Method for releasing at least portion of halide from surface

Abstract

Contacting an inner surface of a petrochemical or refinery process vessel (optionally a metal) with a halide or halide-containing compound wherein at least a portion of the halide is coupled to the inner surface due to shrinkage; and releasing at least a portion of the halide coupled to the inner surface via contacting the inner surface with hydrogen.

Description

Technical Field

[0001] This disclosure relates to a method for releasing at least a portion of a halide from the surface of a refining or petrochemical process vessel after the surface has been exposed to a halide (e.g., during the regeneration of spent aromatization catalyst). Background Technology

[0002] In industrial chemical processing plants and oil refineries, there are many types of process vessels, tanks, reactors, etc., made of metal and with internal surfaces that come into contact with process fluids and reactants. In various petrochemical and refining processes, one or more of these internal surfaces may come into contact with halides or halide-containing compounds. In the presence of halides, their corrosive properties (especially chlorides and fluorides) can damage the internal surfaces of metallic materials, causing pitting, stress corrosion cracking, and generalized corrosion.

[0003] An example of a chemical process using halides is the aromatization of linear or aliphatic hydrocarbons into aromatic compounds, such as benzene, toluene, and xylene, through a series of chemical reactions. The aromatization process typically occurs in the presence of an aromatization catalyst. This catalyst can be regenerated through processes such as chlorination, oxidation, and fluorination. During regeneration, the spent catalyst is typically contacted with chlorine gas, followed by a combustion step to remove the waste residue and redisperse metals, such as platinum. During this contact, chlorine and / or fluoride can adsorb onto the inner surfaces of the reactor vessel, particularly those with metals such as stainless steel. Adsorbed chlorides and / or fluorides can react with metallurgical materials, causing pitting and cracking, ultimately leading to vessel failure. Adsorbed chlorides and / or fluorides are particularly destructive when the vessel is left open to air and exposed to moisture during maintenance. Therefore, it is necessary to minimize the damage to the vessel caused by the adsorption of chlorides and / or fluorides onto the inner surfaces during vessel use, such as during catalyst regeneration. Summary of the Invention

[0004] Other technical features may be apparent to those skilled in the art from the following figures, description and claims.

[0005] In some respects, the techniques described herein relate to a method comprising contacting a catalyst with a halide within a container having a surface, wherein at least a portion of the halide is coupled to the surface; and regenerating the catalyst with a reducing fluid under suitable conditions, for example, to release at least a portion of the halide coupled to the surface.

[0006] In some aspects, the technology described herein relates to a method for removing all or a portion of residual metal halides from a container wall surface, the method comprising contacting a container wall surface containing a first amount of residual metal halides with a reducing fluid of about 500℉ to about 1,300℉ for at least about 1 hour to form a halide gas, and removing at least a portion of the residual metal halides from the container wall surface to provide a second amount of residual metal halides, wherein the second amount is less than the first amount.

[0007] In some aspects, the technology described herein relates to a method comprising contacting a hydrocarbon feedstock with an aromatization catalyst comprising a transition metal and a catalyst support in a metal reactor under reforming conditions to produce an aromatic product; conducting contact for a period of time sufficient to form spent aromatization catalyst; stopping contact with the hydrocarbon feedstock; stripping with hydrogen; purging with nitrogen; halogenating the spent aromatization catalyst with a first halide; purging with nitrogen; oxidizing at a temperature less than or equal to about 400℉; oxidizing at a temperature greater than or equal to about 400℉ and less than or equal to about 1,000℉; halogenating the spent aromatization catalyst with a second halide; purging with a gas containing oxygen; cooling the metal reactor to less than or equal to 500℉; purging with nitrogen; and reducing with a reducing fluid to remove the metal halide from the surface of the metal reactor walls.

[0008] In some respects, the technology described herein relates to a method comprising contacting an inner surface (optionally metal) or an internal metal surface region of a reactor vessel or reactor system with a halide or a halide-containing compound, wherein at least a portion of the halide is coupled to the inner surface; and releasing at least a portion of the halide coupled to the inner surface via contact with hydrogen.

[0009] In some respects, the technology described herein relates to a method for regenerating a spent catalyst comprising a transition metal and a catalyst support in a metal reactor, the method comprising: (1) contacting the spent catalyst with a chlorinated stream containing a chlorinated compound to produce a chlorinated spent catalyst; (2) contacting the chlorinated spent catalyst with a decoking stream containing oxygen to produce a decoking catalyst; (3) contacting the decoking catalyst with a fluorinated stream containing a fluorinated compound to produce a regenerated catalyst, wherein the fluorinated compound includes hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), fluorocarbons (FCs), or combinations thereof; wherein contact (1), contact (2), or both produce residual halides on the inner surface or inner surface region of the metal reactor; and (4) removing at least a portion of the residual halides by contact with hydrogen.

[0010] In some respects, the technology described herein relates to a method for regenerating a spent catalyst comprising a transition metal and a catalyst support in a metal reactor, the method comprising: (1) contacting the spent catalyst with a chlorinated stream containing a chlorinated compound to produce a chlorinated spent catalyst; (2) contacting the chlorinated spent catalyst with a decoking stream containing oxygen to produce a decoking catalyst; (3) contacting the decoking catalyst with a fluorinated stream containing a fluorinated compound to produce a regenerated catalyst, wherein the fluorinated compound includes hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), fluorocarbons (FCs), or combinations thereof; wherein contact (1), contact (2), or both produce residual halides on the inner surface or inner surface region of the metal reactor; and (4) contacting the residual halides with hydrogen gas under conditions that effectively remove at least a portion of the residual halides from the inner surface or inner surface region. Attached Figure Description

[0011] For a more complete understanding of this disclosure, reference is now made to the following description in conjunction with the accompanying drawings, wherein:

[0012] Figure 1 Exemplary schematic diagrams are shown of embodiments of a furnace, a container containing a catalyst, and a fluid-connected absorber for, for example, an aromatization process.

[0013] Figure 2 An exemplary elevation cross-sectional view of an embodiment of a container containing a catalyst is shown.

[0014] Figure 3 It is a planar cross-sectional view of one or more sector-shaped embodiments of a container containing a catalyst.

[0015] Figure 4 This is a top plan view of an implementation scheme for a reactor tube divided into four sections.

[0016] Figure 5 This is a top plan view of an embodiment of the flow branch section of the reactor tube located above the catalyst bed.

[0017] Figure 6 This is a top plan view of an embodiment of a flow branch section of a reactor tube located at approximately the same height as the catalyst bed.

[0018] Figure 7 This is a top plan view of an embodiment of the split section of the reactor tube located below the catalyst bed. Detailed Implementation

[0019] It should be understood that the following disclosure describes aspects, features, structure, and / or functionality of this disclosure. The exemplary components, arrangements, and configurations described below are provided as examples only and are not intended to limit the scope of this disclosure. Furthermore, the exemplary components, arrangements, and configurations described below may exist in any circulation; for example, any element of one component, arrangement, or configuration may be used in any other component, arrangement, or configuration without departing from the scope of this disclosure.

[0020] Furthermore, certain terms are used in the following description and claims to refer to specific components. Those skilled in the art will understand that the naming conventions used for the elements described herein are not intended to limit the scope of the claimed subject matter, unless otherwise expressly defined herein. Moreover, the naming conventions used herein are not intended to distinguish between components with different names but identical functions.

[0021] The term "coupling" refers to the physical or chemical absorption, adsorption, or reaction of substances (such as atoms or compounds) to form halides, typically metal halides.

[0022] The term "halogen" refers to a negatively charged halogen atom, including fluorides, chlorides, bromides, iodides, and astatides, and can form metal halides (such as ferric chloride) or gaseous halides (such as hydrogen chloride). As used herein, fluorine can be used interchangeably with fluoride, and chlorine can be used interchangeably with chloride.

[0023] 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, iodides, astatine, and astatides. Furthermore, the use of the terms "fluoride" and "chloride" in describing catalyst components or catalyst composition (such as weight percentages or molar percentages of these components) does not depend on their presence in the catalyst in any particular molecular or ionic form.

[0024] As used herein, the term “absorption” generally refers to the penetration and / or binding of a substance into a material, and “adsorption” generally refers to the binding of a substance to the surface of a material. The terms “absorption” and “adsorption” and their derivatives are used interchangeably, and as used herein, “absorption” and “adsorption” each refer to the process of absorption and / or adsorption.

[0025] The term "tin compound" refers to an intermetallic compound comprising tin and one or more other metals, and can be in the form of a coating. Examples of tin compounds include Fe. x Sn y Ni x Sn y Or combinations thereof, and other tin compounds, such as Mg, may also exist. x Sn y Kx Sn y 、Sr x Sn y Li x Rh y Sn z Mg x Ru y Sn z and / or Nb x Sn y .

[0026] The term "and / or" refers to any combination of one or more items in a list, such as "A and / or B" meaning "A, B, or a combination of A and B".

[0027] In some embodiments, the method may include contacting an inner surface (optionally metal) of a petrochemical or refining process vessel with a halide or a halide-containing compound, wherein at least a portion of the halide is coupled to the inner surface due to contraction; and releasing at least a portion of the halide coupled to the inner surface by contacting the inner surface with hydrogen. Release can be achieved by contacting the halide-coupled inner surface (e.g., a halide-treated surface or a halide-treated vessel surface) with hydrogen under conditions suitable and / or effective for removing all or part of the halide from the surface.

[0028] Examples of suitable petrochemical or refining process vessels having an inner surface that can contact one or more halides or halogen-containing compounds to form a halogenated surface include storage tanks such as crude oil storage tanks, product tanks, and feedstock tanks; reaction vessels such as batch reactors, continuous stirred tank reactors (CSTRs), plug flow reactors, tubular reactors, and catalytic reactors (including fixed-bed reactors and fluidized-bed reactors); separation equipment such as distillation columns, absorbers, strippers, extractors, decanters, and centrifuges; heat exchangers such as shell-and-tube heat exchangers, plate heat exchangers, and air-cooled head heat exchangers; pressure vessels such as autoclaves, pressure reactors, and gas holders; mixing equipment such as mixers, blenders, mixing tanks, and stirred tanks; and specialized vessels such as electrolyzers, crystallizers, and evaporators.

[0029] During any suitable process involving the use of halides or halogen-containing compounds, an inner surface may come into contact with halogens to form a halogenated surface, for example, as a catalyst, reactant, intermediate, product, or byproduct. For instance, during reactions involving halogenation, dehalogenation, dehydrogenation, or other halide-related or halide-catalyzed chemical transformations, an inner surface may come into contact with halogens to form a halogenated surface.

[0030] Contact between hydrogen and the halided surface can occur under suitable and / or effective conditions for the removal of all or part of the halides from the surface. Hydrogen can be in a reducing stream comprising about 10 mol% to about 100 mol% hydrogen, about 10 mol% to about 90 mol% hydrogen, and about 20 mol% to about 80 mol% hydrogen, with the balance being nitrogen. The reduction temperature can range from about 500℉ to about 1,300℉, alternatively from about 550℉ to about 1,200℉, or alternatively from about 600℉ to about 1,100℉; the reduction pressure can range from about 1 bar to about 34 bar, about 1 bar to about 20 bar, or about 1.5 bar to about 20 bar; and the contact time can range from about 1 hour (h) to about 72 h, alternatively from about 2 h to about 48 h, or alternatively from about 2 h to about 24 h, or within any suitable time range for the removal of halides, depending on, for example, the type of container, the flow rate, and the residence time.

[0031] In some embodiments, the inner surface is contacted with a halide or a halide-containing compound to form a halogenated surface, and at least a portion of the halide coupled to the inner surface is released by contacting the inner surface with hydrogen gas, in an aromatization process employing one or more aromatization catalysts containing one or more halides. The remainder of the detailed description relates to embodiments of the aromatization process without limiting the overall inventive aspects or subject matter disclosed and claimed herein.

[0032] In some embodiments, the method may include contacting a hydrocarbon feedstock with an aromatization catalyst comprising a transition metal and a catalyst support in a metal reactor under reforming conditions to produce aromatic products. A catalyst may be used to facilitate the reaction. Prior to use (e.g., contact with the hydrocarbon feedstock), the catalyst may comprise at least one metal of IUPAC Groups 8-11, at least one halide, and a support. Typically, the at least one metal may comprise platinum, the at least one halide may comprise chlorides, fluorides, or combinations thereof, and the support may comprise zeolite, L-zeolite, bound zeolite-based materials, or combinations thereof. In some aspects, the support comprises bound zeolite-based materials, such as bound L-zeolite, or bound barium ion-exchange L-zeolite. In some other embodiments, the bound zeolite-based material may comprise silica-bound K / L zeolite. In some embodiments, the catalyst support may comprise zeolite, amorphous inorganic oxides, or any combination thereof (or may consist substantially of, or may be composed of). Generally, catalyst supports may include L-zeolites, γ-zeolites, mordenite, ω-zeolites, and / or β-zeolites, particularly potassium L-zeolites or barium ion-exchange L-zeolites (or may be substantially composed of, or may be composed of, them). In some aspects, catalyst supports may include a binder comprising alumina, a binder comprising silica, a binder comprising a mixed oxide of alumina and silica, or mixtures thereof (or may be substantially composed of, or may be composed of, them).

[0033] In some embodiments, the catalyst may include a transition metal, including group 8-11 transition metals. Typically, the transition metal may include platinum (or may consist essentially of, or may be composed of, platinum). Typically, the catalyst includes any weight percentage range of transition metals disclosed herein, for example, about 0.1 wt% to about 10 wt%, or about 0.3 wt% to about 3 wt% of transition metals.

[0034] In some aspects, the catalyst comprises about 0.3 wt% to about 3 wt%, about 0.5 wt% to about 2.5 wt%, about 0.5 wt% to about 2 wt%, or about 0.7 wt% to about 1.5 wt% of platinum; about 0.1 wt% to about 7.0 wt%, about 0.2 wt% to about 6.0 wt%, about 0.3 wt% to about 5.0 wt%, about 0.4 wt% to about 4.5 wt%, about 0.5 wt% to about 4.0 wt%, about 0.6 wt% to about 3.5 wt%, about 0.7 wt% to about 3.0 wt%, or about 0.8 wt% to about 2.5 wt% of chlorine; and about 0.2 wt% to about 1.5 wt%, about 0.25 wt% to about 1.3 wt%, about 0.3 wt% to about 1.1 wt%, or about 0.3 wt% to about 1.0 wt% of fluorine, all based on the total weight of the supported fresh catalyst (optionally reduced). In some embodiments, the catalyst comprises about 0.3 wt% to about 3 wt%, about 0.5 wt% to about 2.5 wt%, about 0.5 wt% to about 2 wt%, or about 0.7 wt% to about 1.5 wt% of platinum; about 0.3 wt% to about 1.5 wt%, about 0.4 wt% to about 1.2 wt%, or about 0.5 wt% to about 1.1 wt% of chlorine; and about 0.2 wt% to about 1.5 wt%, about 0.25 wt% to about 1.3 wt%, about 0.3 wt% to about 1.1 wt%, or about 0.3 wt% to about 1.0 wt% of fluorine; all based on the total weight of the supported fresh catalyst (optionally reduced). In some aspects, the catalyst comprises about 0.3 wt% to about 3 wt%, about 0.5 wt% to about 2.5 wt%, about 0.5 wt% to about 2 wt%, or about 0.7 wt% to about 1.5 wt% of platinum; about 1.5 wt% to about 5 wt%, about 1.7 wt% to about 4.5 wt%, or about 1.8 wt% to about 4 wt% of chlorine; and about 0.2 wt% to about 1.5 wt%, about 0.25 wt% to about 1.3 wt%, about 0.3 wt% to about 1.1 wt%, or about 0.3 wt% to about 1.0 wt% of fluorine; all based on the total weight of the supported fresh catalyst (optionally reduced). Typically, the bound zeolite matrix comprises silica-bound K / L zeolite; the metal comprises platinum; and the chlorine:fluorine weight ratio is in the range of about 0.5:1 to about 5:1. In some aspects, the catalyst may comprise platinum supported on KL zeolite (or may consist essentially of, or may be composed of).

[0035] The catalyst can be reduced after the application of chlorine, fluorine, or both. The reducing gas may include about 20 mol% to about 100 mol%, about 25 mol% to about 90 mol%, or about 30 mol% to about 80 mol% of hydrogen, with the balance being nitrogen. The catalyst is reduced in the same vessel as the hydrocarbon. Sometimes, halides can be eluted from the fresh catalyst in the presence of a gas stream, and the eluted halides may accumulate on the inner surface of the vessel. After installation, the fresh catalyst can be contacted with hydrocarbons, and a hydrogen feed can be continued for a period of time sufficient to form spent aromatization catalyst. Typically, the spent catalyst may contain platinum in any weight percentage range disclosed herein, such as about 0.3 wt% to about 3 wt%, about 0.5 wt% to about 2.5 wt%, about 0.5 wt% to about 2 wt%, or about 0.7 wt% to about 1.5 wt%.

[0036] Waste aromatization catalysts can be regenerated by introducing halogenated streams over a given period of time. In some aspects, the metal surfaces and internal structures of the vessel (such as fan-shaped sections and reactor tubes) may be halogenated during contact of the catalyst with one or more halogenated streams. Specifically, in some aspects, halogenation of the catalyst within a vessel connected to a furnace before the passage of reducing fluid can result in the formation and / or deposition of at least a portion of the residual metal halide on the inner surfaces and internal structures of the vessel. For example, the vessel wall surface may react with halogens during catalyst halogenation.

[0037] In some embodiments, a method for regenerating spent catalysts (such as spent aromatization catalysts) is employed. In some embodiments, the methods herein include contacting the spent catalyst with a chlorinated stream containing a chlorinated compound to produce a chlorinated spent catalyst; contacting the chlorinated spent catalyst with a decoking stream containing oxygen to produce a decoking catalyst; and contacting the decoking catalyst with a fluorinated stream containing a fluorinated compound to produce a reduced, regenerated catalyst. In some embodiments, the fluorinated compound includes hydrofluorocarbons (HFCs), fluorocarbons (FCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), or combinations thereof.

[0038] In some embodiments, the halogen-containing stream (such as a chlorine-containing stream or a fluorine-containing stream) also includes an inert gas, air, or a combination thereof. In some embodiments, chlorination can be carried out at temperatures of about 75℉ to about 600℉, about 200℉ to about 550℉, or about 250℉ to about 450℉. Generally, the chlorination step can be carried out for any of the chlorination time periods disclosed herein, such as about 0.1 hours to about 72 hours, about 0.1 hours to about 60 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. The contact time can vary depending on specific circumstances, such as reactor size, flow rate, residence time, target amount of chlorine absorbed on the catalyst, or other factors. Typically, the contact will be carried out for an appropriate time to allow the halide to be absorbed onto the catalyst.

[0039] The amount of chlorine absorbed on the regenerated catalyst can be from about 0.3 wt% to about 1.5 wt%, from about 0.4 wt% to about 1.2 wt%, or from about 0.5 wt% to about 1.1 wt%, although in some embodiments the chlorination level can be higher, as disclosed herein with respect to fresh catalysts. Subsequently, oxidation can be carried out at a temperature of about 500℉ to about 1,000℉, about 600℉ to about 950℉, or about 650℉ to about 900℉. The volume ratio of inert gas to air (including oxygen) can be from about 3:1 to about 30:1 (inert gas: air). The amount of oxygen in the fluorinated gas (including fluorinated compounds) can be from about 1 mol% to about 21 mol%, from about 1 mol% to about 15 mol%, or from about 1 mol% to about 10 mol%. In some embodiments, fluorination can be carried out at a temperature of about 300℉ to about 1,100℉, from about 300℉ to about 1,000℉, or from about 300℉ to about 950℉. The amount of fluorine adsorbed on the regenerated catalyst can be from about 0.1 wt% to about 1.5 wt%, from about 0.15 wt% to about 1.3 wt%, or from about 0.2 wt% to about 1.2 wt%. Fluorine-containing compounds can be present in an effective amount in the fluorine-containing stream such that the fluorine concentration in the stream is from about 0.1 mol% to about 3.0 mol%, from about 0.12 mol% to about 2.0 mol%, or from about 0.15 mol% to about 1.8 mol%. Chlorine and fluorine can be added at target times and concentrations to obtain the chlorides and fluorides required for catalyst reactivation. In some aspects, the halogen concentration in the regenerated catalyst can be from about 0.4 wt% to about 3 wt%.

[0040] In some embodiments, the chlorine-containing stream may include a chlorine-containing compound and any inert gas (e.g., nitrogen) disclosed herein (or may consist substantially of, or may consist of, nitrogen). Typically, the chlorine-containing stream may include chlorine (Cl2) and nitrogen (or may consist substantially of, or may consist of, nitrogen). Typically, the amount of the chlorine-containing compound in the chlorine-containing stream can be controlled to obtain a desired concentration of chlorine (Cl) on the catalyst, such as less than any maximum amount or within any range disclosed herein, for example, less than about 50,000 parts per million (ppmv), in the range of about 5 ppmv to about 25,000 ppmv, in the range of about 10 ppmv to about 10,000 ppmv, in the range of about 50 ppmv to about 5,000 ppmv, or in the range of about 100 ppmv to about 1,000 ppmv. Sometimes, the chlorine-containing stream may be substantially free of oxygen-containing compounds and / or fluorine-containing compounds, for example, less than about 100 parts per million (ppmw) by weight.

[0041] In some aspects, chlorine-containing compounds may include hydrochloric acid, chlorine (Cl2), carbon tetrachloride, tetrachloroethylene, chlorobenzene, chloromethane, dichloromethane, chloroform, allyl chloride, trichloroethylene, chloramine, chlorine oxides, 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 (or may consist essentially of, or may consist of). In some alternative aspects, chlorine-containing compounds may include chlorine (Cl2) (or may consist essentially of, or may consist of).

[0042] In some embodiments, the fluorinated stream may include (or may consist essentially of, or may consist 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; or (iii) a fluorinated compound and air; wherein when the fluorinated stream may include an inert gas and air, the inert gas and air may be present in a ratio of about 3:1 to about 20:1 or about 6:1, or the molar percentage of oxygen in the fluorinated stream may be about 1 mol% to about 21 mol%, about 1 mol% to about 15 mol%, or about 1 mol% to about 10 mol%.

[0043] In some respects, the fluorinated stream (e.g., containing fluorine molecules) may be substantially free of oxygen-containing and / or chlorine-containing compounds that do not contain fluorine atoms, for example, less than about 100 ppmw, and the fluorination step may be carried out at (i) a fluorination temperature within any suitable fluorination temperature range. As an example, the temperature range may be about 68℉ to about 700℉, about 100℉ to about 650℉, or about 200℉ to about 600℉, and (ii) a fluorination pressure of about atmospheric pressure to about 15 bar, about atmospheric pressure to about 10 bar, about atmospheric pressure to about 9 bar, about 0.5 bar to about 10 bar, about 0.5 bar to about 9 bar, or about 0.5 bar to about 8 bar. Generally, the fluorination step may be carried out for a period of time within any fluorination time range disclosed herein, for example, 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.

[0044] In some embodiments, the contact between the decoking catalyst and the halogen-containing stream occurs at a temperature of about 75℉ to about 1,000℉, at a pressure of about 0.5 bar to about 10 bar, for a period of about 0.1 hours to about 48 hours, or a combination thereof. In some embodiments, the method further includes recovering at least a portion of the halogen-containing stream to produce a recovered halogen-containing stream. Recovery may be performed after the decoking catalyst is contacted with the fluorine-containing stream, and after the decoking catalyst is contacted with the recovered fluorine-containing stream.

[0045] In some implementations, at the end of the reactivation process, the catalyst can be reduced in a hydrogen-rich atmosphere and then reused. Adding a reducing gas (such as hydrogen) may remove some adsorbed halogens (such as chlorine). Therefore, the reducing gas environment may include hydrogen chloride desorbed from metal surfaces. Nevertheless, halides can still accumulate on the vessel walls and / or internal structures during the vessel's service life, thus affecting the vessel's integrity.

[0046] In some embodiments, specific procedures can be used to remove halides from the surface and / or wall structure of the vessel. In some aspects, the method may include contacting the catalyst with the halides within a vessel having a surface. Generally, at least a portion of the halides can be coupled to the surface. Subsequently, the catalyst can be reduced with a reducing fluid (such as a reducing gas, e.g., hydrogen), and under appropriate conditions, at least a portion of the halides coupled to the vessel surface can be released. In some embodiments, a hydrogen reducing fluid can remove up to about 10,500 parts per million (ppm) of chloride from the internal surfaces of the vessel (such as reactor walls, pipes, and / or other internal structures).

[0047] Residual metal halides or halides can be removed from the container wall surface, or residual metal halides can be converted into metals in a quantifiable amount. In some cases, the halide portion of the metal halide is removed in gaseous form, such as hydrogen chloride or hydrogen fluoride, while the metal is restored to a reduced state, such as metal. + (M + ) to M 0 The reducing gas may comprise about 10 mol% to about 100 mol%, about 10 mol% to about 90 mol%, about 20 mol% to about 100 mol%, about 20 mol% to about 80 mol%, about 25 mol% to about 90 mol%, about 30 mol% to about 80 mol%, or about 35 mol% to about 70 mol% of hydrogen, with the balance being nitrogen. Regeneration using the reducing gas can be carried out at at least about 700℉, about 750℉, about 800℉, about 850℉, about 920℉, about 940℉, about 950℉, about 960℉, about 970℉, about 980℉, about 990℉, or about 1,000℉, preferably above about 930℉. The reduction of the regenerated catalyst using a reducing gas lasts for at least about 2 hours, about 12 hours, about 24 hours, about 36 hours, about 48 hours, about 60 hours, or about 72 hours, or a suitable time depending on the container size and shape, flow rate, and residence time, to desorb or otherwise remove halides from the container surface. In some cases, the container is purged with nitrogen prior to reduction.

[0048] Typically, the furnace can be in fluid communication with the vessel. Therefore, the furnace can be configured to supply a heated feed (optionally reactants) to the vessel. In some embodiments, the halide may include chlorides, fluorides, or combinations thereof, and the halide may be coupled to the surface and contained within a metal halide.

[0049] In some aspects, metal halides may include FeCl3, FeCl2, CrCl3, CrCl2, FeF3, FeF2, CrF3, CrF2, or combinations thereof, and the halides may be chlorides, fluorides, bromides, or combinations thereof. While not wishing to be bound by theory, halides can bind to the surface inside the container through two mechanisms, such as by the formation of metal halides (e.g., FeCl3) and by the binding of halides to the metal surface (e.g., surface chlorides). Metal halides may be present at depths of less than or equal to about 1 micrometer, about 2 micrometers, about 3 micrometers, about 4 micrometers, about 5 micrometers, about 6 micrometers, about 7 micrometers, about 8 micrometers, about 9 micrometers, about 10 micrometers, about 50 micrometers, or about 100 micrometers. The surface may have a halide concentration of less than or equal to about 50,000 ppm, about 40,000 ppm, about 20,000 ppm, or about 10,000 ppm, as measured by energy-dispersive spectroscopy (EDS).

[0050] Typically, the container containing spent catalyst can be any suitable container, such as a reactor. In some embodiments, the reactor can be a radial flow reactor for hydrocarbon reactions (such as aromatization reactions). In some aspects, the reactor walls and / or internal supports can comprise iron, chromium, nickel, aluminum, or combinations thereof, such as stainless steel (SS), for example 347SS, 321SS, 316SS, or 304SS. The reactor may include a protective coating on the stainless steel, and the protective coating may comprise tin; tin compounds; titanium; aluminum; chromium; oxides of tin, tin compounds, titanium, aluminum, chromium, or combinations thereof; nitrides of tin, tin compounds, titanium, aluminum, chromium, or combinations thereof; carbides of tin, tin compounds, titanium, aluminum, chromium, or combinations thereof; or combinations thereof. In some aspects, the protective coating comprises titanium nitride.

[0051] Figure 1 Exemplary schemes for processing feed 58 containing hydrocarbons are depicted, such as during reforming operations in some embodiments. During maintenance and catalyst regeneration, feed 58 may contain or consist of other substances, typically in a gaseous state, including hydrogen, nitrogen, halogens including chlorine and fluorine, oxygen, chlorofluorocarbons, fluorocarbons, fluorocarbons, or combinations thereof. In some aspects, the method or process may include furnace 60, vessel 100, and absorber 160. Although only a single furnace 60, a single vessel 100, and a single absorber 160 are shown, it should be understood that multiple furnaces and vessels may be used, arranged in any suitable order, such as in series or in parallel. Furthermore, other equipment, such as adsorbers and absorbers, compressors, exchangers, and flash tanks, may be included, but these are not depicted for the sake of simplicity.

[0052] During the manufacturing operation, feed 58 (comprising one or more hydrocarbons in some embodiments) can be supplied to furnace 60. Subsequently, heated feed 68 can be supplied to vessel 100 for any suitable reaction, such as aromatization. Reference will be made below. Figures 2 to 3 Container 100 is described in further detail. Container effluent 154 can be sent from container 100 to any suitable destination, including to other equipment for additional processing.

[0053] After the catalyst has been degraded for some time, in some respects, the container effluent 154 during regeneration can be sent to absorber 160 to remove halogens from the container effluent 154, depending on whether absorbent 164 is suitable for absorbing halogens. Absorber effluent 168 can be sent to any suitable destination for further treatment, recovery, or disposal.

[0054] refer to Figures 2 to 3The container 100 can form any suitable enclosure, which may include a reactor 108 or reactor system 108, including an aromatization reactor, such as a radial flow reactor 116, although the container 100 may be suitable for processes other than aromatization. Although the container 100 is depicted as cylindrical, the container 100 can take any suitable shape, and the container 100 can be designed as top flow, bottom flow, or side flow, although the depicted container 100 is designed as top flow. In some embodiments, the container 100 may be a reactor 108 and made of any suitable material, such as metal, e.g., stainless steel, as described above. The container 100 (such as reactor 108) may form an inner surface 104 (such as inner wall surface 110) having surface areas. As shown, reactor 108 may be a radial flow reactor 116 having an inlet 120, an outlet 124, one or more sectors 128, and a central tube 132. The radial flow reactor 116 may also include a plurality of reactor tubes 112 surrounding the central tube 132. The inner wall surface (or wall) 110 of container 100, the plurality of reaction tubes 112, one or more sectors 128, and other internal structures may also be considered to provide all or part of the inner surface 104 having the surface area of ​​container 100. For example... Figures 2 to 3 As shown, one or more sectors 128 may be spaced apart around the inner wall surface 110 of the container 100. The central tube 132 may be surrounded by catalyst 136 inside one or more sectors 128.

[0055] During regeneration, a halogenated fluid (such as a gas) may contact the catalyst in one or more separation applications. The halogenated gas may contain chlorine, fluorine, chlorides, fluorides, fluorides, or combinations thereof, and may be introduced via a series of steps, for example, a halogenated gas containing chlorine followed by a halogenated gas containing fluorine or a fluoride. The introduced halogenated gas may react with the metallic surfaces of container 100, including its internal structures. In some embodiments, halogens in at least one halogenated gas entering inlet 120 may react substantially with surface 144 adjacent to inlet 120. In some embodiments, the amount of halide formed may be as high as about 7,000 ppm of halogen, such as 7,000 ppm of chlorine. This reaction forms metal halides at or within surface 144, thereby weakening the integrity of container 100, especially when exposed to moisture. Container 100 may include a length 140, and in some embodiments, "adjacent to inlet 120" may typically be about one-third of the length 148 of the length 140 of container 100.

[0056] refer to Figures 1 to 2To release halides from one or more surfaces inside container 100, a reducing fluid 152 comprising any suitable fluid, such as a gas, may be introduced into inlet 120. In some embodiments, the reducing fluid 152 may be hydrogen. Contact between the reducing fluid 152 and the inner surface 104 of container 100 releases halide gases, such as hydrogen chloride and / or hydrogen fluoride. The halide gases may exit container 100 through outlet 124. Reactor effluent 154 containing halide gases may be sent to absorber 160 to remove the halide gases and minimize their concentration in absorber effluent 168. Removing halides from the inner surface 104 restores the integrity of the walls of container 100 and extends the operational life of container 100. Although hydrocarbon reactors have been discussed above, it should be understood that the methods disclosed herein are applicable to any platform, container, apparatus, or method for addressing halide corrosion problems, such as chloride corrosion.

[0057] Example

[0058] The implementation scheme has been generally described. The following embodiments are given as specific examples to demonstrate the practice and advantages of this disclosure. It should be understood that the embodiments are given by way of illustration and are not intended to limit the specification or claims in any way.

[0059] A 17-inch reactor tube, made of 321SS with an outer diameter (OD) of one inch, was loaded with 160 g of alumina spheres with a diameter of one-eighth inch, followed by 30 g of waste platinum, chloride, and fluoride / L zeolite catalyst, and topped with another 90 g of alumina spheres with a diameter of one-eighth inch. The reactor was purged with nitrogen and the temperature was raised to 400℉, then maintained at 400℉ until the moisture content was below 10 ppm by weight. Once stabilized, approximately 250 ppmv chlorine (Cl) was added and maintained for 180 minutes. The reactor was then purged with nitrogen at 400℉ overnight. Next, 0.5 mol% oxygen was introduced, and the temperature was maintained at 400℉ for 30 minutes. Moisture and carbon dioxide levels were monitored using a traction tube. The oxygen concentration was then increased to 3 mol%, and the temperature was raised to 850℉ and maintained for 3 hours. The temperature was then set to the values ​​in Table 1 for hydrochlorofluorocarbon materials, which are typically manufactured by Chemours Company FC, LLC in Wilmington, Delaware under the trade name... For sale. Once the temperature stabilizes, introduce approximately 530 ppmv of 1,1,1,2-tetrafluoroethane for 100 minutes. Then, reduce the temperature to 500℉ in a flowing nitrogen atmosphere containing 3 mol% oxygen, and cool the catalyst to room temperature in pure nitrogen.

[0060] Next, reduction steps were performed on the second and fourth runs. The first run was maintained at 500℉ in flowing nitrogen to thoroughly purge all oxygen from the reactor. Hydrogen was introduced to obtain a 50 mol% mixture with nitrogen, the temperature was raised to 970℉, and held for 20 minutes. The reactor was then cooled to room temperature in a flowing mixture of 50 mol% hydrogen and 50 mol% nitrogen.

[0061] After each test, the reactor tube was removed and cut into four parts, as follows: Figure 4 As shown. Figure 5 , Figure 6 and Figure 7 As shown, the chlorine content in the extracted tube was analyzed by energy-dispersive spectroscopy (EDS). The chlorine content was determined using a JEOL JSM-6610LV scanning electron microscope (SEM) from Jeol, Ltd., Tokyo, Japan, equipped with an Oxford Instruments INCA Energy 350EDS system from Oxford Instruments plc, Abingdon, UK, including an 80mm... 2 Area silicon drift detector (SDD). Averaging of multiple points across three metal sections: above the catalyst bed ( Figure 5 ), catalyst bed ( Figure 6 ) and below the catalyst bed ( Figure 7 And report in parts per million (ppmw) in Table 1 below:

[0062] Table 1

[0063]

[0064]

[0065] By comparing Run 1 with Run 2 and Run 3 with Run 4, the effect of reduction on adsorbed chlorine on metallurgical materials can be determined. When fluorination was performed at 730℉ (Run 1 and Run 2), a reduction in adsorbed chlorine was observed ranging from 670 ppmw to 2,000 ppmw. When fluorination was performed at 850℉ (Run 3 and Run 4), a reduction in adsorbed chlorine was observed ranging from 5,270 ppmw to 10,400 ppmw. This indicates that a reduction step on metallurgical materials adsorbed with halides (such as chlorides) reduces the concentration of halides adsorbed on the surface.

[0066] Additional Notes

[0067] Therefore, the scope of protection is not limited to the description set forth above, but only to the following claims, the scope of which includes all equivalents of the subject matter of the claims. Each claim is incorporated herein as an embodiment of this disclosure. Thus, the claims are a further description and an addition to the specific embodiments of this disclosure. All disclosures of patents, patent applications, and publications cited herein are hereby incorporated by reference.

[0068] The aspect for releasing at least a portion of the halide coupled to the surface by a reducing fluid, as described above. The following are specific, non-limiting aspects according to this disclosure:

[0069] Aspect 1. A method comprising contacting a catalyst with a halide within a container 100 having a surface 104, wherein at least a portion of the halide is coupled to the surface 104; and regenerating the catalyst with a reducing fluid 152 to release the at least a portion of the halide coupled to the surface 104.

[0070] Aspect 2. The method of aspect 1, the method further comprising a furnace 60 in fluid communication with the container 100, wherein the furnace 60 is configured to provide a heated feed 68 (optionally reactants) to the container 100.

[0071] Aspect 3. The method as described in aspect 1 or 2, wherein the halide comprises chloride, fluoride, or a combination thereof.

[0072] Aspect 4. The method of any one of Aspects 1 to 3, wherein the halide coupled to the surface 104 is contained in a metal halide.

[0073] Aspect 5. The method of any one of Aspects 1 to 4, wherein the metal halide comprises FeCl3, FeCl2, CrCl3, CrCl2 or combinations thereof.

[0074] Aspect 6. The method of any one of Aspects 1 to 5, wherein the metal halide may be present at a depth of less than or equal to about 1 micrometer, about 2 micrometer, about 3 micrometer, about 4 micrometer, about 5 micrometer, about 6 micrometer, about 7 micrometer, about 8 micrometer, about 9 micrometer, about 10 micrometer, about 50 micrometer or about 100 micrometer.

[0075] Aspect 7. The method of any one of Aspects 1 to 6, wherein the halide comprises a chloride.

[0076] Aspect 8. The method of any one of claims 1 to 7, wherein the halide comprises a fluoride.

[0077] Aspect 9. The method of any one of Aspects 1 to 8, wherein the container 100 includes a reactor 108, the reactor including an inlet 120, an outlet 124, one or more sectors 128 and a central tube 132 surrounded by the catalyst, and the reactor 108 having a length 140, and the halide coupled to a surface 104 adjacent to the inlet 120.

[0078] Aspect 10. The method as described in aspect 9, wherein approximately one-third 148 of the length 140 of the container 100, measured from the inlet 120, is located near the inlet 120.

[0079] Aspect 11. The method as described in aspect 9 or 10, wherein the reactor 108 comprises a radial flow reactor 116.

[0080] Aspect 12. The method of any one of Aspects 9 to 11, wherein the reactor 108 comprises stainless steel.

[0081] Aspect 13. The method of aspect 12, wherein the stainless steel is selected from the group consisting of 347SS, 321SS, 316SS and 304SS.

[0082] Aspect 14. The method of any one of Aspects 9 to 13, wherein the reactor 108 comprises a protective coating on the stainless steel, and the protective coating comprises tin; tin oxide; titanium; aluminum; chromium; oxides of tin, tin oxide, titanium, aluminum, chromium or combinations thereof; nitrides of tin, tin oxide, titanium, aluminum, chromium or combinations thereof; carbides of tin, tin oxide, titanium, aluminum, chromium or combinations thereof; or combinations thereof.

[0083] Aspect 15. The method of aspect 14, wherein the protective coating comprises titanium nitride.

[0084] Aspect 16. The method of any one of Aspects 1 to 15, wherein the surface 104 has a halide concentration of less than or equal to about 50,000 ppm, about 40,000 ppm, about 20,000 ppm or about 10,000 ppm, as measured by energy dispersive spectroscopy (EDS).

[0085] Aspect 17. The method of any one of Aspects 1 to 16, wherein the reducing fluid 152 comprises a reducing gas.

[0086] Aspect 18. The method of aspect 17, wherein the reducing gas comprises about 10 mol% to about 100 mol%, about 10 mol% to about 90 mol%, about 20 mol% to about 100 mol%, about 20 mol% to about 80 mol%, about 25 mol% to about 90 mol%, about 30 mol% to about 80 mol%, about 35 mol% to about 70 mol%, about 40 mol% to about 80 mol%, or about 50 mol% to about 70 mol% of hydrogen and the balance being nitrogen.

[0087] Aspect 19. The method as described in Aspect 17 or 18, wherein the regeneration using the reducing gas is carried out at at least about 700℉, about 750℉, about 800℉, about 850℉, about 920℉, about 940℉, about 950℉, about 960℉, about 970℉, about 980℉, about 990℉ or about 1,000℉, preferably above about 930℉.

[0088] Aspect 20. The method of any one of Aspects 17 to 19, wherein the regeneration using the reducing gas is for at least about 1 hour, about 2 hours, about 12 hours, about 24 hours, about 36 hours, about 48 hours, about 60 hours, or about 72 hours.

[0089] Aspect 21. The method of any one of Aspects 1 to 20, wherein the container 100 is purged with nitrogen prior to regeneration.

[0090] Aspect 22. A method for removing all or a portion of residual metal halides from a container wall surface 110, the method comprising contacting the container wall surface 110 containing a first amount of the residual metal halide with a reducing fluid of at least about 700℉ for at least about 1 hour to form a halide gas, and removing at least a portion of the residual metal halide from the container wall surface 110 to provide a second amount of the residual metal halide, wherein the second amount is less than the first amount.

[0091] Aspect 23. The method of aspect 22, the method further comprising, prior to passing the reducing fluid through, halogenating the catalyst in a container 100 in communication with the furnace 60, and depositing at least a portion of the first amount of the residual metal halide.

[0092] Aspect 24. The method of claim 22 or 23, wherein the container wall 110 comprises iron.

[0093] Aspect 25. The method of any one of Aspects 22 to 24, wherein the container wall 110 comprises iron, chromium and nickel.

[0094] Aspect 26. The method of any one of Aspects 22 to 25, wherein the halide comprises a chloride, a fluoride, a bromide, or a combination thereof.

[0095] Aspect 27. The method of any one of Aspects 22 to 26, wherein the halide comprises a chloride.

[0096] Aspect 28. The method of any one of Aspects 22 to 27, wherein the halide comprises a fluoride.

[0097] Aspect 29. The method of any one of Aspects 22 to 28, wherein the metal halide comprises FeCl3, FeCl2, CrCl3, CrCl2 or combinations thereof.

[0098] Aspect 30. The method of any one of Aspects 22 to 29, wherein the metal halide comprises FeF3, FeF2, CrF3, CrF2 or combinations thereof.

[0099] Aspect 31. The method of any one of Aspects 22 to 30, wherein the reducing fluid comprises hydrogen.

[0100] Aspect 32. The method of any one of aspects 22 to 31, wherein a quantifiable amount of the residual metal halide is removed from the container wall surface 110.

[0101] Aspect 33. The method of any one of aspects 22 to 32, wherein the container 100 includes a reactor 108, wherein the container wall surface 110 includes a reactor wall surface 110.

[0102] Aspect 34. The method of any one of Aspects 23 to 33, wherein prior to contact, the catalyst comprises at least one metal of IUPAC Groups 8-11, at least one halide, and a support.

[0103] Aspect 35. The method of aspect 34, wherein the at least one metal comprises platinum, the at least one halide comprises chloride, fluoride or a combination thereof, and the support comprises zeolite, L-zeolite, combined zeolite-based or a combination thereof.

[0104] Aspect 36. The method as described in aspect 34 or 35, wherein the carrier comprises a bound zeolite base, such as bound L-zeolite.

[0105] Aspect 37. The method of aspect 36, wherein the combined L-zeolite comprises combined barium ion-exchange L-zeolite.

[0106] Aspect 38. The method as described in aspect 36 or 37, wherein the combined zeolite base comprises silica-bonded K / L zeolite.

[0107] Aspect 39. The method of any one of Aspects 34 to 38, wherein the at least one halide comprises a chloride and a fluoride.

[0108] Aspect 40. The method of any one of Aspects 23 to 39, wherein the catalyst comprises about 0.3 wt% to about 3 wt%, about 0.5 wt% to about 2.5 wt%, about 0.5 wt% to about 2 wt%, or about 0.7 wt% to about 1.5 wt% of platinum; about 0.1 wt% to about 7.0 wt%, about 0.2 wt% to about 6.0 wt%, about 0.3 wt% to about 5.0 wt%, about 0.4 wt% to about 4.5 wt%, about 0.5 wt% to about 4.0 wt%, about 0.6 wt% to about 3.5 wt%, or about 0.7 wt% to about 3.0 wt%. Chlorine of about 0.8 wt% to about 2.5 wt%, about 0.3 wt% to about 1.5 wt%, about 0.4 wt% to about 1.2 wt%, about 0.5 wt% to about 1.1 wt%, about 1.5 wt% to about 5 wt%, about 1.7 wt% to about 4.5 wt%, or about 1.8 wt% to about 4 wt%; and fluorine of about 0.2 wt% to about 1.5 wt%, about 0.25 wt% to about 1.3 wt%, about 0.3 wt% to about 1.1 wt%, or about 0.3 wt% to about 1.0 wt%; all based on the total weight of the supported fresh catalyst (optionally reduced).

[0109] Aspect 41. The method of any one of Aspects 35 to 40, wherein the combined zeolite base comprises silica-bonded K / L zeolite; the metal comprises platinum; and the weight ratio of chlorine to fluorine is in the range of about 0.5:1 to about 5:1.

[0110] Aspect 42. The method of any one of Aspects 22 to 41, wherein the container wall surface 110 reacts with halogens during the halogenation of the catalyst.

[0111] Aspect 43. The method of any one of Aspects 22 to 42, wherein the halide gas comprises hydrogen chloride.

[0112] Aspect 44. The method of any one of Aspects 22 to 43, the method further comprising, prior to the introduction of the reducing fluid, contacting the catalyst with a halogenated fluid containing a halogenated compound in the gas phase to produce a halogenated catalyst and a halogenated container wall surface 110.

[0113] Aspect 45. The method of any one of Aspects 22 to 44, the method further comprising passing the halide gas through an absorbent 164 downstream of the container 100.

[0114] Aspect 46. A method comprising, under reforming conditions, contacting a hydrocarbon feedstock with an aromatization catalyst comprising a transition metal and a catalyst support in a metal reactor 108 to produce an aromatic product; maintaining contact for a period sufficient to form spent aromatization catalyst; ceasing contact with the hydrocarbon feedstock; stripping with hydrogen; purging with nitrogen; halogenating the spent aromatization catalyst with a first halide; purging with nitrogen; oxidizing at a temperature less than or equal to about 400℉; oxidizing at a temperature greater than or equal to about 400℉ and less than or equal to about 850℉ or less than or equal to about 1,000℉; halogenating the spent aromatization catalyst with a second halide; purging with a gas containing oxygen; cooling the metal reactor 108 to less than or equal to 500℉; purging with nitrogen; and reducing with a reducing fluid to remove the metal halide from the metal reactor wall surface 110.

[0115] Aspect 47. A method comprising contacting an inner surface 104 (optionally metallic) or an internal metallic surface region of a reactor vessel 100 or reactor system 108 with a halide or a halide-containing compound, wherein at least a portion of the halide is coupled to the inner surface 104; and releasing at least a portion of the halide coupled to the inner surface 104 by contacting it with an amount of hydrogen gas effective in protecting the integrity of the vessel.

[0116] Aspect 48. The method of aspect 47, the method further comprising a furnace 60 in fluid communication with the reactor vessel 100 or the reactor system 108, wherein the furnace 60 is configured to provide a heated feed 68 (optionally reactants) to the reactor vessel 100 or the reactor system 108.

[0117] Aspect 49. The method as described in aspect 47 or 48, wherein the halide comprises chloride, fluoride, or a combination thereof.

[0118] Aspect 50. The method of any one of Aspects 47 to 49, wherein the halide coupled to the surface 104 is contained in a metal halide.

[0119] Aspect 51. The method of any one of Aspects 47 to 50, wherein the metal halide comprises FeCl3, FeCl2, CrCl3, CrCl2 or combinations thereof.

[0120] Aspect 52. The method of aspect 50 or 51, wherein the metal halide may be present at a depth of about 1 micrometer, about 2 micrometers, about 3 micrometers, about 4 micrometers, about 5 micrometers, about 6 micrometers, about 7 micrometers, about 8 micrometers, about 9 micrometers, about 10 micrometers, about 50 micrometers, or about 100 micrometers.

[0121] Aspect 53. The method of any one of Aspects 47 to 52, wherein the halide or the halide-containing compound comprises a chloride.

[0122] Aspect 54. The method of any one of Aspects 47 to 53, wherein the halide or the halide-containing compound comprises a fluoride.

[0123] Aspect 55. The method of any one of Aspects 47 to 54, wherein the reactor vessel 100 or reactor system 108 includes a reactor 108, the reactor including an inlet 120, an outlet 124, one or more sectors 128 and a central tube 132 surrounded by the catalyst, and the reactor 108 having a length, and the halide coupled to a surface adjacent to the inlet 120.

[0124] Aspect 56. The method as described in aspect 55, wherein approximately one-third of the length 148 of the reactor 108, as measured from the inlet 120, is located near the inlet 120.

[0125] Aspect 57. The method as described in aspect 55 or 56, wherein the reactor 108 comprises a radial flow reactor 116.

[0126] Aspect 58. The method of any one of aspects 47 to 57, wherein the catalyst is disposed within the reactor vessel 100 or the reactor system 108.

[0127] Aspect 59. The method of aspect 58, wherein the catalyst is an aromatization catalyst.

[0128] Aspect 60. The method of aspect 59, wherein prior to contact, the aromatization catalyst comprises at least one metal of IUPAC Groups 8-11, at least one halide and a support, and the halide is a chloride gas.

[0129] Aspect 61. The method of any one of Aspects 47 to 60, wherein the release is carried out at at least about 700℉, about 750℉, about 800℉, about 850℉, about 920℉, about 940℉, about 950℉, about 960℉, about 970℉, about 980℉, about 990℉ or about 1,000℉, preferably above about 930℉.

[0130] Aspect 62. The method of any one of Aspects 47 to 61, wherein the release is for at least about 2 hours, about 12 hours, about 24 hours, about 36 hours, about 48 hours, about 60 hours, or about 72 hours.

[0131] Aspect 63. The method of any one of Aspects 47 to 62, wherein the release is carried out at a temperature of at least about 700℉ or about 970℉ for at least about 2 hours or at least about 24 hours, preferably at about 700℉ for at least about 24 hours or at about 970℉ for at least about 12 hours.

[0132] Aspect 64. The method of any one of Aspects 55 to 63, wherein the reactor 108 comprises a plurality of reactor tubes 112 providing the inner surface 104 or the inner surface region.

[0133] Aspect 65. The method of any one of Aspects 55 to 64, wherein the reactor 108 comprises a reactor metal, the reactor metal comprising one or more metals, including iron, chromium, nickel, or combinations thereof.

[0134] Aspect 66. The method of any one of Aspects 55 to 65, wherein the reactor 108 comprises stainless steel.

[0135] Aspect 67. The method of aspect 66, wherein the stainless steel is selected from the group consisting of 347SS, 321SS, 316SS and 314SS.

[0136] Aspect 68. The method of any one of aspects 47 to 67, wherein the inner surface 104 has a halide concentration of less than or equal to about 50,000 ppm, about 40,000 ppm, about 20,000 ppm or about 10,000 ppm, as measured by energy dispersive spectroscopy (EDS).

[0137] Aspect 69. A method for regenerating a spent catalyst comprising a transition metal and a catalyst support in a metal reactor 108, the method comprising: (1) contacting the spent catalyst with a chlorinated stream containing a chlorinated compound to produce a chlorinated spent catalyst; (2) contacting the chlorinated spent catalyst with a decoking stream containing oxygen to produce a decoking catalyst; and (3) contacting the decoking catalyst with a fluorinated stream containing a fluorinated compound to produce a regenerated catalyst, wherein the fluorinated compound comprises hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), or combinations thereof.

[0138] The contact (1), the contact (2), or both of them generate residual halides on the inner surface 104 or the inner surface region of the metal reactor 108, and (4) remove at least a portion of the residual halides by contact with hydrogen.

[0139] Aspect 70. A method for regenerating a spent catalyst comprising a transition metal and a catalyst support in a metal reactor 108, the method comprising: (1) contacting the spent catalyst with a chlorinated stream containing a chlorinated compound to produce a chlorinated spent catalyst; (2) contacting the chlorinated spent catalyst with a decoking stream containing oxygen to produce a decoking catalyst; (3) contacting the decoking catalyst with a fluorinated stream containing a fluorinated compound to produce a regenerated catalyst, wherein the fluorinated compound comprises hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), or combinations thereof; wherein the contact (1), the contact (2), or both produce residual halides on an inner surface 104 or an inner surface region of the metal reactor 108; and (4) contacting the residual halides with hydrogen gas under conditions that effectively remove at least a portion of the residual halides from the inner surface 104 or the inner surface region.

[0140] Aspect 71. A reforming method comprising: (A) in a metal reactor system, under reforming conditions, contacting a hydrocarbon feedstock with an aromatization catalyst comprising a transition metal and a catalyst support to produce an aromatic product; (B) performing step (A) for a time sufficient to form a spent catalyst; (C) contacting the spent catalyst with a chlorinated stream containing a chlorinated compound to produce a chlorinated spent catalyst; (D) contacting the chlorinated spent catalyst with a decoking stream containing oxygen to produce a decoking catalyst; and (E) contacting the decoking catalyst with a fluorinated stream containing a fluorinated compound, wherein the fluorinated compound comprises hydrofluorocarbons (HFCs), fluorocarbons (FCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), or combinations thereof.

[0141] Aspect 72. The method of aspect 71, the method further comprising reactivating the catalyst after step (E).

[0142] Aspect 73. The method as described in aspect 71 or 72, wherein the reforming method is an in-situ process, for example, steps (A) through (E) are carried out in the same reactor system.

[0143] Aspect 74. The method of any one of Aspects 71 to 73, wherein steps (C) to (E) are performed outside the reactor system of steps (A) to (B), for example, steps (C) to (E) are performed in a metal reactor not in the reforming reactor system.

[0144] While preferred embodiments of the invention have been shown and described, modifications can be made to them by those skilled in the art without departing from the teachings of this disclosure. The embodiments described herein are merely exemplary and not intended to be limiting. Many variations and modifications of the invention disclosed herein are possible and are within the scope of the invention.

[0145] While this disclosure and its advantages have been described in detail, it should be understood that various changes, substitutions, and modifications may be made herein without departing from the spirit and scope of this disclosure as defined by the appended claims. Furthermore, the scope of this application is not intended to be limited to the specific embodiments of the processes, machines, manufactures, compositions of matter, means, methods, and steps described in the specification. As will readily be understood by one of ordinary skill in the art from this disclosure, processes, machines, manufactures, compositions of matter, means, methods, or steps that are currently existing or will be developed thereafter can be utilized to perform substantially the same function or achieve substantially the same results as the corresponding embodiments described herein. Therefore, the appended claims are intended to include such processes, machines, manufactures, compositions of matter, means, methods, or steps within their scope.

Claims

1. A method, the method comprising: The catalyst is brought into contact with the halide in a container having a surface, wherein at least a portion of the halide is coupled to the surface; as well as The catalyst is regenerated with a reducing fluid to release at least a portion of the halides coupled to the surface.

2. The method of claim 1, further comprising a furnace in fluid communication with the container, wherein the furnace is configured to provide a heated feed, optionally reactants, to the container.

3. The method of claim 1, wherein the halide comprises chloride, fluoride, or a combination thereof.

4. The method of claim 3, wherein the halide coupled to the surface is contained in a metal halide.

5. The method of claim 4, wherein the metal halide comprises FeCl3, FeCl2, CrCl3, CrCl2, or a combination thereof.

6. The method of claim 4, wherein the metal halide is present at a depth of less than or equal to about 100 micrometers.

7. The method of claim 1, wherein the halide comprises a chloride.

8. The method of claim 1, wherein the container comprises a reactor, the reactor comprising an inlet, an outlet, one or more fan-shaped sections and a central tube surrounded by the catalyst, and the reactor having a length, and the halide coupled to a surface adjacent to the inlet.

9. The method of claim 8, wherein approximately one-third of the length of the container measured from the inlet is located near the inlet.

10. The method of claim 8, wherein the reactor comprises stainless steel.

11. The method of claim 10, wherein the reactor comprises a protective coating on the stainless steel, and the protective coating comprises tin; tin oxide; titanium; aluminum; chromium; oxides of tin, tin oxide, titanium, aluminum, chromium or combinations thereof; nitrides of tin, tin oxide, titanium, aluminum, chromium or combinations thereof; carbides of tin, tin oxide, titanium, aluminum, chromium or combinations thereof; or combinations thereof.

12. The method of claim 1, wherein the surface has a halide concentration of less than or equal to about 50,000 ppm, as measured by energy dispersive spectroscopy (EDS).

13. The method of claim 1, wherein the reducing fluid comprises a reducing gas.

14. The method of claim 13, wherein the reducing gas comprises about 10 mol percent to about 100 mol percent of hydrogen and the balance being nitrogen.

15. The method of claim 14, wherein the regeneration using the reducing gas occurs at about 500℉ to about 1,300℉ and lasts for at least about 2 hours.

16. A method for removing all or part of residual metal halides from the surface of a container wall, the method comprising: The container wall surface containing the first amount of the residual metal halide is brought into contact with a reducing fluid at about 500℉ to about 1,300℉ for at least about 1 hour to form halide gas. At least a portion of the residual metal halide is removed from the surface of the container wall to provide a second amount of the residual metal halide, wherein the second amount is less than the first amount.

17. The method of claim 16, further comprising halogenating the catalyst in a vessel in communication with the furnace and depositing at least a portion of the first amount of the residual metal halide before passing the reducing fluid through it.

18. The method of claim 16, wherein the container wall comprises iron.

19. The method of claim 17, wherein prior to contact, the catalyst comprises at least one metal of IUPAC Groups 8-11, at least one halide, and a support.

20. A method comprising: The inner surface (optionally metal) of the reactor vessel is brought into contact with a halide or a halide-containing compound, wherein at least a portion of the halide is coupled to the inner surface; And by contacting the inner surface with an amount of hydrogen gas that effectively protects the integrity of the container to release at least a portion of the halide coupled to the inner surface.

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