Use of continuous catalyst regeneration reformer for AROMAX catalyst process

Abstract

The present disclosure relates to aromatization of hydrocarbons with an aromatization catalyst, including methods of aromatization using a continuous catalyst regeneration reformer.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] not applicable. Background Art

[0003] The catalytic conversion of non-aromatic hydrocarbons into aromatic compounds, known as aromatization, is an important industrial process for producing basic building block chemicals on which most of the chemical industry is based. Aromatization reactions can include dehydrogenation, isomerization, and hydrocracking of hydrocarbons, each of which produces certain aromatic compounds. These reactions are usually carried out in one or more aromatization reactors containing aromatization catalysts. These catalysts can increase the selectivity to the desired aromatic compounds, and / or the conversion rate of the reaction to the desired aromatic compounds. Under commercial aromatization conditions, these catalysts slowly lose activity, as evidenced by the loss of selectivity to the desired product; loss of endothermic heat and / or a decrease in conversion rate. For example, the catalyst may be poisoned by the presence of contaminants, thereby reducing its activity. Continued use of the catalyst may result in the catalyst no longer effectively catalyzing the process desired by the user and / or producing a large amount of by-products, which are referred to as spent catalysts. In view of its commercial importance and the cost of producing fresh or regenerated catalysts and replacing spent catalysts with the same catalyst, there is a continuous need for improved systems and methods for effectively utilizing aromatization catalysts. Summary of the invention

[0004] Certain aspects of the present disclosure relate to a method for operating a reforming reactor system, the method comprising: operating a reactor of a stacked reactor system comprising at least one reactor stack, wherein each reactor stack comprises at least two stacked radial flow reactors; each radial flow reactor contains a reforming catalyst capable of catalyzing the conversion of hydrocarbons in a hydrocarbon feed to provide a reactor effluent comprising aromatic hydrocarbons, and wherein the reforming catalyst comprises a Group VIII metal, a zeolite carrier, and at least one halogen. In a related embodiment, the method comprises operating the reactor of the stacked reactor system via operation of the radial flow reactor as a stationary fixed bed, so that the reforming catalyst is stationary, i.e., does not move, during the running operation. In another aspect, the hydrocarbons in the hydrocarbon feed include convertible hydrocarbons selected from hydrocarbons having six or seven carbon atoms without internal quaternary carbons, i.e., C6 or C7 hydrocarbons, and C6 hydrocarbons lacking two adjacent internal tertiary carbons. Further embodiments relate to the operation of a reforming reactor system for converting convertible hydrocarbons in a hydrocarbon feed until the reforming catalyst is determined to be a spent reforming catalyst.

[0005] In addition, the method may include, after determining that the catalyst has expired, ceasing introduction of hydrocarbon feed, purging the reactor until the reactor effluent contains less than about 200 ppm hydrocarbons, bringing the reactor to ambient temperature, removing spent reforming catalyst within the radial flow reactor of each reactor stack via the bottommost radial flow reactor of each reactor stack or via the bottommost reactor of the final reactor stack using interstack transfer, wherein the catalyst flows downward through at least one radial flow reactor stack for removal, and adding fresh reforming catalyst to the top of the topmost radial flow reactor of each reactor stack or to the top of the topmost radial flow reactor of the first reactor stack using interstack transfer, wherein the fresh reforming catalyst flows downward through at least one radial flow reactor stack. In various aspects, the method may further involve using a reforming reactor system comprising at least one purge chamber attached to the bottommost radial flow reactor of each reactor stack or to the bottommost reactor of the final reactor stack using an interstack transfer fluid, wherein the spent reforming catalyst is removed from the bottommost radial flow reactor by the purge chamber prior to removing the catalyst from the stacked reactor system.

[0006] In certain embodiments, the purge chamber of the reactor system is optionally purged with a gas comprising hydrogen, nitrogen, argon, helium or a combination thereof. In a related aspect, the reforming reactor system includes a first purge chamber located upstream of the second purge chamber and connected to the second purge chamber fluid. In a further embodiment, the reactor system purge may include purging the first purge chamber with a first purge gas, and purging the second purge chamber with a second purge gas, wherein the first purge gas and the second purge gas may be the same or different. For example, in non-limiting aspects, the first purge gas comprises hydrogen and the second purge gas comprises nitrogen, or the first purge gas comprises nitrogen and the second purge gas comprises hydrogen. In some embodiments, the stacked reactor system described herein further comprises a purge chamber connected to the topmost radial flow reactor of each reactor stack using an inter-stack transfer fluid, or connected to the topmost reactor of the first reactor stack using a fluid, wherein fresh reforming catalyst can advantageously be added to the topmost radial flow reactor via the purge chamber, and in related aspects, purged with a purge gas comprising one or more of hydrogen, nitrogen, argon and / or helium, including nitrogen as a separate purge gas.

[0007] In non-limiting aspects, one or more zeolite carriers used according to the disclosed method can include an L-zeolite carrier combined with silica. In other embodiments, the stacked reactor system disclosed herein can be advantageously operated to provide a reforming catalyst to move through at least one reactor stack over a considerable period of time, and the time period includes at least about 180 days, at least about 270 days, at least about 365 days or a period longer than 365 days. In various aspects, the stacked reactor system can also be operated to provide a reforming catalyst to move through at least one reactor stack, and arrive at a regeneration system via a catalyst transfer system. Therefore, the relevant embodiment related to the catalyst transfer system relates to using inter-stack transmission to transfer the reforming catalyst to the regeneration system by at least one purge chamber, and the purge chamber is attached to the bottom radial flow reactor of each of the at least one reactor stack or attached to the bottom radial flow reactor of the final reactor stack of at least one reactor stack.

[0008] In certain aspects, the catalyst transfer system is arranged or positioned to fluidly connect at least one purge chamber to the top of the regeneration system, as further described herein, so that the movement of the reforming catalyst through the catalyst transfer system to the regeneration system can be optimally controlled by an operator and / or an operating or control system, including embodiments in which the movement of the reforming catalyst is intermittent. Further aspects of the disclosed technology relate to transferring the reforming catalyst in one of the at least one radial flow reactor stacks to the regeneration system via the catalyst transfer system at regular intervals and / or based on a transfer schedule, for example, transferring the reforming catalyst after about 180 days, about 270 days, about 365 days, or more.

[0009] In some embodiments, the method involves regenerating the reforming catalyst via a regeneration process during circulation through a regeneration system, and introducing the regenerated reforming catalyst into the topmost radial flow reactor of each of at least one reactor stack or into the topmost radial flow reactor of the first reactor stack via inter-stack transfer, and then introducing the regenerated reforming catalyst into the topmost radial flow reactor via at least one purge chamber and at least one regenerated catalyst delivery system. In related aspects, the regenerated catalyst can be reduced by one or more of decoking, halogenation, oxychlorination, chlorination, fluorination (including but not limited to low temperature fluorination), reduction, or a combination thereof before or after it is delivered to the top of at least one reactor stack. The reforming catalyst can be characterized by any number of physicochemical measurements or properties known to those skilled in the art (including but not limited to crush strength). Thus, in some aspects, the crush strength of the reforming catalyst is less than about 15 pounds force (lbf). f ), about 13 lb f , or about 10lb f .

[0010] In embodiments, the regeneration system of the disclosed method is operable to provide movement of the reforming catalyst through a series of radial flow regeneration reactors, including aspects of the reforming catalyst passing through the regeneration system and returning to the stacked reactor system via a regenerated catalyst transfer system over a period of about one week. Additional aspects relate to extracting spent reforming catalyst via at least one purge vessel attached to the bottom of at least one reactor stack, wherein the spent reforming catalyst is replaced by a "replacement" reforming catalyst (which, in related embodiments, includes fresh catalyst, regenerated reforming catalyst, or a combination thereof), which "replacement" reforming catalyst can be added back to at least one reactor stack via at least one purge vessel and at least one reduction vessel, wherein the purge vessel is operable to purge air and replace it with a reactive or inert gas atmosphere (such as a nitrogen or hydrogen atmosphere).

[0011] In a further embodiment, at least one reduction vessel is operable to subject the catalyst to a reducing gas, such as hydrogen. In yet a further aspect, a regenerated catalyst is provided by transporting the spent reforming catalyst to a regenerator co-located in the same facility or in a separate regeneration facility and regenerating the catalyst. The catalyst can be regenerated continuously or in batches, wherein the batch regeneration is generally associated with at least some aspects of the disclosed method, including embodiments associated with extracting spent reforming catalyst from at least one reactor stack and subsequently regenerating the spent reforming catalyst. As described in the additional catalyst moving process and steps associated with the present technology, embodiments of the disclosed method are associated with moving the reforming catalyst through at least one reactor stack to a purge vessel attached to the bottom of at least one reactor stack over a period of at least about 180 days, about 270 days, about 365 days, or more than 365 days.

[0012] Embodiments of the disclosed method are characterized by reducing and / or eliminating components, features, processes, steps, etc. that may adversely reduce the effectiveness or life of the catalyst. Therefore, in some aspects, the internal components, surfaces, etc. of the regenerator are not coated with compositions that are potentially capable of poisoning the catalyst, including but not limited to tin-containing metal protective layers, also referred to herein as MPT or tin MPT. In addition, the stacked reactor system may also include a regenerator that can be used for the storage of spent catalysts, etc., wherein when the amount of spent catalyst stored in the regenerator reaches a predetermined threshold amount, the spent catalyst stored therein can be regenerated. In a further embodiment, when the amount of spent catalyst stored in the regenerator reaches a predetermined threshold amount, the spent catalyst is removed from the regenerator and replaced with an additional (replacement) catalyst including a fresh reforming catalyst. In related aspects, the method also includes loading the fresh reforming catalyst into a purge chamber and a reduction vessel located before the topmost reactor of at least one reactor stack, and reducing the fresh reforming catalyst before introducing it into the topmost reactor of at least one reactor stack as a replacement catalyst.

[0013] The stacked reactor system can be configured in various arrangements to optimally perform the disclosed method, including aspects in which the stacked reactor system is configured for one or more of the following: 1) initially introducing reforming catalyst into a purge tank connected to a reduction vessel connected to a topmost radial flow reactor in one of at least one reactor stack; and / or 2) introducing fresh hydrocarbon feed into the topmost radial flow reactor such that the reduced reforming catalyst and the hydrocarbon feed flow co-currently or in parallel through at least one reactor stack. In additional aspects, the operating temperature of the topmost radial flow reactor is lower than the operating temperature of the radial flow reactor located downstream of the topmost radial flow reactor, and movement of the reforming catalyst through at least one reactor stack occurs over a period of at least about 180 days, about 270 days, about 365 days, or greater than 365 days.

[0014] Aspects associated with the stacked reactor system may also include a configuration for introducing fresh hydrocarbon feed into the bottom reactor of one of the at least one reactor stacks, such that the reforming catalyst and the hydrocarbon feed flow countercurrently through the at least one reactor stack, wherein the movement of the reforming catalyst through the at least one reactor stack occurs over a period of at least about 180 days, about 270 days, about 365 days, or greater than 365 days. In a further embodiment, the operating temperature of the bottom reactor of each of the at least one reactor stack is lower than the operating temperature of its top reactor, and the bottom reactor of each of the at least one reactor stack is also capable of serving as a guard bed to advantageously protect the downstream reactor in one or more reactor stacks (which contain a more active catalyst) from at least one undesirable compound, including but not limited to compounds that can poison the catalyst and / or reduce the catalyst's effectiveness, such as sulfur, heavy components, nitrogen, or combinations thereof. Thus, aspects of the reforming reactor system associated with the disclosed method are advantageously associated with the absence of a sulfur conversion agent adsorber (SCA) being incorporated or used upstream of the stacked reactor system, i.e., the absence of an SCA in the system.

[0015] In some aspects, the present disclosure relates to a reforming reactor system, the system includes a continuous catalyst regeneration (CCR) system, the continuous catalyst regeneration system includes at least one reactor stack, wherein each reactor stack includes at least two radial flow reactors, each radial flow reactor contains a reforming catalyst, the reforming catalyst is capable of catalyzing the conversion of hydrocarbons in a hydrocarbon feed to provide a reactor effluent containing aromatic hydrocarbons, and wherein the reforming catalyst comprises a Group VIII metal, a zeolite carrier, and at least one halogen. In some aspects, the system may also include a regeneration reactor system, the regeneration reactor system is connected to at least one reactor stack via a spent catalyst transfer system and is configured to regenerate the reforming catalyst. In an embodiment, the reforming reactor system may be further configured to promote the movement of the reforming catalyst through at least one reactor stack over a longer period of time, the period of time including but not limited to at least about 180 days, about 270 days, about 365 days, or greater than 365 days. Certain aspects of the system may include one or more of the following: 1) optionally coating one or more components of the reforming reactor system with tin MPT; 2) incorporating a silica-bound L-zeolite support into the reforming catalyst, which in some embodiments may be in the form of an extrudate characterized by a crush strength of less than about 15 lb f , about 13lb f or about 10lb f In a related aspect, the at least one halogen of the reforming catalyst comprises fluorine, and wherein the regeneration reactor system is operable to refluorinate any spent reforming catalyst received, for example, from a spent catalyst transfer system. In an advantageous embodiment, the inner surfaces of the regeneration reactor and the reactor interior of the regeneration reactor system are operable in the absence of a protective coating, for example, the inner surfaces of the regeneration reactor and the reactor interior of the regeneration reactor system do not have to be coated with a metal protective layer, for example, tin MPT.

[0016] In some aspects, the CCR system is configured to introduce a reforming catalyst into at least one topmost reactor by using a purge container and a reduction reactor, wherein at least one topmost reactor is the topmost reactor of one of at least one reactor stack. In a related embodiment, the CCR system is configured to introduce a fresh hydrocarbon feed into the top reactor so that the reforming catalyst and the hydrocarbon feed are passed through at least one reactor stack in parallel or in parallel, and is further configured to promote the movement of the reforming catalyst through at least one reactor stack within a time period of at least about 180 days, about 270 days, about 365 days, or longer than 365 days. In a further aspect, the CCR system can be configured to introduce a fresh hydrocarbon feed into the bottommost radial flow reactor of one of the at least one reactor stack so that the reforming catalyst and the hydrocarbon feed flow countercurrently through at least one reactor stack, including a time period of at least about 180 days, about 270 days, about 365 days, or longer than 365 days. In further embodiments, the bottom reactor of each of the at least one reactor stack is capable of acting or functioning as a guard bed to protect a downstream reactor in the at least one reactor stack containing a more active catalyst from at least one undesirable compound including, but not limited to, sulfur, heavies, nitrogen, or a combination thereof. Thus, the disclosed reforming reactor system can advantageously be characterized by the absence of a sulfur converter adsorber (SCA) positioned upstream of the CCR system.

[0017] In some aspects, the disclosed system may include at least two reactor stacks configured for introducing reforming catalyst into the top reactor of each of the at least two reactor stacks, wherein spent catalyst is removed from the bottom reactor of each of the at least two reactor stacks, and wherein fresh hydrocarbon feed is introduced into and passed through the bottom reactor of one of the at least two reactor stacks, and through the bottom reactor of the second of the at least two reactor stacks, and then sequentially upward through the next reactor of the first of the at least two reactor stacks, to the next reactor of the second of the at least two reactor stacks, and so on, through multiple reactors of each of the at least two reactor stacks until passing through the top reactor of the second of the at least two reactor stacks, from which a reactor effluent is extracted. In an advantageous embodiment, the bottom reactor of each of the at least two reactor stacks can be used as a guard bed, etc., to protect the downstream reactor (which contains a more active catalyst) in each of the at least two reactor stacks from at least one undesirable compound selected from sulfur, heavies, nitrogen, and combinations thereof, thereby eliminating the need for an SCA unit positioned upstream of the CCR system.

[0018] Aspects of the present disclosure also relate to methods of operating a continuous catalyst regeneration (CCR) system comprising at least one radial flow reactor stack, the method comprising operating the CCR system to convert hydrocarbons in a hydrocarbon feed into aromatics, wherein the catalyst is continuously circulated in a flow loop within the CCR system and all of the catalyst is regenerated at least once a week; shutting down the CCR system to cease converting convertible hydrocarbons into aromatics; replacing an existing catalyst within the CCR system with a replacement catalyst comprising platinum (Pt), fluorine (F) and / or chlorine (Cl) on a silica-bound L zeolite support; and starting the CCR to continue converting hydrocarbons in the hydrocarbon feed into aromatics, wherein the replacement catalyst is not continuously circulated in a flow loop within the CCR system. In a further embodiment, in the process of converting hydrocarbons in a hydrocarbon feed into an aromatic hydrocarbon product as described herein, the replacement catalyst is static in the CCR system, and the aromatic hydrocarbon product comprises hydrocarbons selected from hydrocarbons having six or seven carbon atoms without internal quaternary carbons and hydrocarbons having six carbon atoms without two adjacent internal tertiary carbons. Additional aspects related to the operation of the reformer reactor system include converting convertible hydrocarbons in the hydrocarbon feed until the reforming catalyst is determined to be a spent reforming catalyst, at which time or thereafter the catalyst can be regenerated as described herein.

[0019] In some embodiments, the disclosed method of operating a continuous catalyst regeneration (CCR) system may further include, after determining that the catalyst has failed, ceasing introduction of hydrocarbon feed, purging the reactor until the reactor effluent contains less than about 200 ppm of hydrocarbons, bringing the reactor to ambient temperature, removing spent reforming catalyst within the radial flow reactor of each reactor stack via the bottommost radial flow reactor of each reactor stack or via the bottommost reactor of the final reactor stack using inter-stack transfer, wherein the catalyst flows downwardly through at least one radial flow reactor stack for removal, and adding fresh reforming catalyst to the top of the topmost radial flow reactor of each reactor stack or to the top of the topmost radial flow reactor of the first reactor stack using inter-stack transfer, wherein the fresh reforming catalyst flows downwardly through at least one radial flow reactor stack.

[0020] In a related aspect, the reforming reactor system further comprises at least one purge chamber or lock hopper, which is attached to the bottommost radial flow reactor of each reactor stack, or to the bottommost reactor of the final reactor stack, using an inter-stack transfer fluid, wherein the spent reforming catalyst is removed from the bottommost radial flow reactor by the purge chamber before the catalyst is removed from the stacked reactor system. In an embodiment, the method further comprises purging the purge chamber with a gas comprising hydrogen, nitrogen, or both. In another embodiment, the reforming reactor system of the disclosed method comprises a first purge chamber located upstream of the second purge chamber and fluidly connected thereto, so that purging the first purge chamber with the first purge gas and purging the second purge chamber with the second purge gas are operable or executable. In a related aspect, the first purge gas comprises hydrogen and the second purge gas comprises nitrogen, or alternatively, the first purge gas comprises hydrogen and the second purge gas comprises nitrogen. With respect to the reactor system of the method, the stacked reactor system may further include a purge chamber fluidly connected to the topmost radial flow reactor of each reactor stack, or fluidly connected to the topmost reactor of the first reactor stack, capable of being conveyed or transferred between stacks, wherein, for example, fresh reforming catalyst can be added to the topmost radial flow reactor through the purge chamber and optionally purged with a purge gas such as nitrogen.

[0021] Some aspects of the present disclosure relate to a method of operating a continuous catalyst regeneration (CCR) system, the method comprising operating the CCR system to convert hydrocarbons in a hydrocarbon feed into aromatics, wherein catalyst is continuously circulated in a flow loop within the CCR system and all of the catalyst is regenerated at least once a week; shutting down the CCR system to cease converting the convertible hydrocarbons into aromatics; replacing an existing catalyst within the CCR system with a replacement catalyst, the replacement catalyst comprising platinum (Pt), fluorine (F) and / or chlorine (Cl) on a silica-bound L zeolite support; and starting the CCR to continue converting the convertible hydrocarbons into aromatics, wherein the replacement catalyst may be intermittently circulated in a flow loop within the CCR system so that all of the catalyst is regenerated no more than once a year. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] The following drawings illustrate embodiments of the subject matter disclosed herein. The claimed subject matter may be understood by reference to the following description in conjunction with the accompanying drawings, wherein like reference numerals refer to like elements unless otherwise indicated, and wherein:

[0023] Figure 1 is a flow diagram of a stacked reactor system for an aromatization process according to an embodiment of the present disclosure; and

[0024] Figure 2 is a flow diagram of a stacked reactor system for an aromatization process according to another embodiment of the present disclosure. DETAILED DESCRIPTION

[0025] First, it should be understood that although illustrative implementations of one or more embodiments are provided below, the disclosed systems and / or methods may be implemented using any number of techniques, whether currently known or in existence. The present disclosure should in no way be limited to the illustrative implementations, drawings, and techniques shown below, including the exemplary designs and implementations shown and described herein, but may be modified within the scope of the appended claims along with their full scope of equivalents.

[0026] The present disclosure provides methods and systems related to the operation of a reforming reactor system including at least one reactor stack. In an embodiment, the reforming reactor system is an existing CCR (continuous catalyst regeneration) system previously operated to produce higher octane hydrocarbons via reforming with a reforming catalyst, which is reused as described herein to convert light naphtha into benzene, toluene and xylenes (BTX) via an aromatization catalyst that may include a zeolite support. Although the reuse of a continuous catalyst regeneration reforming system is described in detail herein, it is contemplated that systems based on other reforming technologies (including semi-regeneration and cyclic regeneration) may also be reused according to the present disclosure, and these are intended to be within the scope of the present disclosure.

[0027] Due to a variety of reasons, including ethanol blending and a decline in overall gasoline demand, the demand for higher octane hydrocarbons in the United States has dropped significantly. As a result, in some cases, reformer utilization has dropped to the point where its operation is no longer economical. According to an embodiment of the present disclosure, such reforming units do not need to be shut down, but can be reused to produce chemicals. One of the most common types of reformers utilizes a continuous catalyst regeneration (or "CCR") process. CCR units conventionally operate via a constant catalyst flow through a stacked radial flow reactor to a regenerator, but according to alternative aspects, previously reported non-stacked radial flow reactors can be incorporated into the disclosed system and method. In the regenerator, the coke is burned out and the activity of the catalyst is restored. This catalyst regeneration is usually performed at least once a week. This conventional CCR process typically uses four reactors, with heating applied between each reactor to provide heat for the endothermic reforming reaction. Since CCR operates via a moving bed, the CCR catalyst is typically mechanically strong and is typically composed of platinum / alumina (Pt / Al2O3).

[0028] Aromatization (also referred to herein as "reforming") processes such as The present invention relates to a process for converting light naphtha into benzene and toluene via a fixed bed radial flow reactor. As in the CCR process, the hydrocarbon to be aromatized is heated as it flows from one reactor to the next to provide the endothermic heat of the reaction. The aromatization catalyst (also referred to herein as a reforming catalyst), such as The catalyst may include Pt, Cl and F supported on silica-bound L zeolite. Aromatization catalysts (such as The typical operating life of a catalyst may be about 1.5 to 2.5 years, after which the catalyst is removed and either discarded or regenerated. This turnover cost is quite high due to downtime and other expenses.

[0029] Conventional fixed bed radial flow aromatization reactor designs typically result in underutilization of the catalyst located closer to the center tube because as the feed moves from the outside of the aromatization reactor to the inside it cools down in response to the endothermic reaction. Therefore, the catalyst located inside the fixed bed radial flow reactor typically still has some additional life when it is discarded at the end of a run.

[0030] It has been unexpectedly discovered that stacked reactors designed for moving bed operation, such as the reactors of a CCR system, can be used to generate a catalyst for aromatization via an aromatization catalyst, such as Catalyst) for aromatization of hydrocarbons. Although reference is made herein to Although the present invention relates to an aromatization catalyst, the systems and methods of the present disclosure may be suitable for use with other aromatization catalysts that are generally considered too weak (e.g., too low a crush strength, as further described herein) to be used in moving bed reactor systems, and the use of the systems and methods disclosed herein with such catalysts is intended to be included within the scope of the present disclosure.

[0031] CCR process and The difference between the processes is in the catalyst regeneration step. In the CCR process, the catalyst flows down through the stack reactor system and then to the regenerator where it is typically contacted with oxygen to burn the coke, chlorine for platinum redispersion, and hydrogen for reduction before being sent back to the stack reactor. The catalyst is able to move to the regenerator fairly quickly, with the catalyst being able to pass through the regenerator approximately once a week. In contrast, The catalyst is not significantly regenerated, only coke combustion and platinum redispersion, and regeneration may not occur more than once a week or even once a month. Three variations of a CCR or stacked reactor arrangement (either a pre-existing or a grass-roots design) of a catalyst. The first variation comprises operating the radial flow reactor of the stacked reactor system as a stationary fixed bed; the second variation comprises operating the radial flow reactor of the stacked reactor system wherein the catalyst is moved therefrom to a downstream regeneration system and the regenerated catalyst is reintroduced into the stacked reactor; the third variation comprises operating the radial flow reactor of the stacked reactor system wherein the catalyst is moved therefrom but without downstream regeneration and the catalyst is reintroduced into the stacked reactor.

[0032] like Figure 1As shown, aspects related to a method of operating a reforming reactor system are provided, the reforming reactor system comprising at least one reactor stack, wherein each reactor stack comprises at least two stacked radial flow reactors, and each radial flow reactor contains a reforming catalyst capable of catalyzing the conversion of hydrocarbons in a hydrocarbon feed to provide a reactor effluent comprising aromatic hydrocarbons. In embodiments, the reforming catalyst comprises a Group VIII metal, a zeolite support, and at least one halogen. In embodiments, the reforming reactor system comprises a continuous catalyst regeneration (CCR) system modified and / or operated with an aromatization catalyst as described herein.

[0033] Now refer to Figure 1 Describe embodiments related to reforming systems and processes according to the present disclosure, Figure 1 Flow chart of a stacked reactor system 100 for aromatization process according to an embodiment of the present disclosure. The reforming reactor system of the present disclosure includes at least one reforming reactor stack. The stacked reactor system 100 includes two reforming reactor stacks, namely a first reforming reactor stack S1 and a second reforming reactor stack S2. The reforming reactor system according to the present disclosure may also include a heat transfer device configured to heat the effluent of a reforming reactor before introducing it into a reactor downstream thereof. System 100 includes a heat exchanger 120A and a heat exchanger 120B. In an embodiment, the first heat exchanger 120A and the second heat exchanger 120B are single heat exchangers.

[0034] The reforming reactor system of the present disclosure may also include an inter-stack delivery line, which is operable to transmit reforming catalyst between reactor stacks of a multi-stack system. Stacked reactor system 100 includes an inter-stack delivery line 134. Valve V1 is operable to control the flow rate of catalyst flowing out of the first reactor stack S1. The reforming reactor system of the present disclosure may also include one or more containers, which are operable as a lock hopper, a purge container and / or a reduction container, which are attached to the bottom reforming reactor of each reactor stack and / or are fluidically connected thereto, or are attached to the bottom reactor of the last stack in a system including a series (i.e., multiple) of reactor stacks that adopt inter-stack transmission and / or are fluidically connected thereto. Stacked reactor system 100 includes container 150A, which is fluidically connected to the bottom reactor (i.e., the fourth reforming reactor 110D) of the last reactor stack (i.e., the second reactor stack S2).

[0035] The reforming reactor system of the present disclosure may also include one or more containers that are operable as purge containers and / or reduction containers, which are attached to and / or fluidically connected to the topmost reforming reactor of each reactor stack, or attached to and / or fluidically connected to the topmost reactor of the first stack in a system including a series (i.e., multiple) of stacks with inter-stack transfer. The stacked reactor system 100 includes a container 150B that is fluidly connected to the topmost reactor (i.e., the first reforming reactor 110A) of the first reactor stack (i.e., the first reactor stack S1).

[0036] The reforming reactor system of the present disclosure may also include a spent catalyst delivery line (also referred to herein as a "waste" catalyst delivery line) configured to transfer spent catalyst leaving the reforming reactor stack to a downstream device, such as a catalyst regenerator, a storage container, etc. The stacked reactor system 100 includes a spent catalyst delivery line 135. The reforming reactor system of the present disclosure may also include downstream devices, such as catalyst regenerators, storage containers, etc. The stacked reactor system 100 includes a downstream device 140. The spent catalyst delivery line 135 may fluidly connect the final stack of the stacked reactor system to the downstream device 140, optionally via a container 150A. One or more valves V2 may be operated to control the flow rate of the catalyst flowing out of the second reactor stack S2. Although the valve V2 is indicated to be positioned upstream of the container 150A, in an embodiment, the valve V2 may be positioned upstream or downstream of the container 150A. The stacked reactor system 100 may include a supplementary catalyst inlet line 130 and a valve V4, which may be operated to control the amount of supplementary catalyst introduced into the downstream device 140.

[0037] The reforming reactor system of the present disclosure may also include an alternative catalyst transfer line or delivery system configured to deliver catalyst (which may be regenerated catalyst, fresh catalyst, make-up catalyst, or a combination thereof in various embodiments) from a downstream unit to the topmost reforming reactor of each reactor stack, or to the topmost reactor of the first reactor stack, using inter-stack delivery in a system including a series (i.e., a plurality) of reactor stacks, optionally via one or more reduction vessels, purge vessels, and / or lock hoppers. For example, in embodiments, an existing CCR is reused for aromatization (e.g., Catalyst). Such a CCR system may include a catalyst transfer line, whereby the catalyst can be continuously circulated around the system during operation. The stacked reactor system 100 includes an alternative catalyst delivery line or delivery system 131, which is configured to deliver catalyst from the downstream device 140 to the first or top-most reforming reactor 110A in the first reactor stack S1. The alternative catalyst delivery system 131 is operable to introduce the catalyst into the top-most reactor 110A via a container 150B using inter-stack delivery, and the container is fluidly connected to the top-most radial flow reactor of each reactor stack or the top-most reactor of the first reactor stack. The container 150B may include a purge chamber. The purge line or "catalyst waste" line 132 can be fluidly connected to the alternative catalyst delivery system 131 via a valve V3, and can be operated to control the catalyst from the system 100 via the catalyst purge line 132.

[0038] The reforming reactor systems of the present disclosure may also include a plurality of valves configured to direct the flow of catalyst throughout the system, as further discussed herein. Figure 1 The stacked reactor system 100 includes valves V1, V2, V3 and V4. Figure 1 The valves shown and described herein are used as a tool to describe flow paths and are not intended to limit the present disclosure to a particular operating protocol or equipment setup.The foregoing components of a reforming reactor system according to the present disclosure will be described in greater detail herein.

[0039] The hydrocarbon feed (comprising hydrocarbons to be converted into aromatic hydrocarbons) is introduced into the first heat exchanger 120A via hydrocarbon feed line 105, wherein the temperature of the hydrocarbon feed is raised to the desired first reforming reactor inlet temperature. The heated hydrocarbon feed is introduced from the first heat exchanger 120A into the first or "topmost" reforming reactor 110A of the first reactor stack S1 via the first reactor inlet line 106.

[0040] The hydrocarbon feed comprises convertible hydrocarbons and non-convertible hydrocarbons, in some aspects, comprising at least about 96% by weight of C6 to C8 hydrocarbons, and up to about 4% of C9 or larger hydrocarbons. As used herein, "convertible" hydrocarbons include hydrocarbons with six or seven carbon atoms without internal quaternary carbons, and hydrocarbons with six carbon atoms without two adjacent internal tertiary carbons. Such convertible hydrocarbons may include methylpentane, methylhexane, dimethylpentane, and mixtures thereof. Convertible components may include 2-methylpentane, 3-methylpentane, 2,4-dimethylpentane, 2,3-dimethylpentane, normal hexane, 2-methylhexane, 3-methylhexane, normal heptane, and mixtures thereof. As used herein, "non-convertible" hydrocarbons include highly branched hydrocarbons comprising six or seven carbon atoms and with internal quaternary carbons, and hydrocarbons with six carbon atoms and two adjacent tertiary carbons. Highly branched hydrocarbons include dimethylbutane (DMB), trimethylbutane, dimethylpentane, and mixtures thereof. Highly branched hydrocarbons with six or seven carbon atoms and internal quaternary carbons may include, for example, 2,2-dimethylbutane, 2,2-dimethylpentane, 3,3-dimethylpentane, 2,2,3-trimethylbutane, and combinations thereof. Highly branched hydrocarbons with six carbon atoms and adjacent internal tertiary carbon atoms may include 2,3-dimethylbutane. Highly branched hydrocarbons are not easily converted to aromatic products, but tend to be converted to light hydrocarbons. As used herein, "unreacted" hydrocarbons refer to convertible hydrocarbons that have passed through the reforming reactor stack but have not yet been converted to aromatic hydrocarbons.

[0041] In the first / top reforming reactor 110A, the convertible hydrocarbons in the hydrocarbon feed are converted (or partially converted) to reformer products containing BTX via contact with an aromatization catalyst and under operating conditions as described herein. The effluent containing aromatic hydrocarbons is removed from the first reforming reactor 110A via the first reactor effluent line 107. The first reactor effluent is introduced into the first heat exchanger 120A via the first reactor effluent line 107, where it is heated to the required downstream reforming reactor inlet temperature. The heated first reactor effluent is introduced into the second reforming reactor 110B from the first heat exchanger 120A via the second reforming reactor inlet line 108. In the second reforming reactor 110B, the convertible hydrocarbons are converted into reformer products containing BTX via contact with an aromatization catalyst and under operating conditions as described herein. The effluent containing aromatic hydrocarbons is removed from the second reforming reactor 110B via the second reforming reactor effluent line 109. The second reactor effluent is introduced into the first heat exchanger 120A via the first reforming reactor effluent line 109, where it is heated to the desired downstream reforming reactor inlet temperature. The heated second reactor effluent is introduced from the first heat exchanger 120A and optionally the second heat exchanger 120B (which may be introduced into the heat exchanger via the inter-stack hydrocarbon delivery line 116A that delivers hydrocarbons between the first reactor stack S1 and the second reactor stack S2) into the third or "topmost" reforming reactor 110C of the second reactor stack S2 via the third reforming reactor inlet line 116B.

[0042] In the third reforming reactor 110C, convertible hydrocarbons are converted into reformer products containing BTX via contact with an aromatization catalyst and under operating conditions as described herein. The effluent containing aromatic hydrocarbons is removed from the third reforming reactor 110C via the third reforming reactor effluent line 117. The third reactor effluent is introduced into the second heat exchanger 120B via the third reforming reactor effluent line 117, where it is heated to the required downstream reforming reactor inlet temperature. The heated third reactor effluent is introduced into the fourth reforming reactor 110D via the fourth reforming reactor inlet line 118 from the second heat exchanger 120B. In the fourth reforming reactor 110D, convertible hydrocarbons are converted into reformer products containing BTX via contact with an aromatization catalyst and under operating conditions as described herein. The effluent containing aromatic hydrocarbons is removed from the fourth or bottom reforming reactor 110D of the second reactor stack S2 via the fourth reforming reactor effluent or "hydrocarbon product" outlet line 125.

[0043] The reforming reactor system 100 includes a first reactor stack S1, which includes first and second reforming reactors 110A and 110B, respectively. The first reforming reactor 110A is the topmost reforming reactor of the first reactor stack S1, and is positioned above the second reforming reactor 110B, which is the bottommost reforming reactor of the first reactor stack S1. The third reforming reactor 110C is the topmost reforming reactor of the second reactor stack S2, and is positioned above the fourth reforming reactor 110D, which is the bottommost reforming reactor of the second reactor stack S2. The reforming reactor system of the present disclosure may include a single stack or multiple stacks, including but not limited to two, three or four reactor stacks. In an embodiment, such as Figure 1 In embodiments, hydrocarbon feed is transferred between reactor stacks. In embodiments, reforming catalyst is transferred between reactor stacks. In embodiments, hydrocarbon feed and reforming catalyst are transferred between reactor stacks.

[0044] The reforming reactor system disclosed herein includes a reforming reactor stack. As generally understood, the reforming "reaction" generally occurs in a reforming "reactor". The reforming reactor used in the system and method described herein can be any conventional type of reactor, which keeps the catalyst in the reactor and can accommodate the continuous flow of hydrocarbons. The catalytic reactor system described herein may include a fixed catalyst bed system, a moving catalyst bed system, a fluidized catalyst bed system, or a combination thereof. Suitable reactors may include, but are not limited to, fixed bed reactors (including radial flow reactors), bubbling bed reactors, and ebullating bed reactors. The feed may flow upward, downward, or radially through the reactor. In various embodiments, the catalytic reactor system described herein may be operated as an adiabatic catalytic reactor system or an isothermal catalytic reactor system. As used herein, a "hydrocarbon stream" contains hydrocarbons, but other components (such as hydrogen) may be present in the stream except for molecules containing hydrogen and carbon. In some embodiments, "hydrocarbons" may include single molecules containing one or more atoms (such as nitrogen, oxygen, etc.) except for hydrogen and carbon.

[0045] In an embodiment, the reforming reactor is a radial flow reactor in which the hydrocarbon stream passes through the reactor in an inward or outward flow. The reactor may be sized according to known techniques, and the size of all reactors may be the same. Alternatively, one or more reactors may have different sizes. For example, in an embodiment, as described herein, the reforming reactor system includes a CCR that has been modified and / or readjusted for an aromatization catalyst as described herein. In an embodiment, the size (i.e., volume) of the reactor stack may increase from the topmost reactor to the bottommost reactor. For example, in an embodiment, when the total volume of catalyst of all reforming reactors in the stack is equal to 100%, the dual reactor stack may include a first or topmost reactor containing 30%, 40% or 50% by volume of catalyst, and the second or bottommost reactor of the stack may contain 50%, 60% or 70% by volume of catalyst. In an alternative embodiment, a three-reactor stack may include a first or topmost reactor that contains 10%, 20%, or 30% catalyst by volume, a second or middle reactor of the stack may contain 20%, 30%, or 40% catalyst by volume, and a third or bottommost reactor of the stack may contain 30%, 40%, or 50% catalyst by volume. In an alternative embodiment, a four-reactor stack may include a first or topmost reactor that contains 10%, 20%, or 30% catalyst by volume, a second reactor of the stack may contain 20%, 30%, or 40% catalyst by volume, a third reactor of the stack may contain 20%, 30%, or 40% catalyst by volume, and a fourth or bottommost reactor of the stack may contain 30%, 40%, or 50% catalyst by volume.

[0046] In embodiments, the multi-stack system includes two stacks, with catalyst being transferred between the stacks, and each stack includes two reforming reactors. In some such embodiments, the volume percentage of the total reforming catalyst in the first reactor (the topmost reactor of the first reactor stack) (the total volume of the catalyst in all reforming reactors of the reforming reactor system is equal to 100%) is about 10% to about 30% by volume, wherein the volume percentage of the catalyst in the second reactor (the bottommost reactor of the first reactor stack) is about 10% to about 30% by volume, the volume percentage of the catalyst in the third reactor (the topmost reactor of the second reactor stack) is about 10% to about 30% by volume, and the volume percentage of the catalyst in the fourth reactor (the bottommost reactor of the second reactor stack) is about 10% to about 30% by volume.

[0047] In an embodiment, a multi-reactor system includes two reactors with catalyst being transferred between the reactors, and each reactor includes three reforming reactors. In some such embodiments, the volume percentage of the total reforming catalyst (the total volume of the catalyst in all the reforming reactors of the reforming reactor system equals 100%) in the first reactor (the topmost reactor of the first reactor bank) is about 10 to about 30%, the volume percentage of the catalyst in the second reactor (the middle reactor of the first reactor bank) is about 10 to about 30%, the volume percentage of the catalyst in the third reactor (the bottommost reactor of the first reactor bank) is about 10 to about 30%, the volume percentage of the catalyst in the fourth reactor (the topmost reactor of the second reactor bank) is about 10 to about 30%, the volume percentage of the catalyst in the fifth reactor (the middle reactor of the second reactor bank) is about 10 to about 30%, and the volume percentage of the catalyst in the sixth reactor (the bottommost reactor of the second reactor bank) is about 10 to about 30%.

[0048] Under catalytic conditions, the activity of the catalyst will decrease with the prolongation of the reaction time, thus producing "spent" catalyst. So that when the activity of the fresh catalyst is x, the activity of the spent catalyst is y, where x is greater than y. In one embodiment, the catalytic activity of the spent catalyst can be increased by reactivating the spent catalyst, thereby producing catalytic activity z, where z is greater than y but less than x (y < z < x). The method for restoring the activity of the spent catalyst will be described in more detail below.

[0049] Variant 1: Operation of the reforming reactor as a stationary radially fixed bed

[0050] Inside the reforming reactor, the hydrocarbon feed contacts the reforming catalyst. In a first variant of the reforming method according to the present disclosure, the stacked reactor operates as a stationary fixed bed, and the reforming catalyst remains fixed during the aromatization of the hydrocarbon feed. In such embodiments, the reforming catalyst does not move during the operation of the run. The stacked reactor system can be configured to initially introduce the reforming catalyst into one or more vessels 150B, which can operate as a purge tank or a reduction vessel, and the purge tank or reduction vessel is connected to or connected with the topmost radial flow reactor of at least one of at least one reactor bank, so that the catalyst therein can be stored and / or reduced before being introduced into the first reactor bank S1.

[0051] The reforming reactor system is operable to convert the convertible hydrocarbons in the hydrocarbon feed until the reforming catalyst is determined to be a "spent" reforming catalyst. According to the embodiment of Variant One, the reforming catalyst does not move at all during the operation, and the reactor acts as a stationary radial fixed bed. In such embodiments, Figure 1 valves V1 to V4 can be closed during the operation. In this way, the CCR system can be like a conventional The process operates the same as that of the conventional CCR process, i.e., using a stationary fixed bed radial flow reactor. By way of a first variation, in an embodiment, an existing CCR may be utilized for aromatization without utilizing the moving bed or catalyst regeneration capabilities of a conventional CCR process.

[0052] As is known in the art, it can be determined that the catalyst has failed. For example, when the outlet temperature of the final or fourth reforming reactor 110D increases, such as to a temperature equal to or greater than a threshold temperature, it can be determined that the catalyst has failed, and the threshold temperature indicates a catalyst deactivation level sufficient to warrant replacement of the catalyst. In another example, when the selectivity of the final or fourth reforming reactor 110D to the desired aromatic compound decreases, such as to a selectivity equal to or less than a threshold selectivity (which indicates that the selectivity loss level of the catalyst is sufficient to warrant replacement of the catalyst), it can be determined that the catalyst has failed. In an embodiment, when a radial flow reactor is used as a stationary fixed bed, the activity of the spent catalyst extracted via the spent catalyst transfer line 135 is less than or equal to about 90%, about 80%, about 70%, about 50%, and about 25% of the optimal activity of the fresh catalyst. Once it is determined that the catalyst has failed, the introduction of the hydrocarbon feed is stopped. The reforming reactor can be purged, for example, until the reactor effluent (e.g., the product extracted from the fourth reforming reactor 110D via the product outlet pipeline 125) contains less than about 200ppm, about 100ppm, about 50ppm, and about 50ppm of hydrocarbons. The reforming reactor can be brought to ambient temperature and / or can be cooled to ambient temperature. The ambient temperature can be a temperature less than or equal to about 60°C, about 50°C, about 40°C, about 30°C, and about 25°C, depending on the geographical location, altitude, and other factors known to those skilled in the art. Once the desired temperature is reached, the spent reforming catalyst can be removed from the radial flow reactor of each reactor stack by inter-stack transfer via the bottom radial flow reactor of each reactor stack or via the bottom reactor of the final reactor stack, wherein the catalyst flows downward through at least one radial flow reactor stack to be removed. For example, the spent reforming catalyst can be removed from the fourth reactor 110D. In one embodiment, catalyst is removed or purged from the fourth reactor 110D, followed by the third reactor 110C, followed by the second reactor 110B (via inter-stack transfer line 134), and followed by the first reactor 110A (via inter-stack transfer line 134) via catalyst transfer line 135. Fresh reforming catalyst may be introduced into the top of the topmost radial flow reactor of each reactor stack using inter-stack transfer, or introduced into the top of the topmost radial flow reactor of the first reactor stack, and flowed downward through at least one radial flow reactor stack. For example, in Figure 1In an embodiment of the present invention, fresh catalyst can be introduced via transfer line 131, lock hopper and / or reduction vessel 150B, and first reforming reactor 110A. In one embodiment, catalyst is added or filled via transfer line 131 to fourth reactor 110D (via inter-stack transfer line 134), followed by third reactor 110C (via inter-stack transfer line 134), followed by second reactor 110B, followed by first reactor 110A.

[0053] The spent reforming catalyst may be removed from the bottom-most radial flow reactor by a purge chamber or lock hopper that is attached to or fluidly connected to the bottom-most radial flow reactor of each reactor stack or the bottom-most reactor of the final reactor stack using an inter-stack transfer fluid, and then removes the spent catalyst from the stacked reactor system. Figure 1 In the embodiment of FIG. 1 , spent catalyst may be removed after passing through vessel 150A, which may be a purge vessel or a lock hopper.

[0054] The spent catalyst within the purge chamber 150A may be purged with a gas comprising hydrogen or nitrogen. In an embodiment, the vessel 150A comprises a first and a second purge chamber fluidly connected in series. In such embodiments, the first purge chamber may be purged with a first purge gas, and the second purge chamber may be purged with a second purge gas. The first purge gas may comprise hydrogen, the second purge gas may comprise nitrogen, or the first purge gas may comprise hydrogen and the second purge gas may comprise nitrogen.

[0055] Fresh reforming catalyst may be added to the topmost radial flow reactor via vessel 150B, which may be a purge chamber, lock hopper, reduction vessel, or one or more vessels operable to purge, store and / or reduce fresh catalyst prior to introduction into the first reforming reactor 110A.

[0056] In embodiments, the fresh reforming catalyst is contacted with a purge gas in purge chamber 150B prior to being introduced into the topmost radial flow reforming reactor. In embodiments, the purge gas comprises nitrogen.

[0057] Variant 2: Operation in which the catalyst moves slowly through the reactor stack and reaches the regenerator

[0058] In the second modification of the reforming method according to the present disclosure, the radial stacked reactor is not operated as a stationary fixed bed, but is operated to provide a reforming catalyst by the movement of at least one reactor stack (for example, S1 and / or S2), and arrives at the downstream device including the regeneration system via a used or waste catalyst transfer system, in which the used catalyst is regenerated. In embodiments, the stacked reactor system is operable to provide a reforming catalyst by the movement of at least one reactor stack in a time period of at least about 180 days, about 200 days, about 250 days, about 270 days, about 300 days, about 325 days, about 350 days, about 360 days, about 365 days or more than 365 days. In embodiments, the catalyst moves very slowly to the regeneration part. Once entering the regenerator, the catalyst can be regenerated, as discussed in more detail below, for example, via coke combustion (for example, via contact with chlorine and oxygen), metal (for example, platinum) redispersion and halogenation (for example, fluorine is used for refluorination). The catalyst regenerated can then be returned to the stacked reforming reactor part.

[0059] Although referred to as used or "spent" catalyst, the catalyst removed via the used catalyst transfer line 135 may retain substantial catalytic activity. In embodiments, when operating a radial flow reactor with continuously moving catalyst (via the second or third variation described herein), the activity y of the spent catalyst extracted via the used catalyst transfer line 135 is less than or equal to about 90%, about 80%, about 70%, about 50%, about 10%, or about 5% of the activity "x" of the fresh catalyst. In various aspects, operating catalysts having up to about 50% reduced catalyst activity, about 80% reduced catalyst activity, and about 95% reduced catalyst activity may be discarded first.

[0060] In an embodiment, the reforming method disclosed herein includes extracting spent reforming catalyst, which may also pass through at least one purge vessel, which is attached to or fluidically connected to the bottommost reforming reactor of each reactor stack or the bottommost reforming reactor of the final reactor stack using inter-stack transfer; and replacing the spent reforming catalyst with a replacement catalyst, which is added back to the topmost reforming reactor of each reactor stack or the topmost reforming reactor of the first reactor stack using inter-stack transfer, and may also pass through at least one purge vessel and / or at least one reduction vessel before being introduced into the topmost reactor.

[0061] The stacked reactor system 100 includes a spent or "spent" catalyst delivery line or conveying system 135. Spent or spent catalyst may be removed from the last or bottommost reactor (fourth reactor 110D) of the second reactor stack S2 via the spent or "spent" catalyst delivery line or conveying system 135. The spent or spent catalyst may pass through one or more containers 150A before being delivered to the downstream device 140.

[0062] In embodiments, the catalyst transfer system uses inter-stack transfer to transfer reforming catalyst through at least one purge chamber or lock hopper attached to the bottommost radial flow reactor of each of the at least one reactor stack or the bottommost radial flow reactor of the final stack of at least one reactor stack. The spent catalyst transfer system 135 is operable to transfer catalyst from the bottommost radial flow reforming reactor 110D through the purge vessel or lock hopper 150A. Vessel 150A may be integrated with the fourth reforming reactor 110D, or as Figure 1 As indicated in the embodiments of , the reforming catalyst may be connected thereto via a spent catalyst delivery system 135. In embodiments, movement of the reforming catalyst through at least one reactor stack to the purge vessel or lock hopper 150A occurs over a period of at least about 180 days, about 270 days, about 365 days, or greater than 365 days.

[0063] The spent catalyst delivery system 135 may fluidly connect at least one purge chamber 150A to the top of the regeneration system 140. The spent catalyst delivery system 135 may be operable to transfer the catalyst using pneumatic or non-pneumatic methods, using but not limited to methods using one or more of a conveyor belt, a screw, a shuttle hopper, and an oversized bag, and pneumatic methods utilizing one or more of air, hydrogen, nitrogen, argon, and additional inert or non-inert commercial gases. The movement of the spent reforming catalyst through the delivery system 135 to the regeneration system 140 may be continuous, intermittent, or batchwise. In an embodiment, extracting the spent reforming catalyst from at least one reactor stack (e.g., S1 and / or S2) and regenerating the spent reforming catalyst in the regeneration system 140 is performed in batches.

[0064] In embodiments, the reforming catalyst in one of the at least one radial flow reactor stacks (e.g., S1 and / or S2) is transferred to the regeneration system every about 180 days, about 270 days, about 365 days, or more than 365 days via the spent catalyst delivery system 135. When the amount of spent catalyst stored in the regenerator reaches a predetermined threshold amount, the spent catalyst introduced into the regenerator 140 continuously, semi-continuously, or batchwise may be regenerated therein.

[0065] As described herein, via this second variation, the downstream device 140 includes a regenerator or regeneration system operable to regenerate the spent catalyst. Via regeneration, the catalytic activity of the spent catalyst introduced into the regeneration system 140 via the spent catalyst transfer line 135 can be increased by reactivating the spent catalyst to produce a catalytic activity z, where z is greater than y (the activity of the spent catalyst) but less than the activity "x" of the fresh catalyst (where y is greater than y) but less than the activity "x" of the fresh catalyst (where y is greater than y) <z<x)。

[0066] In an embodiment, the interior of the regenerator is not coated with a tin-containing metal protective layer, which may also be referred to as a tin MPT. Although the tin MPT coating can be beneficially used in some systems and methods, for example, to prevent carburization of components and / or containers in the process, the presence of the coating in the regenerator may disadvantageously lead to varying degrees of catalyst poisoning. In an embodiment, the inner surface of the regeneration reactor and / or the interior of the reactor of the regenerator is not coated with tin MPT. In an embodiment, the inner surface of the regeneration reactor and / or the interior of the reactor of the regenerator is coated with tin MPT.

[0067] In an embodiment, the spent aromatization catalyst introduced into the regeneration system or regenerator 140 is regenerated by any method known to those skilled in the art. The material for regenerating the spent catalyst is introduced into the regeneration system or container 140 via pipeline 141. The regenerated exhaust gas can be removed from the regeneration container or system 140 via the regeneration exhaust gas outlet pipeline 142. In an embodiment, the regeneration process includes decoking, halogenation, reduction or a combination thereof. In an embodiment, the aromatization catalyst comprises a catalyst support, one or more catalytically active metals and at least one halide. In an embodiment, the aromatization catalyst comprises a catalyst support, one or more catalytically active metals and at least two halides. In an embodiment, the reforming catalyst comprises a Group VIII metal, a zeolite support and at least one halogen. In an embodiment, at least one halogen comprises fluorine, and the regenerator is operable to refluorinate the spent reforming catalyst. Such aromatization catalysts are further described in detail herein.

[0068] In embodiments, regeneration includes reducing the amount of carbonaceous material present in the spent catalyst, redispersing the metal around the catalyst support, and reactivating the catalyst to restore at least a portion of the catalytic activity. In embodiments, the regeneration process includes decoking, oxychlorination, fluorination, reduction, or a combination thereof. Such regeneration methods are described by way of non-limiting examples in U.S. Pat. Nos. 8,664,144 and 9,421,529, the disclosures of which are incorporated herein in their entirety for all purposes not inconsistent with the present disclosure.

[0069] In embodiments, the regeneration process comprises chlorination, decoking, fluorination, reduction, or a combination thereof. U.S. Patent Application Serial No. 14 / 230,373; U.S. Patent No. 8,716,161; U.S. Patent No. 8,912,108; U.S. Patent No. 9,174,895; and U.S. Patent No. 9,421,530 describe such regeneration methods by way of non-limiting examples, each of which is incorporated herein by reference. In embodiments, fluorination comprises low temperature fluorination. Such regeneration methods are described in U.S. Patent No. 10,300,476 by way of non-limiting example, the disclosure of which is incorporated herein in its entirety.

[0070] In embodiments, the spent catalyst is first contacted with chlorine and oxygen to burn the coke and redisperse the platinum. Regeneration may also include the addition of fluorine.

[0071] Regeneration catalyst

[0072] As described above, regenerating the spent catalyst can include reducing the amount of carbonaceous material present in the spent catalyst. Regeneration can also include redispersing the metal around the catalyst support. The metal can be redispersed via contact with one or more redispersing compounds. The metal can be redispersed around the catalyst, in one or more layers (e.g., surface layers) of the catalyst, throughout the catalyst, or various combinations thereof, and such dispersion can be uniform or non-uniform. The metal in the catalyst support can then be reactivated by contacting the material with a reactivation composition. The reactivation composition can include one or more halides. Regeneration can also include thermal treatment of the composition. Although various decoking, redispersion, and reactivation steps are described herein in a certain order, such steps can be reordered in accordance with the U.S. patents described herein and incorporated by reference.

[0073] Reducing the amount of carbonaceous material associated with the catalyst may also be referred to as decoking. Decoking involves converting the carbonaceous material into carbon oxides and water, and may be performed by heating the spent catalyst at a temperature ranging from about 25°C to about 1000°C, alternatively from about 50°C to about 900°C, alternatively from about 100°C to about 800°C, alternatively from 200°C to 700°C, alternatively from 300°C to 600°C, to produce a decoked spent catalyst. The decoking process may be performed by heating the spent catalyst for a period of about 1 hour to about 40 hours, alternatively from about 2 hours to about 25 hours, alternatively from about 3 hours to about 20 hours, alternatively from 4 hours to 15 hours, alternatively from 5 hours to 10 hours, to produce a decoked spent catalyst. The decoking process may be performed by heating the spent catalyst in the presence of oxygen, wherein the oxygen concentration is from about 0.01 mol % to about 20 mol %, alternatively from about 0.1 mol % to about 15 mol %, alternatively from about 0.2 mol % to about 10 mol %, alternatively from 0.5 mol % to 5 mol %, alternatively from 1 mol % to 3 mol %, to produce a decoked spent catalyst.

[0074] Regeneration can include redispersing the metal on the catalyst support. In embodiments, after the spent catalyst is decoked, the metal on the decoked spent catalyst is redispersed on the catalyst support. Although not wishing to be bound by theory, the previously described decoking process and / or the hydrocarbon conversion process to which the spent catalyst is subjected may unfavorably cause the metal to aggregate on the catalyst support. Aggregated metals are physically and chemically inadequately available for catalytic reactions and, therefore, should be redispersed if maximum catalyst activity is to be restored. In embodiments, the metal on the spent catalyst (which may be a decoked spent catalyst at this time) is redispersed by a number of processes commonly referred to as oxychlorination. Oxychlorination of the spent catalyst can be carried out by contacting the spent catalyst with a redispersible composition of the type described herein under conditions described herein.

[0075] In one embodiment, the spent catalyst is contacted with a redispersible composition comprising a chlorine-containing compound and oxygen. The chlorine-containing compound can be in a solid phase, a liquid phase, a gas phase, or a combination thereof. Examples of chlorine-containing compounds suitable for use in the redispersible composition include, but are not limited to, hydrochloric acid, chlorine, carbon tetrachloride, tetrachloroethylene, chlorobenzene, methyl chloride, methylene chloride, chloroform, propylene chloride, trichloroethylene, chloramines, chlorine oxides, chloric acid, chlorine dioxide, dichlorine monoxide, dichlorine heptoxide, chloric acid, perchloric acid, or a combination thereof.

[0076] The contact of the spent catalyst with the redispersion composition may be carried out over a period of about 0.5 hours to about 50 hours, alternatively about 1 hour to about 20 hours, alternatively about 2 hours to about 10 hours, at a temperature range of about 25°C to about 1000°C, alternatively about 50°C to about 900°C, alternatively about 100°C to about 800°C, alternatively about 200°C to about 400°C, alternatively about 400°C to about 600°C. The contact of the spent catalyst with the redispersion composition may be carried out in the presence of oxygen. When oxygen is used, the oxygen concentration used is about 0.01 mol% to about 20 mol%, alternatively about 1 mol% to about 18 mol%, alternatively about 5 mol% to about 15 mol%, alternatively about 8 mol% to about 12 mol%.

[0077] In alternative embodiments, the spent catalyst is contacted with a redispersible composition comprising a chlorine-containing compound of the type described herein (e.g., HCl) and oxygen in the presence of water. When water is used, the molar ratio of water to HCl (H2O:HCl) can be from about 0.01:1 to about 10:1, alternatively from about 0.5:1 to about 5:1, alternatively from about 1:1 to about 3:1. When a chlorine-containing compound other than HCl is used, the H2O:HCl molar ratio is calculated based on the equivalent amount of HCl generated in the presence of the spent catalyst.

[0078] In one embodiment, a weak base may be included when the metal is redispersed to neutralize any free acid that may be present. Examples of weak bases suitable for use in the present disclosure include, but are not limited to, ethylenediamine (EDA). The resulting material is a redispersed spent catalyst, which may be further dried under appropriate conditions. In addition, or alternatively, the spent catalyst (e.g., decoked and / or redispersed spent catalyst) may be calcined at a temperature ranging from about 25°C to about 1000°C, alternatively from about 50°C to about 900°C, alternatively from about 100°C to about 800°C, alternatively from about 200°C to 700°C, alternatively from about 300°C to about 600°C. Calcination may be performed for a time of about 1 hour to about 40 hours, alternatively from about 2 hours to about 25 hours, alternatively from about 3 hours to about 20 hours, alternatively from about 4 hours to about 15 hours, alternatively from about 5 hours to about 10 hours. The calcination process may be performed by heating the spent catalyst in the presence of oxygen, wherein the oxygen concentration is from about 0.01 mol % to about 20 mol %, alternatively from about 0.1 mol % to about 15 mol %, alternatively from about 0.2 mol % to about 10 mol %, alternatively from about 0.5 mol % to about 5 mol %, alternatively from about 1 mol % to about 3 mol %.

[0079] The spent catalyst (e.g., decoked, redispersed, calcined and / or untreated spent catalyst) may be subjected to at least one reactivation step. The reactivation of the spent catalyst may be carried out using a reactivation composition comprising one or more halogenating agents, including a gas phase halogenating agent, a liquid phase halogenating agent, a solid phase halogenating agent, or a combination thereof. In one embodiment, the reactivation of the spent catalyst is carried out by contacting the spent catalyst with a fluorine-containing solution, a process generally referred to as fluorination. The fluorine-containing compound may be a solid phase, a liquid phase, a gas phase, or a combination thereof. Examples of fluorine-containing compounds suitable for use in the present disclosure include, but are not limited to, tetramethylammonium fluoride (TMAF), ammonium fluoride (NH4F or AF), tetrafluoroethylene, 2,2,2-trifluoroethanol (TFE), fluorine gas (F2), hydrofluoric acid (HF), or a combination thereof. In one embodiment, the fluorine-containing compound is a perfluoroalkane, a perfluoroalcohol, or a mixture thereof. Examples of perfluoroalcohols suitable for use in the present disclosure include, but are not limited to, 2,2,2-trifluoroethanol (TFE), hexafluoroisopropanol, tetrafluoropropanol, pentafluoropropanol, hexafluorophenylpropanol, perfluorobutanol, hexafluoro-2-propanol, pentafluoro-1-propanol, tetrafluoro-1-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, and combinations thereof.

[0080] In one embodiment, the fluorine-containing compound is an organic ammonium halide compound, and may include one or more compounds represented by the general formula N (R) 4F, wherein R represents hydrogen or a substituted or unsubstituted carbon chain molecule with 1 to 20 carbons, wherein each R may be the same or different. In one embodiment, R is methyl, ethyl, propyl, butyl or a combination thereof. Alternatively, R is methyl. Examples of suitable organic ammonium compounds include ammonium fluoride (AF), tetramethylammonium fluoride (TMAF), tetraethylammonium fluoride (TEAF), tetrapropylammonium fluoride, tetrabutylammonium fluoride, methyltriethylammonium fluoride or a combination thereof. Alternatively, the organic ammonium halide compound may also include at least one hydrofluoric acid and at least one ammonium hydroxide represented by the formula N (R ') 4OH, wherein R 'is hydrogen or a substituted or unsubstituted carbon chain molecule with 1 to 20 carbon atoms, wherein each R 'may be the same or different. In one embodiment, R 'is methyl, ethyl, propyl, butyl or a combination thereof. Alternatively, R 'contains methyl. Examples of organic ammonium hydroxides suitable for use in the present disclosure include ammonium hydroxide, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or combinations thereof.

[0081] In one embodiment, the spent catalyst (e.g., decoked, redispersed, calcined, and / or untreated spent catalyst) is contacted with a TMAF solution at a temperature ranging from about 0° C. to about 200° C., alternatively from about 20° C. to about 100° C., alternatively from about 40° C. to about 60° C., for a period of about 1 minute to about 100 hours, alternatively from about 0.1 hours to about 50 hours, alternatively from about 1 hour to about 24 hours. The solution also contains any suitable solvent.

[0082] In alternative embodiments, the spent catalyst is reactivated by contact with a gas-phase fluorinating agent such as, for example, fluorine. In such embodiments, the gas-phase fluorinating agent may be contacted with the spent catalyst for a period of about 1 minute to about 100 hours, alternatively about 0.1 hours to about 50 hours, alternatively about 1 hour to about 24 hours, alternatively about 4 hours to about 11 hours.

[0083] In an alternative embodiment, the spent catalyst is reactivated by contact with a solid phase fluorinating agent (such as an organic ammonium halide compound, such as ammonium fluoride, tetramethylammonium fluoride, or a combination thereof). In this embodiment, the solid phase fluorinating agent may be contacted with the spent catalyst at an elevated temperature. The contact may occur for a period of about 1 minute to about 100 hours, alternatively about 0.1 hours to about 50 hours, alternatively about 1 hour to about 24 hours, alternatively about 4 hours to about 11 hours. The elevated temperature may be in the temperature range of about 0°C to about 200°C, alternatively about 20°C to about 100°C, alternatively about 40°C to about 60°C. Although not wishing to be limited by theory, it is believed that under these conditions, some of the solid phase fluorinating agent will sublime and migrate into the spent catalyst (e.g., into the decoked, redispersed, calcined and / or untreated spent catalyst).

[0084] In the reactivation of the spent catalyst, chlorine-containing compounds may also be used. The chlorine-containing compound may be a solid phase, a liquid phase, a gas phase, or a combination thereof. In one embodiment, the chlorine-containing compound is of the type previously described herein. Examples of chlorine-containing compounds suitable for reactivation compositions include, but are not limited to, compounds represented by the general formula N(R)4Cl, wherein R represents hydrogen or a substituted or unsubstituted carbon chain molecule having 1 to 20 carbon atoms, wherein each R may be the same or different. In one embodiment, R is a methyl, ethyl, propyl, butyl, or a combination thereof. Alternatively, R is a methyl substituent. Specific examples of suitable organic ammonium chloride compounds include ammonium chloride, tetramethylammonium chloride (TMAC), tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, methyltriethylammonium chloride, or a combination thereof. Alternatively, the chlorine-containing compound is TMAC.

[0085] In any of the above methods for reactivating a spent catalyst, the resulting composition may be dried in a temperature range of about 0°C to about 250°C, alternatively about 25°C to about 200°C, alternatively about 50°C to about 150°C and / or calcined in a temperature range of about 25°C to about 1000°C, alternatively about 50°C to about 900°C, alternatively about 100°C to about 800°C. Drying and / or calcination may be carried out at ambient pressure or under vacuum. During the drying and / or calcination process, the contacted spent catalyst particles may be stationary or moving, such as in a rotary dryer. In one embodiment, a weak base may be included in the reactivation process of the metal to neutralize free acids that may be present. Examples of weak bases suitable for use in the present disclosure include, but are not limited to, EDA. After fluorination, the resulting composition may be a decoked, redispersed, and reactivated spent catalyst.

[0086] In an embodiment, the spent catalyst (e.g., a spent catalyst that has been decoked, redispersed, and / or reactivated) undergoes multiple reactivation steps. The reactivation steps may be the same, alternatively the reactivation steps may be different. For example, the spent catalyst (e.g., a spent catalyst that has been decoked and / or redispersed) may be reactivated multiple times with a gas phase fluorinating agent. Alternatively, the spent catalyst may be reactivated a first time with a liquid phase fluorinating agent and a second time with a gas phase fluorinating agent. In one embodiment, the spent catalyst undergoes two reactivation steps.

[0087] The spent catalyst (e.g., decoked, redispersed and / or reactivated spent catalyst) may be thermally treated as described previously herein to produce a thermally treated spent catalyst. The thermal treatment may be performed in a stationary or flowing gas (i.e., hydrogen, oxygen, air, helium, nitrogen, argon, etc.). For example, the thermal treatment may be performed in a flowing gas comprising nitrogen and / or oxygen, air, nitrogen-diluted air, or a combination thereof. In one embodiment, the thermal treatment comprises calcination and the calcination process may be performed by heating the spent catalyst in the presence of oxygen, wherein the oxygen concentration is from about 0.01 mol% to about 20 mol%, alternatively from about 0.1 mol% to about 18 mol%, alternatively from about 0.2 mol% to about 15 mol%, alternatively from about 1 mol% to about 11 mol%, alternatively from about 4 mol% to about 9 mol%. In one embodiment, the spent catalyst is thermally treated by calcining at a temperature ranging from about 25°C to about 1000°C, alternatively from about 50°C to about 900°C, alternatively from about 100°C to about 800°C, alternatively from about 200°C to about 700°C, alternatively from about 300°C to about 600°C. Calcination can be performed for a time of about 1 hour to about 40 hours, alternatively from about 2 hours to about 25 hours, alternatively from about 3 hours to about 20 hours, alternatively from about 4 hours to about 15 hours, alternatively from about 5 hours to about 10 hours. The calcination process can be performed by heating the spent catalyst in the presence of oxygen, wherein the oxygen concentration is about 0.01 mol% to about 20 mol%, alternatively from about 0.1 mol% to about 15 mol%, alternatively from about 0.2 mol% to about 10 mol%, alternatively from about 0.5 mol% to about 5 mol%, alternatively from about 1 mol% to about 3 mol%. After completing the regeneration process described herein, the catalyst is referred to as a regenerated catalyst or a reactivated catalyst.

[0088] According to the present disclosure, the activity of the reactivated catalyst may be represented by z, while the activity of the fresh catalyst may be represented by x, where x is greater than z. In one embodiment, the reactivated catalyst may have an activity z of about 0.001x to about 0.95x, alternatively about 0.7x to about 0.95x, alternatively about 0.8x to about 0.95x, alternatively about 0.95x.

[0089] After regeneration as described herein, the amount of metal present in the regenerated catalyst may be about 0.1 wt % to about 50 wt %, alternatively about 0.1 wt % to about 10 wt %, alternatively about 0.2 wt % to about 5 wt %, alternatively about 0.3 wt % to about 3 wt %, alternatively about 0.3 wt % to about 2 wt %. As used herein, the weight percentage of the metal is based on the total weight of the catalyst. The amount of chloride present in the regenerated catalyst may be about 0.1 wt % to about 10 5 wt %, alternatively about 0.2 wt % to about 5 3 wt %, alternatively about 0.3 wt % to about 3 2 wt %. The amount of fluoride present in the regenerated catalyst may be about 0.1 wt % to about 10 wt %, alternatively about 0.2 wt % to about 5 wt %, alternatively about 0.3 wt % to about 3 wt %, alternatively about 0.6 wt % to about 2 wt %.

[0090] In an embodiment, the regeneration system 140 is operable to provide movement of the reforming catalyst through a series of radial flow regeneration reactors. The regeneration reactor can be a stacked reactor that is operable to provide a substantially uniform distribution of regeneration components (e.g., halogens). The speed at which the catalyst circulates through such a regeneration container stack is significantly faster than the speed of circulation through the reforming reactor stack (e.g., a catalyst circulates through a regeneration reactor stack for about a week, then, as described herein, a catalyst circulates through a reforming reactor for about a year or more).

[0091] The regenerated reforming catalyst can be introduced into the top radial flow reactor of each of at least one reactor stack by inter-stack transmission, or introduced into the top radial flow reactor of the first reactor stack. The regenerated reforming catalyst can be introduced into the top radial flow reactor via container 150B (for example, at least one purge chamber) and alternative catalyst delivery system or delivery line 131. The regenerated catalyst can be reduced before or after being transferred to the top of at least one reactor stack. In an embodiment, container 150B includes a reduction container integrated and / or fluidly connected with the top radial flow reactor (for example, the first reactor 110A) to which the regenerated catalyst is introduced, and the regenerated catalyst is reduced in container 150B. In an embodiment, the regenerated catalyst is reduced via a reducing gas including hydrogen, nitrogen, carbonaceous reducing gas such as carbon monoxide (CO) or a mixture thereof. In an embodiment, container 150B includes a purge container integrated and / or fluidly connected with the top radial flow reactor to which the regenerated catalyst is introduced, and the regenerated catalyst is contacted with a purge gas therein. In an embodiment, the purge gas comprises nitrogen. In an embodiment, a single vessel 150B is used as a purge vessel, lock hopper, and / or reduction vessel.

[0092] In an embodiment, the reforming catalyst passes through the regeneration system and is returned to the stacked reactor system (e.g., container 150B) via an alternative catalyst transfer system over a period of about one week. At the start of operation, the initial fresh catalyst can be introduced into the downstream container or storage device 140 via, for example, a supplementary catalyst line 130 and a valve V4, and arrive at the stacked reactor of the first stack S1, for example, via container 150B, where the fresh catalyst can be purged and / or reduced. Alternatively, the fresh catalyst can be purged and / or reduced in the downstream container 140 before being transferred to the stacked reactor of the first stack S1.

[0093] For this second variation, during operation, valves V1 and V2 can be opened, and valve V3 directs catalyst stream to the first reforming reactor 110A, and valve V4 is closed. In this way, as described above, reforming catalyst can be moved from the first reforming reactor 110A through all reforming reactors (for example, from 110A to 110B via pipeline 134 to 110C to 110D and leave 110D via pipeline 135), as described above, and arrive at regenerator 140. In regenerator, used catalyst can be regenerated. Fresh supplementary catalyst can be introduced into stacked reactor via supplementary catalyst pipeline 130 and valve V4 as needed, and spent catalyst is purged via catalyst purge pipeline 132 and valve V3. After regeneration (in embodiments, regeneration may require about several days to a week), the regenerated catalyst can be returned to the first reforming reactor 110A, optionally via container 150B, in which catalyst can be stored and / or reduced until needed for the first reactor 110A.

[0094] like Figure 1 In an embodiment shown in FIG. 1 , the hydrocarbon feed can flow from the topmost radial flow reactor of each stack to the bottommost radial flow reactor thereof, such that the reforming catalyst and the hydrocarbon feed flow concurrently through at least one reactor stack. In such an embodiment, the operating temperature of a given radial flow reactor can be lower than the operating temperature of a radial flow reactor downstream of the topmost radial flow reactor. For example, in a reactor such as Figure 1 In an embodiment, the first reforming reactor 110A may be operated at a lower temperature than the second reforming reactor 110B, which may be operated at a lower temperature than the third reforming reactor 110C, which itself may be operated at a lower temperature than the fourth reforming reactor 110D. In an alternative embodiment, the CCR or stacked reactor system is configured to flow the hydrocarbon feed from the bottommost reactor of at least one reactor stack to the topmost reactor thereof, such that the reforming catalyst and the hydrocarbon feed flow countercurrently through the at least one reactor stack. Reference will be made herein to Figure 2 The embodiments disclosed in describe this countercurrent flow of catalyst and hydrocarbon feed in more detail.

[0095] Variant 3: Operation with slow movement of catalyst through stacked reactors and storage / removal

[0096] In a third variation of the reforming method according to the present disclosure, the radial stacked reactor is operated to provide reforming catalyst through at least one reactor stack and moved to a downstream device via a used or waste catalyst transfer system for storage and subsequent removal. In such embodiments, the reforming catalyst can be moved very slowly to the existing downstream regeneration section. After arriving there, the waste reforming catalyst is removed from the process and replaced with a fresh catalyst, which is added back to the stacked reforming reactor section. The downstream device can be a dedicated storage container for storage in these embodiments, or a regeneration system for a modified CCR system. In such embodiments, the circulation of the waste catalyst to the downstream device 140 can be as described above with respect to the circulation of the waste catalyst to the regeneration system 140. In these embodiments, the waste catalyst can be stored in the downstream device 140 until the amount of the waste catalyst stored in the regenerator reaches a predetermined threshold amount, at which point the waste catalyst can be removed therefrom, for example, via a catalyst waste line 132 and a valve V3. The removed waste catalyst can be sent to an off-site facility for regeneration, or can be sent for recovery or disposal. Off-site regeneration can include adding a liquid to the catalyst.

[0097] Fresh catalyst can be introduced into the stacked reactor via catalyst replacement line 131. Fresh catalyst can be introduced into a downstream container or storage device 140 via, for example, a supplemental catalyst line 130 and valve V4. As described above, the stacked reactor system can be configured to initially introduce the reforming catalyst into a purge tank or container, which is optionally connected to a reduction container or fluidly connected thereto, which is connected to or fluidically connected to the topmost radial flow reactor of at least one of the at least one reactor stack. In an embodiment, the fresh reforming catalyst is introduced into at least one reactor stack via such a purge container (e.g., a lock hopper) and / or a reduction container, and is purged and / or reduced as described above before being introduced into at least one reactor stack (e.g., the first reactor 110A or reactor stack S1).

[0098] For this third variation, during operation, valves V1 and V2 can therefore be opened, while valve V3 can periodically direct catalyst from the regenerator 140 to the catalyst waste via line 132. Valve V4 can be operated to periodically add fresh catalyst to the downstream device 140. In an embodiment, the fresh catalyst is dried and / or reduced (in the downstream device 140 and / or container 150B) before being fed to the first reforming reactor 110A. In an embodiment, the aromatization catalyst passes through all reactors of the stack and then enters the downstream device 140 (e.g., from 110A to 110B via line 134 to 110C to 110D, and leaves 110D via line 135). According to this third variation of the reforming method of the present disclosure, instead of regenerating in the downstream device 140, the used catalyst stored therein can be sent for treatment. According to aspects of the third variation, in an embodiment, an existing CCR can be used for aromatization without using the catalyst regeneration function of a conventional CCR process.

[0099] In embodiments, after processing the spent catalyst, new or fresh catalyst is loaded into the downstream unit 140. As with the second variation described above, this third variation can provide simplified operations because the unit can have substantially steady-state overall catalyst performance, can provide predictable continuous catalyst demand, and can be changed out without shutting down the unit because replacement catalyst can be introduced from the lock hopper 150B to the first reactor 110A during the regeneration (according to aspects of variation two) or disposal (according to aspects of variation three) of spent catalyst from the downstream vessel 140. As with the second variation, the aromatization catalyst can move very slowly through the stacked reactors, in embodiments requiring 1-3 years to move from the first reactor 110A to the regenerator / storage vessel 140 or lock hopper 150A.

[0100] Operation of catalyst movement via variants two and three described herein can provide a gradient of catalyst life in the reforming reactors (e.g., fresh catalyst is introduced at the inlet of reactor 110A and passes through reactors 110A, 110B, 110C, and 110D, while being sequentially used up and exiting the last reactor 110D as spent catalyst). In embodiments, the temperature of the reforming reactors is adjusted according to the different activity levels of the catalysts therein. In embodiments, the operating temperature in each reforming reactor does not increase significantly during operation, but remains substantially constant. As described above with reference to the second variant, and herein with reference to Figure 2 In more detail, the hydrocarbon feed and catalyst may flow in parallel (e.g. Figure 1 ) or countercurrent flow, and the desired operating temperature in the stacked reforming reactor can be selected accordingly.

[0101] For this third variation of reforming according to the present disclosure, since the spent catalyst can be replaced with fresh catalyst after it is transferred to the regenerator / storage device, rather than being regenerated therein for reuse, suitable aromatization catalysts may be less resistant to attrition than conventional CCR reforming catalysts, including catalysts characterized by one or more of a crush strength of at least about 1.5 lbs / mm and / or a catalyst attrition of less than about 3.0 wt %. In addition, according to this third variation, extrudates that may produce fines when the catalyst is removed from the system may also be suitable because the fines are removed with the spent catalyst when passing through reactor stacks S1 and S2.

[0102] The second or third variations provided herein both employ slow movement of the aromatization catalyst through at least one reactor stack, and both are operable to provide, as compared to via a conventional fixed bed radial flow reforming reactor. More efficient utilization of catalyst and / or providing more uniform catalyst demand. Variant two and variant three may also provide more efficient catalyst utilization than variant one in which the reforming reactor of the stacked reactor system is operated as a stationary fixed bed radial flow reactor. Therefore, in an embodiment, the "waste" catalyst removed from the reactor stack operated via variant two or variant three may retain lower catalytic activity (e.g., may be more completely ineffective) than the corresponding catalyst removed from the reactor stack of the reactor operated as a stationary fixed bed via variant one (due to the nature of the reactant flowing through the fixed radial bed). In some aspects, the "waste" catalyst removed from each reactor operated via variant two or variant three may have substantially the same activity (i.e., substantially uniform catalyst utilization), while the "waste" catalyst removed from the reactor further upstream of the system operated via variant one may retain more catalytic activity than the "waste" catalyst removed from the rear reactor. In another embodiment, the "waste" catalyst removed from each reactor may be characterized by different catalytic activity levels due to, for example, uneven catalyst use.

[0103] Now refer to Figure 2 Describing another stacked reactor system for the aromatization process disclosed herein, the figure is a flow chart of a stacked reactor system 200 for an aromatization process according to another embodiment of the present disclosure. The stacked reactor system 200 includes a first reactor stack S1 and a second reactor stack S2, a heat exchanger 220, a catalyst silo and / or activator 240, a spent catalyst storage container 250, and valves V1, V2, V3, V4, V5, and V6. In aspects of the disclosed technology, the heat exchanger can be associated with or include a component such as a furnace, or can be incorporated into the system, such as a heat exchanger lacking one or more components associated with the furnace, as known to those skilled in the relevant art.

[0104] The reforming reactor system 200 includes a first reactor stack S1 and a second reactor stack S2, the first reactor stack includes three reforming reactors, namely the first, third and fifth reforming reactors 210A, 210C and 210E, respectively, and the second reactor stack includes three reforming reactors, namely the second, fourth and sixth reforming reactors 210B, 210D and 210F. In this embodiment, the first reforming reactor 210A is the bottommost reforming reactor of the first reactor stack S1 and is positioned below the third reforming reactor 210C, which is the middle reforming reactor of the first reactor stack S1. The fifth reforming reactor 210E is the topmost reforming reactor of the first reactor stack S1 and is positioned above the third reforming reactor 210C. The second reforming reactor 210B is the bottommost reforming reactor of the second reactor stack S2 and is positioned below the fourth reforming reactor 210D, which is the middle reforming reactor of the second reactor stack S2. The sixth reforming reactor 210F is the topmost reforming reactor of the second reactor stack S2 and is positioned above the fourth reforming reactor 210D. As discussed above, the reforming reactor system of the present disclosure may include a single stack or multiple stacks, including but not limited to two, three, or four reactor stacks. In embodiments such as Figure 2 In an embodiment of the invention, the reforming system comprises two stacks, and the hydrocarbon feed is passed between the reactor stacks. Figure 1 ), transporting reforming catalyst between reactor stacks. Figure 2 In an embodiment of the present invention, no reforming catalyst is transferred between reactor stacks.

[0105] In an embodiment, the hydrocarbon to be aromatized of the feed is heated to the desired operating temperature by introducing through the heat exchanger 220 via the hydrocarbon feed inlet line 205. The first reactor inlet line 206 transports the heated hydrocarbon feed to the first reforming reactor 210A of the first reactor stack S1. In the first / bottommost reforming reactor 210A, the convertible hydrocarbons are converted into reformer products containing BTX via contact with the aromatization catalyst and under the operating conditions as described herein. The effluent containing aromatic hydrocarbons is removed from the first reforming reactor 210A via the first reactor effluent line 207. The first reactor effluent is introduced into the heat exchanger 220 via the first reactor effluent line 207, where it is heated to the desired downstream reforming reactor inlet temperature. The heated first reactor effluent is introduced into the second reforming reactor 210B of the second reactor stack S2 from the heat exchanger 220 via the second reforming reactor inlet line 208.

[0106] In the second reforming reactor 210B, the convertible hydrocarbons are converted into reformer products containing BTX via contact with an aromatization catalyst and under operating conditions as described herein (via reforming / aromatization). The effluent containing aromatic hydrocarbons is removed from the second reforming reactor 210B via the second reforming reactor effluent pipeline 209. The second reactor effluent is introduced into the heat exchanger 220 via the second reforming reactor effluent pipeline 209, where it is heated to the desired downstream reforming reactor inlet temperature. The heated second reactor effluent is introduced into the third reforming reactor 210C of the first reactor stack S1 from the heat exchanger 220 via the third reforming reactor inlet pipeline 216.

[0107] In the third reforming reactor 210C, the convertible hydrocarbons are converted into reformer products containing BTX via contact with an aromatization catalyst and under operating conditions according to the present disclosure. The effluent containing aromatic hydrocarbons is removed from the third reforming reactor 210C via the third reforming reactor effluent pipeline 217. The third reactor effluent is introduced into the heat exchanger 220 via the third reforming reactor effluent pipeline 217, where it is heated to the desired downstream reforming reactor inlet temperature. The heated third reactor effluent is introduced into the fourth reforming reactor 210D from the heat exchanger 220 via the fourth reforming reactor inlet pipeline 218.

[0108] In the fourth reforming reactor 210D, the convertible hydrocarbons are converted into reformer products containing BTX via contact with an aromatization catalyst and under operating conditions according to the present disclosure. The effluent containing aromatic hydrocarbons is removed from the fourth reforming reactor 210D of the second reactor stack S2 via the fourth reforming reactor effluent outlet pipeline 219. The fourth reactor effluent is introduced into the heat exchanger 220 via the fourth reforming reactor effluent pipeline 219, where it is heated to the required downstream reforming reactor inlet temperature. The heated fourth reactor effluent is introduced into the fifth reforming reactor 210E from the heat exchanger 220 via the fifth reforming reactor inlet pipeline 221.

[0109] In the fifth reforming reactor 210E, the convertible hydrocarbons are converted into reformer products containing BTX via contact with an aromatization catalyst and under operating conditions according to the present disclosure. The effluent containing aromatic hydrocarbons is removed from the fifth reforming reactor 210E of the first reactor stack S1 via the fifth reforming reactor effluent outlet pipeline 222. The fifth reactor effluent is introduced into the heat exchanger 220 via the fifth reforming reactor effluent pipeline 222, where it is heated to the desired downstream reforming reactor inlet temperature. The heated fifth reactor effluent is introduced into the sixth reforming reactor 210F of the second reactor stack S2 from the heat exchanger 220 via the sixth reforming reactor inlet pipeline 223.

[0110] In the sixth reforming reactor 210F, the convertible hydrocarbons are converted to reformer products comprising BTX via contact with an aromatization catalyst and under operating conditions as described herein. The effluent comprising aromatic hydrocarbons is removed from the sixth reforming reactor 210F of the second reactor stack S2 via the sixth or final reforming reactor effluent outlet or "hydrocarbon product" outlet pipeline 225.

[0111] You can refer to Figure 1 The embodiment operates via the first, second or third variation described above such as Figure 2 In an embodiment, a stacked reactor system such as Figure 2 A stacked reactor system in which the reforming reactor is operated as a stationary fixed bed.

[0112] In other embodiments, such as Figure 2 The system shown is operated in a continuous catalyst movement mode, such as the second and third variations described herein. For example, in embodiments, the catalyst silo and / or activator 240 is periodically filled with fresh, regenerated, or spent catalyst (to be regenerated therein). For example, fresh catalyst can be introduced into the catalyst silo and / or activator 240 via the fresh or make-up catalyst inlet line 230 and valve V4. Subsequently, the catalyst can be moved as described above with reference to Figure 1 The catalyst may be dried and / or reduced in the catalyst silo 240, or may be dried and / or reduced via a catalyst silo 240 corresponding to the above reference. Figure 1 The container 150B of the embodiment described in the embodiment is dried and / or reduced. For example, the container 150B can be attached to the top reactor of each reactor stack and / or connected to its fluid (e.g., in Figure 2 In an embodiment of the present invention, the fifth reactor 210E of the reactor stack S1 and the sixth reactor 210F of the second reactor stack S2 are attached to and / or fluidly connected thereto). A process gas, such as hydrogen or nitrogen, can be introduced into the catalyst silo and / or activator 240 via a process component inlet line 241, and an exhaust gas generated during the process can be removed from the catalyst silo and / or activator via an exhaust gas outlet line 242.

[0113] The prepared catalyst can be slowly fed to the top of one or more stacked reactor beds. Figure 2In an embodiment, the catalyst is slowly fed to the fifth reforming reactor 210E, which is the topmost reactor of the first reactor stack S1, via an alternative catalyst delivery line 231A and a valve V5; the catalyst is slowly fed to the sixth reforming reactor 210F, which is the topmost reactor of the second reactor stack S2, via an alternative catalyst delivery line 231B and a valve V6; or the catalyst can be fed to the fifth reactor 210E of stack S1 and the sixth reactor 210F of stack S2 at the same time. The catalyst slowly flows downward along the reactor stack S1 from the fifth reforming reactor 210E to the bottommost reforming reactor of the reactor stack S1 (i.e., the first reforming reactor 210A), and flows downward along the reactor stack S2 from the sixth reforming reactor 210F to the bottommost reforming reactor of the second reactor stack S2 (i.e., the second reforming reactor 210B), thereby providing a catalyst activity gradient, as further discussed herein. Spent catalyst can be removed from the bottommost reactor of each reactor stack. For example, in Figure 2 In aspects of the invention, used or spent catalyst can be removed from the first reforming reactor 210A via valve V1 and used or spent catalyst delivery line 235A, from the second reforming reactor 210B via valve V2 and used or spent catalyst delivery line 235B, or both.

[0114] In an embodiment, spent catalyst is introduced into spent catalyst silo 250 via spent catalyst transfer lines 235A and 235B. The spent catalyst can be regenerated via the second variation described above and returned to the reactor stack, optionally via purging and / or reduction as described above. In an embodiment, spent catalyst is returned to catalyst silo and / or activator 240 for reactivation / regeneration. Regeneration can be performed as described herein with respect to Figure 1 For example, a regeneration component suitable for decoking, oxychlorination, halogenation, or a combination thereof can be introduced into the catalyst silo and / or activator 240 via a process component inlet line 241, and the exhaust gas generated during the regeneration / reactivation process can be removed from the catalyst silo and / or activator via an exhaust gas outlet line 242.

[0115] In an embodiment, system 200 is referred to herein as Figure 1 The embodiment described in Variation Three operates in which the spent catalyst in the spent catalyst silo 250 is directed to recovery and / or treatment via the catalyst purge line 232 and valve V3.

[0116] The time it takes for catalyst to move from the top of a stacked reactor (e.g., the reactors of stacks S1 and / or S2) to the bottom can range from a few months to a few years, depending on the size and operation of the unit. Figure 2The embodiments are described as increasing in size from the top to the bottom of each reactor stack, but the volume of the reactors within the reactor stack can increase, decrease, or remain the same from the topmost to the bottommost reactor, as shown in reference Figure 1 For example, in embodiments, the largest reactor in each stack may be its top reactor. The volume percentage of the catalyst in the reactor may be as described above with reference to Figure 1 For example, in embodiments, the volume ratio / percentage of the total aromatization catalyst in the first, second, third, fourth, fifth, and sixth reactors may be about 10%:10%:10%:20%:20%:30%.

[0117] like Figure 2 As shown in the embodiment of, the stacked reactor or CCR system can be configured to introduce fresh hydrocarbon feed into the bottom reactor of one of the at least one reactor stack and pass upward through each reactor stack so that the reforming catalyst and hydrocarbon feed flow countercurrently through at least one reactor stack. In this way, catalysts with relatively low or reduced activity (e.g., catalysts located lower in the reactor stack) can catalyze the easiest reactions, and lower temperatures may be used in these reactors (e.g., in the first and second reforming reactors 210A and 210B). Using lower temperatures can result in less cracking and greater selectivity. When the conversion rate becomes higher when the feed passes upward through the reactor stack, the feed contacts a fresher / more active catalyst. Higher reaction temperatures can be used for reforming reactors higher above the stack containing the freshest catalyst (e.g., in the fifth and sixth reforming reactors 210E and 210F). This fresher catalyst can promote more difficult reactions with higher selectivity. Therefore, in such embodiments, the operating temperature of the reactor (e.g., the bottom or bottommost reactor) of each of the at least one reactor stack can be lower than the operating temperature of its higher reactor (e.g., the top or topmost reactor).

[0118] Countercurrent operation can also provide risk mitigation associated with process upsets. In embodiments, the bottom-most reactor of each or at least the first reactor stack of at least one reactor stack into which the hydrocarbon feed is introduced serves as a guard bed to protect downstream reactors containing more active catalysts from at least one undesirable compound. For example, in Figure 2In an embodiment, the bottommost reactor of the first reactor stack S1 (i.e., the first reforming reactor 210A) or the first reactor 210A and the bottommost reactor (i.e., the second reforming reactor 210B) of the second reactor stack S2 can be operated as a catalyst guard bed. The guard bed reactor can be used to remove unwanted compounds or poisons, such as but not limited to sulfur, heavy components, nitrogen, iron, or a combination thereof. In addition, after an abnormality occurs, the deactivated catalyst can be easily removed without shutting down the plant or continuing to operate for a long time under poor performance conditions because the spent catalyst in the guard bed is closest to removal from the reactor stack, for example, at the bottom of the reactor stacks S1 and S2, close to the catalyst discharge pipelines 235A and 235B. Using this method, in which the most spent catalyst in each reactor stack encounters the freshest hydrocarbon feed, the reforming reactor system can be made to not include a sulfur converter adsorber (SCA) upstream of the CCR or stacked reactor system.

[0119] Although the hydrocarbon feed is shown to flow from the bottom-most reactor of each reactor stack to its top-most reactor, in embodiments, the stacked reactor system 200 can be configured to flow the hydrocarbon feed from the top-most radial flow reactor of each reactor stack downward to its bottom-most radial flow reactor so that the reforming catalyst and the hydrocarbon feed flow through the reactor stack in parallel. In such embodiments, the operating temperature of a given radial flow reactor can be lower than the operating temperature of the radial flow reactors downstream and / or below it. In addition, the relative sizes of the reactors and the corresponding volume distribution of the catalyst within reactor stacks S1 and S2 may vary. Figure 2 The opposite of what is shown in .

[0120] Aromatization catalyst

[0121] In one embodiment, the aromatization catalyst support includes a support. In embodiments, the support includes an inorganic oxide. The inorganic oxide may include a combination of mesopore and / or large pore zeolites (aluminosilicates), amorphous inorganic oxides, and mixtures thereof. Large pore zeolites include, but are not limited to, L-zeolite, Y-zeolite, mordenite, ω zeolite, beta zeolite, or other types of zeolites. Amorphous inorganic oxides include, but are not limited to, aluminum oxide, silicon oxide, and titanium dioxide. The support may also include a binder, such as, for example, silicon dioxide, aluminum oxide, clay, titanium dioxide, and magnesium oxide. In certain aspects, the support does not primarily include aluminum oxide or is substantially composed of aluminum oxide. In embodiments, the zeolite support contains a silicon dioxide-bound L-zeolite support. In further aspects, the catalyst may be characterized by one or more of: including a granular morphology (compared to, for example, a spherical morphology), a relatively low crush strength, a zeolite support (compared to, for example, an alumina support), a fluoride or fluorine, and platinum (Pt) as the catalytic metal (compared to, for example, the presence of Pt and tin (Sn) or Pt and rhodium (Rh)), and a relatively low acidity compared to typical reforming catalysts. In advantageous embodiments, the catalyst used according to the disclosed systems and methods may be further characterized by significantly higher benzene selectivity, relatively less cracking, and less coking compared to typical reforming catalysts.

[0122] In one embodiment, the catalyst support comprises a medium-pore or large-pore zeolite. The term "zeolite" generally refers to a group of specific hydrated crystalline metal aluminosilicates. These zeolites exhibit a network of SiO4 and AlO4 tetrahedra in which aluminum and silicon atoms are cross-linked in a three-dimensional framework by sharing oxygen atoms. In the framework, the ratio of oxygen atoms to the total number of aluminum and silicon atoms may be equal to 2. The framework exhibits a negative charge, which is usually balanced by including cations such as metals, alkali metals, alkaline earth metals, or hydrogen in the crystal.

[0123] In one embodiment, the catalyst support comprises an L-type zeolite. An L-type zeolite support is a subgroup of zeolite supports. A typical L-type zeolite contains oxides in a molar ratio according to the following formula:

[0124] M 2 / n OA12O 3x SiO 2y H2O

[0125] Wherein "M" represents at least one exchangeable cation, such as barium, calcium, cerium, lithium, magnesium, potassium, sodium, strontium and zinc, and non-metallic cations such as hydronium ions and ammonium ions, which can be replaced by other exchangeable cations without causing substantial changes in the basic crystal structure of L-type zeolite. In the formula, "n" represents the valence of "M"; "x" is 2 or greater; and "y" is the number of water molecules contained in the channels or interconnected voids of the zeolite.

[0126] In one embodiment, the catalyst support includes a potassium-bound L-type zeolite, also referred to as KL zeolite. As used herein, the term "KL zeolite" refers to an L-type zeolite in which the main cation M incorporated into the zeolite is potassium. The KL zeolite can be cation exchanged or impregnated with another metal and one or more halides to produce a platinum-impregnated halogenated zeolite or a KL-loaded Pt-halide zeolite catalyst. In some embodiments, the support is a KL zeolite. In other embodiments, the catalyst support may include a mixture of a zeolite and an inorganic oxide.

[0127] The catalyst support may contain up to about 95 wt % L-zeolite, alternatively about 60 wt % to about 95 wt %, alternatively about 70 wt % to about 92 wt %, alternatively about 80 wt % to about 90 wt %, based on the total weight of the support. According to the present disclosure, the weight percent of the total weight of the catalyst support refers to the weight percent of the component based on the final weight of the catalyst support.

[0128] In one embodiment, the catalyst comprises one or more catalytically active metals. Examples of such metals include, but are not limited to, Group IB metals and Group VIII transition metals in the periodic table, such as iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), silver (Ag), copper (Cu), or combinations thereof. In one embodiment, the metal comprises platinum (Pt).

[0129] In one embodiment, the metal may be present in the catalyst in an amount of about 0.1 wt % to about 50 wt %, alternatively about 0.1 wt % to about 10 wt %, alternatively about 0.2 wt % to about 5 wt %, alternatively about 0.3 wt % to about 3 wt %, alternatively about 0.3 wt % to about 2 wt %, based on the total weight of the catalyst. As used herein, the weight percentage of the metal is based on the total weight of the catalyst.

[0130] In one embodiment, the catalyst comprises at least two halides. The example of suitable halides includes chloride, fluoride, bromide, iodide or a combination thereof. In one embodiment, the catalyst comprises chloride. The amount of chloride present in the catalyst can be about 0.1 wt % to about 5 wt %, alternatively about 0.2 wt % to about 3 wt %, alternatively about 0.3 wt % to about 2 wt % by the gross weight of the catalyst.

[0131] In one embodiment, the catalyst comprises a fluoride. The fluoride may be present in the catalyst in an amount of about 0.1 wt % to about 10 wt %, alternatively about 0.2 wt % to about 5 wt %, alternatively about 0.3 wt % to about 3 wt %, based on the total weight of the catalyst.

[0132] In various embodiments, the catalyst comprises platinum (Pt) and chloride (Cl), wherein the atomic ratio of Pt:Cl is from about 1.0:0.1 to about 1.0:20, alternatively from about 1.0:0.2 to about 1.0:15.0, alternatively from about 1.0:0.3 to about 1.0:10.0, including from about 1.0:0.5 to about 1.0:10, from about 1.0:1.0 to about 1.0:5.0, from about 1.0:2.0 to about 1.0:5.0, and about 1.0:4.5.

[0133] In one embodiment, the role that fresh catalyst can play is to catalyze the process desired by the user, such as the aromatization of one or more hydrocarbons. When the catalyst is used to convert hydrocarbons into desired products (e.g., aromatization), the catalyst activity will decrease over time due to the influence of various factors. For example, carbonaceous materials may accumulate on the catalyst, thereby reducing the number of available catalytic sites and the overall activity of the catalyst. In other cases, catalyst modifiers or activity promoters may precipitate from the catalyst over time, resulting in reduced activity or reduced selectivity of the desired product. The activity or selectivity of the catalyst may be reduced to a certain level, wherein the catalyst is no longer beneficial and / or regeneration is required to enhance / restore the catalyst activity in the process desired by the user. Such catalysts can be characterized as "waste" catalysts.

[0134] In embodiments, the crush strength of the reforming catalyst is less than about 15, 14, 13, 12, 11, or 10 lb. f In embodiments, the crush strength of the reforming catalyst is between about 7.5 and about 15 lb. f In an embodiment, the catalyst is an extrudate. In an embodiment, the catalyst is cylindrical. In an embodiment, the catalyst is spherical. In an embodiment, the catalyst comprises a spherical In embodiments, the catalyst comprises a catalyst in the form of cylindrical and / or spherical extrudates. Catalyst. The length dimension of the catalyst (for cylindrical extrudates) may range from about 0.1 inches (in) to about 0.21 inches, and the circumference (for spherical extrudates) may be from about 0.01 inches to about 0.50 inches, such as from about 0.05 inches to about 0.25 inches.

[0135] Aromatization operating conditions

[0136] Aromatization in the reforming reactor can be carried out under suitable operating conditions known to those skilled in the art. In embodiments, the operating temperature of the reactor is in the range of about 400°C to about 600°C, including about 450°C to about 550°C; the pressure is in the range of about 30 psig to about 100 psig, including about 50 psig to about 70 psig; the liquid hourly space velocity (LHSV) is about 1.0 h -1 About 4 hours -1 , including about 1.0h -1 to about 2.3h -1 capacity is in the range of about 4,000 to about 70,000 barrels per day (BPD); and the molar ratio of hydrogen to hydrocarbon in the feed is in the range of about 1.0 to about 5.0 mol:mol, such as a molar ratio of about 2.0 to about 4.0 mol:mol; or combinations thereof.

[0137] use Catalyst Retrofit CCR System

[0138] As described above, in embodiments, an existing CCR system is reused and / or modified to be used with an aromatization catalyst such as Catalyst) together. In an embodiment, the method of operating a continuous catalyst regeneration (CCR) system according to the present disclosure includes operating a CCR system to convert hydrocarbons in a hydrocarbon feed into aromatics, wherein the catalyst is continuously circulated in a flow loop within the CCR system, so that all catalysts are regenerated at least once a week; shutting down the CCR system to stop converting convertible hydrocarbons into aromatics; and replacing the existing catalyst in the CCR system with an alternative catalyst, the alternative catalyst comprising platinum, fluorine and chlorine on a silica-bound L zeolite carrier. In an embodiment, the method also includes starting the CCR to continue converting hydrocarbons in the hydrocarbon feed into aromatics, wherein the alternative catalyst is not continuously circulated in the flow loop within the CCR system. In an embodiment, during the process of converting hydrocarbons in the hydrocarbon feed into aromatics, the alternative catalyst is static in the CCR system, and the method is performed according to the first variation above, and the moving bed reactor system (i.e., the CCR system) is operated in a stationary or static mode. In an alternative embodiment, the method also includes starting the CCR to continue converting convertible hydrocarbons into aromatics, wherein the alternative catalyst is intermittently or continuously circulated in a flow loop within the CCR system, and the method is performed according to the second or third variation described above. In some such embodiments, the entire catalyst is regenerated no more than once per year. In some such embodiments, the entire catalyst passes through the reforming reactor stack within the CCR no more than once per year.

[0139] Features and potential benefits

[0140] The disclosure describes HYDROGEN(R) available from Chevron Phillips Chemical (The Woodlands, Texas). The CCR reactor device is used in the application of the technology, which is a modification or a new design. The process of operation of the catalyst stack reactor system differs from conventional CCR operation in a number of ways. According to embodiments of the present disclosure, an existing CCR can be reused as a reforming radial flow reactor operated as a stationary fixed bed, thereby utilizing a moving bed reactor system in a fixed bed process. Such operation can provide faster catalyst replacement during replacement compared to conventional fixed bed radial flow reactor systems.

[0141] According to embodiments of the present disclosure, an existing CCR is modified for use with the aromatization catalyst described herein, wherein the catalyst is slowly moved from the stacked reactor section to the regeneration and / or storage section (e.g., according to the second and third variations described herein). Ideally, the conversion from a CCR reformer to The system requires minimal equipment changes when used, as described herein. In an embodiment, the regeneration is modified to provide for the use of fluorine in the catalyst regeneration. In the low sulfur environment of the process, the interior of the reforming reactor is usually coated with tin MPT to prevent metal carburization. However, during conventional regeneration procedures, the presence of tin MPT may cause problems. As described herein, the advantage of using a CCR unit for aromatization catalyst regeneration can be the ability to use regeneration equipment that is not coated with tin MPT. This can advantageously promote efficient catalyst regeneration and lead to significant catalyst cost savings.

[0142] Compared to conventional CCR processes, the regeneration frequency time frame of the process disclosed herein is significantly different. According to embodiments of the present disclosure, since fresher catalyst is located in the first of a series of reforming reactors and spent catalyst is located in the last of the series, the CCR can be operated with an aromatization catalyst in a temperature-variable manner. If an existing CCR can be utilized, it can be used as Retrofitting of an existing CCR at a plant can provide substantial capital savings relative to new construction.

[0143] In conventional CCR processes, all catalysts are typically regenerated approximately once a week; according to the present disclosure, a CCR system can be regenerated on an aromatization catalyst (e.g., The aromatization catalyst can be operated with regeneration once a year or even less frequently. The slow movement of the aromatization catalyst through the stacked reactor system (according to the second and third variations provided herein) can help prevent / minimize the degradation of the catalyst into fines. Such methods can enable the CCR type reactor system to be used with catalysts having attrition characteristics that are generally considered too fine to be suitable for such uses. For example, in an embodiment, the aromatization catalyst is a silica-bound L zeolite. The reduced frequency of catalyst regeneration provided by the methods disclosed herein can enable such silica-bound catalysts to be used in processes (e.g., CCR processes) that are typically operated with tougher or more durable reforming catalysts. In an embodiment, the catalyst undergoes only 2-3 regenerations in 5 years.

[0144] As described herein, conventional fixed-bed radial flow aromatization reactor designs often result in underutilization of catalysts located closer to the center tube, wherein the catalysts located inside the fixed-bed radial flow reactors typically retain some activity when abandoned at the end of operation. Variant 2 and Variant 3 of the reforming method disclosed herein both provide for remixing and reshuffling of the catalyst when it is slowly moved from the first reforming reactor to the regenerator or storage device. Compared with conventional fixed-bed reactor processes, this can provide more thorough catalyst utilization (i.e., more completely and uniformly failed catalysts). Variant 2 and Variant 3 use the slow movement of the catalyst through at least one reactor stack, which also allows the aromatization catalyst to be replaced without shutting down the plant. This can provide significant turnover savings. Variant 2 and Variant 3 can also provide substantially stable performance and more predictable catalyst requirements for the operation of the #imgpt22# catalyst system, thereby facilitating operation.

[0145] As described herein, in embodiments, operation in which the reforming catalyst and the hydrocarbon feed flow in a countercurrent manner enables the hydrocarbon feed to first contact the most spent catalyst (e.g., a catalyst having a relatively low activity compared to the fresh catalyst, or in other words, a catalyst at or near a lower activity value of a catalyst activity gradient that progresses from a higher activity value to a lower activity value). The spent catalyst can be operated to catalyze the simplest reaction, and lower temperatures can be used in these reforming reactors, advantageously resulting in less cracking and higher selectivity. As the conversion rate of the hydrocarbon feed continues to increase, it will contact a fresher catalyst. In such embodiments, a downstream reactor that may contain the freshest catalyst can use a higher reaction temperature. This fresher catalyst can promote more difficult reactions more selectively with high selectivity. This countercurrent operation can also provide risk mitigation associated with process anomalies; sulfur or heavy components in the feed first contact the most spent catalyst that is closest to being removed from the system. Therefore, the spent catalyst can play a role in protecting the fresh catalyst. In addition, after an anomaly occurs, the deactivated catalyst can be easily removed without shutting down the plant or continuing to operate for a long time under poor catalyst performance. Due to the countercurrent catalyst movement, and positioning the most spent catalyst where the hydrocarbon feed enters, in embodiments, such operation can avoid the need for an SCA system (eg, one or more sulfur guard beds are not required). Other advantages discussed above can also be achieved using such countercurrent flow.

[0146] The specific embodiments disclosed above are merely illustrative, because the present disclosure can benefit from the teachings of this article and be modified and practiced in different but equivalent ways known to those skilled in the art. In addition, it is not intended to limit the details of the construction or design shown herein, unless otherwise described in the appended claims. Therefore, it is obvious that the specific illustrative embodiments disclosed above can be changed or modified, and all these changes are considered to be within the scope and spirit of the present disclosure. Alternative embodiments produced by combining, integrating and / or omitting the features of one or more embodiments are also within the scope of the present disclosure. Although the composition and method are described using the broader terms of "having", "including", "containing" or "including" various components or steps, the composition and method can also be "essentially composed of various components and steps" or "composed of various components and steps". The use of the term "optionally" with respect to any element of the claim means that the element is necessary, or alternatively, the element is not necessary, and both alternatives are within the scope of the claim. In addition, the terms in the claims have their ordinary, conventional meanings unless otherwise explicitly and clearly specified by the patentee. In addition, the indefinite article "one" or "an" used in the claims is defined herein as one or more of the elements it guides. If there is any conflict in the usage of a word or term in this specification and one or more patents or other documents, the definition consistent with this specification shall apply.

[0147] The numerical values ​​and ranges disclosed above can be changed by a certain amount. As long as a numerical range with a lower limit and an upper limit is disclosed, any numerical value and any range covered in the range are also specifically disclosed. Specifically, each value range disclosed herein (in the form of "from about a to about b" or equivalently "from about a to b" or equivalently "from about ab") should be understood to set forth each numerical value and range covered in a broader range of values. In the case where a numerical range or restriction is clearly stated, such a range or restriction is understood to include iterative ranges or restrictions of values ​​such as falling within the clearly stated range or restriction (for example, from about 1 to about 10 includes 2, 3, 4, etc.; greater than 0.10 includes 0.11, 0.12, 0.13, etc.). For example, whenever a lower limit R is disclosed, L and upper limit R U In particular, the following numerical values ​​within the range are specifically disclosed: R = R L +k*(R U -R L ), wherein k is a variable ranging from 1% to 100% in increments of 1%, i.e., k is 1%, 2%, 3%, 4%, 5%, ..., 50%, 51%, 52% ..., 95%, 96%, 97%, 98%, 99% or 100%. In addition, any numerical range defined by two R values ​​as defined above is also specifically disclosed.

[0148] Although certain embodiments of the present disclosure have been shown and described, those skilled in the art may modify them without departing from the teachings of the present disclosure. The embodiments described herein are exemplary only and are not intended to be limiting. Many variations and modifications of the invention disclosed herein are possible and within the scope of the present invention.

[0149] Once the above disclosure is fully understood, additional modifications, equivalents and substitutes will be apparent to those skilled in the art. It is intended that, where appropriate, the appended claims be interpreted to include all such modifications, equivalents and substitutes. Therefore, the scope of protection is not limited to the description set forth above, but is only limited to the appended claims, the scope of which includes all equivalents of the subject matter of the claims. Each claim is incorporated into the specification as an embodiment of the present disclosure. Therefore, the claims are further descriptions and are supplementary to the specific embodiments of the present disclosure. The disclosures of all patents, patent applications and publications cited herein are incorporated herein by reference in their entirety.

Claims

1. A reforming reactor system, comprising: a continuous catalyst regeneration (CCR) system comprising at least one reactor stack, wherein each reactor stack comprises at least two radial flow reactors, the radial flow reactors each comprising a reforming catalyst capable of catalyzing the conversion of hydrocarbons in a hydrocarbon feed to provide a reactor effluent comprising aromatic hydrocarbons; a regeneration reactor system connected to the at least one reactor stack via a spent catalyst transfer system and configured to regenerate the reforming catalyst; wherein the reforming reactor system is configured to move the reforming catalyst through the at least one reactor stack over a period of at least 180 days; and wherein the reforming catalyst comprises a Group VIII metal, a silica-bound L zeolite support and at least one halogen.

2. The reforming reactor system of claim 1, wherein the reforming catalyst comprises an extrudate characterized by a crush strength of less than about 15, 13, or 10 lb. f .

3. The reformer reactor system of claim 1, wherein the at least one halogen comprises fluorine, and wherein the regeneration reactor system is operable to refluorinate the reformer catalyst after it has expired.

4. The reforming reactor system of claim 1, wherein at least one surface or component of the regeneration reactor system is not coated with Tin MPT.

5. The reforming reactor system of claim 1, wherein the CCR system is configured for one or more of the following: initially introducing a reforming catalyst into at least one topmost reactor via a purge vessel and a reduction reactor, wherein the at least one topmost reactor is a topmost reactor in one of the at least one reactor stack; introducing a fresh hydrocarbon feed into the topmost reactor such that the reforming catalyst and the hydrocarbon feed flow co-currently through the at least one reactor stack; or Fresh hydrocarbon feed is introduced into the bottommost radial flow reactor of one of the at least one reactor stack so that the reforming catalyst and the hydrocarbon feed flow countercurrently therethrough, wherein the bottommost radial flow reactor of each of the at least one reactor stack acts as a guard bed to protect downstream reactors in the at least one reactor stack containing a more active catalyst from damage by at least one undesirable compound selected from sulfur, heavies, nitrogen, or a combination thereof.

6. The reformer reactor system of claim 1, wherein the reformer reactor system does not include a sulfur converter adsorber (SCA) upstream of the CCR system.

7. A method of operating a reforming reactor system, the method comprising: operating a reactor of a stacked reactor system comprising at least one reactor stack, wherein each of the at least one reactor stack comprises at least two stacked radial flow reactors; each radial flow reactor contains a reforming catalyst capable of catalyzing the conversion of hydrocarbons in a hydrocarbon feed to provide a reactor effluent comprising aromatic hydrocarbons, the hydrocarbon feed being selected from convertible hydrocarbons having six or seven carbon atoms without internal quaternary carbons, and convertible hydrocarbons having six carbon atoms without two adjacent internal tertiary carbons, and wherein the reforming catalyst comprises a Group VIII metal, a silica-bound L-zeolite support, and at least one halogen; The stacked reactor system is operable to provide for movement of the reforming catalyst through the at least one reactor stack and via the catalyst transfer system to a regeneration system over a period of at least 180 days.

8. The method of claim 7, wherein operating the reactors of the stacked reactor system comprises operating the radial flow reactor as a stationary fixed bed, and wherein the reforming catalyst does not move during running operation.

9. The method of claim 7, further comprising: converting the convertible hydrocarbons in the hydrocarbon feed until the reforming catalyst is determined to be a spent reforming catalyst, and after the catalyst is determined to be spent; stopping the introduction of the hydrocarbon feed; purging the reactor until the reactor effluent contains less than about 200 ppm hydrocarbons; allowing the reactor to reach ambient temperature; removing the spent reforming catalyst within the radial flow reactor of each reactor stack via the bottommost radial flow reactor of each reactor stack or via the bottommost reactor of a final reactor stack using inter-stack transfer, wherein the catalyst flows downwardly through the at least one radial flow reactor stack for removal; as well as Fresh reforming catalyst is added to the top of the topmost radial flow reactor of each reactor stack or to the top of the topmost radial flow reactor of the first reactor stack using inter-stack transfer, wherein the fresh reforming catalyst flows downwardly through the at least one radial flow reactor stack.

10. The method of claim 7, wherein the reforming reactor system further comprises at least one purge chamber attached to the bottommost radial flow reactor of each reactor stack, or to the bottommost reactor of a final reactor stack, using an inter-stack transfer fluid, and wherein spent reforming catalyst is removed from the bottommost radial flow reactor via the purge chamber prior to removing the catalyst from the stacked reactor system.

11. A method as claimed in claim 7, wherein the stacked reactor system further comprises at least one purge chamber, wherein the purge chamber fluid is connected to the topmost radial flow reactor of each reactor stack or the topmost reactor of the first reactor stack, which is operable for inter-stack transfer; and wherein fresh reforming catalyst is added to the topmost radial flow reactor through the purge chamber.

12. A method as claimed in claim 7, wherein the catalyst transfer system connects at least one purge chamber to the top fluid of the regeneration system for transferring the reforming catalyst to the regeneration system through at least one purge chamber by inter-stack transfer, and the purge chamber is attached to the bottommost radial flow reactor of each of the at least one reactor stack or to the bottommost radial flow reactor of the final reactor stack of the at least one reactor stack.

13. The method of claim 7 further comprises regenerating the reforming catalyst via a regeneration process during circulation through the regeneration system, the regeneration process comprising decoking, chlorination, oxychlorination, fluorination, reduction or a combination thereof, and introducing the regenerated reforming catalyst into the topmost radial flow reactor of each of the at least one reactor stack or the topmost radial flow reactor of the first reactor stack by inter-stack transfer.

14. The method of claim 7, wherein the regeneration system is operable to provide movement of the reforming catalyst through a series of radial flow regeneration reactors, and wherein the reforming catalyst passes through the regeneration system and is returned to the stacked reactor system via a regenerated catalyst transfer system over a period of about 170 hours.

15. The method of claim 7, wherein the stacked reactor system further comprises a regenerator, and wherein the regenerator is used to store spent catalyst, and is capable of regenerating the spent catalyst stored in the regenerator when the amount of spent catalyst stored in the regenerator reaches a predetermined threshold amount.

16. The method of claim 7 further comprising loading the fresh reforming catalyst into a purge chamber and a reduction vessel before loading the fresh reforming catalyst into the topmost reactor of the at least one reactor stack, and reducing the fresh reforming catalyst before introducing the fresh reforming catalyst into the topmost reactor of the at least one reactor stack as a replacement catalyst.

17. The method of claim 7, wherein the stacked reactor system is configured for initially introducing reforming catalyst into a purge tank connected to a reduction vessel connected to a topmost radial flow reactor of one of the at least one reactor stack.

18. The method of claim 7, wherein the stacked reactor system is configured to: introducing a fresh hydrocarbon feed into the topmost radial flow reactor such that the reduced reforming catalyst and the hydrocarbon feed flow co-currently through the at least one reactor stack; or Fresh hydrocarbon feed is introduced into the bottom reactor of one of the at least one reactor stack such that reforming catalyst and hydrocarbon feed flow countercurrently through the at least one reactor stack.

19. The method of claim 18, wherein the operating temperature of the topmost radial flow reactor is lower than the operating temperature of radial flow reactors downstream of the topmost radial flow reactor.

20. The method of claim 7, wherein the bottom reactor of each of the at least one reactor stack operates at a lower temperature than the top reactor thereof, and the bottom reactor of each of the at least one reactor stack is capable of serving as a guard bed to protect a downstream reactor in the at least one reactor stack containing a more active catalyst from at least one undesirable compound comprising sulfur, heavies, nitrogen, or a combination thereof.

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