A method for releasing at least a portion of a halide from a surface.

Abstract

The invention involves bringing a metal inner surface of a container used in petrochemical or refining processes into contact with a halide or a halide-containing compound, resulting in at least a portion of the halide bonding to the inner surface, and releasing at least a portion of the halide bonded to the inner surface through contact with hydrogen.

Description

[Technical Field]

[0001] This disclosure relates to a method for releasing at least a portion of halides from a surface of a refining or petrochemical process vessel after the surface has been exposed to halides, for example, during the regeneration of a spent aromatization catalyst. [Background technology]

[0002] Industrial chemical processing plants and oil refineries contain many types of process vessels, tanks, and reactors made of metal, whose inner surfaces come into contact with process fluids and reactants. In various petrochemical and refining processes, one or more of these inner surfaces may come into contact with halides or halide-containing compounds. In the presence of halides, the corrosive nature of halides, particularly chlorides and fluorides, can lead to internal damage such as pitting corrosion and stress corrosion cracking, as well as general corrosion of the metal material.

[0003] One example of a chemical process using halides is aromatization, which converts linear or aliphatic hydrocarbons into aromatic compounds such as benzene, toluene, and xylene through a series of chemical reactions. The aromatization process is usually carried out in the presence of an aromatization catalyst. The aromatization catalyst can be regenerated by processes including chlorination, oxidation, and fluorination. During regeneration, the spent catalyst is usually brought into contact with chlorine gas, and then the coke is removed in a calcination process, and a metal such as platinum is redispersed. During contact, chlorine and / or fluorine may be adsorbed onto the inner surface of the reaction vessel, especially metal reactors such as stainless steel. The adsorbed chlorides and / or fluorides react with the metal, causing pitting corrosion and cracking, which can ultimately lead to vessel failure. These adsorbed chlorides and / or fluorides can cause particularly significant damage when the vessel is exposed to the atmosphere during maintenance and exposed to moisture present in the air. Therefore, it is necessary to minimize damage to the vessel during use, for example, after chlorides and / or fluorides have been adsorbed onto the inner surface of the vessel during catalyst regeneration. [Overview of the project]

[0004] Those skilled in the art will readily understand the other technical features from the following figures, description, and claims.

[0005] In some embodiments, the techniques described herein include methods for regenerating the catalyst, for example, under appropriate conditions, using a reducing fluid, such that a catalyst is brought into contact with a halide in a container having a surface, thereof at least a portion of the halide being bonded to the surface, and at least a portion of the surface-bonded halide being released.

[0006] In some embodiments, the techniques described herein are methods for removing all or part of residual metal halides from a container wall, comprising: contacting a container wall containing a first amount of residual metal halide with a reducing fluid at about 500°F to about 1,300°F for at least about 1 hour to form a halogenated gas; and removing at least part of the halogen from the residual metal halide from the container wall so that the residual metal halide is in a second amount, the second amount being less than the first amount.

[0007] In some embodiments, the techniques described herein include a method comprising contacting a hydrocarbon feed with an aromatization catalyst comprising a transition metal and a catalyst support under reforming conditions in a metal reactor to produce an aromatic product, allowing sufficient time for spent aromatization catalyst to form, ceasing contact with the hydrocarbon feed, stripping with hydrogen, purging with nitrogen, halogenating the spent aromatization catalyst with a first halide, purging with nitrogen, oxidizing at a temperature below about 400°F, oxidizing at a temperature between about 400°F and about 1,000°F, halogenating the spent aromatization catalyst with a second halide, purging with an oxygen-containing gas, cooling the metal reactor below 500°F, purging with nitrogen, and removing metal halides from the metal reactor walls by reduction with a reducing fluid.

[0008] In some embodiments, the techniques described herein include methods for bringing a metal interior surface or an internal metal surface region of a reaction vessel or reactor system into contact with a halide or a halide-containing compound, thereby causing at least a portion of the halide to bond to the interior surface, and releasing at least a portion of the bonded halide to the interior surface through contact with hydrogen.

[0009] In some embodiments, the techniques described herein relate 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 chlorine-containing stream containing a chloride-containing compound to produce a chlorinated spent catalyst; (2) contacting the chlorinated spent catalyst with a decoked gas stream containing oxygen to produce a decoked catalyst; (3) contacting the decoked catalyst with a fluorine-containing stream containing a fluoride-containing compound to produce a regenerated catalyst, wherein the fluoride-containing compound includes hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), fluorocarbons (FCs), or combinations thereof, the contact in (1), the contact in (2), or both, to generate residual halides on the inner surface or internal surface region of the metal reactor; and (4) removing at least a portion of the residual halides via contact with hydrogen.

[0010] In some embodiments, the techniques described herein relate 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 chlorine-containing stream containing a chloride-containing compound to produce a chlorinated spent catalyst; (2) contacting the chlorinated spent catalyst with a decoked gas stream containing oxygen to produce a decoked catalyst; and (3) contacting the decoked catalyst with a fluorine-containing stream containing a fluoride-containing compound to produce a regenerated catalyst, wherein the fluoride-containing compound includes hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), fluorocarbons (FCs), or combinations thereof, the contact in (1), the contact in (2), or both thereof, causes residual halides to form on the inner surface or internal surface region of the metal reactor; and (4) contacting the residual halides with hydrogen under conditions effective in removing at least a portion of the residual halides from the inner surface or internal surface region.

[0011] This disclosure will be better understood by referring to the following description in conjunction with the attached drawings. [Brief explanation of the drawing]

[0012] [Figure 1] This is a schematic diagram illustrating an example of one embodiment of a heating furnace, a catalyst-containing vessel, and an absorption device for an aromatization process, all in fluid communication. [Figure 2] This is a vertical cross-sectional view showing an example of one embodiment of a container for housing a catalyst. [Figure 3] This is a plan cross-sectional view of one embodiment of one or more scallops in a container for housing a catalyst. [Figure 4] This is a top plan view of one embodiment of a reactor tube divided into four parts. [Figure 5] This is a top plan view of one embodiment of a divided section of a reactor tube located above the catalyst bed. [Figure 6]It is a top plan view of an embodiment of a split portion of a reactor tube located at approximately the same height as the catalyst bed. [Figure 7] It is a top plan view of an embodiment of a split portion of a reactor tube located below the catalyst bed.

Best Mode for Carrying Out the Invention

[0013] It should be understood that the following disclosure describes aspects, features, structures, and / or functions of the present disclosure. The exemplary components, arrangements, and configurations described below are merely shown as examples and are not intended to limit the scope of the present disclosure. Also, the exemplary components, arrangements, and configurations described below can exist in any flow-through, for example, any component, arrangement, or element of a certain configuration can be used in any other component, arrangement, or configuration without departing from the scope of the present disclosure.

[0014] Furthermore, throughout the following description and claims, specific terms are used to refer to specific components. As those skilled in the art will understand, the naming rules of the elements described in this specification are not intended to limit the scope of the claimed subject matter unless otherwise specifically defined in this specification. Furthermore, the naming rules used in this specification are not intended to distinguish components that have different names but the same function.

[0015] The term "combined" refers to the physical or chemical absorption or adsorption of substances such as atoms or compounds, or the formation of a halide, which is usually a metal halide, by reaction.

[0016] The term "halide" refers to a halogen atom with a negative charge, including fluoride, chloride, bromide, iodide, and astatide, and can form metal halides such as iron chloride or gaseous halides such as hydrogen chloride. As used herein, fluorine may be used synonymously with fluoride, and chlorine may be used synonymously with chloride.

[0017] The term "halogen" has its ordinary meaning and includes halides as far as admitted in the context. That is, examples of halogens include fluorine, fluoride, chlorine, chloride, bromine, bromide, iodine, iodide, astatine, and astatide. Further, the use of the terms "fluoride" and "chloride" is not dependent on the particular molecular or ionic form in which they are present in the catalyst, for example when describing the catalyst component or composition, such as their weight percentage or molar percentage.

[0018] As used herein, the term "absorption" generally means a substance that penetrates into and / or binds to a material, and the term "adsorption" generally means a substance that binds to the surface of a material. The terms "absorption" and "adsorption", and their derivatives, may be used synonymously, and each of the terms "absorption" and "adsorption" as used herein means the process of absorption and / or adsorption. [[ID= ]]

[0019] The term "stannide" refers to an intermetallic compound containing tin and one or more other metals, and may be in the form of a coating. Examples of stannides include Fe Sn y 、Ni x Sn y 、or combinations thereof, and also Mg x Sn y 、K x Sn y 、Sr x Sn y 、Li x Rh y Sn[[ID= ]] z 、Mg x Ru y Sn z 、and / or Nb x Sn y and other stannides such as may also be present.

[0020] The term "and / or" refers to one or more items in any combination of those listed; for example, "A and / or B" means "A, B, or a combination of A and B."

[0021] In some embodiments, the method may involve contacting a metal interior surface of a vessel for a petrochemical or refining process with a halide or a halide-containing compound, such that at least a portion of the halide is bonded to the interior surface as a result of the contact, and releasing at least a portion of the bonded halide through contact with hydrogen. This release can be achieved by contacting the halogen-bonded interior surface (e.g., a halogenated surface or a halogenated vessel surface) with hydrogen under conditions suitable and / or effective for removing all or part of the halide from the surface.

[0022] Suitable petrochemical or refining process vessels having an inner surface capable of forming a halogenated surface upon contact with one or more halides or halogenated compounds include storage tanks such as crude oil storage tanks, product tanks, and raw material tanks; reaction vessels such as batch reactors, continuous stirred tank reactors (CSTRs), plug flow reactors, tubular reactors, and catalytic reactors including fixed-bed and fluidized-bed reactors; separation equipment such as distillation columns, absorption units, strippers, extraction units, decanters, and centrifuges; heat exchangers such as shell-and-tube heat exchangers, plate heat exchangers, and air-cooled heat exchangers; pressure vessels such as autoclaves, pressure reactors, and gas holders; mixers such as mixers, blenders, mixing tanks, and stirring tanks; and special vessels such as electrolytic cells, crystallizers, and evaporators.

[0023] In any appropriate process involving the use of halides or halide-containing compounds, such as as catalysts, reactants, intermediates, products, or by-products, a halogenated surface can be formed by contacting the inner surface with a halogen. For example, a halogenated surface can be formed by contacting the inner surface with a halogen during halogenation, dehalogenation, dehydrohalogenation, or other reactions involving chemical transformations of halides or halide catalysts.

[0024] Contact between hydrogen and a halogenated surface may be carried out under conditions suitable and / or effective for removing all or part of the halide from the surface. This hydrogen may be in a reducing stream containing about 10 mol% to about 100 mol%, about 10 mol% to about 90 mol%, and about 20 mol% to about 80 mol%, with the remainder being nitrogen. The reduction temperature can be in the range of approximately 500°F to 1,300°F, or approximately 550°F to 1,200°F, or approximately 600°F to 1,100°F. The reduction pressure can be in the range of approximately 1 bar to 34 bar, approximately 1 bar to 20 bar, or approximately 1.5 bar to 20 bar. The contact time can be in the range of approximately 1 hour (h) to 72 hours, or approximately 2 hours to 48 hours, or approximately 2 hours to 24 hours, or any time suitable for halogen removal depending on the type of container, flow rate, residence time, etc.

[0025] In some embodiments, the formation of a halogenated surface by contacting the inner surface with a halide or a halide-containing compound, and the release of at least a portion of the halide bonded to the inner surface via contact with hydrogen, are carried out in an aromatization process using one or more aromatization catalysts containing one or more halides. The following detailed description relates to embodiments of the aromatization process but does not limit the overall aspects or subject matter of the invention disclosed and claimed herein.

[0026] In some embodiments, the method may involve contacting a hydrocarbon feed with an aromatization catalyst comprising a transition metal and a catalyst support under reforming conditions in a metal reactor to produce an aromatic product. The catalyst may be used to accelerate the reaction. Before use, for example, before contact with the hydrocarbon feed, the catalyst may comprise at least one metal from groups 8-11 according to IUPAC, at least one halide, and a support. Typically, the at least one metal may be platinum, the at least one halide may be a chloride, a fluoride, or a combination thereof, and the support may comprise a zeolite, L-type zeolite, a bonded zeolite substrate, or a combination thereof. In some embodiments, the support comprises a bonded L-type zeolite or a bonded zeolite substrate such as barium-ion-exchanged bonded L-type zeolite. In some other embodiments, the bonded zeolite substrate may comprise silica-bonded K / L-type zeolite. In some embodiments, the catalyst support may comprise (or essentially consist of, or be composed of) a zeolite, amorphous inorganic oxide, or any combination thereof. Typically, catalyst supports may include (or essentially consist of, or be composed of) L-type zeolites, Y-type zeolites, mordenite, omega-zeolites, and / or beta-zeolites, particularly potassium L-type zeolites, or barium-exchanged L-type zeolites. In some embodiments, catalyst supports may include (or essentially consist of, or be composed of) binders comprising alumina, silica, mixed oxides thereof, or mixtures thereof.

[0027] In some embodiments, the catalyst may contain transition metals, including transition metals of Groups 8 to 11. Typically, the transition metals may include platinum (or may consist of, or be composed of, platinum). Typically, the catalyst contains any of the weight percentage ranges of transition metals disclosed herein, for example, about 0.1 wt% to about 10 wt%, or about 0.3 wt% to about 3 wt%.

[0028] In some embodiments, the catalyst is composed of approximately 0.3 wt% to 3 wt%, 0.5 wt% to 2.5 wt%, 0.5 wt% to 2 wt%, or 0.7 wt% to 1.5 wt% of platinum, approximately 0.1 wt% to 7.0 wt%, 0.2 wt% to 6.0 wt%, or 0.3 wt% to 5.0 wt%, relative to the total weight of the supported fresh catalyst which may be reduced. It contains approximately 0.4 wt% to 4.5 wt%, approximately 0.5 wt% to 4.0 wt%, approximately 0.6 wt% to 3.5 wt%, approximately 0.7 wt% to 3.0 wt%, or approximately 0.8 wt% to 2.5 wt% of chlorine, and approximately 0.2 wt% to 1.5 wt%, approximately 0.25 wt% to 1.3 wt%, approximately 0.3 wt% to 1.1 wt%, or approximately 0.3 wt% to 1.0 wt% of fluorine. 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%, 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, based on the total weight of the supported fresh catalyst, which may all be reduced. In some embodiments, the catalyst each contains, with respect to the total weight of the supported fresh catalyst which may be reduced, 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. Typically, the bonded zeolite substrate contains silica-bonded K / L type zeolite, the metal contains platinum, and the chlorine:fluorine weight ratio is in the range of approximately 0.5:1 to approximately 5:1. In some embodiments, the catalyst may contain platinum on the KL type zeolite (or may consist of, or be composed of, essentially these).

[0029] The catalyst may be reduced after the addition of chlorine, fluorine, or both. The reducing gas may contain about 20 mol% to about 100 mol%, about 25 mol% to about 90 mol%, or about 30 mol% to about 80 mol%, with the remainder being nitrogen. The catalyst is reduced in the same vessel in which contact with hydrocarbons takes place. Occasionally, halides may leach from the fresh catalyst, typically in the presence of a gas stream, and the leached halides may accumulate on the inner surface of the vessel. After installation, a spent aromatic catalyst may be formed by contacting the fresh catalyst with hydrocarbons and supplying hydrogen for a sufficient amount of time. Typically, the spent catalyst may contain platinum in any of the weight percent ranges disclosed herein, for example, 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%.

[0030] Used aromatic catalysts can be regenerated by introducing a halogenated flow for a certain period of time. In some embodiments, the metal surface of the container and internal structures such as scallops and reactor tubes can be halogenated while the catalyst is in contact with one or more halogen-containing flows. In particular, in some embodiments, at least some of the residual metal halides can be formed and / or deposited on the inner surface and internal structure of the container by halogenating the catalyst in a container communicating with a heating furnace before the reducing fluid is circulated. As an example, the container wall can react with halogens during the halogenation of the catalyst.

[0031] In some embodiments, methods are used to regenerate spent catalysts, such as spent aromatic catalysts. In some embodiments, the methods described herein include contacting the spent catalyst with a chlorine-containing stream containing a chlorine-containing compound to produce a chlorinated spent catalyst, contacting the chlorinated spent catalyst with a decoked gas stream containing oxygen to produce a decoked catalyst, and contacting the decoked catalyst with a fluorine-containing stream containing a fluorine-containing compound to produce a regenerated catalyst to be reduced. In some embodiments, the fluorine-containing compound includes hydrofluorocarbons (HFCs), fluorocarbons (FCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), or combinations thereof.

[0032] In some embodiments, the halogen-containing stream, such as a chlorine-containing stream or a fluorine-containing stream, may also include an inert gas, air, or a combination thereof. In some embodiments, chlorination can be carried out at temperatures of about 75°F to about 600°F, about 200°F to about 550°F, or about 250°F to about 450°F. Typically, the chlorination process can be carried out for any of the chlorination durations disclosed herein, for example, about 0.1 hours to about 72 hours, about 0.1 hours to about 60 hours, about 0.1 to about 48 hours, about 0.1 to about 12 hours, or about 0.1 to about 8 hours. The contact time may vary depending on specific circumstances such as reactor size, flow rate, residence time, target amount of chlorine to be absorbed by the catalyst, or other factors. Typically, contact is carried out over a time suitable for the halogen to be absorbed by the catalyst.

[0033] The amount of chlorine absorbed by the regenerated catalyst can be 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%, but in some embodiments, the chlorination level can be higher, as disclosed herein with respect to fresh catalysts. Oxidation can then be carried out at temperatures of about 500°F to about 1,000°F, about 600°F to about 950°F, or about 650°F to about 900°F. The inert gas and air (containing oxygen) may be present in a volume ratio of about 3:1 to about 30:1 (inert gas:air). The amount of oxygen in the fluorine-containing gas containing the fluorine-containing compound may be about 1 mol% to about 21 mol%, about 1 mol% to about 15 mol%, or about 1 mol% to about 10 mol%. In some embodiments, fluorination can be carried out at temperatures of about 300°F to about 1,100°F, about 300°F to about 1,000°F, or about 300°F to about 950°F. The amount of fluorine absorbed by the regenerating catalyst can be about 0.1 wt% to about 1.5 wt%, about 0.15 wt% to about 1.3 wt%, or about 0.2 wt% to about 1.2 wt%. Fluorine-containing compounds may be present in the fluorine-containing stream in amounts effective to achieve a fluorine concentration of about 0.1 mol% to about 3.0 mol%, about 0.12 mol% to about 2.0 mol%, or about 0.15 mol% to about 1.8 mol%. Chlorine and fluorine can be added at target times and concentrations to obtain the target chlorides and fluorides in the reactivating catalyst. In some embodiments, the halogen concentration in the regenerating catalyst may be about 0.4 wt% to about 3 wt%.

[0034] In some embodiments, the chlorine-containing stream may contain (or essentially consist of, or be composed of) a chlorine-containing compound and any of the inert gases disclosed herein, such as nitrogen. Typically, the chlorine-containing stream may contain (or essentially consist of, or be composed of) chlorine gas (Cl2) and nitrogen. Typically, the amount of chlorine-containing compound in the chlorine-containing stream can be controlled so that the chlorine (Cl) concentration is at the concentration required on the catalyst, for example, less than any of the maximum amounts disclosed herein or within any of the ranges, for example, less than about 50,000 parts per million by volume (ppmv), in the range of about 5 to about 25,000 ppmv, in the range of about 10 to about 10,000 ppmv, in the range of about 50 to about 5,000 ppmv, or in the range of about 100 to about 1,000 ppmv. The chlorine-containing stream may substantially not contain oxygen-containing compounds and / or fluorine-containing compounds, for example, less than about 100 parts per million by weight (ppmw).

[0035] In some embodiments, the chlorine-containing compound may include (or be essentially composed of or comprise of) any of the following: hydrochloric acid, chlorine gas (Cl2), carbon tetrachloride, tetrachloroethylene, chlorobenzene, methyl chloride, methylene chloride, chloroform, allyl chloride, trichloroethylene, chloramine, chlorine oxide, oxoacid of chlorine, chlorine dioxide, dichlorine monoxide, dichlorine heptoxide, chloric acid, perchloric acid, ammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, methyltriethylammonium chloride, or any combination thereof. In some alternative embodiments, the chlorine-containing stream may include (or be essentially composed of or comprise of) chlorine gas (Cl2).

[0036] In some embodiments, the fluorine-containing stream may include (i) a fluorine-containing compound and any of the inert gases disclosed herein, such as nitrogen; (ii) a fluorine-containing compound, any of the inert gases disclosed herein, and air; or (iii) a fluorine-containing compound and air (or may essentially consist of these, or be composed of these). If the fluorine-containing 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 fluorine-containing 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%.

[0037] In some embodiments, for example, the fluorine-containing stream containing fluorine molecules may substantially contain oxygen-containing compounds and / or chlorine-containing compounds that do not contain fluorine atoms, for example, less than about 100 ppmw, and the fluorination process may (i) be carried out at a fluorination temperature within any suitable fluorination temperature range, for example, the temperature in the range of about 68°F to about 700°F, about 100°F to about 650°F, or about 200°F to about 600°F, and (ii) the fluorination pressure may be atmospheric pressure to about 15 bar, atmospheric pressure to about 10 bar, 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. Typically, the fluorination process can be carried out for any of the fluorination periods disclosed herein, for example, about 0.1 hours to about 96 hours, about 0.1 hours to about 72 hours, about 0.1 to about 48 hours, about 0.1 to about 12 hours, or about 0.1 to about 8 hours.

[0038] In some embodiments, contact between the decoked catalyst and the halogen-containing stream is carried out at a temperature of about 75°F to about 1,000°F, a pressure of about 0.5 bar to about 10 bar, a duration of about 0.1 hours to about 48 hours, or a combination thereof. In some embodiments, the method also includes recovering at least a portion of the halogen-containing stream to produce a recovered halogen-containing stream. Recovery can be carried out after contacting the decoked catalyst with the fluorine-containing stream, and then after contacting the decoked catalyst with the recovered fluorine-containing stream.

[0039] In some embodiments, the catalyst may be reduced in a hydrogen-rich atmosphere at the end of the reactivation process before it can be reused. By adding a reducing gas such as hydrogen, some of the adsorbed halogens, such as chlorine, may be removed. Therefore, the reducing gas environment may contain hydrogen chloride desorbed from the metal surface. Nevertheless, halides may still accumulate on the walls and / or internal structure of the container during its lifespan, potentially affecting the integrity of the container.

[0040] In some embodiments, halides can be removed from the surface and / or wall structure of a container by a specific procedure. In some embodiments, the method may involve contacting a catalyst with a halide in a container having a surface. Typically, at least a portion of the halide can be bound to the surface. The catalyst can then be reduced with a reducing fluid, such as a reducing gas, e.g., hydrogen, which, under suitable conditions, can release at least a portion of the halide bound to the container surface. In some embodiments, the reducing fluid, which is hydrogen, can remove up to about 10,500 parts per million by mass (ppm) of chloride from the internal surface of the container, such as the walls, tubes, and / or other internal structures of the reactor.

[0041] A quantifiable amount of residual metal halide or halide can be removed from the container wall, or residual metal halide can be converted to metal. In some embodiments, the halide portion of the metal halide is removed as a gas such as hydrogen chloride or hydrogen fluoride, and the metal is reduced to a reduced state, for example, metal + (M + )~M 0 Return to the previous section. The reducing gas may contain approximately 10 mol% to 100 mol%, approximately 10 mol% to 90 mol%, approximately 20 mol% to 100 mol%, approximately 20 mol% to 80 mol%, approximately 25 mol% to 90 mol%, approximately 30 mol% to 80 mol%, or approximately 35 mol% to 70 mol%, with the remainder being nitrogen. Regeneration with the reducing gas can be carried out at at least approximately 700°F, approximately 750°F, approximately 800°F, approximately 850°F, approximately 920°F, approximately 940°F, approximately 950°F, approximately 960°F, approximately 970°F, approximately 980°F, approximately 990°F, or approximately 1,000°F, preferably above approximately 930°F. The reduction of the regenerating catalyst with reducing gas 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, or an appropriate time depending on the size and shape of the container, the flow rate, and the residence time for desorption or removal of halides from the container surface. In some embodiments, the container is purged with nitrogen before reduction.

[0042] Typically, the heating furnace can be in fluid communication with the container. Thus, the heating furnace can be configured to supply heated feed, optionally reactants, to the container. In some embodiments, the halide may include chlorides, fluorides, or combinations thereof, and the halide may be bonded to a surface and contained within the metal halide.

[0043] In some embodiments, the metal halide may include FeCl3, FeCl2, CrCl3, CrCl2, FeF3, FeF2, CrF3, CrF2, or combinations thereof, and the halide may be a chloride, fluoride, bromide, or combination thereof. While not wishing to be bound by theory, halides may bond to the internal surface of a container by two mechanisms, such as the formation of a metal halide like FeCl3, and halides may bond to the surface of a metal, such as surface chlorides. Metal halides may be present at depths of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 50, or less than about 100 microns. Surface halide concentrations measured by energy-dispersive spectroscopy (EDS) may be about 50,000 ppm, 40,000 ppm, 20,000 ppm, or less than about 10,000 ppm.

[0044] Typically, the container for housing the 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 embodiments, the reactor may include stainless steel (SS) such as iron, chromium, nickel, aluminum, or combinations thereof, for the walls and / or internal supports, e.g., 347SS, 321SS, 316SS, or 304SS. The reactor may be coated with a protective coating on the stainless steel, which may include oxides of tin, stannides, titanium, aluminum, chromium, or combinations thereof; nitrides of tin, stannides, titanium, aluminum, chromium, or combinations thereof; carbides of tin, stannides, titanium, aluminum, chromium, or combinations thereof; or combinations thereof. In some embodiments, the protective coating includes titanium nitride.

[0045] Figure 1 shows an exemplary scheme for processing a feed 58 containing hydrocarbons during a reforming operation, as in several embodiments. During maintenance and catalyst regeneration, the feed 58 may contain, or be composed of, other substances typically in a gaseous state, including hydrogen, nitrogen, halogens including chlorine and fluorine, oxygen, chlorofluorohydrocarbons, fluorohydrocarbons, carbon fluoride, or combinations thereof. In some embodiments, the method or process may include a furnace 60, a vessel 100, and an absorption device 160. Although only a single furnace 60, a single vessel 100, and a single absorption device 160 are illustrated, it should be understood that multiple furnaces and vessels may be used and may be arranged in any order as appropriate, such as in series or in parallel. Also included, though not illustrated for the sake of simplification of the disclosure herein, may be other equipment such as adsorption and sorbing devices, compressors, heat exchangers, and flash drums.

[0046] During the manufacturing process, in some embodiments, a feed 58 containing one or more hydrocarbons can be supplied to the heating furnace 60. The heated feed 68 can then be supplied to the container 100 for any suitable reaction, such as aromatization. The container 100 will be described in more detail below with reference to Figures 2-3. The container outflow 154 can be sent from the container 100 to any suitable destination, including other equipment for further processing.

[0047] After the period in which the catalyst is used, in some embodiments, the regenerating container spill 154 can be sent to an absorber 160, depending on whether the absorbent 164 is suitable for absorbing halogens, to remove halogens from the container spill 154. The absorber spill 168 can be sent to any suitable destination for further processing, recycling, or disposal.

[0048] Referring to Figures 2-3, the vessel 100 can form any suitable enclosure that may include an aromatization reactor, such as a reactor 108 or reactor system 108 including a radial flow reactor 116, but the vessel 100 may also be suitable for processes other than aromatization. Although the vessel 100 is shown as cylindrical, the vessel 100 may be of any suitable shape, and although a vessel 100 designed for top flow is shown, the vessel 100 may also be designed as top flow, bottom flow, or side flow. In some embodiments, the vessel 100 may be a reactor 108, which, as described above, can be made from any suitable material such as metal, for example, stainless steel. The vessel 100 (reactor 108, etc.) may form an inner surface 104 (inner wall surface 110, etc.) having a surface area. As shown, the reactor 108 may be a radial flow reactor 116 with an inlet 120, an outlet 124, one or more scallops 128, and a central pipe 132. Furthermore, the radial flow reactor 116 may include a plurality of reactor tubes 112 surrounding the central pipe 132. The inner wall (or wall) 110 of the vessel 100, the plurality of reactor tubes 112, one or more scallops 128, and other internal structures can also be considered to constitute all or part of the inner surface 104 having a surface area of ​​the vessel 100. As shown in Figures 2-3, one or more scallops 128 can be arranged on the inner circumference of the inner wall 110 of the vessel 100. The central pipe 132 may be surrounded by a catalyst 136 inside one or more scallops 128.

[0049] During regeneration, a halogen-containing fluid, such as a gas, can be brought into contact with the catalyst in one or more separation applications. The halogen-containing gas may include chlorine, fluorine, chloride, fluoride, fluorocarbon, or a combination thereof, and can be introduced, for example, by a series of steps using one halogen-containing gas containing chlorine and a subsequent halogen-containing gas containing fluorine or fluoride. The introduction of one or more halogen-containing gases enables a reaction with metal surfaces, including the internal structure of the container 100. In some embodiments, halogens in at least one halogen-containing gas entering the inlet 120 may substantially react with the surface 144 adjacent to the inlet 120. In some embodiments, the amount of halide formed may be up to about 7,000 ppm of halogen, for example, 7,000 ppm of chlorine. This reaction results in the formation of metal halides on or within the surface 144, which weakens the integrity of the container 100, especially when exposed to moisture. The container 100 may have a length of 140, and the "proximity to the inlet 120" can, in some embodiments, be a length of 148, which is typically about one-third of the length 140 of the container 100.

[0050] Referring to Figures 1-2, a reducing fluid 152 containing any suitable fluid, such as a gas, may be introduced into the inlet 120 to release halides from one or more surfaces inside the container 100. In some embodiments, the reducing fluid 152 can be hydrogen. By bringing the reducing fluid 152 into contact with the inner surface 104 of the container 100, halogenated gases such as hydrogen chloride and / or hydrogen fluoride can be released. The halogenated gas can exit the container 100 through the outlet 124. The reactor effluent 154 containing the halogenated gas can be sent to an absorber 160 to remove the halogenated gas so that its concentration in the absorber effluent 168 is minimized. By removing halides from the inner surface 104, the integrity of the walls of the container 100 can be restored and the operating life of the container 100 can be extended. Although a hydrocarbon reactor has been described above, it should be understood that the methods disclosed herein are applicable to any platform, container, apparatus, or process that solves the problem of corrosion by halides such as chlorides. [Examples]

[0051] While embodiments have been described in general terms, the following examples are provided as specific examples to illustrate the implementation and benefits of this disclosure. It should be understood that these examples are illustrative and not intended to limit the scope of this specification or the claims in any way. A 321SS reactor tube with an outer diameter (OD) of 1 inch and a length of 17 inches is filled with 160 grams (g) of 1 / 8-inch diameter alumina spheres, followed by 30 grams of spent platinum, chloride, and fluoride / L-type zeolite catalyst, and finally a further 90 grams of 1 / 8-inch diameter alumina spheres. The reactor is purged with nitrogen and the temperature is raised to 400°F, then maintained at 400°F until the moisture content is less than 10 pp by weight. Once stable, approximately 250 ppmv of chlorine (Cl) gas is added for 180 minutes. The reactor is purged with nitrogen at 400°F overnight. Next, 0.5 mol% oxygen is introduced and the temperature is maintained at 400°F for 30 minutes. Moisture and carbon dioxide are monitored using a Dräger detector tube. Next, the oxygen concentration is increased to 3% molar ratio, and the temperature is raised to 850°F and maintained for 3 hours. Next, set the temperature to the values ​​listed in Table 1 for the addition of the hydrochlorofluorocarbon material, which is normally sold by The Chemours Company FC, LLC (Wilmington, Delaware) under the trademark name FREON (trademark). Once the temperature stabilizes, introduce 1,1,1,2-tetrafluoroethane at approximately 530 ppmv for 100 minutes. Then, while oxygen in the nitrogen is flowing at 3 mol%, lower the temperature to 500°F and cool the catalyst to room temperature in pure nitrogen. Next, the reduction process is carried out in runs 2 and 4. In the previous run, the reactor is maintained at 500°F while nitrogen is flowed to thoroughly purge all oxygen from the reactor. Hydrogen is introduced to create a 50 mol% mixture with nitrogen, and the temperature is raised to 970°F and held for 20 minutes. After that, the reactor is cooled to room temperature while a mixture of 50 mol% hydrogen and 50 mol% nitrogen is flowed through it. After each test, the reactor tube is removed and divided into four sections as shown in Figure 4. Energy-dispersive spectroscopy (EDS) is used to analyze the chlorine content in the removed tube sections shown in Figures 5, 6, and 7. For chlorine content measurement, an area of ​​80 mm² is used. 2A JEOL JSM-6610LV scanning electron microscope (SEM) at Jeol, Ltd. (Tokyo, Japan) equipped with an Oxford Instruments INCA Energy350 EDS system from Oxford Instruments plc (Abbingdon, United Kingdom) including a silicon drift detector (SDD) was used. The average values ​​of multiple spots were calculated for three metal parts: above the catalyst bed (Figure 5), in the catalyst bed (Figure 6), and below the catalyst bed (Figure 7), and are shown in Table 1 below as parts per million by weight (ppmw). TIFF2026509457000002.tif73165 The effect of reduction on chlorine adsorbed on metal can be determined by comparing the results between runs 1 and 2, and between runs 3 and 4. When fluorination is performed at 730°F (runs 1 and 2), a decrease in adsorbed chlorine is observed in the range of 670 ppmw to 2,000 ppmw. When fluorination is performed at 850°F (runs 3 and 4), a decrease in adsorbed chlorine is observed in the range of 5,270 ppmw to 10,400 ppmw. Thus, it is shown that applying a reduction process to metals on which halides such as chlorides are adsorbed reduces the concentration of halides adsorbed on the surface.

[0052] Note Accordingly, the scope of protection is not limited by the above description but is limited only by the appended claims below, which include all equivalents of the subject matter of the claims. Each and every claim is incorporated into the specification as an embodiment of the present disclosure. Thus, the claims are further description and an addition to the detailed description of the present disclosure. All patents, patent applications and publications cited herein are incorporated herein by reference.

[0053] As described above, an embodiment of a reducing fluid for releasing at least a portion of the halides bonded to the surface. The following are non-limiting specific embodiments in accordance with this disclosure.

[0054] Embodiment 1. A method comprising contacting a catalyst with a halide in a container 100 having a surface 104, thereby bonding at least a portion of the halide to the surface 104, and regenerating the catalyst using a reducing fluid 152 such that at least a portion of the halide bonded to the surface 104 is released.

[0055] Embodiment 2. The method according to Embodiment 1, further comprising a heating furnace 60 in fluid communication with the container 100, wherein the heating furnace 60 is configured to supply heated feed 68 and optionally reactants to the container 100.

[0056] Embodiment 3. The method according to Embodiment 1 or 2, wherein the halogenated material includes chlorides, fluorides, or combinations thereof.

[0057] Embodiment 4. The halide bonded to the surface 104 is contained in a metal halide, according to any one of Embodiments 1 to 3.

[0058] Embodiment 5. The method according to any one of Embodiments 1 to 4, wherein the metal halide includes FeCl3, FeCl2, CrCl3, CrCl2, or a combination thereof.

[0059] Embodiment 6. The method according to any one of Embodiments 1 to 5, wherein the metal halide is present at a depth of about 1, about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, about 10, about 50, or about 100 microns or less.

[0060] Embodiment 7. The method according to any one of Embodiments 1 to 6, wherein the halogenated compound includes a chloride.

[0061] Embodiment 8. The method according to any one of Embodiments 1 to 7, wherein the halogenated material includes a fluoride.

[0062] Embodiment 9. The method according to any one of Embodiments 1 to 8, wherein the vessel 100 includes a reactor 108 having an inlet 120, an outlet 124, one or more scallops 128, and a central pipe 132 surrounded by the catalyst, the reactor 108 having a length of 140, and the halogen is bonded to a surface 104 adjacent to the inlet 120.

[0063] Embodiment 10. The method according to Embodiment 9, wherein approximately one-third of the length 140 of the container 100, measured from the inlet 120, is in close proximity to the inlet 120, portion 148.

[0064] Embodiment 11. The method according to Embodiment 9 or 10, wherein the reactor 108 includes a radial flow reactor 116.

[0065] Embodiment 12. The method according to any one of Embodiments 9 to 11, wherein the reactor 108 includes stainless steel.

[0066] Embodiment 13. The method according to Embodiment 12, wherein the stainless steel is selected from the group consisting of 347SS, 321SS, 316SS, and 304SS.

[0067] Embodiment 14. The method according to any one of Embodiments 9 to 13, wherein the reactor 108 includes a protective coating on the stainless steel, the protective coating comprising oxides of tin, stannides, titanium, aluminum, chromium, or combinations thereof; nitrides of tin, stannides, titanium, aluminum, chromium, or combinations thereof; carbides of tin, stannides, titanium, aluminum, chromium, or combinations thereof.

[0068] Embodiment 15. The method according to Embodiment 14, wherein the protective coating comprises titanium nitride.

[0069] Embodiment 16. The method according to any one of Embodiments 1 to 15, wherein the surface 104 has a halide concentration measured by energy dispersive spectroscopy (EDS) of approximately 50,000 ppm, approximately 40,000 ppm, approximately 20,000 ppm, or approximately 10,000 ppm or less.

[0070] Embodiment 17. The method according to any one of Embodiments 1 to 16, wherein the reducing fluid 152 includes a reducing gas.

[0071] Embodiment 18. The method according to Embodiment 17, wherein the reducing gas contains approximately 10 mol% to approximately 100 mol%, approximately 10 mol% to approximately 90 mol%, approximately 20 mol% to approximately 100 mol%, approximately 20 mol% to approximately 80 mol%, approximately 25 mol% to approximately 90 mol%, approximately 30 mol% to approximately 80 mol%, approximately 35 mol% to approximately 70 mol%, approximately 40 mol% to approximately 80 mol%, or approximately 50 mol% to approximately 70 mol%, with the remainder being nitrogen.

[0072] Embodiment 19. The method according to Embodiment 17 or 18, wherein the regeneration using the reducing gas is carried out at a temperature of at least about 700°F, about 750°F, about 800°F, about 850°F, about 920°F, about 940°F, about 950°F, about 960°F, about 970°F, about 980°F, about 990°F, or about 1,000°F, preferably above about 930°F.

[0073] Embodiment 20. The method according to any one of Embodiments 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.

[0074] Embodiment 21. The method according to any one of Embodiments 1 to 20, wherein the container 100 is purged with nitrogen before regeneration.

[0075] Embodiment 22. A method for removing all or part of a residual metal halide from a container wall 110, comprising: contacting the container wall 110 containing a first amount of the residual metal halide with a reducing fluid at at least about 700°F for at least about 1 hour to form a halogenated gas; and removing at least part of the halogen from the residual metal halide from the container wall 110 so that the residual metal halide is in a second amount, wherein the second amount is less than the first amount.

[0076] Embodiment 23. The method according to Embodiment 22, further comprising halogenating the catalyst in a container 100 communicating with a heating furnace 60 before circulating the reducing fluid, thereby depositing at least a portion of the first amount of the residual metal halide.

[0077] Embodiment 24. The method according to Embodiment 22 or 23, wherein the container wall 110 contains iron.

[0078] Embodiment 25. The method according to any one of Embodiments 22 to 24, wherein the container wall 110 comprises iron, chromium, and nickel.

[0079] Embodiment 26. The method according to any one of Embodiments 22 to 25, wherein the halogenated material includes chlorides, fluorides, bromides, or combinations thereof.

[0080] Embodiment 27. The method according to any one of Embodiments 22 to 26, wherein the halogenated material includes a chloride.

[0081] Embodiment 28. The halogenated compound comprises a fluoride, as described in any of Embodiments 22 to 27.

[0082] Embodiment 29. The method according to any one of Embodiments 22 to 28, wherein the metal halide includes FeCl3, FeCl2, CrCl3, CrCl2, or a combination thereof.

[0083] Embodiment 30. The method according to any one of Embodiments 22 to 29, wherein the metal halide includes FeF3, FeF2, CrF3, CrF2, or a combination thereof.

[0084] Embodiment 31. The method according to any one of Embodiments 22 to 30, wherein the reducing fluid contains hydrogen.

[0085] Embodiment 32. The method according to any one of Embodiments 22 to 31, wherein a quantifiable amount of the residual metal halide is removed from the container wall surface 110.

[0086] Embodiment 33. The method according to any one of Embodiments 22 to 32, wherein the container 100 includes a reactor 108, and the container wall 110 includes a reactor wall 110.

[0087] Embodiment 34. The method according to any one of Embodiments 23 to 33, wherein the catalyst before contact comprises at least one metal from groups 8 to 11 according to IUPAC, at least one halide, and a support.

[0088] Embodiment 35. The method according to Embodiment 34, wherein the at least one metal includes platinum, the at least one halide includes chloride, fluoride, or a combination thereof, and the carrier includes zeolite, L-type zeolite, bonded zeolite substrate, or a combination thereof.

[0089] Embodiment 36. The method according to Embodiment 34 or 35, wherein the carrier includes the bound zeolite substrate such as bound L-type zeolite.

[0090] Embodiment 37. The method according to Embodiment 36, wherein the bonded L-type zeolite includes a barium ion-exchanged bonded L-type zeolite.

[0091] Embodiment 38. The method according to Embodiment 36 or 37, wherein the bonded zeolite substrate comprises silica-bonded K / L type zeolite.

[0092] Embodiment 39. The method according to any one of Embodiments 34 to 38, wherein the at least one halogenated compound includes chlorides and fluorides.

[0093] Embodiment 40. The catalyst is in the following proportions relative to the total weight of the supported fresh catalyst which may be reduced: approximately 0.3 wt% to approximately 3 wt%, approximately 0.5 wt% to approximately 2.5 wt%, approximately 0.5 wt% to approximately 2 wt%, or approximately 0.7 wt% to approximately 1.5 wt% of platinum, approximately 0.1 wt% to approximately 7.0 wt%, approximately 0.2 wt% to approximately 6.0 wt%, approximately 0.3 wt% to approximately 5.0 wt%, approximately 0.4 wt% to approximately 4.5 wt%, approximately 0.5 wt% to approximately 4.0 wt%, approximately 0.6 wt% to approximately 3.5 wt%, approximately 0.7 wt% to approximately The method according to any one of embodiments 23 to 39, comprising 3.0 wt%, approximately 0.8 wt% to approximately 2.5 wt%, approximately 0.3 wt% to approximately 1.5 wt%, approximately 0.4 wt% to approximately 1.2 wt%, approximately 0.5 wt% to approximately 1.1 wt%, approximately 1.5 wt% to approximately 5 wt%, approximately 1.7 wt% to approximately 4.5 wt%, or approximately 1.8 wt% to approximately 4 wt%, and approximately 0.2 wt% to approximately 1.5 wt%, approximately 0.25 wt% to approximately 1.3 wt%, approximately 0.3 wt% to approximately 1.1 wt%, or approximately 0.3 wt% to approximately 1.0 wt% of fluorine.

[0094] Embodiment 41. The method according to any one of Embodiments 35 to 40, wherein the bonded zeolite substrate comprises silica-bonded K / L type 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.

[0095] Embodiment 42. The method according to any one of Embodiments 22 to 41, wherein the container wall 110 reacts with halogen during the halogenation of the catalyst.

[0096] Embodiment 43. The method according to any one of Embodiments 22 to 42, wherein the halogenated gas contains hydrogen chloride.

[0097] Embodiment 44. The method according to any one of Embodiments 22 to 43, further comprising contacting the catalyst with a halogen-containing fluid in a gas phase containing a halogen-containing compound before introducing the reducing fluid to generate a halogenation catalyst and a halogenation container wall 110.

[0098] Embodiment 45. The method according to any one of Embodiments 22 to 44, further comprising passing the halogenated gas through the absorbent 164 downstream of the container 100.

[0099] Embodiment 46. A method comprising contacting a hydrocarbon feed with an aromatization catalyst containing a transition metal and a catalyst support under reforming conditions in a metal reactor 108 to produce an aromatic product, allowing sufficient time for spent aromatization catalyst to form, stopping contact with the hydrocarbon feed, stripping with hydrogen, purging with nitrogen, halogenating the spent aromatization catalyst with a first halide, purging with nitrogen, oxidizing at a temperature of about 400°F or less, oxidizing at a temperature of about 400°F to about 850°F or about 1,000°F or less, halogenating the spent aromatization catalyst with a second halide, purging with an oxygen-containing gas, cooling the metal reactor 108 to 500°F or less, purging with nitrogen, and removing metal halides from the metal reactor wall 110 by reduction with a reducing fluid.

[0100] Embodiment 47. A method comprising contacting a metal inner surface 104 or an internal metal surface region of a reaction vessel 100 or reactor system 108 with a halide or a halide-containing compound, thereby bonding at least a portion of the halide to the inner surface 104, and releasing at least a portion of the halide bonded to the inner surface 104 via contact with hydrogen in an amount effective in protecting the integrity of the vessel.

[0101] Embodiment 48. The method according to Embodiment 47, further comprising a heating furnace 60 in fluid communication with the reaction vessel 100 or the reactor system 108, wherein the heating furnace 60 is configured to supply heated feed 68, optionally reactants, to the reaction vessel 100 or the reactor system 108.

[0102] Embodiment 49. The method according to Embodiment 47 or 48, wherein the halogen is a chloride, a fluoride, or a combination thereof.

[0103] Embodiment 50. The halide bonded to the surface 104 is contained in a metal halide, according to any one of Embodiments 47 to 49.

[0104] Embodiment 51. The method according to any one of Embodiments 47 to 50, wherein the metal halide includes FeCl3, FeCl2, CrCl3, CrCl2, or a combination thereof.

[0105] Embodiment 52. The method according to either Embodiment 50 or 51, wherein the metal halide is present at a depth of about 1, about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, about 10, about 50, or about 100 microns or less.

[0106] Embodiment 53. The method according to any one of Embodiments 47 to 52, wherein the halide or the halide-containing compound includes a chloride.

[0107] Embodiment 54. The method according to any one of Embodiments 47 to 53, wherein the halogenated compound or the halogenated compound contains a fluoride.

[0108] Embodiment 55. The method according to any one of Embodiments 47 to 54, wherein the reaction vessel 100 or reactor system 108 includes a reactor 108 having an inlet 120, an outlet 124, one or more scallops 128, and a central pipe 132 surrounded by the catalyst, the reactor 108 having length, and the halogen is bonded to a surface adjacent to the inlet 120.

[0109] Embodiment 56. The method according to Embodiment 55, wherein approximately one-third of the length 148 of the reactor 108, measured from the inlet 120, is close to the inlet 120.

[0110] Embodiment 57. The method according to Embodiment 55 or 56, wherein the reactor 108 includes a radial flow reactor 116.

[0111] Embodiment 58. The method according to any one of Embodiments 47 to 57, wherein the catalyst is placed in the reaction vessel 100 or the reactor system 108.

[0112] Embodiment 59. The method according to Embodiment 58, wherein the catalyst is an aromatizing catalyst.

[0113] Embodiment 60. The method according to Embodiment 59, wherein the aromatizing catalyst before contact comprises at least one metal from groups 8 to 11 according to IUPAC, at least one halide, and a support, the halide being a chloride gas.

[0114] Embodiment 61. The method according to any one of Embodiments 47 to 60, wherein the emission is carried out at at least about 700°F, about 750°F, about 800°F, about 850°F, about 920°F, about 940°F, about 950°F, about 960°F, about 970°F, about 980°F, about 990°F, or about 1,000°F, preferably above about 930°F.

[0115] Embodiment 62. The method according to any one of Embodiments 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.

[0116] Embodiment 63. The method according to any one of Embodiments 47 to 62, wherein the emission is carried out at a temperature of at least about 700°F or about 970°F for at least about 2 hours or at least about 24 hours, preferably at about 700°F for at least about 24 hours or at about 970°F for at least about 12 hours.

[0117] Embodiment 64. The method according to any one of Embodiments 55 to 63, wherein the reactor 108 includes a plurality of reactor tubes 112 that constitute the inner surface 104 or the inner surface region.

[0118] Embodiment 65. The method according to any one of Embodiments 55 to 64, wherein the reactor 108 includes a reactor metal comprising one or more metals including iron, chromium, nickel, or a combination thereof.

[0119] Embodiment 66. The method according to any one of Embodiments 55 to 65, wherein the reactor 108 includes stainless steel.

[0120] Embodiment 67. The method according to Embodiment 66, wherein the stainless steel is selected from the group consisting of 347SS, 321SS, 316SS, and 314SS.

[0121] Embodiment 68. The method according to any one of Embodiments 47 to 67, wherein the inner surface 104 has a halide concentration measured by energy dispersive spectroscopy (EDS) of approximately 50,000 ppm, approximately 40,000 ppm, approximately 20,000 ppm, or approximately 10,000 ppm or less.

[0122] Embodiment 69. A method for regenerating a spent catalyst comprising a transition metal and a catalyst support in a metal reactor 108, comprising: (1) contacting the spent catalyst with a chlorine-containing stream containing a chloride-containing compound to produce a chlorinated spent catalyst; (2) contacting the chlorinated spent catalyst with a decoked gas stream containing oxygen to produce a decoked catalyst; (3) contacting the decoked catalyst with a fluorine-containing stream containing a fluoride-containing compound to produce a regenerated catalyst, wherein the fluoride-containing compound includes hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), or a combination thereof, wherein the contact in (1), the contact in (2), or both of these causes residual halides to form on the inner surface 104 or internal surface region of the metal reactor 108; and (4) removing at least a portion of the residual halides via contact with hydrogen.

[0123] Embodiment 70. A method for regenerating a spent catalyst comprising a transition metal and a catalyst support in a metal reactor 108, comprising: (1) contacting the spent catalyst with a chlorine-containing stream containing a chloride-containing compound to produce a chlorinated spent catalyst; (2) contacting the chlorinated spent catalyst with a decoked gas stream containing oxygen to produce a decoked catalyst; and (3) contacting the decoked catalyst with a fluorine-containing stream containing a fluoride-containing compound to produce a regenerated catalyst, wherein the fluoride-containing compound includes hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), or a combination thereof, wherein the contact in (1), the contact in (2), or both causes residual halides to form on the inner surface 104 or internal surface region of the metal reactor 108; and (4) contacting the residual halides with hydrogen under conditions effective in removing at least a portion of the residual halides from the inner surface 104 or internal surface region.

[0124] Embodiment 71. A reforming method comprising: (A) contacting a hydrocarbon feed with an aromatization catalyst comprising a transition metal and a catalyst support under reforming conditions in a metal reactor system to produce an aromatic product; (B) carrying out step (A) for a sufficient time to form a spent catalyst; (C) contacting the spent catalyst with a chlorine-containing stream comprising a chlorine-containing compound to produce a chlorinated spent catalyst; (D) contacting the chlorinated spent catalyst with a decoked gas stream comprising oxygen to produce a decoked catalyst; and (E) contacting the decoked catalyst with a fluorine-containing stream comprising a fluorine-containing compound, wherein the fluorine-containing compound comprises a hydrofluorocarbon (HFC), a fluorocarbon (FC), a chlorofluorocarbon (CFC), a hydrochlorofluorocarbon (HCFC), or a combination thereof.

[0125] Embodiment 72. The method according to Embodiment 71, further comprising reactivating the catalyst after step (E).

[0126] Embodiment 73. The method according to Embodiment 71 or 72, wherein the modification method is an in-situ process, and for example, steps (A) to (E) are performed in the same reactor system.

[0127] Embodiment 74. The method according to any one of Embodiments 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 located within the reforming reactor system.

[0128] While preferred embodiments of the present invention have been shown and described, those skilled in the art can modify them without departing from the teachings of this disclosure. The embodiments described herein are illustrative and not limiting. Many variations and modifications of the invention disclosed herein are possible and within the scope of the invention.

[0129] While the present disclosure and its merits have been described in detail, it should be understood that various changes, substitutions, and modifications can be made herein without departing from the spirit and scope of the disclosure as defined by the appended claims. Furthermore, the scope of this application is not intended to be limited to specific embodiments of the processes, machines, manufactures, compositions, means, methods, and steps described in the specification. As will be readily apparent to those skilled in the art from this disclosure, existing or subsequently developed processes, machines, manufactures, compositions, means, methods, or steps that perform substantially the same function or achieve substantially the same results as the corresponding embodiments described herein can be utilized in accordance with this disclosure. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufactures, compositions, means, methods, or steps.

Claims

1. The catalyst is brought into contact with a halide in a container having a surface, and at least a portion of the halide is bonded to the surface there, and A method comprising regenerating the catalyst using a reducing fluid such that at least a portion of the halide bonded to the surface is released.

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

3. The method according to claim 1, wherein the halogenated material includes chlorides, fluorides, or combinations thereof.

4. The method according to claim 3, wherein the halide bonded to the surface is contained in the metal halide.

5. The aforementioned metal halide is FeCl ３ FeCl ２ , CrCl ３ , CrCl ２ The method according to claim 4, including, or a combination thereof.

6. The method according to claim 4, wherein the metal halide is present at a depth of approximately 100 microns or less.

7. The method according to claim 1, wherein the halogenated material includes a chloride.

8. The method according to claim 1, wherein the vessel comprises a reactor including an inlet, an outlet, one or more scallops, and a central pipe surrounded by the catalyst, the reactor having length, and the halogen is bonded to a surface adjacent to the inlet.

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

10. The method according to claim 8, wherein the reactor includes stainless steel.

11. The method according to claim 10, wherein the reactor includes a protective coating on the stainless steel, the protective coating comprising oxides of tin, stannide, titanium, aluminum, chromium, or combinations thereof; nitrides of tin, stannide, titanium, aluminum, chromium, or combinations thereof; carbides of tin, stannide, titanium, aluminum, chromium, or combinations thereof.

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

13. The method according to claim 1, wherein the reducing fluid includes a reducing gas.

14. The method according to claim 13, wherein the reducing gas contains about 10 mole percent to about 100 mole percent of hydrogen, with the remainder being nitrogen.

15. The method according to claim 14, wherein the regeneration with the reducing gas is performed at a temperature of approximately 500°F to approximately 1,300°F for at least approximately 2 hours.

16. A method for removing all or part of residual metal halides from the container wall, The container wall containing a first amount of the residual metal halide is brought into contact with a reducing fluid at approximately 500°F to approximately 1,300°F for at least approximately 1 hour to form a halogenated gas, and The method comprises removing at least a portion of the halide from the residual metal halide from the container wall so that the residual metal halide is in a second amount, wherein the second amount is less than the first amount.

17. The method according to claim 16, further comprising halogenating the catalyst in a container communicating with a heating furnace before circulating the reducing fluid, thereby depositing at least a portion of the first amount of the residual metal halide.

18. The method according to claim 16, wherein the container wall contains iron.

19. The method according to claim 17, wherein the catalyst before contact comprises at least one metal from groups 8 to 11 according to IUPAC, at least one halide, and a support.

20. The inner surface of the reaction vessel, which may be made of metal, is brought into contact with a halide or a halide-containing compound, so that at least a portion of the halide is bonded to the inner surface, and A method comprising releasing, in an amount effective in protecting the integrity of the container, at least a portion of the halide bonded to the inner surface via contact with hydrogen.

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