature within any of the chlorine purging temperature ranges disclosed herein, such as 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 performed for a period of time within any of the chlorine purging time ranges disclosed herein, such as about 1 hour to about 96 hours, or about 1 to about 48 hours. The duration of the chlorine purging step is sufficient to reduce the chlorine content of the discharged chlorine purging effluent to below any of the maximum chlorine content described herein, such as below about 100 ppmw, below about 50 ppmw, or below about 25 ppmw of chlorinated compounds after contact with the catalyst (e.g., chlorinated spent catalyst).

[0134] Fluorine purging procedure

[0135] The method described herein may also include a fluorine purging step. The fluorine purging step may be performed at any point in the method described herein, for example, after the fluorination step. The fluorine purging step may include contacting a catalyst (e.g., a decoked and fluorinated catalyst) with a fluorine purging stream. The fluorine purging stream may include any inert gas disclosed herein, such as nitrogen.

[0136] The fluorine purge stream may include any compounds disclosed herein, and any compounds disclosed herein may be excluded from the fluorine purge stream. In some embodiments, the fluorine purge stream is substantially free of oxygen-containing compounds. The fluorine purge stream is "substantially free" of oxygen-containing compounds when the concentration of oxygen-containing compounds is less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw. The fluorine purge stream may be substantially free of halogen-containing compounds (substantially halogen-free). The fluorine purge stream is "substantially free" of halogen-containing compounds when the concentration of halogen-containing compounds is less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw.

[0137] The fluorine purging step can be performed under any effective conditions (e.g., time, temperature, pressure, etc.). In some embodiments, the fluorine purging step is performed at a fluorine purging temperature within any of the fluorine purging temperature ranges disclosed herein, such as 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 performed for a period of time within any of the fluorine purging time ranges disclosed herein, such as about 0.25 hours to about 72 hours, or about 1 to about 48 hours. The duration of the fluorine purging step is sufficient to reduce the fluorine content of the discharged fluorine purging effluent to below any of the maximum fluorine content described herein, such as below about 100 ppmw, below about 50 ppmw, or below about 25 ppmw of fluorinated compounds after contact with the decoking and fluorinated catalyst.

[0138] Oxygen purging procedure

[0139] The methods provided herein may include an oxygen purging step. The oxygen purging step may be performed at any point in time in the methods provided herein, for example, after a carbon combustion step or a fluorine purging step.

[0140] The oxygen purging step may include contacting the catalyst with an oxygen purge stream. The oxygen purge stream may include any inert gas disclosed herein, such as nitrogen. The oxygen purge stream may include any compounds disclosed herein, and any compounds disclosed herein may be excluded from the oxygen purge stream. The oxygen purge stream may be substantially free of oxygen-containing compounds, for example, the concentration of oxygen-containing compounds may be less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw. The oxygen purge stream may be substantially free of halogen-containing compounds (substantially halogen-free), for example, the concentration of halogen-containing compounds present may be less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw.

[0141] The oxygen purging step can be performed under any effective conditions (e.g., time, temperature, pressure, etc.). For example, the oxygen purging step can be performed at an oxygen purging temperature within any of the oxygen purging temperature ranges disclosed herein, such as 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 performed for a period of time within any of the oxygen purging time ranges disclosed herein, such as about 0.5 hours to about 96 hours, or about 1 hour to about 48 hours. The oxygen purging step can be performed for a period of time sufficient to reduce the oxygen content of the purged oxygen effluent to below any of the maximum oxygen contents described herein, such as less than about 100 ppmw, less than about 50 ppmw, or less than about 25 ppmw of oxygenated compounds after contact with the catalyst.

[0142] Hydrocarbon processing steps

[0143] The methods provided herein may include a hydrocarbon treatment step. The hydrocarbon treatment step may be performed at any point in time in the methods described herein, for example, prior to the carbon combustion step. The hydrocarbon treatment step includes contacting chlorinated spent catalyst with a hydrocarbon treatment stream comprising a hydrocarbon feedstock.

[0144] The hydrocarbon feed may include one or more alkanes and / or one or more cycloalkanes, such as C6-C8 alkanes and / or cycloalkanes.

[0145] The hydrocarbon processing step can be performed under any effective conditions (e.g., time, temperature, pressure, etc.). In some embodiments, the hydrocarbon processing step is performed at a hydrocarbon processing temperature within any of the hydrocarbon processing temperature ranges disclosed herein, such as from about 400°C (about 752°F) to about 600°C (about 1,112°F). The hydrocarbon processing step can be performed for a period of time within any of the hydrocarbon processing time periods disclosed herein, such as from about 1 to about 48 hours.

[0146] Restoration steps

[0147] The methods provided herein may include a reduction step. The reduction step may be performed at any point in time in the methods provided herein, for example, after a fluorination step. The reduction step may include contacting a catalyst (e.g., a regenerated catalyst or a decoked and fluorinated catalyst) with a reducing gas stream. The reducing gas stream may include molecular hydrogen. The reducing gas stream may contain greater than any minimum amount disclosed herein or in any range of mol% such as greater than about 25 mol% or greater than about 75 mol% of molecular hydrogen.

[0148] The reduction step can be carried out under any effective conditions (e.g., time, temperature, pressure, etc.). The reduction of the catalyst (e.g., a regenerated catalyst) can be carried out at temperatures of about 600℉ to about 1,200℉, about 700℉ to about 1,100℉, about 800℉ to about 1,000℉, about 900℉ to about 1,000℉, or about 950℉ to about 1,000℉. The reduction of the catalyst (e.g., a regenerated catalyst) can be carried out, at least partially, in an atmosphere containing an inert gas (e.g., nitrogen), hydrogen (H2), or a combination thereof. The reduction step can be carried out at a peak reduction temperature within any of the peak reduction temperature ranges disclosed herein, such as about 200°C to about 600°C, or about 400°C to about 600°C. The reduction step can be initiated at an initial reduction temperature that is the same as any oxygen purging temperature disclosed herein, such initial reduction temperature being, 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 can be carried out for a period of time within the time range of any reduction step disclosed herein, for example, about 0.5 hours to about 48 hours, or about 10 hours to about 30 hours.

[0149] catalyst

[0150] The catalyst subjected to the methods provided herein may include any known catalyst, which may include any known catalyst support. The catalyst support may include zeolite, amorphous inorganic oxide, or any combination thereof.

[0151] The catalyst support may include L zeolite, Y zeolite, mordenite, ω zeolite, and / or β zeolite. The catalyst support may also include potassium L zeolite or barium ion-exchange L zeolite.

[0152] The catalyst may include a binder, such as a binder comprising alumina, silica, mixed oxides thereof, or mixtures thereof.

[0153] The catalyst may contain metals, such as transition metals. Transition metals may include group 8-11 transition metals. Transition metals may include platinum. The catalyst may contain any weight percentage range of transition metals; for example, about 0.1 wt% to about 10 wt%, or about 0.3 wt% to about 5 wt% of transition metals.

[0154] The spent catalyst may contain any weight percentage range of transition metals, such as platinum. For example, the spent catalyst may contain any amount of platinum, from about 0.1 wt% to about 10 wt% or from about 0.5 wt% to about 2 wt%.

[0155] In some embodiments, the catalyst comprises platinum on KL zeolite. The catalyst may also comprise chlorine and fluorine. For example, the catalyst may comprise any weight percentage range of chlorine and / or fluorine disclosed herein, such as about 0.01 wt% to about 5 wt%, or about 0.3 to about 1.3 wt% of fluorine, 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 comprise a chlorine:fluorine molar ratio of about 0.5:1 to about 4:1.

[0156] Regenerated / Reactivated Catalyst

[0157] This document also provides catalysts that have been processed by the methods provided herein, such as reactivated or regenerated catalysts produced by the methods described herein. In some embodiments, the reactivated or regenerated catalyst comprises any amount of iron disclosed herein, such as 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 comprises any amount of iron disclosed herein, such as an iron concentration difference between the reactivated catalyst and the spent catalyst of 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.

[0158] In some embodiments, the reactivation catalyst or regenerated catalyst includes any amount of carbon disclosed herein, such as 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% of carbon.

[0159] In some embodiments, the reactivation catalyst or regenerated catalyst comprises any amount of chlorine disclosed herein, such as 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%, about 0.3 wt% to about 1.3 wt% of chlorine.

[0160] In some embodiments, the reactivation catalyst or regeneration catalyst comprises any amount of fluorine disclosed herein, such as 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%.

[0161] In some embodiments, the reactivation catalyst or regeneration catalyst comprises any amount of fluorine disclosed herein, such as 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%.

[0162] In some embodiments, the reactivated or regenerated catalyst is characterized in that its TEOR is within about 50℉, about 40℉, about 30℉, or about 20℉ of the TEOR of the fresh reference catalyst. The reactivated or regenerated catalyst is characterized in that its TSO is within about 50℉, about 40℉, about 30℉, or about 20℉ of the TSO of the fresh reference catalyst. The reactivated or regenerated catalyst is characterized in that its scaling rate (FR) is within any range disclosed herein, for example, about 0.01℉ / hour to about 0.25℉ / hour, about 0.02℉ / hour to about 0.2℉ / hour, about 0.03℉ / hour to about 0.2℉ / hour, or about 0.03℉ / hour to about 0.15℉ / hour. The reactivated or regenerated catalyst is characterized in that its benzene + toluene selectivity is within any 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 is characterized in that the benzene + toluene selectivity is within any selectivity range disclosed herein, for example, greater than about 0.88 or greater than 0.90.

[0163] The methods provided herein also include methods using reactivated and / or regenerated catalysts. In some embodiments, the method includes providing a catalyst that has been subjected to any one or more regeneration / reactivation methods provided herein, and contacting the catalyst with reactants (e.g., hydrocarbons) to generate products (e.g., aromatic products).

[0164] Example

[0165] This disclosure is further illustrated by the following embodiments, which should not be construed as limiting the scope of the technology in any way. After reading this description, those skilled in the art will conceive of various other aspects, embodiments, modifications, and equivalents without departing from the spirit of this disclosure or the scope of the appended claims.

[0166] Unless otherwise specified, the weight percentages of Pt, Cl, F, and Fe were determined using X-ray fluorescence (XRF) and based on the total weight of the aromatization catalyst. Carbon (wt%) was determined using a CHNS analyzer (Carlo Erba). Platinum dispersion was determined by CO pulse chemisorption.

[0167] In some of the examples below, the scaling rate (FR, in °F / h) of the regenerated catalysts was tested, and its relationship with activity was given by the formula y = FR * t + TSOR, where y is temperature, FR is scaling rate, t is time, and TSOR is the initial operating temperature. The FR of the regenerated catalyst samples was determined by plotting the temperature required to maintain a total aromatic compound yield of 75 wt% over time under standard test conditions, as described later in this document. The slope of the calculated data was then fitted to determine the FR. The total operating time was typically 40 hours, and the end-of-operation temperature (TEOR) was also determined.

[0168] In each embodiment, the following standard test procedure was used. The catalyst was ground and sieved to approximately 20-40 mesh, and 2 cc of the sieved catalyst was placed in a 1 / 4-inch OD stainless steel reactor vessel in a temperature-controlled furnace. After reducing the catalyst under a flow of hydrogen, a feed stream of aliphatic hydrocarbons (approximately 12 mL / h) and molecular hydrogen (approximately 65 mL / min) was introduced into the reactor vessel at a pressure of approximately 65 psig, an H2:hydrocarbon molar ratio of 2.0:1, and a liquid hourly space velocity (LHSV) of 6 hr. -1 To obtain catalyst performance data over time, the aliphatic hydrocarbon feed contained approximately 22 to 32 wt% n-hexane, approximately 4 to 8 wt% n-heptane, approximately 33 to 37 wt% C6 isoalkanes, approximately 15 to 21 wt% C7 isoalkanes, and approximately 6 to 10 wt% C8 isoalkanes, with the remainder being C6 and C7 alkenes, cycloalkanes, and aromatic compounds. Gas chromatography was used to analyze the reactor effluent composition to determine the total aromatic compounds and benzene + toluene selectivity.

[0169] In the examples, the effectiveness of various processes and steps for regenerating spent catalysts was experimentally demonstrated, with the performance of fresh aromatization catalysts serving as the target benchmark. 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 injection pore volume is approximately 0.19 cc / g, and the micropore volume is approximately 0.0615 cc / g. The spent catalyst is derived from fresh catalyst that has been deactivated after prolonged use during aromatization. In these examples, the spent catalyst is subjected to a mild partial decoking treatment prior to use to remove unreacted hydrocarbons and light carbonaceous deposits from the catalyst.

[0170] Example 1A - Preparation of Fluorine-Containing Regeneration Catalyst

[0171] For comparison, the following regeneration procedure involving the use of fluorine gas was performed. Approximately 42 g of spent catalyst was loaded into a new metal fixed-bed reactor (containing 347 stainless steel) and, unless otherwise specified, contacted for 12 hours at approximately 400℉ (approximately 204.4°C) with a nitrogen gas stream (approximately 1500 mL / min), followed by contacting for approximately 3 hours at approximately 300℉ (approximately 148.9°C) with a chlorine-containing gas stream (approximately 37 mL / min) containing nitrogen gas (approximately 1463 mL / min) and chlorine gas (e.g., a mixture of N2 and 2% Cl2) (approximately 37 mL / min), followed by contacting for approximately 3 hours at approximately 400℉ (approximately 204.4°C) with a nitrogen gas stream (1463 mL / min or 1500 mL / min), or approximately 12 hours. The process involves contacting the gas with a decoking gas stream containing a mixture of air (75 mL / min) and nitrogen (1425 mL / min) at approximately 850℉ (approximately 454.4 °C) for approximately 44 hours, then contacting the gas with a fluorinated gas stream containing nitrogen (approximately 1350 mL / min) and fluorine gas (e.g., a mixture of F2 gas in N2) at approximately 300℉ (approximately 148.9 °C) for approximately 3 hours, and then contacting the gas with a nitrogen gas stream (approximately 1353 mL / min or approximately 1500 mL / min) at approximately 400℉ (approximately 204.4 °C) for approximately 3 hours, or approximately 12 hours to approximately 16 hours.

[0172] Example 1B - Preparation of regenerated catalyst from hydrofluorocarbons in two reactors

[0173] A certain amount of spent catalyst is loaded into a new metal fixed-bed reactor (containing stainless steel 347), unless otherwise specified (e.g., in some tests, fluorine is in a container containing stainless steel 347, while hydrofluorocarbons are in a container containing stainless steel 321). The spent catalyst is then contacted at about 400℉ (about 204.4°C) with a nitrogen stream (about 1500 mL / min) for about 12 hours, then at about 300℉ (about 148.9°C) with a chlorine stream containing nitrogen (about 1463 mL / min) and chlorine (e.g., 2% Cl2 in N2) (about 37 mL / min) for about 3 hours, then at about 400℉ (about 204.4°C) with a nitrogen stream (about 1463 mL / min) for about 3 hours, or about 12 hours to about 16 hours, and then at about 850℉ (about 454.4°C) with a decoking stream containing air (about 500 mL / min) for about 2 hours to generate a decoking catalyst. Reduce the temperature to 700℉ and the air flow rate to 200 mL / min. Repeat this process several times to produce a large batch of chlorination decoking catalyst.

[0174] Approximately 45 g of chloride decoking catalyst was transferred to a reactor (stainless steel 347) with an outer diameter of 1 inch. A stream of 1,1,1,2-tetrafluoroethane (20%) in N2 at a flow rate of approximately 17 mL / min was mixed with a second air stream at a flow rate of 200 mL / min to generate a mixed stream. The decoking catalyst and the mixed stream were contacted at a pressure of 50 psi for approximately 60 minutes. At the end of the 60-minute contact time, the FREON was stopped. TM Fluorinated organic compounds / N2 stream. Purge continuously for 30 minutes at 200 mL / min air at 730℉ and 50 psi. Reduce temperature to 500℉; once below 500℉, stop the air purge and begin N2 at 200 mL / min. Cool the catalyst to room temperature in the N2 stream.

[0175] Example 1C - Preparation of regenerated catalyst from hydrofluorocarbons in a reactor

[0176] Approximately 60 g of spent catalyst was loaded into a new metal fixed-bed reactor (containing 321 stainless steel) and, unless otherwise specified, contacted with a nitrogen stream (approximately 1700 mL / min) at approximately 400℉ (approximately 204.4 °C) for 12 hours, then contacted with a chlorine stream containing nitrogen (approximately 1640 mL / min) and chlorine (e.g., a mixture of N2 and 2% Cl2) (approximately 40 mL / min) at approximately 300℉ (approximately 148.9 °C) for approximately 3 hours, then contacted with a nitrogen stream (approximately 1640 mL / min) at approximately 400℉ (approximately 204.4 °C) for approximately 3 hours, or approximately 12 hours to approximately 16 hours, then contacted with an air decoking stream (680 mL / min) at approximately 850℉ (approximately 454.4 °C) for approximately 2 hours.

[0177] Reduce the air flow rate (approximately 280 mL / min) and mix the air with a stream of 1,1,1,2-tetrafluoroethane (20%) in N2 at a flow rate of approximately 22 mL / min to create a mixed stream. Contact the decoking catalyst with the mixed stream at 50 psi for approximately 60 minutes. At the end of the 60-minute contact time, stop the FREON. TM Fluorinated organic compounds / N2 stream. Purge continuously for 30 minutes at 730℉ and 50psi using air at 200 mL / min. Reduce the temperature to 500℉, and once below 500℉, stop the air and cool the catalyst to room temperature in an N2 stream (approximately 500 mL / min).

[0178] Example 1D - Preparation of regenerated catalyst from hydrofluorocarbons in a reactor

[0179] Approximately 30 g of spent catalyst was loaded into a new metal fixed-bed reactor (containing 321 stainless steel) and, unless otherwise specified, contacted with a nitrogen stream (approximately 2363 mL / min) at approximately 400℉ (approximately 204.4 °C) for 12 hours, followed by contact with a mixture of nitrogen (approximately 2333 mL / min) and chlorine (e.g., 2% N2) at approximately 400℉ (approximately 148.9 °C). The reactor is then contacted with a chlorine-containing stream (a mixture of Cl2 and nitrogen) at approximately 30 mL / min for about 3 hours, followed by contact with a nitrogen stream (approximately 2333 mL / min) at approximately 400℉ (approximately 204.4 °C) for about 3 hours, or approximately 12 hours to approximately 16 hours. Next, the reactor is contacted with a decoking stream consisting of air (112 mL / min) and nitrogen (2258 mL / min) at approximately 400℉ (approximately 204.4 °C) for about 30 minutes, followed by contact with a decoking stream consisting of air (336 mL / min) and nitrogen (2025 mL / min) at approximately 850℉ (approximately 454.4 °C) for about 3 hours.

[0180] The air flow continued (approximately 336 mL / min), the nitrogen flow decreased (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 the air to create a mixed flow. The decoking catalyst was contacted with the mixed flow at a pressure of 50 psi for approximately 60 minutes. At the end of the 60-minute contact time, the FREON was stopped. TM Fluorinated organic compounds / N2 stream. Purge continuously for 30 minutes at 700℉ and 50psi using air (approx. 336 mL / min) and nitrogen (approx. 2,000 mL / min) streams. Reduce the temperature to 500℉, and once below 500℉, stop the air purge and cool the catalyst to room temperature in the N2 stream.

[0181] The resulting regenerated catalyst was then tested to determine its fluorine concentration. Two samples of the regenerated catalyst were collected from the vertical reactor for testing: the first sample came from the "upper" half of the reactor, and the second sample came from the "lower" half. The results of these tests are shown in the table below.

[0182]

[0183] The results in this table demonstrate that 1,1,1,2-tetrafluoroethane achieved an improved fluorine distribution in the regenerated catalyst. While the distribution of 1,1,1,2-tetrafluoroethane was better than that of fluorine in Example 1B, it is important to note that the aforementioned 1,1,1,2-tetrafluoroethane treatment was carried out on spent catalyst that had been treated with the aforementioned chlorine-containing and decoking gas streams before being transferred to a different reactor for 1,1,1,2-tetrafluoroethane treatment. This transfer between reactors may expose the catalyst to moisture, thereby improving the fluorine distribution. If this potential moisture exposure is avoided (e.g., by performing the three steps described above in a single reactor), the fluorine distribution may not conform to the aforementioned results, but it is still likely to exceed the results obtained using fluorine to a surprising degree. The same fluorine distribution trend was also observed in Examples 1C and 1D. The reactivation processes in these examples were carried out in a single reactor, thus eliminating the possibility of exposure to moisture.

[0184] Then a series of aromatization reactions were carried out to test and compare the catalyst tuning temperature and selectivity of the reactivated catalyst: Figure 2 A graph depicting the catalyst's temperature versus time is presented. Figure 3 The selectivity of aromatic compounds versus time is plotted for (1) fresh aromatization catalyst, (2) spent aromatization catalyst, (3) spent aromatization catalyst treated with Cl2 and O2 for 8 hours according to the above procedure, (4) spent aromatization catalyst treated with Cl2, O2 and fluorine gas according to Example 1A, and (5) spent aromatization catalyst after the reactivation procedure of Example 1B, including treatment of the catalyst with 1,1,1,2-tetrafluoroethane.

[0185] Figure 4 A graph depicting catalyst regulation of temperature versus time was presented, and Figure 5 A graph depicting the selectivity of aromatic compounds versus time is presented for (1) an embodiment of a fresh aromatization catalyst, (2) an embodiment of a spent aromatization catalyst, and (3) a spent aromatization catalyst subjected to the reactivation procedure of Example 1C, which includes treatment of the catalyst with 1,1,1,2-tetrafluoroethane.

[0186] Figure 6 A graph depicting catalyst regulation of temperature versus time was presented, and Figure 7 A graph depicting the selectivity of aromatic compounds versus time is presented for (1) an embodiment of a fresh aromatization catalyst, (2) an embodiment of a spent aromatization catalyst, and (3) a spent aromatization catalyst subjected to the reactivation procedure of Example 1D, which includes treatment of the catalyst with 1,1,1,2-tetrafluoroethane.

[0187] Figures 2 to 7 Data indicates that the use of fluorine or Freon gas... TMFluorinated organic compounds, as fluoride sources, can restore activity that is essentially the same as that of fresh catalysts.

[0188] Example 2 - Preparation of regenerated catalyst using hydrofluorocarbons and a downstream reactor

[0189] FREON TM Fluorinated organic compounds can be used as fluorinating agents. When using FREON... TM When fluorinating organic compounds, the spent catalyst and FREON TM The temperature at which fluorinated organic compounds are exposed can be between 700℉ and 850℉ to decompose fluorine. TM Fluorinated organic compounds are used to deposit fluorine onto the spent catalyst.

[0190] Laboratory-scale testing included using FREON in nitrogen (with an oxygen content of up to 3%). TM Fluorinated organic compounds are fluorinated via a single-pass process using spent catalyst. When using a single pass, it was observed that a temperature of at least 850℉ was required to decompose the desired portion of the FREON. TM Fluorinated organic compounds are used to deposit fluorine onto the catalyst.

[0191] However, in these laboratory-scale tests, the distribution of fluorine in the catalyst bed was generally poor, and there were concerns about furnace / reactor metallurgy.

[0192] Therefore, a lower decomposition temperature was tested. At the lower decomposition temperature, a single pass resulted in only a small fraction of FREON. TM Fluorinated organic compounds decompose, but the fluorine distribution throughout the catalyst bed is improved. Therefore, lower temperatures are advantageous in some respects.

[0193] If the process is carried out in a commercial facility where all furnaces / reactors are maintained at decomposition temperature, then only a portion of the Freon... TM The decomposition of fluorinated organic compounds, followed by contact with each subsequent catalyst bed, results in a similar proportion of Freon deposited in the feed (now lower than the previous bed), which is believed to cause uneven loading and potentially other problems. There is also a concern that Freon in the furnace... TM Fluorinated organic compounds decompose to produce hydrogen fluoride, which can damage the furnace metal or other components of the system. Therefore, it is crucial to maintain the target reactor at the appropriate temperature to decompose the Freon, while keeping the rest of the unit below Freon levels. TMThe decomposition temperature of fluorinated organic compounds, and the recycling of reactor effluent back to the target reactor, will ensure an appropriate fluorine loading on the catalyst. To demonstrate that Freon or decomposition products in the target reactor effluent will not affect downstream metallurgy, the following tests were performed, and the results of one of these tests are presented in the table below. In the tests, the fluorinated stream (including Freon) TM Fluorinated organic compounds are sequentially circulated through reactor 1, furnace tubes, and reactor 2. Reactors 1 and 2 contain spent catalyst that has previously been dried, chlorinated, purged, and oxidized as described in Example 1D. The furnace tubes are filled with support balls to aid heat transfer.

[0194] Results of Example 2 (Single Pass)

[0195]

[0196] To mitigate one or more of these problems, fluorination is 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, FREON is fluorinated in the lower-temperature furnace / reactor. TM The decomposition of fluorinated organic compounds is reduced or minimized; therefore, a large portion of FREON... TM Fluorinated organic compounds (if any) do not deposit in these reactors.

[0197] Example 3 - Preparation of regenerated catalysts using recycled and hydrofluorocarbons

[0198] Approximately 61 g of spent catalyst was loaded into a metal fixed-bed reactor (containing 321 stainless steel) and, unless otherwise specified, contacted with a nitrogen stream (approximately 9291 mL / min) at approximately 400℉ (approximately 204.4 °C) for approximately 12 hours, followed by contact with a mixture of nitrogen (approximately 9236 mL / min) and chlorine (e.g., 2% N2) at approximately 400℉ (approximately 148.9 °C). The mixture of Cl2 (approximately 55 mL / min) was contacted for approximately 3 hours, followed by contact with a nitrogen stream (approximately 9236 mL / min) at approximately 400℉ (approximately 204.4 °C) for approximately 3 hours, or approximately 12 hours to approximately 16 hours. Then, it was contacted with a decoking stream consisting of air (444 mL / min) and nitrogen (8847 mL / min) at approximately 400℉ (approximately 204.4 °C) for approximately 30 minutes. Finally, it was contacted with a decoking stream consisting of air (1325 mL / min) and nitrogen (7966 mL / min) at approximately 850℉ (approximately 454.4 °C) for approximately 3 hours.

[0199] An air stream (approximately 258 mL / min) and a nitrogen stream (approximately 1522 mL / min) are continuously fed into the reactor. As the air and nitrogen mixture flows into the reactor, the compressor is configured to return a total flow rate of 1800 sccm to the reactor. A feedback loop (or, in other words, a recirculation loop) is used. Figure 1 The flow measurement system on the “feedback loop” (102) shown is used to check the circulation flow rate. Once the circulation flow rate is confirmed, the feed of the air and nitrogen mixture is stopped, and the circulation loop in the reactor system is blocked. This allows the system to operate in 100% circulation mode without introducing fresh gas into the reactor, while maintaining the reactor pressure at 50 psig. The circulation loop is run for 10 minutes, and then a flow of 1,1,1,2-tetrafluoroethane (5%) in N2 at a flow rate of 20 mL / min is mixed with the circulation flow at the reactor inlet to generate a mixed flow. The decoking catalyst is contacted with the mixed flow at 730℉ at a pressure of 50 psig. After 10 minutes, a gas bag sample of the reactor effluent is collected, such as... Figure 1 As shown. Stop FREON after 60 minutes. TM Fluorinated organic compounds were introduced, and the compressor continued to run in the circulation loop for 120 minutes. After 180 minutes, the second sample bag was removed. The compressor was stopped, and the reactor was purged for 30 minutes at 730℉ and 50psi with a mixed stream of air (approximately 286 mL / min) and nitrogen (approximately 1714 mL / min). The reactor was then cooled to room temperature in a stream of air and nitrogen.

[0200] Results of Example 3

[0201]

[0202] During reactivation, FREON TM Fluorinated organic compounds are returned to the target furnace / reactor via a circulation loop, i.e., the furnace / reactor maintained at the decomposition temperature. This process sometimes requires FREON. TM Fluorinated organic compounds pass through the recycling loop multiple times, but the process is believed to maximize the amount of fluorine that comes into contact with and deposits on the target reactor (i.e., the reactor maintained at the decomposition temperature).

[0203] aspect

[0204] The following are the non-restrictive aspects:

[0205] Aspect 1. A restructuring method comprising any two or more of the following steps, substantially consisting of any two or more of the following steps, or consisting of any two or more of the following steps:

[0206] (A) In a metal reactor system, under reforming conditions, a hydrocarbon feed is contacted with an aromatization catalyst comprising a transition metal and a catalyst support to generate aromatic products.

[0207] (B) The time period during which step (A) is sufficient to form spent catalyst;

[0208] (C) Contact the spent catalyst with hydrogen to generate stripped spent catalyst;

[0209] (D) The stripped spent catalyst is subjected to carbon combustion at a certain temperature, for example, not exceeding about 500℉, for a period of time to effectively remove at least a portion of the hydrogen-carbon feed, at least a portion of the aromatic products, or combinations thereof from the spent catalyst, to form a treated spent catalyst.

[0210] (E) The treated spent catalyst is contacted with a chlorine-containing stream containing chlorine compounds to generate chlorinated spent catalyst;

[0211] (F) The spent chlorinated catalyst is subjected to carbon combustion at a certain temperature, for example, not exceeding 900℉, for a period of time to effectively improve the dispersion of transition metals in the spent chlorinated catalyst, forming a redistributed spent catalyst; and

[0212] (G) Contacting the redistributed spent catalyst with a fluorinated stream containing fluorinated compounds to form a regenerated catalyst; and

[0213] (H) reduction and regeneration catalyst.

[0214] Aspect 2. The method as defined in Aspect 1, wherein the reforming method is an in-situ process, for example, steps (A)-(H) are carried out in the same reactor system.

[0215] Aspect 3. The method as defined in Aspect 1, wherein steps (C)-(H) are carried out outside the reactor system of steps (A)-(B), for example, steps (C)-(H) are carried out in a metal reactor not in the reforming reactor system.

[0216] Aspect 4. The method as defined in any of Aspects 1-3 further includes the step of reactivating the catalyst after step (H).

[0217] Aspect 5. A method for regenerating spent catalyst comprising a transition metal and a catalyst support in a metal reactor, the method comprising any two or more of the following steps, substantially comprising any two or more of the following steps, or comprising any two or more of the following steps:

[0218] (1) Contact the spent catalyst with hydrogen to generate stripped spent catalyst;

[0219] (2) The stripped waste catalyst is subjected to carbon combustion at a certain temperature, for example, not exceeding about 500℉, for a period of time to effectively remove at least a portion of the hydrogen-carbon feed, at least a portion of the aromatic products, or combinations thereof from the waste catalyst, thereby forming a treated waste catalyst;

[0220] (3) The treated waste catalyst is contacted with a chlorine-containing stream containing chlorine compounds to generate chlorinated waste catalyst;

[0221] (4) The chlorinated waste catalyst is subjected to carbon combustion at a certain temperature, for example, not exceeding 900℉, for a period of time to effectively improve the dispersion of transition metals in the chlorinated waste catalyst and form a redistributed waste catalyst.

[0222] (5) Contacting the redistributed spent catalyst with a fluorinated stream containing fluorine compounds to form a regenerated catalyst; and

[0223] (6) Reduction and regeneration of catalyst.

[0224] Aspect 6. A restructuring method comprising any two or more of the following steps, substantially consisting of any two or more of the following steps, or consisting of any two or more of the following steps:

[0225] (A) In a metal reactor system, under reforming conditions, a hydrocarbon feed is contacted with an aromatization catalyst comprising a transition metal and a catalyst support to generate aromatic products.

[0226] (B) The time period during which step (A) is sufficient to form spent catalyst;

[0227] (C) The spent catalyst is contacted with a chlorinated stream containing chlorinated compounds to generate chlorinated spent catalyst, wherein the chlorinated compounds optionally include chlorine, chlorinated hydrocarbons, chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), or combinations thereof.

[0228] (D) Contacting chlorinated spent catalyst with a decoking gas stream containing oxygen to generate a decoking catalyst; and

[0229] (E) The decoking catalyst is contacted with a fluorinated stream containing fluorinated compounds, wherein the fluorinated compounds include hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), fluorocarbons (FCs), or combinations thereof.

[0230] Aspect 7. The method as defined in Aspect 6, wherein the reforming method is an in-situ process, for example, steps (A)-(E) are carried out in the same reactor system.

[0231] Aspect 8. The method as defined in aspect 6, wherein steps (C)-(E) are carried out outside the reactor system of steps (A)-(B), for example, steps (C)-(E) are carried out in a metal reactor not in the reforming reactor system.

[0232] Aspect 9. The method as defined in any of Aspects 6-8 further includes a step of reactivating the catalyst after step (E).

[0233] Aspect 10. A method for regenerating spent catalyst comprising a transition metal and a catalyst support in a metal reactor, the method comprising, substantially comprising, or comprising the following:

[0234] (1) The spent catalyst is contacted with a chlorine-containing stream containing chlorine compounds to generate chlorinated spent catalyst;

[0235] (2) The chlorinated spent catalyst is contacted with a decoking gas stream containing oxygen to generate a decoking catalyst; and

[0236] (3) The decoking catalyst is contacted with a fluorinated stream containing fluorinated compounds to generate a regenerated catalyst, wherein the fluorinated compounds include hydrofluorocarbons (HFC), chlorofluorocarbons (CFC), hydrochlorofluorocarbons (HCFC), fluorocarbons (FC), or combinations thereof.

[0237] Aspect 11. The method as defined in any of the preceding aspects, wherein the contact between the spent catalyst and hydrogen is carried out at least in part at a temperature above 25℉, above 100℉, above 200℉, above 300℉, above 400℉, or above 500℉.

[0238] Aspect 12. The method as defined in any of the preceding aspects, wherein the contact between the spent catalyst and hydrogen is carried out at least in part at a temperature of about 300℉ to about 800℉, about 400℉ to about 800℉, or about 500℉ to about 800℉.

[0239] Aspect 13. The method as defined in any of the preceding aspects, wherein the contact between the spent catalyst and hydrogen is carried out for a period 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.

[0240] Aspect 14. The method as defined in any of the preceding aspects, wherein the fluorinated compound includes hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), fluorocarbons (FCs) or combinations thereof, is substantially composed of, or is composed of, them.

[0241] Aspect 15. The method as defined in any of the preceding aspects, wherein the fluorinated stream comprises (or is substantially composed of): (i) a fluorinated compound and any inert gas disclosed herein, such as nitrogen; (ii) a fluorinated compound, any inert gas disclosed herein, and air; (iii) a fluorinated compound and air; or (iv) a fluorinated compound, oxygen (O2), and any inert gas disclosed herein, such as nitrogen; wherein when the fluorinated stream comprises an inert gas and air, the volume ratio of the inert gas to air may be 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 fluorinated 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)).

[0242] Aspect 16. The method as defined in any of the preceding aspects, wherein contact between the redistributed spent catalyst and the fluorinated stream comprises (consisting substantially of or consisting of) a circulating inert gas and the injection of a fluorinated compound into the circulating inert gas.

[0243] Aspect 17. The method as defined in any of the preceding aspects, wherein the injection of the fluorinated compound is achieved at least in part using a spraying device configured to disperse the fluorinated compound in a circulating inert gas.

[0244] Aspect 18. The method as defined in any of the preceding aspects, wherein contact between the redistributed spent catalyst and the fluorinated stream comprises (consisting substantially of or consisting of) circulating a stream containing an inert gas and oxygen (O2) and injecting the fluorinated compound into the circulating stream.

[0245] Aspect 19. The method as defined in any of the preceding aspects, wherein the concentration of oxygen (O2) in the circulating stream is, by volume, about 0.01% to about 10%, about 0.01% to about 8%, about 0.01% to about 6%, about 0.01% to about 4%, about 1% to about 4%, about 2% to about 4%, about 2.5% to about 3.5% or about 3%.

[0246] Aspect 20. The method as defined in any of the preceding aspects, wherein (i) the amount of fluorinated compound in the fluorinated stream, (ii) the duration of contact between the spent catalyst and the fluorinated 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 placed on the redistributed spent catalyst.

[0247] Aspect 21. The method as defined in any of the preceding aspects, wherein the contact between the spent catalyst and the fluorinated stream is at least partially carried out at a temperature of about 500℉ to about 1,000℉, about 600℉ to about 1,000℉, about 600℉ to about 900℉, about 700℉ to about 900℉, or about 700℉ to about 850℉.

[0248] Aspect 22. The method as defined in any of the preceding aspects, wherein the fluorinated compound comprises (or substantially consists of) or consists of:

[0249] (i) Compound of formula (I) –

[0250] C a H b Cl c F d Formula (I),

[0251] in-

[0252] a ranges from 1 to 6.

[0253] b is between 0 and 14.

[0254] c ranges from 0 to 14.

[0255] d ranges from 1 to 14.

[0256] Where b and / or c are optionally not 0, and

[0257] Where b + c + d = 2a + 2,

[0258] In this case, the compound of formula (I) is optionally substituted;

[0259] (ii) 1,1,1,2-Tetrafluoroethane;

[0260] (iii) difluoromethane; or

[0261] (iv) Dichlorodifluoromethane.

[0262] Aspect 23. The method as defined in any of the preceding aspects, wherein the fluorinated compound consists of 1,1,1,2-tetrafluoroethane.

[0263] Aspect 24. The method as defined in any of the preceding aspects, wherein the amount of fluorinated compound in the fluorinated stream is controlled such that the concentration of fluorine [F] on the catalyst 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%, within the range of 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%.

[0264] Aspect 25. The method as defined in any of the preceding aspects, wherein the fluorinated stream is substantially free of oxygen-containing and / or chlorine-containing compounds that do not contain fluorine atoms, for example less than about 100 ppmw, less than about 50 ppmw or less than about 25 ppmw.

[0265] Aspect 26. The method as defined in any of the preceding aspects, wherein the amount of fluorinated compound in the fluorinated stream is controlled such that the concentration of fluorine (F) or the fluorinated compound is less than any maximum amount disclosed herein or within any range, 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. The range is 0.00 ppmv, the range is about 50 to about 15,000 ppmv, the range is about 50 to about 10,000 ppmv, the range is about 50 to about 5,000 ppmv, the range is about 50 to about 2,500 ppmv, the range is about 50 to about 1,000 ppmv, the range is about 500 to about 1,000 ppmv, the range is about 600 to about 900 ppmv, the range is about 700 to about 800 ppmv, or about 750 ppmv.

[0266] Aspect 27. The method as defined in any of the preceding aspects, wherein the fluorination step is carried out under the following conditions: (i) the fluorination temperature is 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; (ii) the fluorination pressure is 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.

[0267] Aspect 28. The method as defined in any of the preceding aspects, wherein the fluorination step is carried out for a period of time within any fluorination time range 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.

[0268] Aspect 29. The method as defined in any of the preceding aspects, wherein the chlorine-containing stream comprises (or substantially consists of) a chlorine-containing compound and any inert gas disclosed herein, such as nitrogen.

[0269] Aspect 30. The method as defined in any of the preceding aspects further includes circulating an inert gas and injecting a chlorine-containing compound into the circulating inert gas.

[0270] Aspect 31. The method as defined in any of the preceding aspects, wherein the injection of the chlorine-containing compound is achieved at least in part by using a spraying device configured to disperse the chlorine-containing compound in a circulating inert gas.

[0271] Aspect 32. The method as defined in any of the preceding aspects, wherein the chlorine-containing stream comprises (or consists substantially of) chlorine (Cl2) and nitrogen.

[0272] Aspect 33. The method as defined in any of the preceding aspects, wherein the amount of chlorine-containing compound in the chlorine-containing stream is controlled such that the concentration of chlorine (Cl) or the chlorine-containing compound is less than any maximum amount disclosed herein or within any range, such as 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, in the range of about 50 to about 10,000 ppmv, in the range of about 50 to about 5,000 ppmv, in the range of about 50 to about 2,500 ppmv, in the range of about about 50 to about 1,000 ppmv, in the range of about 50 to about 500 ppmv, in the range of about 50 to about 100 ppmv, in the range of about 100 to about 750 ppmv, or in the range of about 500 to about 600 ppmv.

[0273] Aspect 34. The method as defined in any of the preceding aspects, 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 to place 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 0.6 wt% to about 1 wt% of chlorine or chlorine-containing compound on the treated spent catalyst.

[0274] Aspect 35. The method as defined in any of the preceding aspects, wherein the chlorine-containing stream is substantially free of oxygen-containing compounds and / or fluorine-containing compounds, for example less than about 100 ppmw.

[0275] Aspect 36. The method as defined in any of the preceding aspects, wherein the chlorination step is carried out at a chlorination temperature within any chlorination temperature range disclosed herein, such as about 0℉ to about 600℉, about 100℉ to about 600℉, about 200℉ to about 600℉, about 3000℉ to about 600℉, about 400℉ to about 600℉, about 400℉ to about 500℉, about 400℉ to about 450℉, about 300℉ to about 500℉, about 350℉ to about 500℉, or about 350℉ to about 450℉.

[0276] Aspect 37. The method as defined in any of the preceding aspects, wherein the chlorination step is carried out for a period of time within any of the chlorination time periods 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.

[0277] Aspect 38. The method as defined in any of the preceding aspects, wherein the decoking gas stream comprises (or is substantially composed of) any combination of one or more inert gases disclosed herein and oxygen, such as a mixture of nitrogen and oxygen, air, or a mixture of air and nitrogen.

[0278] Aspect 39. The method as defined in any of the preceding aspects, wherein the decoking gas stream contains a molar percentage of oxygen less than any maximum amount disclosed herein or in 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%.

[0279] Aspect 40. The method as defined in any of the preceding aspects, wherein the decoking gas stream is substantially free of halogenated compounds, such as added halogenated compounds (e.g. substantially free of halogens, substantially free of chlorine), for example less than about 100 ppmw.

[0280] Aspect 41. The method as defined in any of the preceding aspects, wherein the decoking gas stream is substantially free of water (e.g., added water), for example less than about 100 ppmw.

[0281] Aspect 42. The method as defined in any of the preceding aspects, wherein the carbon combustion temperature of the stripped waste catalyst is about 300℉ to about 600℉, about 350℉ to about 550℉, about 350℉ to about 500℉, or about 400℉ to about 475℉.

[0282] Aspect 43. The method as defined in any of the preceding aspects, wherein the carbon combustion of the stripped waste catalyst is carried out for a period 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.

[0283] Aspect 44. The method as defined in any of the preceding aspects, wherein carbon combustion of stripped waste catalyst removes at least 90% by weight, at least 95% by weight, at least 99% by weight, or 100% by weight of hydrocarbon feed from the waste catalyst.

[0284] Aspect 45. The method as defined in any of the preceding aspects, wherein carbon combustion of stripped waste catalyst removes at least 90% by weight, at least 95% by weight, at least 99% by weight, or 100% by weight of aromatic products from the waste catalyst.

[0285] Aspect 46. The method as defined in any of the preceding aspects, wherein a certain amount of soft coke is absorbed and / or adsorbed onto the spent catalyst, and the carbon combustion of the stripped spent catalyst reduces the amount of soft coke absorbed and / or adsorbed onto the spent catalyst.

[0286] Aspect 47. The method as defined in any of the preceding aspects, wherein the carbon combustion temperature of the chlorinated waste catalyst is about 500℉ to about 1,200℉, about 500℉ to about 1,100℉, about 500℉ to about 1,000℉, about 600℉ to about 1,000℉, about 700℉ to about 1,000℉, about 700℉ to about 900℉, about 800℉ to about 900℉, or about 850℉.

[0287] Aspect 48. The method as defined in any of the preceding aspects, wherein the carbon combustion of the chlorinated waste catalyst is carried out for a period 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.

[0288] Aspect 49. The method as defined in any of the preceding aspects, wherein carbon combustion of the chlorination catalyst increases the dispersibility of transition metals in the chlorinated waste catalyst by at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, or at least 90%.

[0289] Aspect 50. The method as defined in any of the preceding aspects, wherein the carbon combustion temperature of the chlorinated waste catalyst is about 500℉ to about 1,200℉, about 500℉ to about 1,100℉, about 500℉ to about 1,000℉, about 600℉ to about 1,000℉, about 700℉ to about 1,000℉, about 700℉ to about 900℉, about 800℉ to about 900℉, or about 850℉.

[0290] Aspect 51. The method as defined in any of the preceding aspects, wherein the carbon combustion of the chlorinated waste catalyst is carried out for a period 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.

[0291] Aspect 52. The method as defined in any of the preceding aspects, wherein carbon combustion of the chlorination catalyst increases the dispersibility of transition metals in the chlorinated waste catalyst by at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, or at least 90%.

[0292] Aspect 53. The method as defined in any of the preceding aspects, wherein the carbon combustion step is carried out at a peak decoking temperature within any of the peak decoking temperature ranges disclosed herein, such as 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.

[0293] Aspect 54. The method as defined in any of the preceding aspects, wherein the carbon combustion step is initiated at an initial decoking temperature that is the same as any chlorine purging temperature disclosed herein, such as 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.

[0294] Aspect 55. The method as defined in any of the preceding aspects, wherein the carbon combustion step is performed for a period of time within any of the decoking time periods 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 hour to about 72 hours, about 12 hours to about 48 hours, or about 1 hour to about 6 hours.

[0295] Aspect 56. The method as defined in any of the preceding aspects, wherein the carbon combustion step is carried out for a period of time sufficient to reduce the carbon weight percentage on the chlorinated waste catalyst to below any maximum carbon weight percentage disclosed herein, such as below about 1 wt%, below about 0.5 wt%, or below about 0.2 wt%.

[0296] Aspect 57. The method as defined in any of the preceding aspects, wherein the method further comprises a partial decoking step prior to the chlorination step, the partial decoking step comprising contacting the spent catalyst with a partially decoking gas stream containing oxygen.

[0297] Aspect 58. The method as defined in any of the preceding aspects, wherein the partial decoking gas stream comprises (or is substantially composed of) any combination of one or more inert gases disclosed herein and oxygen, such as a mixture of nitrogen and oxygen, or air.

[0298] Aspect 59. The method as defined in any of the preceding aspects, wherein the molar percentage of oxygen contained in the partially decoked gas stream is less than any maximum amount disclosed herein or in any range, 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%.

[0299] Aspect 60. The method as defined in any of the preceding aspects, wherein a portion of the decoking gas stream is substantially free of halogen compounds (e.g., substantially free of halogens), for example less than about 100 ppmw.

[0300] Aspect 61. The method as defined in any of the preceding aspects, wherein the decoking gas stream is substantially free of water, for example less than about 100 ppmw.

[0301] Aspect 62. The method as defined in any of the preceding aspects, wherein the partial defocusing step is performed at a partial defocusing temperature within any partial defocusing temperature range disclosed herein, such as from about 150°C to about 600°C, or from about 150°C to about 250°C.

[0302] Aspect 63. The method as defined in any of the preceding aspects, wherein the time period for which a partial defocusing step is performed is within the range of any partial defocusing time period disclosed herein, for example, about 1 hour to about 48 hours, or about 2 to about 24 hours.

[0303] Aspect 64. The method as defined in any of the preceding aspects, wherein the duration of the partial decoking step is sufficient to reduce the carbon weight percentage on the spent catalyst to any range of carbon weight percentages disclosed herein, such as 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%.

[0304] Aspect 65. The method as defined in any of the preceding aspects, wherein the method further comprises a pre-drying step prior to the chlorination step, the pre-drying step comprising contacting the spent catalyst with a pre-drying gas stream containing (or substantially consisting of) any inert gas (e.g., nitrogen) disclosed herein.

[0305] Aspect 66. The method as defined in any of the preceding aspects, wherein the pre-drying gas stream is substantially free of oxygen-containing compounds, for example less than about 100 ppmw.

[0306] Aspect 67. The method as defined in any of the preceding aspects, wherein the pre-drying step is carried out at a pre-drying temperature within any pre-drying temperature range disclosed herein, such as 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.

[0307] Aspect 68. The method as defined in any of the preceding aspects, wherein the pre-drying step is performed for a period of time within any of the pre-drying time periods disclosed herein, for example, about 1 hour to about 96 hours, or about 1 to about 48 hours.

[0308] Aspect 69. The method as defined in any of the preceding aspects, wherein the pre-drying step is carried out for a period of time sufficient to reduce the moisture content of the spent catalyst to below any maximum moisture content of the spent catalyst disclosed herein, for example, below about 4% by weight or below about 1% by weight.

[0309] Aspect 70. The method as defined in any of the preceding aspects, wherein the method further comprises a chlorine purging step prior to the carbon combustion step, the chlorine purging step comprising contacting the chlorinated waste catalyst with a chlorine purging stream comprising (or substantially comprising) any inert gas (e.g., nitrogen) disclosed herein.

[0310] Aspect 71. The method as defined in any of the preceding aspects, wherein the chlorine purge stream is substantially free of oxygen-containing compounds, for example less than about 100 ppmw.

[0311] Aspect 72. The method as defined in any of the preceding aspects, wherein the chlorine purge stream is substantially free of halogenated compounds (substantially halogen-free), for example less than about 100 ppmw.

[0312] Aspect 73. The method as defined in any of the preceding aspects, wherein the chlorine purging step is performed at a chlorine purging temperature within any chlorine purging temperature range disclosed herein, such as 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.

[0313] Aspect 74. The method as defined in any of the preceding aspects, wherein the chlorine purging step is performed for a period of time within any of the chlorine purging time periods disclosed herein, for example, about 1 hour to about 96 hours, about 1 hour to about 48 hours.

[0314] Aspect 75. The method as defined in any of the preceding aspects, wherein the chlorine purging step is performed for a period of time sufficient to reduce the chlorine content of the discharged purging effluent to below any maximum chlorine content described herein, for example, below about 100 ppmw of chlorinated compounds, after contact with the chlorinated spent catalyst.

[0315] Aspect 76. The method as defined in any of the preceding aspects, wherein the method further comprises a fluorine purging step following the fluorination step, the fluorine purging step comprising contacting the decoked and fluorinated catalyst with a fluorine purging stream containing (or substantially consisting of or consisting of) any inert gas (e.g., nitrogen) disclosed herein.

[0316] Aspect 77. The method as defined in any of the preceding aspects, wherein the fluorine purge stream is substantially free of oxygen-containing compounds, for example less than about 100 ppmw.

[0317] Aspect 78. The method as defined in any of the preceding aspects, wherein the fluorine purge stream is substantially free of halogenated compounds (substantially halogen-free), for example less than about 100 ppmw.

[0318] Aspect 79. The method as defined in any of the preceding aspects, wherein the fluorine purging step is performed at a fluorine purging temperature within any fluorine purging temperature range disclosed herein, such as 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.

[0319] Aspect 80. The method as defined in any of the preceding aspects, wherein the fluorine purging step is performed for a period of time within any of the fluorine purging time periods disclosed herein, for example, about 0.25 hours to about 72 hours, or about 1 to about 48 hours.

[0320] Aspect 81. The method as defined in any of the preceding aspects, wherein the fluorine purging step is performed for a period of time sufficient to reduce the fluorine content of the discharged fluorine purging effluent to below any maximum fluorine content described herein, for example, below about 100 ppmw of fluorine-containing compounds, after contact with the decoking and fluorinating catalyst.

[0321] Aspect 82. The method as defined in any of the preceding aspects, wherein the method further comprises an oxygen purging step following a carbon combustion step or a fluorine purging step, the oxygen purging step comprising contacting the catalyst with an oxygen purging stream comprising (or substantially comprising or consisting of) any inert gas disclosed herein (e.g., nitrogen).

[0322] Aspect 83. The method as defined in any of the preceding aspects, wherein the oxygen purge stream is substantially free of oxygen-containing compounds, for example less than about 100 ppmw.

[0323] Aspect 84. The method as defined in any of the preceding aspects, wherein the oxygen purge stream is substantially free of halogenated compounds (substantially halogen-free), for example less than about 100 ppmw.

[0324] Aspect 85. The method as defined in any of the preceding aspects, wherein the oxygen purging step is performed at an oxygen purging temperature within any oxygen purging temperature range disclosed herein, such as 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.

[0325] Aspect 86. The method as defined in any of the preceding aspects, wherein the oxygen purging step is performed for a period of time within any oxygen purging time range disclosed herein, for example from about 0.5 hours to about 96 hours, or from about 1 hour to about 48 hours.

[0326] Aspect 87. The method as defined in any of the preceding aspects, wherein the oxygen purging step is performed for a period of time sufficient to reduce the oxygen content of the discharged oxygen purging effluent to below any maximum oxygen content described herein, for example, below about 100 ppmw of oxygenated compounds after contact with the catalyst.

[0327] Aspect 88. The method as defined in any of the preceding aspects, wherein the method further comprises a hydrocarbon treatment step prior to the carbon combustion step, the hydrocarbon treatment step comprising contacting the chlorinated waste catalyst with a hydrocarbon treatment stream containing the hydrocarbon feed.

[0328] Aspect 89. The method as defined in any of the preceding aspects, wherein the hydrocarbon feed comprises (or is substantially composed of) C6-C8 alkanes and / or cycloalkanes.

[0329] Aspect 90. The method as defined in any of the preceding aspects, wherein the hydrocarbon treatment step is performed at a hydrocarbon treatment temperature within any hydrocarbon treatment temperature range disclosed herein, for example, from about 400°C to about 600°C.

[0330] Aspect 91. The method as defined in any of the preceding aspects, wherein the time period for which the hydrocarbon treatment step is performed is within any hydrocarbon treatment time period disclosed herein, for example, about 1 to about 48 hours.

[0331] Aspect 92. The method as defined in any of the preceding aspects, wherein the method further comprises a reduction step following the fluorination step.

[0332] Aspect 93. The method as defined in any of the preceding aspects, wherein the reduction step comprises contacting a regenerated catalyst, a fluorinated waste catalyst, or a decoking fluorinated catalyst with a reducing gas stream containing (or substantially consisting of or consisting of) molecular hydrogen.

[0333] Aspect 94. The method as defined in any of the preceding aspects, wherein the reduction of the fluorinated waste catalyst or the regenerated catalyst is carried out at a temperature of about 600℉ to about 1,200℉, about 700℉ to about 1,100℉, about 800℉ to about 1,000℉, about 900℉ to about 1,000℉ or about 950℉ to about 1,000℉.

[0334] Aspect 95. The method as defined in any of the preceding aspects, wherein the reduction of the fluorinated waste catalyst or the regenerated catalyst is carried out at least in part in an atmosphere containing (consisting substantially of or consisting of) an inert gas (e.g., nitrogen), hydrogen (H2), or a combination thereof; wherein optionally the volume ratio of the inert gas to 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.

[0335] Aspect 96. The method as defined in any of the preceding aspects, wherein the reducing gas stream comprises a molecular hydrogen in a quantity greater than any minimum amount disclosed herein or in any range of mol%, for example, greater than about 25 mol% or greater than about 75 mol%.

[0336] Aspect 97. The method as defined in any of the preceding aspects, wherein the reduction step is performed at a peak reduction temperature within any of the peak reduction temperature range disclosed herein, such as from about 200°C to about 600°C, or from about 400°C to about 600°C.

[0337] Aspect 98. The method as defined in any of the preceding aspects, wherein the reduction step begins 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.

[0338] Aspect 99. The method as defined in any of the preceding aspects, wherein the time period for which the reduction step is performed is within the range of any reduction step time period disclosed herein, for example, about 0.5 hours to about 48 hours, about 10 hours to about 30 hours.

[0339] Aspect 100. The method as defined in any of the preceding aspects, wherein the catalyst support comprises (or is substantially composed of) zeolite, amorphous inorganic oxide or any combination thereof.

[0340] Aspect 101. The method as defined in any of the preceding aspects, wherein the catalyst support comprises (or is substantially composed of) L-zeolite, γ-zeolite, mordenite, ω-zeolite and / or β-zeolite.

[0341] Aspect 102. The method as defined in any of the preceding aspects, wherein the catalyst support comprises (or is substantially composed of) potassium L-zeolite or barium ion-exchange L-zeolite.

[0342] Aspect 103. The method as defined in any of the preceding aspects, wherein the catalyst support comprises (or is substantially composed of) a binder containing alumina, silica, mixed oxides thereof, or mixtures thereof.

[0343] Aspect 104. The method as defined in any of the preceding aspects, wherein the transition metals include group 8-11 transition metals.

[0344] Aspect 105. The method as defined in any of the preceding aspects, wherein the transition metal comprises (or is substantially composed of) platinum.

[0345] Aspect 106. The method as defined in any of the preceding aspects, wherein the catalyst comprises a transition metal in any weight percentage range disclosed herein, such as from about 0.1 wt% to about 10 wt%, or from about 0.3 wt% to about 5 wt%.

[0346] Aspect 107. The method as defined in any of the preceding aspects, wherein the waste catalyst contains platinum in any weight percentage range disclosed herein, such as from about 0.1 wt% to about 10 wt%, or from about 0.5 wt% to about 2 wt%.

[0347] Aspect 108. The method as defined in any of the preceding aspects, wherein the catalyst comprises platinum on KL-zeolite comprising (or substantially consisting of) KL-zeolite.

[0348] Aspect 109. The method as defined in any of the foregoing aspects, wherein the catalyst further comprises chlorine and fluorine.

[0349] Aspect 110. The method as defined in any of the preceding aspects, wherein the catalyst comprises chlorine and / or fluorine in any weight percentage range disclosed herein, for example, about 0.01 wt% to about 5 wt%, or about 0.3 to about 1.3 wt% of fluorine, 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.

[0350] Aspect 111. The method as defined in any of the preceding aspects, wherein the catalyst comprises any molar ratio of chlorine to fluorine disclosed herein, for example, about 0.5:1 to about 4:1.

[0351] Aspect 112. The method as defined in any of the preceding aspects, wherein the chlorine-containing compound comprises (or is substantially composed of) hydrochloric acid, chlorine (Cl2), carbon tetrachloride, tetrachloroethylene, chlorobenzene, chloromethane, dichloromethane, chloroform, chloropropene, trichloroethylene, chloramine, chlorine oxide, chloric acid, chlorine dioxide, dichloride, dichloride heptaoxide, chloric acid, perchloric acid, ammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, methyltriethylammonium chloride, or any combination thereof.

[0352] Aspect 113. The method as defined in any of the preceding aspects, wherein the chlorine-containing compound includes (or consists substantially of) chlorine gas (Cl2).

[0353] Aspect 114. A reactivated catalyst or regenerated catalyst prepared by the method defined in any of the preceding aspects.

[0354] Aspect 115. A reactivated catalyst or regenerated catalyst as defined in any of the preceding aspects, wherein the reactivated catalyst or regenerated catalyst contains any amount of iron disclosed herein, such as 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.

[0355] Aspect 116. A reactivated catalyst or regenerated catalyst as defined in any of the preceding aspects, wherein the reactivated catalyst or regenerated catalyst comprises any amount of carbon disclosed herein, such as 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% of carbon.

[0356] Aspect 117. A reactivated catalyst or regenerated catalyst as defined in any of the preceding aspects, wherein the reactivated catalyst or regenerated catalyst comprises any amount of chlorine disclosed herein, such as 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.

[0357] Aspect 118. A reactivated catalyst or regenerated catalyst as defined in any of the preceding aspects, wherein the reactivated catalyst or regenerated catalyst comprises any amount of fluorine disclosed herein, such as 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%.

[0358] Aspect 119. A reactivated catalyst or regenerated catalyst as defined in any of the preceding aspects, wherein the reactivated catalyst or regenerated catalyst is characterized in that its TEOR is within about 50℉, about 40℉, about 30℉ or about 20℉ of the TEOR of the fresh reference catalyst.

[0359] Aspect 120. A reactivated catalyst or regenerated catalyst as defined in any of the preceding aspects, wherein the reactivated catalyst or regenerated catalyst is characterized in that its TSOR is within about 50℉, about 40℉, about 30℉ or about 20℉ of the TSOR of the fresh reference catalyst.

[0360] Aspect 121. A reactivated catalyst or regenerated catalyst as defined in any of the preceding aspects, wherein the reactivated catalyst or regenerated catalyst is characterized in that the scaling rate (FR) is in any range disclosed herein, for example, about 0.01℉ / hour to about 0.25℉ / hour, about 0.02℉ / hour to about 0.2℉ / hour, about 0.03℉ / hour to about 0.2℉ / hour, or about 0.03℉ / hour to about 0.15℉ / hour.

[0361] Aspect 122. A reactivated catalyst or regenerated catalyst as defined in any of the preceding aspects, wherein the benzene + toluene selectivity is 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.

[0362] Aspect 123. The method or catalyst as defined in any of the preceding aspects, wherein the metal reactor (or metal reactor system) comprises (or is substantially composed of) stainless steel, such as 347SS or 321SS.

[0363] Aspect 124. The method or catalyst as defined in any of the preceding aspects, further comprising, substantially comprising, or comprising: recovering at least a portion of the fluorinated stream to generate a recovered fluorinated stream, wherein optionally the recovery is carried out after the decoking catalyst has been contacted with the fluorinated stream; and contacting the decoking catalyst with the recovered fluorinated stream.

[0364] Aspect 125. The method or catalyst as defined in any of the preceding aspects, wherein the fluorine concentration in the regenerated catalyst is from about 0.15% by weight to about 1.2% by weight, or from about 0.2% by weight to about 1.2% by weight.

[0365] Aspect 126. The method or catalyst as defined in any of the preceding aspects, 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.

[0366] Aspect 127. A method for generating a product, the method comprising, substantially comprising, or comprising: (A) providing a reactivated or regenerated catalyst, such as any of the preceding aspects, and (B) contacting a hydrocarbon with the reactivated / regenerated catalyst to generate a product, such as an aromatic product.

[0367] Aspect 128. The method as defined in any of the preceding aspects, wherein the contact between the hydrocarbon and the reactivated / regenerated catalyst is carried out for an effective time to generate a second waste catalyst, and the method further includes subjecting the second waste catalyst to the method as defined in any of the preceding aspects.

[0368] Aspect 129. (I) A method for contacting spent catalyst with a fluorinated stream, or (II) a method as defined in any of the preceding aspects, wherein contacting the spent catalyst (e.g., redistributed spent catalyst) with the fluorinated stream comprises, substantially comprises, or comprises the following.

[0369] (a) Providing two or more reactors in fluid communication with each other, wherein the two or more reactors (e.g., 2 to 10 or more reactors) are connected in series, thereby allowing a fluorinated stream to (i) be injected at an injection point selected from one or more injection points, (ii) be circulated sequentially through each of the two or more reactors downstream of the injection point, (iii) return to the first of the two or more reactors, and optionally (iv) be circulated sequentially through each of the two or more reactors, wherein each of the two or more reactors includes a reservoir in which spent catalyst is disposed;

[0370] (b) Heating one of the two or more reactors to a temperature equal to or above the fluorination temperature, and maintaining each of the remaining two or more reactors at a temperature below the fluorination temperature, wherein the fluorination temperature effectively at least partially decomposes the fluorinated compounds in the fluorinated stream; and

[0371] (c) Inject a fluorinated stream and circulate or recirculate the fluorinated stream for a period of time to effectively achieve the desired level of fluorination of the spent catalyst in one of two or more reactors at a temperature equal to or above the fluorination temperature.

[0372] Aspect 130. The method as defined in any of the foregoing aspects further includes, substantially consists of, or comprises:

[0373] (d) Heating one of the two or more reactors to a temperature equal to or above the fluorination temperature, and maintaining each of the remaining reactors at a temperature below the fluorination temperature; and

[0374] (e) Inject a fluorinated stream and circulate or recirculate the fluorinated stream for a period of time to effectively achieve the desired level of fluorination of the spent catalyst in one of two or more reactors at a temperature equal to or above the fluorination temperature.

[0375] Aspect 131. The method as defined in any of the preceding aspects further includes repeating steps (d) and (e) until the spent catalyst in each of the one or more reactors is fluorinated to the desired level.

[0376] Aspect 132. The method as defined in any of the preceding aspects, wherein the temperature equal to or above the fluorination temperature is at least 650℉ or at least 700℉.

[0377] Aspect 133. The method as defined in any of the preceding aspects, wherein the temperature equal to or above the fluorination temperature is about 650℉ to about 850℉, about 700℉ to about 850℉, about 700℉ to about 800℉, about 700℉ to about 775℉, or about 700℉ to about 750℉.

[0378] Aspect 134. The method as defined in any of the preceding aspects, wherein the temperature below the fluorination temperature is about 600℉ or lower.

[0379] Aspect 135. The method as defined in any of the preceding aspects, wherein the temperature below the fluorination temperature is about 300℉ to about 600℉, about 400℉ to about 600℉, or about 500℉ to about 600℉.

[0380] Aspect 136. The method as defined in any of the foregoing aspects, wherein the injection of the fluorine-containing flow comprises, substantially comprises, or comprises the following:

[0381] (1) Select an injection point from one or more injection points, wherein optionally the selected injection point is located upstream of a reactor (or different reactors) heated to a temperature equal to or above the fluorination temperature, and

[0382] (2) Inject the fluorine-containing fluid into an injection connector selected from one or more injection points.

[0383] Aspect 137. The method as defined in any of the preceding aspects, wherein the amount of fluorinated compound or fluorinated stream injected and recycled effectively places 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 on the spent catalyst.

[0384] Aspect 138. The method as defined in any of the preceding aspects further includes, substantially consists of, or comprises: analyzing the fluorinated stream during circulation or recirculation to determine the amount or concentration of fluorinated compounds and / or fluorine in the fluorinated stream.

[0385] Aspect 139. The method as defined in any of the preceding aspects further includes, substantially consists of, or consists of the following: stopping the circulation / recycling of the fluorinated stream when the amount or concentration of the fluorinated compound and / or fluorine is equal to or below a threshold concentration or amount indicating successful deposition of fluorine on the spent catalyst.

[0386] Aspect 140. A system for fluorinating waste catalyst, the system comprising, substantially consisting of, or consisting of:

[0387] (a) Two or more reactors in fluid communication with each other, wherein the two or more reactors are connected in series, thereby allowing a fluid flow, such as a fluorinated flow, to (i) be injected at an injection point selected from one or more injection points, (ii) circulate sequentially through each of the two or more reactors downstream of the injection point, (iii) return to the first of the two or more reactors, and optionally (iv) circulate sequentially again through each of the two or more reactors; and

[0388] (b) Two or more heating devices configured to heat each of the two or more reactors to the same or different temperatures.

[0389] Aspect 141. The system of aspect 140, wherein the system includes at least one injection point for each reactor.

[0390] Aspect 142. The system of aspect 141, wherein the location of at least one injection point allows for the injection of a fluorinated stream into the immediate upstream of any one of two or more reactors.

Claims

1. A method for regenerating spent catalyst comprising a transition metal and a catalyst support in a metal reactor, the method comprising: (1) The waste catalyst is contacted with hydrogen to generate stripped waste catalyst; (2) The stripped waste catalyst is subjected to carbon combustion at a temperature not exceeding about 500℉ to generate treated waste catalyst; (3) The treated waste catalyst is contacted with a chlorine-containing stream containing chlorine compounds to generate chlorinated waste catalyst; (4) The chlorinated spent catalyst is subjected to carbon combustion at a temperature not exceeding 900℉ for a period of time to effectively improve the dispersion of transition metals in the chlorinated spent catalyst, thereby forming a redistributed spent catalyst; and (5) The redistributed waste catalyst is contacted with a fluorine-containing stream containing fluorine compounds to form a regenerated catalyst; as well as (6) Reduce the regenerated catalyst.

2. The method of claim 1, wherein the fluorinated compound comprises a compound of formula (I): C a H b Cl c F d Formula (I), in- a ranges from 1 to 6. b is between 0 and 14. c is between 0 and 14, and d ranges from 1 to 14. Whereby, optionally (i) b is not 0, (ii) c is not 0, or (iii) a combination thereof, and Where b+c+d=2a+2.

3. The method of claim 1, wherein the fluorinated compound is composed of 1,1,1,2-tetrafluoroethane.

4. The method of claim 1, wherein the fluorinated compound is composed of difluoromethane.

5. The method of claim 1, wherein the fluorinated compound is composed of dichlorodifluoromethane.

6. The method of claim 1, wherein the fluorinated stream further comprises an inert gas, oxygen (O2), or a combination thereof.

7. The method of claim 6, wherein the volume ratio of the inert gas to oxygen (O2) in the fluorine-containing stream is about 95:5 to about 99:1 (inert gas: oxygen (O2)).

8. The method of claim 1, wherein (i) the amount of fluorinated compound in the fluorinated stream, (ii) the duration of contact between the redistributed spent catalyst and the fluorinated stream, or (iii) a combination thereof, are selected such that about 0.15% by weight to about 1.2% by weight of fluorine is placed on the redistributed spent catalyst.

9. The method of claim 1, wherein the fluorinated stream is substantially free of (i) oxygen-containing compounds, (ii) chlorine-containing compounds that do not contain fluorine atoms, or (iii) both oxygen-containing compounds and chlorine-containing compounds that do not contain fluorine atoms.

10. The method of claim 1, wherein the carbon combustion temperature of the stripped waste catalyst is from about 400℉ to about 500℉, and the carbon combustion of the stripped catalyst is carried out for about 1 minute to about 24 hours.

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

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

13. The method of claim 1, wherein the carbon combustion temperature of the chlorinated waste catalyst is from about 700℉ to about 1,000℉, and the carbon combustion of the chlorinated waste catalyst is carried out for about 1 minute to about 24 hours.

14. The method of claim 1, wherein the carbon combustion of the chlorination catalyst improves the dispersibility of the transition metals in the chlorinated waste catalyst by at least 70%.

15. The method of claim 1, wherein the reduction of the regenerated catalyst is carried out at a temperature of about 800℉ to about 1,000℉.

16. The method of claim 1, wherein the reduction of the regenerated catalyst is carried out at least in part in an atmosphere containing an inert gas, hydrogen (H2), or a combination thereof.

17. The method of claim 16, wherein the volume ratio of the inert gas to the hydrogen (H2) is about 20:80 to about 80:

20.

18. The method of claim 1, further comprising contacting a hydrocarbon feedstock with an aromatization catalyst under reforming conditions to generate an aromatic product, wherein the contact between the hydrocarbon feedstock and the aromatization catalyst lasts for a period sufficient to form the spent catalyst.

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

20. The method of claim 19, wherein the metal reactor is formed of stainless steel.

21. A method for contacting spent catalyst with a fluorine-containing stream, the method comprising: (a) Providing two or more reactors in fluid communication with each other, wherein the two or more reactors are connected in series, thereby allowing a fluorinated stream to (i) be injected at an injection point selected from one or more injection points, (ii) be circulated sequentially through each of the two or more reactors downstream of the injection point, (iii) return to the first of the two or more reactors, and optionally (iv) be circulated sequentially through each of the two or more reactors, wherein each of the two or more reactors includes a reservoir in which the spent catalyst is disposed; (b) Heating one of the two or more reactors to a temperature equal to or above the fluorination temperature, and maintaining each of the remaining two or more reactors at a temperature below the fluorination temperature, wherein the fluorination temperature effectively decomposes at least partially the fluorinated compounds in the fluorinated stream; as well as (c) Inject the fluorinated stream and circulate or recirculate the fluorinated stream for a period of time to effectively achieve the desired level of fluorination of the spent catalyst in one of the two or more reactors at a temperature equal to or above the fluorination temperature.

22. The method of claim 21, further comprising: (d) Heating one of the two or more reactors to a temperature equal to or above the fluorination temperature, and maintaining each of the remaining two or more reactors at a temperature below the fluorination temperature; as well as (e) Injecting a fluorinated stream and circulating or recirculating the fluorinated stream for a period of time to effectively achieve the desired level of fluorination of the spent catalyst in one of the two or more reactors at a temperature equal to or above the fluorination temperature.

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

24. The method of any one of claims 21 to 23, wherein the temperature equal to or above the fluorination temperature is at least 650℉, and wherein the temperature below the fluorination temperature is about 600℉ or lower.

25. The method of any one of claims 21 to 23, wherein the temperature equal to or higher than the fluorination temperature is from about 650℉ to about 850℉.

26. The method of any one of claims 21 to 23, wherein the temperature equal to or higher than the fluorination temperature is about 700℉ to about 850℉.

27. The method of any one of claims 21 to 23, wherein the temperature below the fluorination temperature is from about 300℉ to about 600℉.

28. The method of any one of claims 21 to 23, wherein the injection of the fluorine-containing flow comprises: (1) Select the injection point from the one or more injection points, and (2) Inject the fluorine-containing fluid into an injection connector selected from one or more injection points.

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

30. The method of any one of claims 21 to 23, wherein the amount of the injected and recycled / circulated fluorine-containing compound or the fluorine-containing stream effectively places about 0.1% by weight to about 1.5% by weight of fluorine on the spent catalyst.

31. The method of any one of claims 21 to 23, wherein the amount of the fluorinated compound or the fluorinated stream injected and recycled effectively places about 0.15% by weight to about 1.2% by weight of fluorine on the spent catalyst.

32. The method of any one of claims 21 to 23, further comprising analyzing the fluorinated stream during cycling or recirculation to determine the amount or concentration of fluorinated compounds and / or fluorine in the fluorinated stream.

33. The method of any one of claims 21 to 23, further comprising stopping the circulation / recycling of the fluorinated stream when the amount or concentration of the fluorinated compound and / or fluorine is equal to or below a threshold concentration or amount indicating successful deposition of fluorine on the spent catalyst.

34. A system for fluorinating spent catalysts, the system comprising: (a) Two or more reactors in fluid communication with each other, wherein the two or more reactors are connected in series, thereby allowing a fluid flow, such as a fluorinated flow, to (i) be injected at an injection point selected from one or more injection points, (ii) circulate sequentially through each of two or more reactors downstream of the injection point, (iii) return to the first of the two or more reactors, and optionally (iv) circulate sequentially through each of the two or more reactors. as well as (b) Two or more heating devices configured to heat each of the two or more reactors to the same or different temperatures.

35. The system of 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 of claim 34, wherein the two or more heating devices comprise two or more tubular furnaces.

37. The system of 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 of claim 37, wherein the system comprises exactly two, three, four, five, six, seven, eight, nine, or ten reactors, and at least two, three, four, five, six, seven, eight, nine, or ten injection points.

39. The system of claim 34, further comprising the spent catalyst, wherein the spent catalyst is disposed 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 of claim 34, wherein the two or more reactors comprise two or more metal reactors.

41. A method for regenerating spent catalyst comprising a transition metal and a catalyst support in a metal reactor, the method comprising: (1) The spent catalyst is contacted with a chlorine-containing stream containing chlorine compounds to generate chlorinated spent catalyst; (2) The chlorinated waste catalyst is contacted with a decoking gas stream containing oxygen to generate a decoking catalyst; as well as (3) The decoking catalyst is contacted with a fluorinated stream containing fluorinated compounds to generate a regenerated catalyst, wherein the fluorinated compounds include hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), or combinations thereof.

42. The method of claim 41, wherein the fluorinated compound comprises a compound of formula (I): C a H b Cl c F d Formula (I), in- a ranges from 1 to 6. b is between 0 and 14. c is between 0 and 14, and d ranges from 1 to 14. Whereby, optionally (i) b is not 0, (ii) c is not 0, or (iii) a combination thereof, and Where b+c+d=2a+2.

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

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

45. The method of claim 41, wherein the fluorinated compound comprises 1,1,1,2-tetrafluoroethane.

46. ​​The method of claim 41, wherein the fluorinated compound comprises dichlorodifluoromethane, difluoromethane, or a combination thereof.

47. The method of claim 41, wherein the fluorinated stream further comprises an inert gas, air, or a combination thereof.

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

49. The method of claim 41, wherein the presence of the fluorinated compound in the fluorinated stream effectively makes the fluorine [F] concentration in the fluorinated stream about 0.05% by weight to about 3% by weight.

50. The method of claim 41, wherein the fluorinated stream is substantially free of oxygen-containing compounds, chlorinated compounds that do not contain fluorine atoms, or oxygen-containing compounds and chlorinated compounds that do not contain fluorine atoms.

51. The method of claim 41, wherein the contact between the decoking catalyst and the fluorinated stream is carried out at a temperature of about 0°C to about 500°C.

52. The method of claim 41, wherein the contact between the decoking catalyst and the fluorinated stream is carried out at a pressure of about 0.5 bar to about 7 bar.

53. The method of claim 41, wherein the decoking catalyst is contacted with the fluorinated stream for a period of about 0.5 to about 96 hours.

54. The method of claim 41, further comprising: At least a portion of the fluorinated stream is recovered to generate a recovered fluorinated stream, wherein the recovery is carried out after the decoking catalyst is contacted with the fluorinated stream; as well as The decoking catalyst is brought into contact with the recovered fluorine-containing stream.

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

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

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

58. The method of claim 41, wherein the chlorine-containing stream is substantially free of oxygen-containing and fluorine-containing compounds.

59. The method of claim 41, wherein the decoking gas is substantially free of water.

60. The method of claim 41, wherein the chlorine-containing stream comprises chlorine (Cl2) and nitrogen (N2).

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