Chemical treatment with hydrogen containing supplemental fuel for catalyst treatment

Abstract

A method for processing a chemical stream includes contacting a feed stream with a catalyst in a reactor portion of a reactor system, the reactor system including the reactor portion and a catalyst treatment portion. The catalyst includes platinum, gallium, or both, and contacting the feed stream with the catalyst causes a reaction, the reaction forming an effluent stream. The method includes: separating the effluent stream from the catalyst; passing the catalyst to the catalyst treatment portion; and treating the catalyst in the catalyst treatment portion. Treating the catalyst includes: passing the catalyst to a combustor; combusting a supplemental fuel in the combustor to heat the catalyst; treating the heated catalyst with an oxygen-containing gas to produce a reactivated catalyst; and passing the reactivated catalyst from the catalyst treatment portion to the reactor portion. The supplemental fuel can include hydrogen in a molar ratio of at least 1:1 to another combustible fuel.

Description

[0001] This application is a divisional application of the invention patent application filed on June 26, 2019, with application number 201980037569.6 (international application number PCT / US2019 / 039209) and entitled "Chemical Processing Using Hydrogen-Containing Supplemental Fuel for Catalytic Treatment".

[0002] Cross-reference to related applications

[0003] This application claims the benefit of U.S. Provisional Patent Application Serial No. 62 / 694,193, filed July 5, 2018, which is incorporated herein by reference in its entirety. Technical Field

[0004] This disclosure generally relates to chemical processing systems and their operation, and more specifically, to processes comprising supplemental fuel streams for processing catalysts. Background Technology

[0005] Light olefins can be used as base materials to produce many types of goods and materials. For example, ethylene can be used to manufacture polyethylene, vinyl chloride, or ethylene oxide. These products can be used in product packaging, construction, textiles, and so on. Therefore, light olefins, such as ethylene, propylene, and butene, are industrially needed.

[0006] Depending on the given chemical feedstream (such as the product stream from crude oil refining operations), light olefins can be produced through various reaction processes. Many light olefins can be produced through a variety of catalytic processes, such as catalytic dehydrogenation, in which the feedstream is contacted with a fluidized catalyst that facilitates the conversion of the feedstream into light olefins. Summary of the Invention

[0007] Many reaction processes used to produce light olefins are endothermic and require heat input into the system to propagate the catalytic reaction. During catalyst regeneration, coke deposits on the catalyst may burn, but the heat provided by the burning may not be sufficient to propagate the endothermic reaction. Supplemental fuel can be introduced during catalyst regeneration to increase the heat input into the reaction system.

[0008] There is a continued need for improved processes for reactor systems used to process chemical streams to produce light olefins or other chemical products, processes that incorporate improved supplemental fuel sources for heating the catalyst. Many reactor systems for processing chemical streams to produce light olefins and other chemicals utilize relatively hot catalysts, such as those heated to temperatures above 350°C. The catalyst can be recycled through the fluidized reactor system, such as through the reactor section (in which the chemical product is produced) and through the catalyst treatment section (in which the catalyst is treated, such as, but not limited to, removing coke, heating the catalyst, reactivating the catalyst, other catalyst treatment operations, or combinations thereof).

[0009] In endothermic fluidized reactor systems, the reactor system may include a heat source to drive the process. For example, in a fluidized catalytic cracking (“FCC”) reaction, coke generated by the reaction and deposited on the catalyst can be burned in a burner in the catalyst treatment section to provide most of the heat to drive the reaction process. As another non-limiting example, in a fluidized catalytic dehydrogenation (FCDh) reaction, supplemental fuel can be added to the burner to provide additional heat for the endothermic reaction while burning a relatively small amount of coke generated by the dehydrogenation reaction. Due to the relatively low cost of methane and its energy efficiency at relatively high temperatures, such as the temperature of the catalyst during reactor system operation (e.g., above 650°C), supplemental fuel can contain a large amount of methane and / or other hydrocarbons. However, burning supplemental fuel that mainly contains methane and other hydrocarbons (e.g., greater than or equal to 50 mol% methane and other hydrocarbons) during catalyst treatment may result in reduced catalyst activity (e.g., catalysts containing platinum, gallium, or both).

[0010] Decreased catalyst activity can reduce the achievable conversion rate. In some fluidized reactor systems utilizing supplemental fuels primarily consisting of methane and other hydrocarbons, the productivity of the reactor system can be maintained by increasing the amount of catalyst in the reactor system or by increasing the amount of active metals (such as platinum, gallium, or both) in the catalyst. However, increasing the amount of active metals such as platinum, gallium, or both in the reactor system may increase the operating costs of the reactor system.

[0011] Therefore, there is a ongoing need for reactor systems and processes that increase chemical feed conversion rates by reducing catalyst deactivation. Specifically, there is a ongoing need for reactor systems and methods that incorporate the combustion of supplemental fuel, which reduces catalyst deactivation during combustion, thereby increasing catalyst activity. According to one or more embodiments, this disclosure relates to processes and reactor systems that include burning supplemental fuel having a relatively high concentration of hydrogen (e.g., a hydrogen-to-other combustible fuel molar ratio of at least 1:1) in a burner of the catalyst treatment section of the reactor system to heat the catalyst. Following combustion, the catalyst may be subjected to oxygen treatment, which involves exposing the catalyst to oxygen-containing gas for a duration sufficient to reactivate the catalyst.

[0012] Surprisingly and unexpectedly, under the same operating conditions (including the same post-combustion oxygen treatment), burning supplemental fuel with a relatively high concentration of hydrogen resulted in greater catalyst activity and increased reactor system conversion compared to the conventional method of burning supplemental fuel containing a relatively large amount of hydrocarbons (e.g., methane). Furthermore, burning supplemental fuel with a relatively high concentration of hydrogen resulted in a longer catalyst lifetime and enabled the achievement of the same target conversion with less bulk catalyst stock compared to the requirement for achieving the target conversion when the supplemental fuel was primarily hydrocarbons (e.g., >50 mol% hydrocarbons). In some embodiments, burning supplemental fuel with a high concentration of hydrogen allowed the reactor system to operate with less active metal on the catalyst (e.g., platinum, gallium, or both).

[0013] According to one or more aspects of this disclosure, a method for treating a chemical stream may include contacting a feed stream with a catalyst in a reactor section of a reactor system. The reactor system may include a reactor section and a catalyst treatment section, and the catalyst may comprise platinum, gallium, or both. Contacting the feed stream with the catalyst causes a reaction that forms an effluent stream comprising at least one product. The method may further include: separating at least a portion of the effluent stream from the catalyst; transferring the catalyst to the catalyst treatment section of the reactor system; and treating the catalyst in the catalyst treatment section of the reactor system. Treating the catalyst may include: transferring the catalyst to a burner in the catalyst treatment section; burning supplemental fuel in the burner in the presence of the catalyst to produce a heated catalyst; treating the heated catalyst with an oxygen-containing gas (oxygen treatment) to produce a reactivated catalyst; and transferring the reactivated catalyst from the catalyst treatment section to the reactor section. The supplemental fuel may comprise hydrogen and other combustible fuels, and the molar ratio of hydrogen to the other combustible fuel in the supplemental fuel is at least 1:1.

[0014] According to one or more other aspects of this disclosure, a method for dehydrogenating a hydrocarbon to produce one or more olefins may comprise contacting a hydrocarbon feed stream with a catalyst in a reactor section of a reactor system. The reactor system may include a reactor section and a catalyst treatment section, and the catalyst may comprise platinum, gallium, or both. Contacting the feed stream with the catalyst can induce a reaction that forms an effluent stream comprising at least one product. The method may further comprise: separating at least a portion of the effluent stream from the catalyst; transferring the catalyst to the catalyst treatment section of the reactor system; and treating the catalyst in the catalyst treatment section of the reactor system. Treating the catalyst may comprise: transferring the catalyst to a burner in the catalyst treatment section; introducing supplemental fuel into the burner; burning the supplemental fuel in the burner in the presence of the catalyst; subjecting the heated catalyst to oxygen treatment to produce a reactivated catalyst; and transferring the reactivated catalyst from the catalyst treatment section to the reactor section. The supplemental fuel stream may comprise hydrogen and at least one hydrocarbon, and the molar ratio of hydrogen to other combustible fuels in the supplemental fuel is at least 1:1.

[0015] It should be understood that both the foregoing summary and the following detailed description present embodiments of the present technology and are intended to provide an overview or framework for understanding the nature and features of the claimed technology. Drawings are included to provide a further understanding of the technology, and these drawings are incorporated in and form a part of this specification. The drawings illustrate various embodiments and, together with the description, serve to explain the principles and operation of the present technology. Furthermore, the drawings and description are intended to be illustrative only and are not intended to limit the scope of the claims in any way.

[0016] Further features and advantages of the techniques disclosed herein will be set forth in the detailed description below, and will be recognized in part by those skilled in the art from the description or by practice of the techniques as described herein (including the detailed description below, the claims and the drawings).

[0017] The present invention further relates to the following embodiments:

[0018] 1. A method for processing chemical streams, the method comprising:

[0019] The feed stream is brought into contact with the catalyst in the reactor section of the reactor system, wherein:

[0020] The reactor system includes a reactor section and a catalyst processing section;

[0021] The catalyst comprises platinum, gallium, or both; and

[0022] The process involves contacting the feed stream with the catalyst to initiate a reaction, the reaction forming an effluent stream comprising at least one product.

[0023] At least a portion of the effluent stream is separated from the catalyst;

[0024] The catalyst is transferred to the catalyst treatment section of the reactor system;

[0025] The catalyst is treated in the catalyst treatment section of the reactor system, wherein the catalyst treatment includes:

[0026] The catalyst is delivered to the burner of the catalyst processing section;

[0027] In the presence of the catalyst, supplemental fuel is burned in the burner to produce a heated catalyst, wherein the supplemental fuel comprises hydrogen and other combustible fuels, and the molar ratio of hydrogen to the other combustible fuels in the supplemental fuel is at least 1:1;

[0028] The heated catalyst is treated with oxygen-containing gas to produce a reactivated catalyst; and the reactivated catalyst is transferred from the catalyst treatment section to the reactor section.

[0029] 2. A method for dehydrogenating a hydrocarbon stream to produce one or more olefins, the method comprising:

[0030] The hydrocarbon feed stream is brought into contact with the catalyst in the reactor section of the reactor system, wherein:

[0031] The reactor system includes a reactor section and a catalyst processing section;

[0032] The catalyst comprises platinum, gallium, or both; and

[0033] The process involves contacting the feed stream with the catalyst to initiate a reaction, the reaction forming an effluent stream comprising one or more of the olefins.

[0034] At least a portion of the effluent stream is separated from the catalyst;

[0035] The catalyst is transferred to the catalyst treatment section of the reactor system;

[0036] The catalyst is treated in the catalyst treatment section of the reactor system, wherein the catalyst treatment includes:

[0037] The catalyst is delivered to the burner of the catalyst processing section;

[0038] Supplemental fuel is introduced into the burner, the supplemental fuel stream comprising hydrogen and at least one hydrocarbon, and the molar ratio of hydrogen to other combustible fuel in the supplemental fuel is at least 1:1;

[0039] The supplemental fuel is burned in the burner in the presence of the catalyst;

[0040] To produce a reactivated catalyst by subjecting a heated catalyst to oxygen treatment; and

[0041] The reactivated catalyst is transferred from the catalyst treatment section to the reactor section.

[0042] 3. The method according to any one of the preceding items, wherein the supplementary fuel further comprises at least one hydrocarbon.

[0043] 4. The method according to claim 3, wherein the at least one hydrocarbon is selected from methane, ethane, propane, n-butane, isobutane, ethylene, propylene, 1-butene, 2-butene, isobutene, pentene, benzene, toluene, xylene, natural gas, or combinations thereof.

[0044] 5. The method according to claim 3, wherein the at least one hydrocarbon comprises methane.

[0045] 6. The method according to any one of the preceding items, wherein the molar ratio of hydrogen to other combustible fuel in the supplementary fuel is from 1:1 to 99:1.

[0046] 7. The method according to any one of the preceding items, wherein treating the heated catalyst with the oxygen-containing gas comprises exposing the heated catalyst to the oxygen-containing gas for a period of time greater than 2 minutes.

[0047] 8. The method according to any one of the preceding items, further comprising passing a hydrogen-containing waste gas stream from a hydrocarbon processing system to the burner, wherein at least a portion of the supplemental fuel stream introduced into the burner comprises the hydrogen-containing waste gas stream.

[0048] 9. The method according to item 8, further comprising: increasing the concentration of hydrogen in the hydrogen-containing waste gas stream.

[0049] 10. The method according to any one of the preceding items, wherein the supplemental fuel comprises at least a portion of the exhaust gas stream from a light hydrocarbon cracking process or a dehydrogenation process.

[0050] 11. The method according to any one of the preceding items, further comprising:

[0051] The effluent stream is separated into a product stream and a waste gas stream; and

[0052] At least a portion of the exhaust gas stream is transferred to the catalyst treatment section, wherein the supplemental fuel comprises the at least a portion of the exhaust gas stream.

[0053] 12. The method according to any one of the preceding items, wherein the catalyst comprises platinum, gallium and optionally an alkali metal or alkaline earth metal supported on a support, wherein the support is selected from one or more of silica, alumina, alumina-containing silica, TiO2, ZrO2 or combinations thereof.

[0054] 13. The method according to claim 1, wherein the reactor system comprises a dehydrogenation reaction system.

[0055] 14. The method according to any one of the preceding items, wherein the product in the effluent stream comprises at least one light olefin selected from ethylene, propylene or butene.

[0056] 15. The method according to any one of the preceding items, further comprising operating the burner at a temperature of 650°C to 850°C. Attached Figure Description

[0057] The following detailed description of specific embodiments of the present disclosure will be best understood when read in conjunction with the following accompanying drawings, wherein similar structures are indicated by similar reference numerals, and in the drawings:

[0058] Figure 1 A reactor system according to one or more embodiments described herein is schematically depicted;

[0059] Figure 2 A flow diagram of a reactor system according to one or more embodiments described herein is schematically depicted;

[0060] Figure 3 Another reactor system flow diagram according to one or more embodiments described herein is schematically depicted;

[0061] Figure 4 A schematic diagram of yet another reactor system flow according to one or more embodiments described herein is depicted.

[0062] Figure 5 A schematic diagram illustrates the variation of propane conversion (y-axis) of a fluidized catalytic dehydrogenation reactor system according to one or more embodiments described herein with the hydrogen composition (x-axis) of the supplemental fuel introduced into the burner of the fluidized catalytic dehydrogenation reactor system; and

[0063] Figure 6 A schematic diagram depicts the propane conversion (left y-axis) and propylene selectivity (right y-axis) of a fluidized catalytic dehydrogenation reactor system according to one or more embodiments described herein as varying with the hydrogen composition (x-axis) of the supplemental fuel introduced into the burner of the reactor system.

[0064] It should be understood that the accompanying drawings are schematic in nature and do not include some components commonly used in reactor systems in the art, such as, but not limited to, temperature transmitters, pressure transmitters, flow meters, pumps, valves, etc. These components are known to be within the spirit and scope of the disclosed embodiments of the invention. However, operating components, such as those described herein, may be added to the embodiments described in this disclosure.

[0065] Reference will now be made in more detail to the various embodiments, some of which are illustrated in the accompanying drawings. Where possible, the same reference numerals will be used throughout these drawings to refer to the same or similar parts. Detailed Implementation

[0066] Several embodiments of this disclosure are discussed in the following detailed description. One or more embodiments of this disclosure relate to a method for treating a chemical stream by heating a catalyst with supplemental fuel in a reactor system. Specifically, one or more embodiments of this disclosure relate to a method for treating a chemical stream in which supplemental fuel containing hydrogen is burned in a catalyst treatment section of the reactor system to heat the catalyst. For example, in some embodiments, the method for treating the chemical stream may include contacting a feed stream with a catalyst in a reactor section of a reactor system, the reactor system including a reactor section and a catalyst treatment section. The catalyst may contain platinum, gallium, or both. Contacting the feed stream with the catalyst can cause a reaction that forms an effluent stream containing at least one product, such as an olefin product. The method may include: separating at least a portion of the effluent stream from the catalyst; and transferring the catalyst to the catalyst treatment section of the reactor system. The method may further include treating the catalyst in the catalyst treatment section. Treating the catalyst may include: transferring the catalyst to a burner in the catalyst treatment section; and burning supplemental fuel containing a high concentration of hydrogen (the molar ratio of hydrogen to other combustible fuel is at least 1:1) in the burner. Combustion of supplemental fuel containing a relatively high concentration of hydrogen can increase the temperature of the catalyst to produce a heated catalyst. Processing the catalyst may further include treating the heated catalyst with oxygen-containing gas to produce a reactivated catalyst. The reactivated catalyst can be returned to the reactor section of the reactor system.

[0067] It has been found that burning supplemental fuel containing a relatively high concentration of hydrogen (e.g., a hydrogen-to-other combustible fuel molar ratio of at least 1:1) to heat the catalyst during catalytic treatment increases reactant conversion in the reactor system compared to burning supplemental fuel composed primarily of methane or other hydrocarbons. This high activity can increase catalyst lifetime and unit capacity in the reactor system. Higher catalyst activity also allows the reactor system to operate with less active metal (such as platinum, gallium, or both) in the reactor system (e.g., less bulk catalyst stock or less active metal in the catalyst).

[0068] As used herein, the term "fluidized reactor system" refers to a reactor system in which one or more reactants are contacted with a catalyst in a fluidized manner (e.g., bubbling, slugging, turbulent, rapid fluidization, pneumatic conveying, or combinations thereof) in different portions of the system. For example, in a fluidized reactor system, a feed stream containing one or more reactants can be contacted with a circulating catalyst at operating temperatures to carry out a continuous reaction to produce a product stream.

[0069] As used herein, "continuous reaction" can refer to a chemical reaction in which reactants, catalysts, or combinations thereof are fed and products are continuously withdrawn from a reactor or reaction zone under steady-state conditions over a period of time, defined by the reaction starting at the beginning of the time period and stopping at the end of the time period. Therefore, the operation of the reactor system described herein can include reaction initiation, continuous reaction, and reaction termination.

[0070] As used herein, “deactivated catalyst” can refer to a catalyst that has reduced catalytic activity due to the accumulation of coke and / or the loss of catalyst active sites.

[0071] As used herein, “catalytic activity” or “catalytic activity” can refer to the degree to which a catalyst can catalyze a reaction in a reactor system.

[0072] As used herein, “catalyst treatment” can refer to the preparation of a catalyst for reintroduction into a reactor section of a reactor system and can include removing coke from the catalyst, heating the catalyst, reactivating the catalyst, stripping one or more gases from the catalyst, other treatment operations, or any combination thereof.

[0073] As used herein, “treated catalyst” can refer to a catalyst that has already been treated in the catalyst treatment section of the reactor system.

[0074] As used herein, "catalyst reactivation" or "reactivating a catalyst" can refer to treating a deactivated catalyst to restore at least some of its activity, thereby producing a reactivated catalyst. A deactivated catalyst can be reactivated by, but is not limited to, restoring catalyst acidity, oxidizing the catalyst, other reactivation processes, or combinations thereof. In some embodiments, catalyst reactivation may involve treating the catalyst with oxygen-containing gas for a period of time greater than 2 minutes.

[0075] As used herein, “supplementary fuel” can refer to any fuel source introduced into the catalyst treatment section of a reactor system to facilitate the removal of coke from the catalyst and / or to heat the catalyst. Supplementary fuel does not contain coke deposited on the catalyst.

[0076] As discussed earlier herein, the methods and processes disclosed herein can be used to carry out reactions in reactor systems for processing one or more chemical streams, according to one or more embodiments. In a non-limiting example, the reactor systems disclosed herein can be used to produce light olefins from a hydrocarbon feed stream through a continuous reaction. For example, in some embodiments, light olefins can be produced by dehydrogenation of a hydrocarbon feed stream in the presence of a catalyst comprising platinum, gallium, or both in a fluidized catalytic dehydrogenation (FCDh) reactor system. While processes and methods for processing chemical streams in reactor systems are described herein in the context of hydrocarbon treatment to form light olefins via fluidized catalytic dehydrogenation, it should be understood that the processes and methods disclosed herein can be used with any reactor system that includes a catalyst having an active metal (such as platinum, gallium, other active metals, or combinations thereof) and includes heating the catalyst by combustion of supplemental fuel. Thus, the currently described methods and processes for processing chemical streams in reactor systems should not be limited to reactor systems designed for producing light olefins or alkyl aromatics via fluidized catalytic dehydrogenation (e.g., Figure 1 An example of a reactor system in [the context of a reactor system].

[0077] Reactor systems and methods for processing chemical streams will now be discussed in further detail. The chemical stream being processed can be referred to as the feed stream, which is treated by a reaction to form a product stream. The feed stream may include a composition, and depending on the feed stream composition, the contents of the feed stream can be converted into a product stream that may contain light olefins or other chemical products using a suitable catalyst. For example, the feed stream for an FCDh reactor system may include at least one of propane, n-butane, isobutane, ethane, or ethylbenzene. In the FCDh system, the feed stream can be converted into light olefins or other products by dehydrogenation in the presence of a dehydrogenation catalyst.

[0078] In some embodiments, the catalyst used for dehydrogenation in an FCDh reactor system may comprise a catalyst including platinum, gallium, or both. In some embodiments, the catalyst may further comprise one or more other noble metals from Groups 9 and 10 of the IUPAC periodic table. For example, in some embodiments, the catalyst may comprise one or more noble metals selected from palladium (Pd), rhenium (Rh), iridium (Ir), or combinations thereof. In some embodiments, the catalyst may also comprise one or more metals selected from indium (In), germanium (Ge), or combinations thereof. The catalyst may also comprise a promoter metal, such as an alkali metal. In some embodiments, the promoter metal may be potassium. The metal of the catalyst may be supported on a support. The support may comprise one or more inorganic bulk metal oxides, such as silica, alumina, alumina-containing silica, zirconium oxide (ZrO2), titanium dioxide (TiO2), other metal oxides, or combinations of metal oxides. In some embodiments, the support may comprise a microporous material, such as ZSM-5 zeolite. Catalytic metals such as platinum, gallium, potassium, and / or other catalytically active metals may be supported on the surface of the support or incorporated into the support. In some embodiments, the catalyst may comprise platinum, gallium, and optionally potassium supported on an alumina-containing silica support.

[0079] Now for reference Figure 1 An example reactor system 102 is schematically depicted. Reactor system 102 typically includes a reactor section 200 and a catalyst processing section 300. As described herein... Figure 1 In the context of this document, reactor section 200 refers to the portion of reactor system 102 where the main process reactions occur. For example, reactor system 102 may be an FCDh system in which the feed stream is dehydrogenated in reactor section 200 of reactor system 102 in the presence of a dehydrogenation catalyst. Reactor section 200 includes reactor 202, which may include a downstream reactor section 230, an upstream reactor section 250, and a catalyst separation section 210 for separating the catalyst from the chemical products formed in reactor 202.

[0080] Similarly, as used in this article, Figure 1The catalyst treatment section 300 of the system generally refers to the section of reactor system 102 that processes the catalyst in some way (e.g., decoking, heating, reactivating, other processing operations, or combinations thereof). In some embodiments, the catalyst treatment section 300 may include a burner 350, a riser 330, a catalyst separation section 310, and an oxygen treatment section 370. The burner 350 of the catalyst treatment section 300 may include one or more lower burner inlet ports 352 and may be in fluid communication with the riser 330. The burner 350 may be in fluid communication with the catalyst separation section 210 via a riser 426, which may supply deactivated catalyst from reactor section 200 to the catalyst treatment section 300 for catalyst treatment (e.g., coke removal, heating, reactivation, etc.). The oxygen treatment section 370 may be in fluid communication with the upstream reactor section 250 (e.g., via a riser 424 and the delivery riser 430), which may supply treated catalyst from the catalyst treatment section 300 back to the reactor section 200. The burner 350 may include a lower burner inlet port 352, at which an air inlet 428 is connected. The air inlet 428 may supply air or other reactive gases, such as oxygen-containing gases, to the burner 350. Air and / or other reactive gases may be introduced into the burner 350 to assist in the combustion of supplementary fuel. The burner 350 may also include a supplementary fuel inlet 354. The supplementary fuel inlet 354 may supply supplementary fuel stream 356 to the burner 350. The supplementary fuel stream 356 may contain supplementary fuel. The oxygen treatment zone 370 may include an oxygen-containing gas inlet 372, which may supply oxygen-containing gas to the oxygen treatment zone 370 for oxygen treatment of the catalyst.

[0081] refer to Figure 1This section describes the general operation of reactor system 102 in a continuous reaction. During operation of reactor section 200 of reactor system 102, a feed stream may enter a conveying riser 430, and a product stream may exit reactor system 102 through conduit 420. According to one or more embodiments, reactor system 102 may be operated by feeding a chemical feed (e.g., in the feed stream) and a fluidized catalyst into an upstream reactor section 250. The chemical feed may contact the catalyst in the upstream reactor section 250 and may each flow upward through a downstream reactor section 230 to produce a chemical product. The chemical product and catalyst may be conveyed away from downstream reactor section 230 to a separation device 220 in catalyst separation section 210. The catalyst and chemical product may be separated in separation device 220. The chemical product may then be conveyed out of catalyst separation section 210. For example, the separated vapor may be removed from reactor system 102 through conduit 420 at gas outlet port 216 of catalyst separation section 210. According to one or more embodiments, the separation device 220 may be a cyclone separation system, which may include two or more cyclone separation stages.

[0082] According to some embodiments, after separation from vapor in the separation unit 220, the catalyst can typically be moved through the stripper 224 to the reactor catalyst outlet port 222, where it can be transferred via riser 426 outside the reactor section 200 and into the catalyst processing section 300. Optionally, the catalyst can also be transferred directly back to the upstream reactor section 250 via riser 422. In some embodiments, the recycled catalyst from the stripper 224 can be premixed with the treated catalyst from the catalyst processing section 300 in the delivery riser 430.

[0083] The separated catalyst can be transferred from catalyst separation section 210 to burner 350 of catalyst processing section 300. The catalyst can be processed in catalyst processing section 300 to remove coke, heat the catalyst, reactivate the catalyst, perform other catalyst treatments, or any combination thereof. As previously discussed, processing the catalyst in catalyst processing section 300 can include removing coke from the catalyst, increasing the temperature of the catalyst by combustion of a fuel source, reactivating the catalyst, stripping one or more components from the catalyst, other processing operations, or combinations thereof. In some embodiments, processing the catalyst in processing section 300 can include burning a fuel source in the burner 350 in the presence of the catalyst to remove coke and / or heating the catalyst to produce a heated catalyst. The heated catalyst can be separated from the combustion gases in catalyst separation section 310. In some embodiments, the heated catalyst can then be reactivated by oxygen treatment. Oxygen treatment can include exposing the catalyst to an oxygen-containing gas for a period of time sufficient to reactivate the catalyst.

[0084] In some embodiments, the combustion fuel source may include coke or other contaminants deposited on the catalyst in the reactor section 200 of the reactor system 102. In some reaction systems, the catalyst may be coked after the reaction in the reactor section 200, and the coke may be removed from the catalyst by a combustion reaction in the burner 350. For example, an oxidant (such as air) may be fed into the burner 350 through air inlet 428.

[0085] However, as previously discussed, in some reaction systems, coke and other contaminants deposited on the catalyst may not be sufficient to heat the catalyst to a temperature adequate for an endothermic reaction in reactor section 200. Therefore, the combustion fuel source may further include supplemental fuel. The supplemental fuel may be part of a supplemental fuel stream 356, which may be introduced into the burner 350 through a supplemental fuel inlet 354. For example, supplemental fuel stream 356 may be injected into the burner 350 through supplemental fuel inlet 354, and the supplemental fuel may be burned to heat the catalyst to a temperature adequate for an endothermic reaction in reactor section 200 and to provide other heat requirements throughout the reactor system 102. In some embodiments, no coke is formed on the catalyst, such that all heat required to raise the catalyst temperature is provided by the supplemental fuel. In some embodiments, a reactive gas, such as an oxygen-containing gas (e.g., air) or other oxidant, may be introduced into the burner 350, for example, through a lower burner inlet port 352, and may react with the supplemental fuel in supplemental fuel stream 356 to promote combustion of the supplemental fuel to heat the catalyst, thereby producing a heated catalyst. As used herein, the term "heated catalyst" refers to a catalyst heated by the combustion of supplemental fuel stream 356, the temperature of which is higher than the temperature of the catalyst transferred from catalyst separation section 210 to catalyst processing section 300 of reactor system 102.

[0086] refer to Figure 1 The treated catalyst can be passed from the burner 350 and through the riser 330 to the riser terminal separator 378, where the gaseous and solid components from the riser 330 can be at least partially separated. Vapor and residual solids can be conveyed to a secondary separation unit 320 in the catalyst separation section 310, where the remaining treated catalyst is separated from gases from the catalyst treatment (e.g., gases emitted from burning coke and supplemental fuel). In some embodiments, the secondary separation unit 320 may comprise one or more cyclone separation units, which may be arranged in series or in pairs of cyclones. Combustion gases from burning coke and / or supplemental fuel during catalyst treatment, or other gases introduced into the catalyst during catalyst treatment, can be removed from the catalyst treatment section 300 via the combustion gas outlet 432.

[0087] As previously discussed, treating the catalyst in the catalyst treatment section 300 of reactor system 102 may include reactivating the catalyst. Combustion of make-up fuel in the presence of the catalyst to heat the catalyst can further deactivate it. Therefore, in some embodiments, the catalyst can be reactivated by conditioning it with oxygen treatment. Oxygen treatment can be performed after make-up fuel combustion to heat the catalyst to reactivate it. Oxygen treatment may involve treating the heated catalyst with oxygen-containing gas for a period of at least two minutes, which can reactivate the catalyst to produce a reactivated catalyst. Based on the total molar flow rate of the oxygen-containing gas, the oxygen-containing gas may contain an oxygen content of 5 mol% to 100 mol%. In some embodiments, the catalyst can be reactivated by conditioning it with oxygen treatment. Oxygen treatment of the catalyst may involve maintaining the catalyst at a temperature of at least 660°C while exposing the catalyst to a flow of oxygen-containing gas for a period of more than two minutes and sufficient to produce a reactivated catalyst with a catalytic activity greater than that of the heated catalyst after being heated by make-up fuel combustion.

[0088] refer to Figure 1 The heated catalyst can be treated with oxygen-containing gas in the oxygen treatment zone 370. In some embodiments, the oxygen treatment zone 370 may be downstream of the catalyst separation zone 310 of the catalyst treatment section 300, such that the heated catalyst is separated from the combustion gases before being exposed to oxygen-containing gas during oxygen treatment. In some embodiments, the oxygen treatment zone 370 may include a fluid-solid contact device. The fluid-solid contact device may include a baffle or grid structure to facilitate contact between the heated catalyst and the oxygen-containing gas. Examples of fluid-solid contact devices are described in further detail in U.S. Patent Nos. 9,827,543 and 9,815,040, both of which are incorporated herein by reference in their entirety.

[0089] In some embodiments, treating the catalyst in the catalyst treatment section 300 of reactor system 102 may further comprise an oxygen-containing reactivated catalyst by stripping molecular oxygen trapped within or between catalyst particles and physically adsorbed oxygen desorbable at a temperature of at least 660°C. The stripping step may comprise maintaining the oxygen-containing reactivated catalyst at a temperature of at least 660°C and exposing the oxygen-containing reactivated catalyst to a stripping gas substantially free of molecular oxygen and combustible fuel for a period of time to remove molecular oxygen from between particles and physically adsorbed oxygen desorbable at a temperature of at least 660°C. Further description of these catalyst reactivation processes is disclosed in U.S. Patent No. 9,834,496, which is incorporated herein by reference in its entirety.

[0090] After catalyst treatment, the treated catalyst can be transferred back to reactor section 200 from catalyst treatment section 300 via riser 424. For example, in some embodiments, the treated catalyst can be transferred from oxygen treatment zone 370 of catalyst treatment section 300 to upstream reactor section 250 via riser 424 and conveying riser 430, wherein the treated catalyst can be further used in catalytic reactions. Thus, in operation, the catalyst can be circulated between reactor section 200 and catalyst treatment section 300. Generally, the treated chemical stream, comprising feed and product streams, can be gaseous, and the catalyst can be fluidized particulate solid.

[0091] Refer again Figure 1 According to one or more embodiments, treating the catalyst in the catalyst treatment section 300 may include: transferring the catalyst from the reactor section 200 of the reactor system 102 to the burner 350 of the catalyst treatment section 300; burning supplemental fuel in the burner 350 to heat the catalyst; subjecting the heated catalyst to oxygen treatment in the oxygen treatment zone 370 to produce a reactivated catalyst; and transferring the reactivated catalyst from the catalyst treatment section 300 back to the reactor section 200. The combustion of supplemental fuel and / or coke in the catalyst treatment section 300 may remove coke or other contaminants deposited on the catalyst, increase the temperature of the catalyst to the operating temperature range of the reactor section 200, or both. For example, in some embodiments, the combustion of supplemental fuel in the burner 350 may increase the temperature of the catalyst to produce a heated catalyst. In some embodiments, coke may not form on the catalyst during the reaction, and the supplemental fuel may provide all the heat in the burner to raise the temperature of the catalyst to produce a heated catalyst.

[0092] In some embodiments, the supplemental fuel may comprise hydrogen and other combustible fuels. The molar ratio of hydrogen to other combustible fuels in the supplemental fuel may be at least 1:1. For example, in some embodiments, the molar ratio of hydrogen to other combustible fuels in the supplemental fuel may be greater than or equal to 7:3, greater than or equal to 4:1, or even greater than or equal to 9:1. In some embodiments, the molar ratio of hydrogen to other combustible fuels in the supplemental fuel may be 1:1 to 999:1, 1:1 to 99:1, 1:1 to 49:1, 1:1 to 19:1, 1:1 to 9:1, 7:3 to 999:1, 7:3 to 99:1, 7:3 to 49:1, 7:3 to 19:1, 7:3 to 9:1, 4:1 to 999:1, 4:1 to 49:1, 4:1 to 19:1, or 4:1 to 9:1.

[0093] In some embodiments, based on the total molar amount of combustible components in the supplemental fuel, the supplemental fuel may contain greater than or equal to 70 mol% hydrogen, such as greater than or equal to 75 mol%, greater than or equal to 80 mol%, greater than or equal to 85 mol%, or greater than or equal to 90 mol% hydrogen. The combustible components may include hydrogen, hydrocarbons, and other combustible fuels or any other components subject to combustion at temperatures within the operating range of burner 350, but excluding components such as inert gases (e.g., nitrogen, argon, etc.) and other components that do not burn at temperatures within the operating range of burner 350. For example, in some embodiments, based on the total molar amount of combustible components in the supplemental fuel, the supplemental fuel may contain 70 mol% to 100 mol%, 70 mol% to 99 mol%, 70 mol% to 95 mol%, 70 mol% to 90 mol%, 70 mol% to 85 mol%, 75 mol% to 100 mol%, 75 mol% to 99 mol%, 75 mol% to 95 mol%, 75 mol% to 90 mol%, 75 mol% to 85 mol%, 80 mol% to 100 mol%, 80 mol% to 99 mol%, 80 mol% to 95 mol%, 80 mol% to 90 mol%, 85 mol% to 100 mol%, 85 mol% to 99 mol%, 85 mol% to 95 mol%, or 90 mol% to 100 mol% of hydrogen. The proportion of hydrogen in the supplemental fuel may also be expressed as a weight percentage (wt.%). For example, in some embodiments, the supplemental fuel may contain 20 wt.% or more, 25 wt.% or more, 30 wt.% or more, 40 wt.% or more, or 50 wt.% or more hydrogen, based on the total mass of the combustible components in the supplemental fuel. For example, in some embodiments, the supplementary fuel may contain 20 wt.% to 100 wt.%, 20 wt.% to 99 wt.%, 20 wt.% to 95 wt.%, 25 wt.% to 100 wt.%, 25 wt.% to 99 wt.%, 25 wt.% to 95 wt.%, 30 wt.% to 100 wt.%, 30 wt.% to 99 wt.%, 30 wt.% to 95 wt.%, 40 wt.% to 100 wt.%, 40 wt.% to 99 wt.%, 40 wt.% to 95 wt.%, 50 wt.% to 100 wt.%, or 50 wt.% to 99 wt.% of hydrogen, based on the total mass of the combustible components in the supplementary fuel.

[0094] Surprisingly, it was found that heating the catalyst with a supplemental fuel having a relatively high concentration of hydrogen (e.g., a hydrogen-to-other-fuel molar ratio of at least 1:1) can improve the conversion rate of the reactor system compared to reactivating the catalyst with a supplemental fuel consisting mainly of methane and other hydrocarbons (>50 mol% methane and / or other hydrocarbons). Reactivating the catalyst by incorporating a relatively high concentration of hydrogen into the supplemental fuel and combining it with oxygen treatment can result in a more catalytically active reactivated catalyst compared to heating the catalyst by burning a supplemental fuel consisting mainly of methane and other hydrocarbons and combining it with oxygen treatment. As previously discussed, burning a supplemental fuel containing a relatively high concentration of hydrogen to heat the catalyst and combining it with oxygen treatment can increase the catalyst lifetime in reactor system 102. Furthermore, burning a supplemental fuel with a relatively high concentration of hydrogen and combining it with oxygen treatment can also increase the capacity of reactor system 102, for example, by increasing the conversion rate of a specific catalyst load or reducing the catalyst load required to achieve a target conversion rate, compared to burning a supplemental fuel with a high hydrocarbon concentration (>50 mol% hydrocarbons) to heat the catalyst. For example, in reactor system 102 that uses a catalyst including platinum, gallium, or both to dehydrogenate propane to produce propylene, operating reactor system 102 using supplemental fuel (with a molar ratio of hydrogen to other combustible fuel of at least 1:1) can produce the same conversion performance with less active metal (e.g., platinum, gallium, or both) compared to operating reactor systems using supplemental fuel that is primarily methane and other hydrocarbons (i.e., >50 mol% hydrocarbons). Operating the reactor system with less active metal (e.g., platinum, gallium, or both) can be achieved by operating the reactor system with reduced catalyst bulk stock or by reducing the amount of active metal in the catalyst (e.g., using a catalyst with less active metal applied to the catalyst or using an aged catalyst).

[0095] In some embodiments, the supplemental fuel may comprise other combustible fuels. Examples of other combustible fuels may comprise one or more hydrocarbons. The hydrocarbons may comprise hydrocarbons or mixtures of hydrocarbons that contribute energy value upon combustion. In some embodiments, the hydrocarbons may comprise one or more hydrocarbons that are gaseous at the burner operating temperature of 350°C (i.e., 650°C to 850°C), such as, but not limited to, alkanes, alkenes, aromatic hydrocarbons, or combinations thereof. Examples of alkanes that may be included as supplemental fuel may include, but are not limited to, methane, ethane, propane, butane, isobutane, pentane, other alkanes, or combinations thereof. Examples of olefins that may be included as supplemental fuel may include, but are not limited to, ethylene, propylene, 1-butene, 2-butene, isobutene, other olefins, or combinations thereof. Examples of aromatic hydrocarbons that may be included as supplemental fuel may include, but are not limited to, benzene, toluene, xylene, other aromatic hydrocarbons, or combinations thereof. In some embodiments, the hydrocarbons may comprise light hydrocarbon (i.e., C1-C4) fuel gases. In other embodiments, the hydrocarbons may comprise heavy hydrocarbon-based fuel oils (C1-C4 ... 5+ In some embodiments, the hydrocarbons in the supplemental fuel may include at least one of methane, ethane, propane, natural gas, other hydrocarbon fuels, or combinations thereof. In addition to hydrocarbons, other combustible fuels may also be included in the supplemental fuel.

[0096] In some embodiments, the supplemental fuel may contain less than 30 mol% hydrocarbons based on the total molar amount of combustible components in the supplemental fuel. For example, in some embodiments, the supplemental fuel may contain less than 25 mol%, less than 20 mol%, less than 15 mol%, or even less than 10 mol% hydrocarbons based on the total molar amount of combustible components in the supplemental fuel. Some hydrocarbon-based combustible fuels (e.g., methane and natural gas) have high calorific values ​​and are relatively inexpensive. Therefore, in some embodiments, hydrocarbon fuels (e.g., methane and natural gas) may be included in the supplemental fuel to reduce the operating costs of reactor system 102. In other embodiments, the hydrocarbons in the supplemental fuel may be provided by an exhaust gas stream, which originates from a hydrocarbon treatment system, and is delivered to burner 350 as at least a portion of the supplemental fuel stream 356. In some embodiments, the supplemental fuel stream 356 may contain other non-combustible components. In some embodiments, the supplemental fuel stream 356 may contain at least 10 mol% combustible components based on the total molar amount of the supplemental fuel. For example, based on the total moles of supplemental fuel stream 356, supplemental fuel stream 356 may contain at least 20 mol%, at least 30 mol%, at least 40 mol%, at least 50 mol%, at least 70 mol%, at least 80 mol%, or at least 90 mol% of combustible components.

[0097] As previously discussed, supplemental fuel stream 356 may comprise supplemental fuel including hydrogen and other combustible fuels. In some embodiments, supplemental fuel stream 356 may comprise a pure hydrogen stream comprising ≥99 mol% hydrogen (based on the total molar flow rate of the pure hydrogen stream). In some embodiments, supplemental fuel stream 356 may comprise exhaust gas streams from hydrocarbon processing equipment. Based on the total molar flow rate of combustible components in the exhaust gas stream, the exhaust gas stream from the hydrocarbon processing equipment / system may comprise ≥50 mol%, ≥60 mol%, ≥70 mol%, ≥80 mol%, or ≥90 mol% hydrogen. For example, in some embodiments, supplemental fuel stream 356 may comprise exhaust gas streams from FCDh reactor systems (such as, but not limited to, propane dehydrogenation processes) and / or exhaust gas streams from light hydrocarbon cracking processes. It should be understood that hydrogen-containing exhaust gas streams from other hydrocarbon processing systems may be included in supplemental fuel stream 356. In some embodiments, supplemental fuel stream 356 may consist of or substantially consist of exhaust gas streams from hydrocarbon processing systems. In other embodiments, supplemental fuel stream 356 may comprise an exhaust stream in combination with one or more other combustible fuel streams, including hydrogen, hydrocarbon components, other combustible fuels, or combinations thereof. In some embodiments, supplemental fuel stream 356 may comprise one or more inert components as a diluent. Examples of inert components may include inert gases (e.g., nitrogen and argon) or other components that do not burn at temperatures within the operating range of burner 350.

[0098] Now for reference Figure 2 This is a process flow diagram of fluidized catalytic dehydrogenation (FCDh) process 502 used to dehydrogenate hydrocarbons to produce olefins and other products (e.g., styrene from ethylbenzene). Figure 2 In the FCDh process 502, the exhaust gas stream 544 recovered from the FCDh process 502 can be passed to the burner 350 to provide at least a portion of the supplemental fuel stream 356. Figure 2 The FCDh process 502 described herein may include Figure 1 The reactor system 102 is depicted in the figure. The FCDh process 502 may include a reactor 202, a catalyst separation section 210, a burner 350, and an oxygen treatment section 370. The FCDh process 502 may further include a product separator 540 downstream of the catalyst separation section 210.

[0099] exist Figure 2During continuous operation of the FCDh process 502, a chemical feed 512 and a reactivated catalyst 532 from an oxygen treatment zone 370 can be introduced into reactor 202. Contact between the reactants in the chemical feed 512 and the reactivated catalyst 532 can convert a portion of the reactants in the chemical feed 512 into one or more reaction products (e.g., ethylene, propylene, styrene, etc.) and byproducts. Reactor effluent 514 can be transferred from reactor 202 to catalyst separation section 210. Reactor effluent 514 may contain at least catalyst, reaction products, and unreacted reactants from the chemical feed, but may also contain byproducts, intermediate compounds, impurities, carrier gas, or other components. Catalyst separation section 210 can separate reactor effluent 514 into a gaseous effluent stream 522 and a deactivated catalyst stream 524. The gaseous effluent stream 522 may contain at least reaction products and unreacted reaction gases. The deactivated catalyst stream 524 can be transferred to burner 350 for at least a portion of catalyst treatment in catalyst processing. In burner 350, supplemental fuel stream 356 can be burned in the presence of deactivated catalyst stream 524 to remove coke from the catalyst, heat the catalyst, or both. After combustion, the heated catalyst 531 can be separated from the combustion gases 534 and transferred to oxygen treatment zone 370. In oxygen treatment zone 370, the heated catalyst 531 can be treated with oxygen-containing gas 533 to produce reactivated catalyst 532. The reactivated catalyst 532 can then be transferred back to reactor 202.

[0100] Still referencing Figure 2The gaseous effluent stream 522 can be passed to a product separator 540, which can be used to separate the gaseous effluent stream 522 into at least one product stream 542 and at least one exhaust gas stream 544. Based on the total molar flow rate of the combustible components in the exhaust gas stream 544, the exhaust gas stream 544 recovered from the product separator 540 of the FCDh process 502 may contain at least 40 mol%, at least 70 mol%, at least 75 mol%, at least 80 mol%, at least 85 mol%, or even at least 90 mol% of hydrogen. The exhaust gas stream 544 may also contain methane, nitrogen, and / or other components. At least a portion of the exhaust gas stream 544 recovered from the product separator 540 can be passed to the burner 350 as at least a portion of the supplementary fuel stream 356. In some embodiments, the exhaust gas stream 544 may be combined with a secondary fuel stream 358 to produce the supplementary fuel stream 356. In some embodiments, secondary fuel stream 358 may be a hydrogen-containing stream with a higher hydrogen concentration than exhaust stream 544. In other embodiments, secondary fuel stream 358 may be a hydrocarbon stream comprising one or more hydrocarbons (e.g., methane or natural gas). In some embodiments, the flow rate of secondary fuel stream 358, the flow rate of exhaust stream 544, or both may be increased or decreased to change the composition (e.g., hydrogen concentration) of supplementary fuel stream 356.

[0101] Now for reference Figure 3The process flow diagram depicts the following embodiment, wherein cracker exhaust gas stream 628 from light hydrocarbon cracking process 602 can be passed to burner 350 of reactor system 102 as at least a portion of supplemental fuel stream 356. As previously discussed, reactor system 102 may include reactor 202, catalyst separation section 210, burner 350, and oxygen treatment zone 370. In continuous operation, chemical feed 104 and reactivated catalyst 112 from oxygen treatment zone 370 can be introduced into reactor 202, where contact between the reactivated catalyst 112 and reactants in chemical feed 104 can convert at least a portion of reactants in chemical feed 104 into one or more reaction products. Reactor effluent 106 can be passed from reactor 202 to catalyst separation section 210, where reactor effluent 106 can be separated into gaseous effluent stream 108 and deactivated catalyst stream 110. A gaseous effluent stream 108, which may contain at least one reaction product, can be passed to one or more downstream operations for further processing. A deactivated catalyst stream 110 can be passed to a combustor 350 for at least a portion of catalyst treatment. In the combustor 350, a supplemental fuel stream 356 can be burned in the presence of the deactivated catalyst stream 110 to remove coke from the catalyst, heat the catalyst, or both. After combustion, the heated catalyst 111 can be separated from the combustion gases 534 and passed from the combustor 350 to an oxygen treatment zone 370. In the oxygen treatment zone 370, the heated catalyst 111 can be treated with oxygen-containing gas 533 to produce a reactivated catalyst 112. The reactivated catalyst 112 can then be passed back to the reactor 202.

[0102] Still referencing Figure 3The light hydrocarbon cracking process 602 may include a light hydrocarbon cracking unit 610 and a light hydrocarbon processing section 620. During continuous operation of the light hydrocarbon cracking process 602, one or more light hydrocarbon streams 612 may be introduced into the light hydrocarbon cracking unit 610, where the light hydrocarbons in the hydrocarbon stream 612 are cracked to produce a cracker effluent 614 containing one or more reaction products. For example, in some embodiments, the light hydrocarbon cracking unit 610 may be a steam cracker, and the light hydrocarbon stream 612 may contain ethane and propane, which may be steam cracked in the steam cracker to produce at least ethylene. The cracker effluent 614 may be transferred to the light hydrocarbon processing section 620 of the light hydrocarbon cracking process 602. The light hydrocarbon processing section 620 may include multiple unit operations, such as, but not limited to, steam compression, separation, sulfur and carbon dioxide removal, drying, or other operations. The light hydrocarbon treatment section 620 can ultimately separate the cracker effluent 614 into multiple gaseous streams, such as, but not limited to, ethylene product stream 622, propylene product stream 624, propane stream 626, cracker exhaust gas stream 628, and other streams.

[0103] Based on the total molar flow rate of the combustible components in the cracker exhaust gas stream 628, the cracker exhaust gas stream 628 may contain at least 40 mol% hydrogen, such as 50 mol% to 90 mol% hydrogen. At least a portion of the cracker exhaust gas stream 628 may be passed to the burner 350 of the reactor system 102 to be included as part of the supplementary fuel stream 356. For example, in some embodiments, the cracker exhaust gas stream 628 may be passed directly to the burner 350 of the reactor system 102 as supplementary fuel stream 356, such that the supplementary fuel stream 356 consists of or is substantially composed of the cracker exhaust gas stream 628. In some embodiments, the cracker exhaust gas stream 628 may be combined with a secondary fuel stream 358 to produce the supplementary fuel stream 356. The secondary fuel stream 358 may be a hydrogen-containing stream with a higher hydrogen concentration than that of the cracker exhaust gas stream 628. Alternatively, in some embodiments, the secondary fuel stream 358 may be a hydrocarbon stream comprising one or more hydrocarbons. In some embodiments, the flow rate of the secondary fuel stream 358, the flow rate of the cracker exhaust gas stream 628, or both, can be increased or decreased to change the composition of the supplemental fuel stream 356 (e.g., hydrogen concentration).

[0104] In some embodiments, at least a portion of the cracker exhaust gas stream 628 may be combined with the exhaust gas stream from reactor system 102 (e.g., from...). Figure 2The exhaust gas stream 544 of the FCDh process 502 is combined to produce a supplementary fuel stream 356. The supplementary fuel stream 356 may comprise exhaust gas streams from other hydrocarbon processes. In some embodiments, the supplementary fuel stream 356 may comprise at least one of the following: exhaust gas from the FCDh process, cracker exhaust gas from a light hydrocarbon cracking unit, pure hydrogen stream, or a combination thereof.

[0105] In some embodiments, reactor system 102 and light hydrocarbon cracking process 602 can be integrated to combine the product streams into a single system. For example, in some embodiments, gaseous effluent stream 108 from reactor system 102 can be combined with cracker effluent 614 from light hydrocarbon cracking unit 610, and the combined effluent stream (not shown) can be transferred to light hydrocarbon processing section 620. Thus, in these embodiments, light hydrocarbon processing section 620 can separate the combined effluent stream (e.g., a combination of both gaseous effluent stream 108 and cracker effluent 614) into multiple gaseous streams, such as, but not limited to, ethylene product stream 622, propylene product stream 624, propane stream 626, cracker exhaust gas stream 628, and other streams. Specifically, in some embodiments, from FCDh process 502 ( Figure 2 ) gaseous effluent stream 522 ( Figure 2 ) can be combined with the cracker effluent 614 of the light hydrocarbon cracking process and can be transferred together with it to the light hydrocarbon treatment section 620 of the light hydrocarbon cracking process 602, such that the cracker exhaust stream 628 comprises the effluent from the light hydrocarbon cracking unit 610 and the FCDh process 502 ( Figure 2 The waste gas produced.

[0106] refer to Figure 4 In some embodiments, the cracker exhaust gas stream 628 may be passed to a separator unit 630, such as a turboexpander or other separation unit. The separator unit 630 may be used to separate the cracker exhaust gas stream 628 into a hydrogen-rich stream 362 and a hydrocarbon-rich stream 360. The hydrogen-rich stream 362 may be passed from the separator unit 630 to the burner 350 of the reactor system 102 as at least a portion of the supplementary fuel stream 356. The supplementary fuel stream 356 may include the hydrogen-rich stream 362 from the separator unit 630. Exhaust gas streams from other hydrocarbon processing systems (e.g., from...) Figure 2 The exhaust gas stream 544 of the FCDh process 502 can also be passed to a separator unit 630 to generate a hydrogen-rich stream and a hydrocarbon-rich stream, and then at least the hydrogen-rich stream is passed to the burner 350 of the reactor system 102 as part of the supplemental fuel stream 356. In some embodiments, the operating parameters of the separator unit 630 can be modified to increase or decrease the hydrogen concentration in the hydrogen-rich stream 362, thereby increasing or decreasing the hydrogen concentration in the supplemental fuel stream 356.

[0107] In some embodiments, the hydrogen concentration of supplemental fuel stream 356 can be altered by removing at least a portion of the hydrocarbon component from supplemental fuel stream 356. Additionally, in some embodiments, the hydrogen concentration of supplemental fuel stream 356 can be altered by combining supplemental fuel stream 356 with supplemental hydrogen-containing stream, supplemental hydrocarbon stream, or a combination of both.

[0108] During the continuous reaction phase of operation of reactor system 102, the catalyst treatment section 300 of reactor system 102, particularly burner 350, can be maintained at a temperature sufficient to reactivate the catalyst within an operating temperature range. For example, in some embodiments, burner 350 can be maintained at a temperature greater than the operating temperature of reactor section 200 of reactor system 102. In some embodiments, the operating temperature range of burner 350 can be greater than or equal to 650°C, greater than or equal to 660°C, even greater than or equal to 680°C, or even greater than or equal to 700°C. In some embodiments, the operating temperature range of burner 350 can be 650°C to 850°C, 660°C to 780°C, or 700°C to 750°C. As previously discussed herein, maintaining the operating temperature in burner 350 can include burning supplemental fuel in burner 350.

[0109] Refer again Figure 1 The supplementary fuel stream 356 can be introduced into the burner 350 of the catalyst treatment section 300. In some embodiments, the supplementary fuel stream 356 can be introduced into the burner 350 via one or more distributors (not shown) arranged within the burner 350. Before introducing the supplementary fuel stream 356 into the burner 350, the supplementary fuel stream 356 can be passed through a compressor (not shown) to increase its pressure. The supplementary fuel stream 356 can be supplied to the burner 350 at a pressure of 5 psig to 200 psig (34.47 kPa to 1378.95 kPa, where 1 psig = 6.89 kPa). In some embodiments, a control valve (not shown) may be included to control the flow rate of the supplementary fuel stream 356 and to regulate the pressure of the supplementary fuel gas to be equal to the operating pressure of the reactor system 102 and / or the burner 350. In some embodiments, the supplementary fuel stream 356 can be preheated, such as by passing it through an optional heat exchanger (not shown).

[0110] According to one or more embodiments, the reaction in reactor system 102 can be an FCDh reaction system for dehydrogenating alkanes and alkyl aromatics to olefins or other products. According to such embodiments, the feed stream can include one or more alkane compounds, such as ethane, propane, n-butane, and isobutane. In some embodiments, the feed stream can contain at least 50 wt.% of ethane, propane, n-butane, isobutane, or combinations thereof. In one or more embodiments, the dehydrogenation reaction can utilize a catalyst comprising platinum, gallium, or a combination thereof. Platinum and / or gallium can be supported by an alumina or silica alumina support and may optionally include potassium. Such platinum catalysts are disclosed in U.S. Patent No. 8,669,406, which is incorporated herein by reference in its entirety. In some embodiments, reactor system 102 can be an FCDh reaction system for dehydrogenating alkyl aromatics to other products. For example, the feed stream can contain ethylbenzene and reactor system 102 can be an FCDh reactor system for dehydrogenating ethylbenzene to styrene.

[0111] In some embodiments, the reaction in reactor system 102 may be a cracking reaction, such that reactor system 102 is a cracking reactor system. According to such embodiments, the feed stream may include one or more of naphtha, n-butane, or isobutane. For example, if the reaction is a cracking reaction, the feed stream may contain at least 50 wt.% naphtha, n-butane, isobutane, or a combination thereof. In one or more embodiments, the cracking reaction may utilize one or more zeolites as catalysts. In some embodiments, the one or more zeolites utilized in the cracking reaction may include ZSM-5 zeolite. However, it should be understood that other suitable catalysts may be used to carry out the cracking reaction. In some embodiments, the cracking catalyst may contain platinum. For example, the cracking catalyst may contain 0.001 wt.% to 0.05 wt.% platinum. Platinum may be sprayed in the form of a soluble platinum compound (such as, but not limited to, platinum nitrate, platinum tetraamine nitrate, platinum acetylacetonate, or combinations thereof) and calcined at an elevated temperature such as about 700°C.

[0112] Example

[0113] The embodiments of this disclosure will be further illustrated by the following examples.

[0114] Example 1: Effect of Hydrogen Content in Propane Dehydrogenation-Supplemental Fuel on Propane Conversion Rate

[0115] In Example 1, the effect of hydrogen concentration in the supplemental fuel stream on propane conversion in a propane dehydrogenation reactor system was evaluated. Propane dehydrogenation was conducted using a Davidson Circulating Riser (DCR) test unit from Grace Davidson, comprising an upflow fluidized bed reactor section and a catalyst handling section. The DCR unit was modified to allow in-situ fuel combustion in the catalyst handling section. Each reaction was run 1A-1D with 4100 g of freshly loaded catalyst comprising platinum and gallium supported on an alumina-containing silica support. The inlet temperature of the riser reactor in the DCR unit was controlled at 630 °C and the pressure was set to 13 psig. The propane feed was HD-5 propane feed with approximately 30 parts per million (ppm) of sulfur (on a molar basis). The propane feed was diluted in nitrogen to achieve a partial pressure of propane in the feed stream of approximately 4.3 psig.

[0116] The catalyst treatment temperature was maintained in the range of 700°C to 750°C. The catalyst treatment involved burning the make-up fuel stream followed by an oxygen treatment in which the catalyst was exposed to an oxygen-containing gas (air) for a specified oxygen permeation time. Propane dehydrogenation was carried out using a make-up fuel stream comprising various compositions of hydrogen and methane for catalyst reactivation. For reaction runs 1A-1D, the molar concentration of hydrogen in the make-up fuel stream was increased from 0 mol% hydrogen to 100 mol% hydrogen to change the molar ratio of hydrogen to methane in the make-up fuel. Propane dehydrogenation was carried out at a constant heat input of approximately 1,600 BTU / h (1.6 KBTU / hr). For each reaction run, the DCR unit operated for a first time period with an oxygen permeation time of 1 minute and a second time period with an oxygen permeation time of 7 minutes.

[0117] Table 1 below provides the propane feed rate (standard liters per hour (SLPH)), catalyst circulation rate (kg / hr), make-up fuel stream composition (mol% and wt.%), make-up fuel stream feed rate (SLPH), heat input (MBTU / hr), catalyst to methane ratio in the catalyst processing section (lbs / lbs), and propane weight hourly space velocity (WHSV hr). -1 The oxygen permeation time for oxygen treatment was determined. The propane conversion rates of the reactor system were determined when the oxygen permeation times were 1 minute and 7 minutes, and these conversion rates are reported in Table 1.

[0118] Table 1: Process parameters and propane conversion rate for Example 1

[0119]

[0120] As shown in Table 1, for Example 1, when the molar concentration of hydrogen in the supplemental fuel increased from 0 mol% to 100 mol% (the molar ratio of hydrogen to methane in the supplemental fuel increased from 0:100 to 100:0), the propane conversion rate was observed to increase from 42.1% to 48.2% with an oxygen permeation time of 1 minute. Therefore, increasing the hydrogen concentration in the supplemental fuel stream from 0 mol% to 100 mol% increased the propane conversion rate by 14.5%.

[0121] Example 2: Propane Dehydrogenation - The Effect of Hydrogen Content in Supplemental Fuel on Propane Conversion Rate under High Heat Input

[0122] In Example 2, the effect of the hydrogen concentration in the make-up fuel stream on propane conversion was evaluated in a propane dehydrogenation reactor system operating under high heat input. Propane dehydrogenation was carried out in the DCR unit described in Example 1. In Example 2, catalyst treatment was performed under high heat input, which was achieved by increasing the make-up fuel stream flow rate to three times that of Example 1. Propane dehydrogenation was carried out under a constant heat input of approximately 4,700 BTU / h (4.7 KBTU / hr). All other operating parameters were the same. Propane dehydrogenation was carried out using a make-up fuel stream comprising hydrogen and methane. For reaction runs 2A-2D, the molar concentration of hydrogen in the make-up fuel stream was increased from 0 mol% hydrogen to 100 mol% hydrogen. Table 2 below provides the propane feed rate, catalyst circulation rate, make-up fuel stream composition, make-up fuel stream feed rate, heat input, catalyst-to-methane ratio in the catalyst treatment section of the reaction system, propane WHSV, and oxygen permeation time for the oxygen treatment. The propane conversion rates of the reactor system were determined when the oxygen immersion time was 1 minute and 7 minutes, and these conversion rates are reported in Table 1.

[0123] Table 2: Process parameters and propane conversion rate in Example 2

[0124]

[0125] As shown in Table 2, for Example 2, when the molar concentration of hydrogen in the supplemental fuel increased from 0 mol% to 100 mol% (the molar ratio of hydrogen to methane in the supplemental fuel increased from 0:100 to 100:0), the propane conversion was observed to increase from 34.9% to 48.5% with an oxygen permeation time of 1 minute. Under high heat input (3 times the feed rate of the supplemental fuel stream in Example 1), the propane conversion in Example 2 increased by 39% by increasing the hydrogen concentration in the supplemental fuel from 0 mol% to 100 mol%. Therefore, under high heat input, the increase in propane conversion due to the increase in hydrogen concentration in the supplemental fuel stream is greater than that in Example 1 (with less heat input).

[0126] refer to Figure 5 Propane dehydrogenation reactions in Examples 1 (902) and 2 (904), with an oxygen permeation time of 1 minute, are presented, showing the propane conversion rate (%) (y-axis) as a function of the hydrogen concentration (wt.%) in the supplemental fuel stream (x-axis). Figure 5 As shown graphically, assuming a constant total heat input to the reactor system, propane conversion increases with increasing hydrogen concentration in the supplemental fuel. The increase in propane conversion is more gradual for hydrogen concentrations in the supplemental fuel ranging from 0 mol% to approximately 50 mol%. When the hydrogen concentration in the supplemental fuel increases to greater than 50 mol%, the rate of increase in propane conversion with increasing hydrogen concentration in the supplemental fuel becomes faster. This indicates that supplemental fuels containing at least 50 mol% hydrogen (i.e., a hydrogen-to-other-fuel molar ratio of at least 1:1) significantly improve propane conversion compared to supplemental fuels with a hydrogen-to-other-fuel molar ratio less than 1:1. The same trend in propane conversion with increasing hydrogen concentration in the supplemental fuel stream was observed when the oxygen permeation time increased to 7 minutes.

[0127] Figure 5 The effects of hydrogen concentration in the supplemental fuel stream on propane conversion are also shown graphically, compared to propane conversion under lower heat input (Example 1 (902)).

[0128] Example 3: The impact of hydrogen concentration in a laboratory-scale propane dehydrogenation-makeup fuel stream

[0129] In Example 3, the effect of varying hydrogen concentration in the supplemental fuel stream on propane conversion was further investigated using a laboratory-scale propane dehydrogenation reactor system. The propane dehydrogenation reaction in Example 3 was conducted using a laboratory-scale fixed-bed test setup containing the same catalyst described in the previous Example 1. The fixed-bed reactor system alternated between propane dehydrogenation operations and catalyst reactivation to simulate a reaction / catalyst treatment cycle.

[0130] During the propane dehydrogenation reaction operation, a feed stream comprising 90 mol% propane and 10 mol% nitrogen is introduced at a 10-hour interval. -1 Propane weight hourly space velocity (WHSV) was introduced into the fixed-bed reactor. Propane dehydrogenation was carried out at a reaction temperature of 625°C under ambient pressure. Each reaction step of the dehydrogenation / catalyst treatment cycle in Example 3 was performed for a total run time of 60 seconds, during which propane conversion and selectivity data were measured 30 seconds after the feed stream was introduced into the fixed-bed reactor.

[0131] During each catalyst treatment step of the dehydrogenation / catalyst treatment cycle, a combustion gas mixture comprising a make-up fuel stream and air is introduced into a fixed-bed reactor at 730°C for 3 minutes. The combustion gas mixture contains 2.5 mol% of the make-up fuel stream, with the remainder being air. The make-up fuel stream consists of methane (CH4) and hydrogen (H2), and the hydrogen concentration in the make-up fuel stream increases from 0 wt.% to 100 wt.% in reaction runs 3A-3F. After 3 minutes of combustion, the catalyst in the fixed bed is subjected to air treatment at 730°C for 15 minutes using high-purity air (>99%).

[0132] Table 3 provides the propane conversion and propylene selectivity for propane dehydrogenation reactions carried out in reaction runs 3A-3F. After performance reached a steady state (typically 20-25 reaction / catalyst treatment cycles under specified conditions in the reactor system), the propane conversion and propane selectivity for each reaction run in Table 3 (3A-3F) were determined.

[0133] Table 3: Propane conversion and propylene selectivity in propane dehydrogenation of Example 3

[0134]

[0135] As shown in Table 3 above, for Example 3, when the concentration of hydrogen in the supplemental fuel increased from 0 mol% to 100 mol% (the molar ratio of hydrogen to methane in the supplemental fuel increased from 0:100 to 100:0), the propane conversion was observed to increase from 48.2% to 53.1%. Therefore, for the laboratory-scale reactor process of Example 3, increasing the hydrogen concentration in the supplemental fuel stream from 0 mol% to 100 mol% increased the propane conversion by 10.2%. Increasing the hydrogen concentration from 0 mol% to 100 mol% also increased the propylene selectivity from 96.4 mol% to 96.8 mol%.

[0136] refer to Figure 6 The graph depicts the changes in propane conversion 910 (left y-axis) and propylene selectivity 912 (right y-axis) as a function of hydrogen concentration (x-axis) in the supplemental fuel stream. Figure 6 As shown graphically, both propane conversion (910) and propylene selectivity (912) increase with increasing hydrogen concentration in the supplemental fuel stream. Figure 6It was also shown that the increase in propane conversion 910 was generally linear as the hydrogen concentration in the supplementary fuel increased from 0 mol% to about 70 mol%. However, compared to the generally linear increase in propane conversion at hydrogen concentrations from 0 mol% to about 70 mol% in the supplementary fuel, the increase in propane conversion 910 was faster when the hydrogen concentration in the supplementary fuel stream increased to above about 70 mol%. This indicates that supplementary fuel streams containing at least 70 mol% hydrogen provide a greater improvement in propane conversion compared to supplementary fuel streams with less than 70 mol% hydrogen.

[0137] For purposes of describing and limiting the invention, it should be noted that the term "about" is used herein to indicate the degree of uncertainty that may be attributable to any quantitative comparison, value, measurement, or other form of representation. The term is also used herein to indicate the degree to which a quantitative representation may vary according to a specified reference without causing a change in the essential function of the subject matter of interest.

[0138] It should be noted that one or more of the following claims use the term "wherein" as a transitional phrase. For the purpose of limiting the invention, it should be noted that this term is introduced in the claims as an open transitional phrase, used to introduce a description of a series of characteristics of the structure and should be interpreted in the same manner as the more commonly used open leading term "comprising".

[0139] Generally, the terms "inlet port" and "outlet port" for any system unit of reactor system 102 as described herein refer to an opening, orifice, channel, aperture, gap, or other similar mechanical feature within the system unit. For example, an inlet port allows material to enter a particular system unit, and an outlet port allows material to exit a particular system unit. Typically, an outlet port or inlet port will define the area to which a pipe, conduit, tube, hose, material delivery line, or similar mechanical feature of system unit 102 is attached, or a portion to which another system unit is directly attached. While inlet and outlet ports may sometimes be described herein as functionally operable, they may have similar or identical physical characteristics, and their respective functions within an operable system should not be construed as limiting their physical structure.

[0140] It will be apparent to those skilled in the art that various modifications and variations can be made to the invention without departing from its spirit and scope. Because those skilled in the art can make modifications, combinations, sub-combinations, and variations of the disclosed embodiments incorporated into the spirit and essence of the invention, the invention should be interpreted as encompassing all things within the scope of the appended claims and their equivalents.

Claims

1. A method for processing chemical streams, the method comprising: The feed stream is brought into contact with the catalyst in the reactor section of the reactor system, wherein: The reactor system includes a reactor section and a catalyst processing section, and the reactor system includes a dehydrogenation reaction system; The catalyst comprises platinum, gallium, or both; and The process involves contacting the feed stream with the catalyst to initiate a reaction, the reaction forming an effluent stream comprising at least one product. At least a portion of the effluent stream is separated from the catalyst; The catalyst is transferred to the catalyst treatment section of the reactor system; The catalyst is treated in the catalyst treatment section of the reactor system, wherein the catalyst treatment includes: The catalyst is delivered to the burner of the catalyst processing section; In the presence of the catalyst, supplemental fuel is burned in the burner to produce a heated catalyst, wherein the supplemental fuel comprises pure hydrogen gas containing greater than or equal to 99 mol.% hydrogen. Treating the heated catalyst with oxygen-containing gas to produce a reactivated catalyst; and The reactivated catalyst is transferred from the catalyst treatment section to the reactor section.

2. The method according to claim 1, wherein the supplementary fuel is composed of the pure hydrogen gas.

3. The method according to claim 1, wherein the supplemental fuel comprises 99 mol.% hydrogen.

4. The method of claim 1, wherein treating the heated catalyst with the oxygen-containing gas comprises exposing the heated catalyst to the oxygen-containing gas for a period of time greater than 2 minutes.

5. The method according to any one of claims 1-3, further comprising passing a hydrogen-containing waste gas stream from a hydrocarbon processing system to the burner, wherein at least a portion of the supplemental fuel stream introduced into the burner comprises the hydrogen-containing waste gas stream.

6. The method of claim 5, further comprising: Increase the concentration of hydrogen in the hydrogen-containing waste gas stream.

7. The method according to any one of claims 1-3, wherein the supplemental fuel comprises at least a portion of the exhaust gas stream from a light hydrocarbon cracking process or a dehydrogenation process.

8. The method according to any one of claims 1-3, further comprising: The effluent stream is separated into a product stream and a waste gas stream; as well as At least a portion of the exhaust gas stream is transferred to the catalyst treatment section, wherein the supplemental fuel comprises the at least a portion of the exhaust gas stream.

9. The method according to any one of claims 1-3, wherein the catalyst comprises platinum, gallium and optionally an alkali metal or alkaline earth metal supported on a support, wherein the support is selected from one or more of silica, alumina, alumina-containing silica, TiO2, ZrO2 or combinations thereof.

10. The method according to any one of claims 1-3, wherein the product in the effluent stream comprises at least one light olefin selected from ethylene, propylene, or butene.

11. The method according to any one of claims 1-3, further comprising operating the burner at a temperature of 650°C to 850°C.

12. A method for dehydrogenating a hydrocarbon stream to produce one or more olefins, the method comprising: The hydrocarbon feed stream is brought into contact with the catalyst in the reactor section of the reactor system, wherein: The reactor system includes a reactor section and a catalyst processing section; The catalyst comprises platinum, gallium, or both; and The process involves contacting the feed stream with the catalyst to initiate a reaction, the reaction forming an effluent stream comprising one or more of the olefins. At least a portion of the effluent stream is separated from the catalyst; The catalyst is transferred to the catalyst treatment section of the reactor system; The catalyst is treated in the catalyst treatment section of the reactor system, wherein the catalyst treatment includes: The catalyst is delivered to the burner of the catalyst processing section; Supplemental fuel is introduced into the burner, the supplemental fuel stream comprising pure hydrogen, wherein the pure hydrogen contains greater than or equal to 99 mol.% hydrogen. The supplemental fuel is burned in the burner in the presence of the catalyst; To produce a reactivated catalyst by subjecting a heated catalyst to oxygen treatment; and The reactivated catalyst is transferred from the catalyst treatment section to the reactor section.

13. The method of claim 12, wherein the supplementary fuel is composed of the pure hydrogen gas.

14. The method of claim 12, wherein the supplemental fuel comprises 99 mol.% hydrogen.

15. The method according to any one of claims 12-14, wherein subjecting the heated catalyst to oxygen treatment comprises exposing the heated catalyst to an oxygen-containing gas for a period of time greater than 2 minutes.

16. The method according to any one of claims 12-14, further comprising passing a hydrogen-containing waste gas stream from a hydrocarbon processing system to the burner, wherein at least a portion of the supplemental fuel stream introduced into the burner comprises the hydrogen-containing waste gas stream.

17. The method of claim 16, further comprising: Increase the concentration of hydrogen in the hydrogen-containing waste gas stream.

18. The method according to any one of claims 12-14, wherein the supplemental fuel comprises at least a portion of the exhaust gas stream from a light hydrocarbon cracking process or a dehydrogenation process.

19. The method according to any one of claims 12-14, further comprising: The effluent stream is separated into a product stream and a waste gas stream; as well as At least a portion of the exhaust gas stream is transferred to the catalyst treatment section, wherein the supplemental fuel comprises the at least a portion of the exhaust gas stream.

20. The method according to any one of claims 12-14, wherein the catalyst comprises platinum, gallium, and optionally an alkali metal or alkaline earth metal supported on a support, the support being selected from one or more of silica, alumina, alumina-containing silica, TiO2, ZrO2, or combinations thereof.

21. The method according to any one of claims 12-14, wherein the product in the effluent stream comprises at least one light olefin selected from ethylene, propylene or butene.

22. The method according to any one of claims 12-14, further comprising operating the burner at a temperature of 650°C to 850°C.

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