Method for dehydrogenating hydrocarbons using a countercurrent regenerator

Abstract

According to one or more embodiments described herein, hydrocarbons can be dehydrogenated by a process comprising contacting a feed stream comprising one or more hydrocarbons with a particulate solid, which can include an oxygen carrier material, to form hydrogen and one or more products. At least a portion of the hydrogen can react with oxygen from the oxygen carrier material. The particulate solids from the dehydrogenation reactor can be sent to a regeneration unit, which can include a first gas inlet and a second gas inlet, which can be located below the first gas inlet. An oxygen-containing gas can enter the regeneration unit through the first gas inlet, and a fuel can enter through the second gas inlet. In a region of the regeneration unit above the second gas inlet and below the first gas inlet, at least a portion of the fuel can react with oxygen from the oxygen carrier material.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Provisional Patent Application No. 63 / 406,444, filed September 14, 2022, which is incorporated herein by reference in its entirety.

[0002] FIELD OF THE INVENTION FIELD OF THE INVENTION Embodiments described herein relate generally to chemical processing, and more particularly to processes and systems utilized for the dehydrogenation of chemical species. [Background technology]

[0003] Olefin compounds can be used as base materials to produce many types of goods and materials. For example, ethylene can be used to make polyethylene, ethylene chloride, or ethylene oxide. Such products can be used in packaging products, construction, fibers, etc. Therefore, there is an industrial demand for light olefins such as ethylene, propylene, butene, and styrene. Summary of the Invention

[0004] One method of producing olefinic compounds is by dehydrogenating alkanes and / or alkylaromatics. In some embodiments, the dehydrogenation reaction can be facilitated by reducing or eliminating the hydrogen formed during the dehydrogenation by reacting the hydrogen with oxygen to form water, which shifts the equilibrium toward light olefin production. In such embodiments, an oxygen carrier material can be utilized to provide the oxygen to react with the hydrogen. The oxygen carrier material can be contained in a particulate solid. Such an oxygen carrier material can be circulated through the reactor and a regeneration unit, and the oxygen content in the oxygen carrier material can be increased in the regeneration unit. In some embodiments, fuel is additionally utilized in the regeneration unit to heat at least the oxygen carrier material.

[0005] As described herein, it has been discovered that it can be beneficial to utilize a particular countercurrent flow pattern for the particulate solids and gases in the regeneration unit. The embodiments described herein include a flow pattern in which the particulate solids move generally downward through the regeneration unit, while gases, such as fuel and oxygen-containing gas, move generally upward. Furthermore, the oxygen-containing gas and fuel enter the regeneration unit through first and second gas inlets, respectively, where the second gas inlet (for fuel) is located below the first gas inlet (for oxygen-containing gas). In such embodiments, the particulate solids can be contacted with the oxygen-containing gas (and optionally the fuel) before later contacting the fuel (which is not the oxygen-containing gas). In the regeneration unit, oxygen from the oxygen carrier material can be utilized to react with the fuel, which reduces the oxygen content of the oxygen carrier material. To maintain the desired activity and selectivity of the oxygen carrier material, it may be desirable to at least partially reduce the oxygen content of the oxygen carrier material when it is sent to the dehydrogenation reactor. The embodiments described herein may address such needs by contacting the oxygen carrier material with the fuel (without additional oxygen-containing gas) after the oxygen carrier material has been contacted with the oxygen-containing gas.

[0006] According to one or more embodiments described herein, hydrocarbons can be dehydrogenated by a process comprising contacting a feed stream comprising one or more hydrocarbons with a particulate solid in a dehydrogenation reactor. The particulate solid can include an oxygen carrier material. In the dehydrogenation reactor, the one or more hydrocarbons can be dehydrogenated to form hydrogen and one or more products. At least a portion of the hydrogen can react with oxygen from the oxygen carrier material to form water, reducing the oxygen content in the oxygen carrier material. The process can further include passing the particulate solid from the dehydrogenation reactor to a regeneration unit. The particulate solid can move in a generally downward direction through the regeneration unit, and the gas can move in a generally upward direction through the regeneration unit, whereby the particulate solid and the gas move through the regeneration unit in a countercurrent pattern. The regeneration unit can include a first gas inlet and a second gas inlet. The second gas inlet can be located below the first gas inlet. The oxygen-containing gas can enter the regeneration unit through the first gas inlet. The fuel can enter the regeneration unit through the second gas inlet. In a region of the regeneration unit above the second gas inlet and below the first gas inlet, at least a portion of the fuel may react with oxygen from the particulate solid oxygen carrier material. The process may further include passing at least a portion of the particulate solids from the regeneration unit to a dehydrogenation unit.

[0007] It should be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and features of the claimed subject matter. Additional features and advantages of the embodiments are set forth in the detailed description, and in part will become readily apparent to those skilled in the art from that description, including the accompanying drawings and claims, or can be learned by practicing the described embodiments. The drawings are included to provide a further understanding of the embodiments and, together with the detailed description, serve to explain the principles and operation of the claimed subject matter. However, the embodiments shown in the drawings are illustrative and exemplary in nature and are not intended to limit the claimed subject matter. [Brief explanation of the drawings]

[0008] Reference will now be made in more detail to various embodiments, some of which are illustrated in the accompanying drawings. [Figure 1] 1 illustrates a schematic diagram of a reactor system according to one or more embodiments of the present disclosure. [Figure 2] 10A and 10B illustrate schematic diagrams of another reactor system according to additional embodiments of the present disclosure.

[0009] 1 and 2, many valves, temperature sensors, electronic controllers, etc., which are available and well known to those skilled in the art, are not included. Additionally, accompanying components often included within such reactor systems, such as air supplies, heat exchangers, surge tanks, etc., are also not included. However, it should be understood that these components are within the scope of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0010] Specific embodiments of the present application will now be described. However, this disclosure may be embodied in different forms and should not be construed as limited to the embodiments set forth in this disclosure. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the present subject matter to those skilled in the art.

[0011] Embodiments of the presently disclosed method are described in detail herein with reference to the reactor system of Figures 1 and 2 operating as a circulating fluidized bed process for dehydrogenating hydrocarbons. However, it should be understood that the principles disclosed and taught herein may be applicable to other systems utilizing different system components oriented in a different manner. For example, the concepts described herein may be equally applicable to other systems with alternative reactor and regeneration units, such as those operating under non-fluidized conditions or those including a downer rather than a riser. Furthermore, it should be understood that not all of the parts of the reactor system of Figures 1 and 2 should be construed as essential to the claimed subject matter. Furthermore, although the method steps recited in the appended claims are described herein in connection with the reactor system of Figures 1 and 2, it should be understood that such recited method steps are adaptable to other systems, as would be understood by one of ordinary skill in the art.

[0012] Referring now to FIG. 1 , an exemplary reactor system 100 that may be suitable for use with the methods described herein is shown schematically. The reactor system 100 may include a dehydrogenation reactor 110 and a regeneration unit 150. A feed stream 102 may be fed into the dehydrogenation reactor 110. Particulate solids 180 may be fed into the dehydrogenation reactor 110 via stream 152. The particulate solids 180 may be contacted with the feed stream 102 in the dehydrogenation reactor 110. The particulate solids 180 may include an oxygen carrier material. The feed stream 102 may include one or more hydrocarbons that may be dehydrogenated in the dehydrogenation reactor 110 to form one or more products and hydrogen. The oxygen from the oxygen carrier material may react with the hydrogen to form water. The one or more products may exit the dehydrogenation reactor 110 via product stream 114.

[0013] Particulate solids 180 may exit dehydrogenation reactor 110 and be sent to regeneration unit 150 via stream 112. Regeneration unit 150 may include a gas / solid separator 158, a first gas inlet 160, and a second gas inlet 170. First gas inlet 160 may be located above second gas inlet 170. Oxygen-containing gas 162 may enter regeneration unit 150 through first gas inlet 160, and fuel 172 may enter regeneration unit 150 through second gas inlet 170. Particulate solids 180 may travel in a generally downward direction through regeneration unit 150, first through separator 158, then through first gas inlet 160, and then through second gas inlet 170. Gases within the regeneration, such as oxygen-containing gas 162 and fuel 172, may move through the regeneration unit 150 in a generally upward direction, causing the particulate solids 180 and gases to move through the regeneration unit 150 in a countercurrent pattern. The particulate solids 180 may then exit the regeneration unit 150 and be sent back to the dehydrogenation reactor 110 via stream 152.

[0014] In some embodiments, reactor system 100 may be operable to perform a circulating fluidized bed (CFB) dehydrogenation process. The CFB dehydrogenation process may include a dehydrogenation reactor 110 and a regeneration unit 150, both of which are fluidized bed based.

[0015] As previously mentioned, in one or more embodiments, the feed stream 102 may be sent into the dehydrogenation reactor 110. In one or more embodiments, the feed stream 102 may include one or more hydrocarbons. In one or more embodiments, the one or more hydrocarbons may include an alkyl moiety. As used in this disclosure, a hydrocarbon includes an "alkyl moiety" if the molecule has at least one carbon-carbon single bond that can be dehydrogenated to form a carbon-carbon double bond. In one or more embodiments, the one or more hydrocarbons may include one or more of ethane, propane, butane, or ethylbenzene. According to one or more embodiments, the one or more hydrocarbons may include at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or even at least 99% ethane by weight. In additional embodiments, the one or more hydrocarbons can comprise at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or even at least 99% by weight of propane. In additional embodiments, the one or more hydrocarbons can comprise at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or even at least 99% by weight of butane. In additional embodiments, the one or more hydrocarbons can comprise at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or even at least 99% by weight of ethylbenzene. In additional embodiments, the one or more hydrocarbons may comprise a total of at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or even at least 99% by weight of ethane, propane, butane, and ethylbenzene.

[0016] According to additional embodiments, the dehydrogenation reactor 110 may be operated in a "backmixed" mode, where the feed stream 102 enters the reactor 110 in a manner that is very close to isothermal. Thus, the fluid velocity in this region may be low enough, and the particulate solids 180 flow rate may be high enough, so that a dense bed may form at or around where the feed stream 102 is injected. In some embodiments, the superficial velocity of the reactor 110 may be between 3 and 80 ft / s, such as between 3 and 40 ft / s, or between 10 and 30 ft / s. The flow rate of the particulate solids 180 in the reactor 110 may be between 1 and 300 lb / ft 2 -s, e.g., 40-200 lb / ft 2 -s, or 60-160 lb / ft 2 -s, etc. The reactor 110 may include multiple diameters and may include one or more frustums to increase or decrease the velocity of the particulate solids 180 and / or gaseous reactants. The reactor 110 may operate at a gas residence time of 0.1 to 10 seconds, such as, for example, 0.5 to 6 seconds.

[0017] Particulate solids 180 may be utilized in the general operation of reactor system 100. As used herein, the term "particulate solids" may refer to one or more solid particles suitable for fluidization. In one or more embodiments, particulate solids 180 may include an oxygen carrier material and a dehydrogenation catalyst material. In some embodiments, particulate solids 180 may consist essentially of an oxygen carrier material. As used herein, "consisting essentially of" refers to a material that contains less than 1 wt. % of an unlisted material (i.e., consisting essentially of A means that A is at least 99 wt. % of the composition). In some embodiments, particulate solids 180 may be free of a dehydrogenation catalyst material. In some embodiments, the oxygen carrier material and the dehydrogenation catalyst material may be separate particles of particulate solids 180. In some embodiments, the oxygen carrier material and the dehydrogenation catalyst may be contained within the same particle of particulate solids 180.

[0018] In embodiments in which the particulate solids 180 include a dehydrogenation catalyst, the dehydrogenation of the one or more hydrocarbons may be at least partially by catalytic dehydrogenation. Catalytic dehydrogenation is the dehydrogenation of hydrocarbons facilitated by the use of a dehydrogenation catalyst. In embodiments in which the particulate solids 180 do not include a dehydrogenation catalyst, the dehydrogenation of the one or more hydrocarbons may be by non-catalytic thermal dehydrogenation. Non-catalytic thermal dehydrogenation refers to the dehydrogenation of hydrocarbons that does not use a dehydrogenation catalyst, and instead may occur through elevated temperatures, pressures, or a combination thereof.

[0019] In some embodiments, particulate solids 180 may include a "dual-purpose material" that can act as both a dehydrogenation catalyst and an oxygen-carrying material. It should be understood that, at least in the embodiments described herein in which an oxygen-carrying material and a dehydrogenation catalyst are utilized in the same reactor vessel (such as that of FIG. 1), such a dual-purpose material may be utilized in place of or in combination with the oxygen-carrying material of particulate solids 180 or the dehydrogenation catalyst of particulate solids 180.

[0020] Unless otherwise specified herein, "oxygen carrier material" may generally refer to an oxygen-rich oxygen carrier material or an oxygen-deficient oxygen carrier material. Unless otherwise specified herein, "dual-purpose material" may generally refer to an oxygen-rich dual-purpose material or an oxygen-deficient dual-purpose material. For example, an oxygen-deficient condition may exist after some oxygen is utilized for combustion, and the oxygen-deficient material may be oxygen-rich after regeneration and prior to combustion. The reaction may be carried out in one or more fluidized bed reactors, such as, for example, a circulating fluidized bed reactor. The reactor may be, for example, a riser or a downer.

[0021] As described herein, in one or more embodiments, the dehydrogenation catalyst and oxygen carrier material may be separate particles of particulate solids 180. One contemplated advantage of such a system is that the functionality of the system can be altered, even while the system is online, by adding, removing, or replacing one or both of the dehydrogenation catalyst and oxygen carrier material. For example, the reaction heat load can be adjusted by adding or removing one or both of the dehydrogenation catalyst and oxygen carrier material. This can be advantageous in some embodiments compared to dual-purpose materials, because the heat balance of dual-purpose particles must be determined prior to the reaction and cannot be easily adjusted by changing the amount of dehydrogenation catalyst relative to the oxygen carrier material. Controlling the ratio of dehydrogenation catalyst to oxygen carrier material can be even more advantageous, because reaction selectivity can be better fine-tuned. For example, the amount of hydrogen in the system can be used to control the degree of combustion, or the component balance can be used to optimize downstream separation processes.

[0022] In some embodiments, the dehydrogenation reactor 110 may include from 1 wt. % to 100 wt. % of the oxygen carrier material, such as from 5 wt. % to 95 wt. % or from 75 wt. % to 25 wt. % of the oxygen carrier material, based on the total weight of the particulate solids 180 in the dehydrogenation reactor 110. In other embodiments, the dehydrogenation reactor 110 may include from 50 wt. % to 75 wt. % of the oxygen carrier material, based on the total weight of the particulate solids 180 in the dehydrogenation reactor 110. In some embodiments, a relatively large amount of the oxygen carrier material may be present (e.g., at least 80 wt. %, at least 85 wt. %, or even at least 90 wt. %), particularly if the release of oxygen by the oxygen carrier material is relatively slow compared to the rate of dehydrogenation. In some embodiments, the dehydrogenation reactor 110 may include from 0 wt. % to 99 wt. % of the dehydrogenation catalyst, such as from 5 wt. % to 95 wt. % or from 25 wt. % to 75 wt. % of the particulate solids 180 in the dehydrogenation reactor 110. In other embodiments, dehydrogenation reactor 110 may include 25% to 50% by weight of dehydrogenation catalyst, based on the total weight of particulate solids 180 in dehydrogenation reactor 110. In some embodiments, dehydrogenation reactor 110 may include up to 95%, 99%, or even 100% by weight of the total weight of particulate solids 180 in dehydrogenation reactor 110 as dual-purpose material. For example, if utilized, all or a majority of the particulate solids 180 may be dual-purpose material. In embodiments, the particulate solids 180 material may include all solids in the system other than coke.

[0023] As previously mentioned, in dehydrogenation reactor 110, hydrogen may be contacted with an oxygen-rich oxygen carrier material in particulate solids 180. The oxygen carrier material may include one or more metal oxides. According to one or more embodiments, the one or more metal oxides may be redox-active metal oxides or mixtures of redox-active metal oxides. Redox-active metal oxides include binary, ternary, or other mixed metal oxides that can undergo reduction in the presence of a reducing agent (e.g., hydrogen) and oxidation in the presence of an oxidizing agent (e.g., oxygen or air). In some embodiments, the redox-active metal oxide is a metal MO xwhere M can be one or more metals from IUPAC Groups 6, 7, 8, 9, 10, 11, or 12, and "x" is the number of bonded oxygen atoms in the structure. For example, the redox-active metal oxide can be Mn2O3, Fe2O3, Co3O4, CuO, (LaSr)CoO3, (LaSr)MnO3, Mg6MnO8, MgMnO3, MnO2, Fe3O4, Mn3O4, Cu2O, NiO, Ni2O3, CrO, Cr2O3, CrO2, ZnO, or any combination of other IUPAC Group 6-12 metal oxides. In some embodiments, the redox-active metal oxide can be cerium oxide. For example, the redox-active metal oxide can be CeO2, Ce2O3, or any other mixed metal oxide containing cerium. In further embodiments, the oxygen carrier material may include lanthanum oxide, La2O3, in combination with other reducible metal oxides. In some embodiments, the redox-active metal oxide may be selected from Mn2O3, Fe2O3, Co3O4, CuO, (LaSr)CoO3, (LaSr)MnO3, Mg6MnO8, MgMnO3, MnO2, Fe3O4, Mn3O4, and Cu2O. In some embodiments, the oxygen carrier material may be a solid. In certain embodiments, the oxygen carrier material may be a pulverized solid or powder. In other embodiments, the oxygen carrier material may be formulated using redox-active metal oxides and binder and / or support materials to produce a flowable material with required physical properties, such as particle size distribution, density, and wear resistance. The binder and / or support material may include alumina, silica, titania, magnesia, zirconia, or a combination thereof.

[0024] In one or more embodiments, the oxygen carrier material may include a hydrogen-selective oxygen carrier material, which may include a promoter or a combination of various promoters. The addition of a promoter may result in the formation of a core-shell morphology. The promoter may include a compound containing an alkali metal oxide or alkaline earth metal oxide from IUPAC Groups 1 and 2, and / or an alkali transition metal oxide or alkaline earth transition metal oxide. In some embodiments, the alkali element may include one or more of sodium, lithium, potassium, and cesium. In some embodiments, the alkaline earth element may include one or more of calcium, magnesium, strontium, and barium. In some embodiments, the transition metal may include one or more of tungsten and molybdenum. For example, the one or more alkali transition metal oxides or alkaline earth transition metal oxides can be Na2WO4, K2MoO4, Na2MoO4, K2WO4, Li2WO4, CsWO4, Li2MoO4, CaWO4, CaMoO4, MgWO4, MgMoO4, SrWO4, SrMoO4, BaWO4, and BaMoO4. In some embodiments, the promoter can include one or more alkali metal or alkaline earth metal salts selected from Group 1 and Group 2 metal cations and a counterion. In some embodiments, the alkali element can include one or more of sodium, lithium, potassium, and cesium. In some embodiments, the alkaline earth element can include one or more of calcium, magnesium, strontium, and barium. In some embodiments, the counterion can include carbonate, sulfate, sulfite, sulfide, phosphate, phosphite, and borate.For example, the alkali metal salt or alkaline earth metal salt can be Na2CO3, Na2SO4, Na3PO4, Li2CO3, Li2SO4, Li3PO4, K2CO3, K2SO4, K3PO4, Cs2CO3, Cs2SO4, Cs3PO4, CaCO3, CaSO4, Ca3(PO4)2, SrCO3, SrSO4, Sr3(PO4)2, MgCO3, MgSO4, Mg3(PO4)2, BaCO3, BaSO4, Ba3(PO4)2, Na2HPO4, KHSO4, Na2SO3, K2B4O7, Na3BO3, or combinations thereof.

[0025] For example, oxygen carrier materials such as those disclosed in U.S. Patent Application No. 62 / 725,504, filed August 31, 2018, entitled "METHODS OF PRODUCING HYDROGEN-SELECTIVE OXYGEN CARRIER MATERIALS," and U.S. Patent Application No. 62 / 725,508, filed August 31, 2018, entitled "HYDROGEN-SELECTIVE OXYGEN CARRIER MATERIALS AND METHODS OF USE," are contemplated as suitable for the processes of the present disclosure, the teachings of which are incorporated herein by reference. In one or more additional embodiments, the oxygen carrier material may include the oxygen carrier materials of U.S. Patent No. 5,430,209, U.S. Patent No. 7,122,495, and / or WO 2018 / 232133, each of which is incorporated by reference in its entirety.

[0026] The oxygen-rich oxygen carrier material may be reducible by releasing oxygen, which may be selective for the combustion of hydrogen. For example, the oxygen carrier material may be selective for the combustion of hydrogen over hydrocarbons. In some embodiments, the oxygen-rich oxygen carrier material comprises about 1% to about 20% by weight of releasable oxygen, based on the total weight of the oxygen-rich oxygen carrier material. In other embodiments, the oxygen-rich oxygen carrier material comprises about 1% to about 10% by weight, about 1% to about 5% by weight, about 5% to about 20% by weight, or about 5% to about 10% by weight of releasable oxygen. As used herein, "releasable oxygen" may refer to oxygen that can be released via redox by the oxygen carrier material. Other oxygen may be present in the oxygen carrier material that is not releasable via redox. It should be understood that in some embodiments, oxygen may be released from the surface of the oxygen carrier material simultaneously with the combustion of hydrogen on the surface of the oxygen carrier material.

[0027] As previously mentioned, the releasable oxygen of an oxygen-rich oxygen carrier material can be selective for the combustion of hydrogen over hydrocarbons. In some embodiments, at least about 60% of the releasable oxygen of the oxygen carrier material is selective for hydrogen combustion. In other embodiments, at least about 55% of the releasable oxygen of the oxygen carrier material is selective for hydrogen combustion.

[0028] In embodiments, contacting hydrogen with an oxygen-rich oxygen carrier material removes a portion of the releasable oxygen from the oxygen-rich oxygen carrier material. In some embodiments, contacting hydrogen with an oxygen-rich oxygen carrier material removes about 1% to about 50% by weight of the releasable oxygen from the oxygen-rich oxygen carrier material. In other embodiments, contacting hydrogen with an oxygen-rich oxygen carrier material removes about 10% to about 50% by weight, about 10% to about 25% by weight, or about 25% to about 50% by weight of the releasable oxygen from the oxygen-rich oxygen carrier material.

[0029] In further embodiments, when hydrogen contacts the oxygen-rich oxygen carrier material, the oxygen-rich oxygen carrier material combusts greater than about 50% of the hydrogen. In other embodiments, when hydrogen contacts the oxygen-rich oxygen carrier material, the oxygen-rich oxygen carrier material combusts about 50% to about 90%, or about 75% to about 90%, of the hydrogen produced.

[0030] When the oxygen-rich oxygen carrier material is contacted with hydrogen, the hydrogen may combust and form an oxygen-depleted oxygen carrier material. To form the oxygen-depleted oxygen carrier material, at least a portion of the oxygen-rich oxygen carrier material may be reduced to a lower oxidation state. After the oxygen carrier material is reduced to form the oxygen-depleted oxygen carrier material, the oxygen-depleted oxygen carrier material may be discharged from the dehydrogenation reactor 110 in the lower oxidation state.

[0031] As described herein, in one or more embodiments, the particulate solid 180 may include a dehydrogenation catalyst. In one or more embodiments, the dehydrogenation catalyst may include gallium, chromium, and / or platinum. As described herein, the gallium and / or platinum dehydrogenation catalyst includes gallium, platinum, or both. The dehydrogenation catalyst may be supported on an alumina or alumina silica support and may optionally include potassium. In one or more embodiments, the dehydrogenation catalyst may include a catalyst disclosed in U.S. Pat. No. 8,669,406, which is incorporated herein by reference in its entirety, such as a Ga, Cr, and / or Fe-based catalyst. According to additional embodiments, a Pt-based catalyst may be utilized. In one or more embodiments, the catalysts disclosed in EP 0948475 B1 and / or WO 2010 / 133565 may be utilized, each of which is incorporated herein by reference in its entirety. Additional catalyst embodiments contemplated as suitable for use in the systems and methods described herein include those described in U.S. Patent No. 8,669,406, which is incorporated herein by reference in its entirety. Such catalysts may contain relatively small amounts of Cr, such as less than 6%, or about 1.5%. However, it should be understood that other suitable dehydrogenation catalysts may be utilized to carry out the dehydrogenation reaction.

[0032] In one or more embodiments, the dehydrogenation catalyst may exhibit suitable stability in the presence of steam. As described herein, combustion of hydrogen may form steam, which may directly contact the dehydrogenation catalyst. It is contemplated that not all dehydrogenation catalysts are equally effective in a steam environment. In one or more embodiments, dehydrogenation catalysts are utilized that maintain a substantial amount of their reactivity and / or selectivity for dehydrogenation of light alkanes. For example, one or more of the dehydrogenation catalysts utilized in the systems and methods of the present disclosure may not degrade alkane conversion and / or selectivity in dehydrogenation by more than 25%, more than 20%, more than 15%, more than 10%, more than 5%, or may even have improved alkane conversion and / or selectivity in dehydrogenation when in the presence of steam in amounts consistent with operation of the systems of the present disclosure. In some embodiments, the dehydrogenation catalyst may function at such conversion and / or selectivity when exposed to at least 10 mol% water (e.g., 10 mol% to 50 mol% water) for a period of up to 120 seconds (the time the catalyst may be exposed to such conditions according to some embodiments of the disclosed systems).

[0033] Suitable examples of dehydrogenation catalysts can be prepared to meet the definition of Geldart A. In some embodiments, the dehydrogenation catalyst is modified with silica, preferably having an average particle size of about 100 square meters per gram (m) as determined by the BET method. 2 gallium and platinum supported on alumina in the delta or theta phase, or the delta+theta phase, or theta+alpha phase, or mixed delta+theta+alpha phase, having a surface area of ​​less than 100 ppm / g. In another embodiment, the dehydrogenation catalyst comprises 0.1 to 34 wt. % gallium oxide (Ga2O3), preferably 0.2 to 3.8 wt. %; 1 to 300 wt. ppm platinum, preferably 50 to 300 wt. ppm; 0 to 5 wt. % alkali and / or alkaline earth, e.g., potassium; 0.08 to 3 wt. % silica; and the balance up to 100 wt. % alumina.

[0034] In one or more embodiments, heat may be gained or lost by the dehydrogenation reaction, and the reoxidation of the oxygen-depleted oxygen carrier material and the reduction of the oxygen-rich oxygen carrier material may generate or use heat (i.e., may be exothermic or endothermic). In one or more embodiments, contacting the hydrocarbon feed with the dehydrogenation catalyst may be endothermic, resulting in a dehydrogenation heat loss. In some embodiments, contacting the hydrogen with the oxygen-rich oxygen carrier material may be exothermic, resulting in a combustion heat gain. The reoxidation of the oxygen-depleted oxygen carrier material may be exothermic, resulting in an oxygenation heat gain. Thus, by incorporating hydrogen combustion during catalytic dehydrogenation, in some embodiments, sufficient heat may be generated during the reoxidation of the oxygen-depleted oxygen carrier material to serve as a heat source for the alkane-to-olefin reaction. Thus, because the heat captured throughout the process by reoxidation of the oxygen carrier material, combustion of hydrogen, or both, can generate the amount of heat necessary for the reaction of alkanes or alkylaromatics to olefins, embodiments of the disclosed process may enable higher alkane conversion rates while reducing or eliminating the need for fuel gas required for conventional cracking.

[0035] As described herein, "dehydrogenation heat loss" refers to the amount of heat lost due to the dehydrogenation of the feed alkane, "combustion heat gain" refers to the amount of heat generated by the combustion of hydrogen, and "oxygenation heat gain" refers to the amount of heat generated by the oxidation of the oxygen-depleted oxygen carrier material. In one or more embodiments, the combustion heat gain may provide heat to the system that accounts for at least a portion of the dehydrogenation heat loss. In additional embodiments, the auxiliary fuel 172 may be burned to heat one or more of the dehydrogenation catalyst or the oxygen carrier material. The auxiliary fuel 172 may compensate for any shortfall in heat generated by the combustion of hydrogen or the oxygenation of the oxygen carrier material. However, it should be understood that in the disclosed embodiments, the amount of auxiliary fuel 172 required may be substantially less than the amount that would be required in a system that does not incorporate an oxygen carrier material.

[0036] Producing olefinic compounds by conventional dehydrogenation processes (e.g., those that do not incorporate hydrogen combustion) can be relatively expensive due to the high heat load required for the endothermic dehydrogenation reaction and / or downstream separation steps that may be required to separate unreacted alkanes or alkylaromatics and remove the hydrogen produced in the dehydrogenation reaction. Regarding heat input reduction, catalytic dehydrogenation processes are generally endothermic and require heat. However, the exothermic combustion of hydrogen can offset that heat input requirement to some extent. Furthermore, if the oxygen content is reduced after combustion, the oxygen carrier material may be regenerated to regain oxygen for the oxygen carrier material, and the regeneration may be exothermic. This exothermic regeneration step may further offset the heat input requirement to sustain the dehydrogenation reaction. In some embodiments, the heat generated by the oxygen carrier regeneration and combustion reaction may fully compensate for the heat required for the endothermic dehydrogenation reaction and other heat demands, such as heating the feed gas (air, hydrocarbons, etc.) or balancing heat losses, or may at least reduce the need for any supplemental fuel 172 in the system. For further generalized information regarding dehydrogenation reactions incorporating hydrogen combustion, those skilled in the art are directed, for example, to U.S. Patent Application Publication No. 2021 / 0292259(A1), the teachings of which are incorporated herein by reference in their entirety.

[0037] 1 , during operation of dehydrogenation reactor 110 of reactor system 100, feed stream 102 may enter a riser within dehydrogenation reactor 110, and product stream 114 may exit reactor system 100 via stream 114. According to one or more embodiments, reactor system 100 may operate by feeding a chemical feed (e.g., in feed stream 102, such as feed stream 102) into dehydrogenation reactor 110.

[0038] According to one or more embodiments, particulate solids 180 may be fed into dehydrogenation reactor 110 via stream 152. Particulate solids 180 may include an oxygen-rich oxygen carrier material. Particulate solids 180 may also include a dehydrogenation catalyst. Feed stream 102 may contact particulate solids 180 in dehydrogenation reactor 110. Each of feed stream 102 and particulate solids 180 may flow upwardly into and pass through dehydrogenation reactor 110 to produce one or more products, an oxygen-depleted oxygen carrier material, and hydrogen. In dehydrogenation reactor 110, one or more hydrocarbons in feed stream 102 may be dehydrogenated to form one or more products and hydrogen. Additionally, in dehydrogenation reactor 110, hydrogen may contact an oxygen-rich oxygen carrier material in dehydrogenation reactor 110. The oxygen-rich oxygen carrier material may be reducible. Contacting the oxygen-rich oxygen carrier material with hydrogen can combust the hydrogen and reduce the oxygen carrier material to form an oxygen-depleted oxygen carrier material and water.

[0039] In one or more embodiments, one or more products may exit dehydrogenation reactor 110 via product stream 114. Stream 114 may be further processed, such as by one or more subsequent separation steps, or may be further reacted. It is contemplated that stream 114 may be utilized as a feed for another reactor system or sold as a chemical product. In embodiments, one or more products in stream 114 may be combined with water produced from reacting hydrogen produced during the dehydrogenation of one or more hydrocarbons with oxygen from the oxygen carrier material. In some embodiments, water may be removed from stream 114 and one or more products utilizing a condenser.

[0040] As noted above, in some embodiments, stream 114 may include one or more products. In one or more embodiments, the one or more products may include one or more olefinic compounds. As used herein, the term "olefinic compound" refers to a hydrocarbon having one or more carbon-carbon double bonds, separate from the formal double bonds in aromatic compounds. For example, ethylene and styrene are olefinic compounds, but ethylbenzene is not an olefinic compound because the only double bonds present in ethylbenzene are formal double bonds present as part of the aromatic structure. In one or more embodiments, the one or more olefinic compounds may include one or more of ethylene, propylene, butylene, or styrene. In some embodiments, product stream 114 may include at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, or even at least 99 wt% ethylene. In additional embodiments, stream 114 may comprise at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or even at least 99% by weight propylene. In additional embodiments, stream 114 may comprise at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or even at least 99% by weight butylenes. In additional embodiments, stream 114 may comprise at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or even at least 99% by weight styrene. In additional embodiments, stream 114 may comprise, in total, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or even at least 99% by weight of one or more of ethylene, propylene, butylene, and styrene.

[0041] In some embodiments, the one or more products and particulate solids 180 may be sent to a separator in a separation section within dehydrogenation reactor 110. In a separator (not shown in FIG. 1 ) within dehydrogenation reactor 110, particulate solids 180 may be separated from the one or more products. The one or more products may then be transported out of the separation section of dehydrogenation reactor 110. For example, separated vapors may be removed from dehydrogenation reactor 110 via a pipe at a gas outlet port of the separation section within dehydrogenation reactor 110. According to one or more embodiments, the separation device may be a cyclone separation system. The cyclone separation system may include two or more stages of cyclone separation.

[0042] In one or more embodiments, the dehydrogenation reactor 110 may operate at a vapor residence time in the dehydrogenation reactor 110 of less than 10 seconds (such as less than 9 seconds, less than 8 seconds, less than 7 seconds, less than 6 seconds, less than 5 seconds, less than 4 seconds, or even less than 3 seconds).

[0043] In one or more embodiments, the dehydrogenation reactor 110 can operate at a temperature of 550°C or higher and 800°C or lower. In some embodiments, the temperature in the dehydrogenation reactor 110 can be 550°C or 600°C to 770°C. In other embodiments, the temperature in the dehydrogenation reactor 110 can be 700°C to 750°C. Without being bound by any particular theory, it is believed that if the temperature is too low (e.g., below 550°C), equilibrium constraints may limit the maximum hydrocarbon conversion rate and slow the rate of dehydrogenation due to heat and catalytic components. If the temperature is too low, the rate of oxygen release from the oxygen carrier material may also be slow, and hydrogen combustion may also be reduced. On the other hand, high temperatures (e.g., above 800°C) may cause thermal degradation of the desired products produced, resulting in lower product selectivities than are economically feasible. In some embodiments, the primary feed components can be propane, ethylbenzene, and / or butane, and the dehydrogenation reactor 110 can operate at temperatures above 600°C. In an additional embodiment, the primary feed component may be ethane and the dehydrogenation reactor 110 may operate at a temperature of at least 625°C.

[0044] In some embodiments, dehydrogenation reactor 110 may operate at a pressure of at least atmospheric pressure (about 14.7 psia). In some embodiments, dehydrogenation reactor 110 may operate at a pressure of about 500 psia. In other embodiments, dehydrogenation reactor 110 may operate at a pressure of about 4 psia to about 160 psia, about 20 psia to about 100 psia, or about 30 psia to about 80 psia. In some embodiments, regeneration unit 150 may operate at a pressure within 30 psia of dehydrogenation reactor 110.

[0045] The residence time of the particles in the dehydrogenation reactor 110 can typically vary from 0.5 seconds (sec) to 360 seconds. In other embodiments, the residence time of the particulate solids 180 can be from about 0.5 seconds to about 200 seconds, from about 0.5 seconds to about 100 seconds, from about 0.5 seconds to about 50 seconds, or from about 0.5 seconds to about 20 seconds.

[0046] In additional embodiments, the ratio of particulate solids 180 in dehydrogenation reactor 110 to feed stream 102 on a weight-to-weight (w / w) basis can range from 5 to 150. In some embodiments, the ratio can range from 10 to 40, such as from 12 to 36, or from 12 to 24.

[0047] In additional embodiments, the flow rate of particulate solids 180 is 1 pound per square foot per second (lb / ft ) in the upstream reactor section. 2 -s)(approx. 4.89kg / m 2 -s)~300lb / ft 2 -s(about 97.7kg / m 2 -s), e.g., 1 to 20 lb / ft 2 -s, etc., and in the downstream reactor section may be 1 lb / ft 2 -s(about 48.9kg / m 2 -s)~300lb / ft 2 -s(about 489kg / m 2 -s), e.g., 10-100 lb / ft 2 -s, etc.

[0048] In one or more embodiments, particulate solid 180 may be capable of fluidization. In some embodiments, particulate solid 180 may exhibit what is known in the industry as "Geldart A" or "Geldart B" properties. Particles may be classified as "Group A" or "Group B" according to D. Geldart, Gas Fluidization Technology, John Wiley & Sons (New York, 1986), 34-37, and D. Geldart, "Types of Gas Fluidization," Powder Technol. 7 (1973) 285-292, which are incorporated herein by reference in their entireties.

[0049] Group A is understood by those skilled in the art to represent aerated powders with bubble-free fluidization; high bed expansion; slow, linear degassing rate; bubble characteristics where splitting / re-coalescing bubbles may predominate, with maximum bubble size and large wake; high levels of solids mixing and gas backmixing assuming equal U-Umf (where U is the carrier gas velocity and Umf is the minimum fluidization velocity, typically but not necessarily measured in meters per second, m / s, i.e., excess gas velocity exists); axisymmetric slug characteristics; and no eruptions except in very shallow beds. Assuming equal cfp, the listed properties tend to improve as the average particle size decreases; or as the fraction less than 45 micrometers (μm) increases; or as the gas pressure, temperature, viscosity, and density increase. Generally, particles with small average particle size and / or low particle density (1.4 grams per cubic centimeter, g / cm) 3 They exhibit a viscosity of less than 1000 psi, are easily fluidized with smooth fluidization at low gas velocities, and may exhibit controlled bubbling with small bubbles even at higher gas velocities.

[0050] Group B begins to foam at Umf; shows moderate bed expansion; rapid degassing; no restriction on bubble size; assuming U-Umf is equal, the levels of solid mixing and gas backmixing are moderate; both axisymmetric and asymmetric slags; and jets only in shallow beds; is understood by those skilled in the art as representing a "sand-like" powder. These characteristics tend to improve as the average particle size decreases, but the particle size distribution and, with some uncertainty, the gas pressure, temperature, viscosity, or density do not appear to contribute much to the improvement of the above characteristics. Generally, most of the particles have a particle size (cfp) of 40 μm < cfp < 500 μm for a density (pp) of 1.4 < pp < 4 g / cm 3 in the case of 4 g / cm 3 is 60 μm < cfp < 500 μm, and for a density (pp) of 1 g / cm 3 in the case of is 250 μm < cfp < 100 μm.

[0051] 1 , in one or more embodiments, particulate solids 180 and gas products may be separated within dehydrogenation reactor 110 by high-efficiency cyclones in a stripping section (not shown in FIG. 1 ) of reactor system 100. The stripping section may be within reactor 110 or may be a separate vessel. In the described embodiment, particulate solids 180 may be sent to regeneration unit 150 via Stream 112. In some embodiments, the dehydrogenation catalyst, the oxygen carrier material, or both may be stripped with a displacement gas, such as nitrogen, steam, methane, natural gas, or other suitable gas, in the stripping section before being sent to regeneration unit 150. In some embodiments, a portion of particulate solids 180 may be sent from the stripping section via Stream 116 to Stream 152 for reuse in reactor 110 without first passing through regeneration unit 150. Without being bound by theory, it is believed that by recycling a portion of the particulate solids 180 back to the reactor 110, the oxygen content of the oxygen carrier material may be better controlled because the oxygen carrier material may have more time to react to release its oxygen, thereby allowing the oxygen carrier material to supply more oxygen to the reactor. It is also believed that recycling the particulate solids 180 may allow for improved temperature control of the reactor 110 because recycling the particulate solids 180 may improve temperature control of the material entering the reactor 110, which may improve the temperature profile of the reactor 110.

[0052] In some embodiments, the dehydrogenation catalyst of the particulate solids 180 may be slightly deactivated after contacting the feed stream 102. In other embodiments, the dehydrogenation catalyst of the particulate solids 180 may still be suitable for reaction in the dehydrogenation reactor 110. As used herein, "deactivated" may refer to a catalyst contaminated with materials such as coke at a temperature lower than that required to promote reaction of the feedstock, or an oxygen-carrying material that is deficient in oxygen. In some embodiments, contaminants such as coke may accumulate on the particulate solids 180 sent from the dehydrogenation reactor 110 to the regeneration unit 150.

[0053] The particulate solids 180 may enter the regeneration unit 150 via stream 112. The particulate solids 180 may then enter a gas / solid separator 158 within the regeneration unit 150. Upon exiting the separator 158, the particulate solids 180 may pass through an air zone 164 and through a first gas inlet 160 through which an oxygen-containing gas 162 enters the regeneration unit 150. The particulate solids 180 may then pass through a fuel zone 174 and through a second gas inlet 170 through which a fuel 172 enters the regeneration unit 150. The particulate solids 180 may then exit the regeneration unit 150 via stream 152 and be sent back to the dehydrogenation reactor 110.

[0054] Regeneration may remove contaminants such as coke, increase the temperature of particulate solids 180, increase the oxygen content of the oxygen-carrying material of particulate solids 180, or a combination thereof. In some embodiments, coke on particulate solids 180 may be removed by combustion in an oxygen-containing environment in regeneration unit 150. In further embodiments, particulate solids 180 may be heated to a target temperature by fuel 172. Particulate solids 180 may then be circulated back to dehydrogenation reactor 110, thereby carrying the heat required for the dehydrogenation reaction. For more generalized information regarding dehydrogenation performed in a fluidized bed, those skilled in the art are referred to, for example, U.S. Patent Application Publication No. 2005 / 0177016 (A1); WO 2005 / 077867 (A1) (corresponding to U.S. Patent Application Publication No. 2008 / 0194891 (A1)); and WO 20107591 (A1).

[0055] The oxygen carrier may be oxidized or reduced when utilized in the dehydrogenation process. Different oxidation states of the oxygen carrier may behave differently within the dehydrogenation process. For example, an oxygen carrier with a lower oxidation state may not combust hydrogen as efficiently within the dehydrogenation reaction as an oxygen carrier with a relatively higher oxidation state. Conversely, an oxygen carrier with a relatively high oxidation state may be more likely to oxidize hydrocarbons during the dehydrogenation reaction compared to an oxygen carrier with a relatively low oxidation state, potentially harming the production of olefins from the process. Passing the oxygen carrier through a regeneration unit 150 may help control the oxidation state of the oxygen carrier material.

[0056] In some embodiments, the oxygen-depleted oxygen carrier material of the particulate solids 180 can be reoxidized to an oxidation state higher than the oxidation state of the oxygen-depleted oxygen carrier material by combustion in an oxygen-containing environment in the regeneration unit 150. In some embodiments, the oxygen-containing environment can be air. In some embodiments, forming an oxygen-rich oxygen carrier material, the oxygen-depleted oxygen carrier material can be restored to its original oxidation state. In some embodiments, the oxygen-depleted oxygen carrier material can have an oxidation state of +2, +3, or +4. The oxygen-rich oxygen carrier material can then be recycled back to the dehydrogenation reactor 110, carrying the heat required for the dehydrogenation reaction. In other embodiments, nitrogen or steam can also be used to transport the oxygen-rich oxygen carrier material to the dehydrogenation reactor 110. The gas stream 154 obtained from the regeneration unit 150 can consist of air that is O2-depleted or contains a lower concentration of O2.

[0057] In one or more embodiments, the supplemental fuel 172 may be combusted in the regeneration unit 150 to generate heat and increase the temperature of the particulate solids 180. The heat generated by the oxidation of the oxygen-depleted oxygen-carrying material and the combustion of the supplemental fuel 172 may be sufficient to maintain the temperature of the dehydrogenation reactor 110 at a desired temperature. The desired temperature may depend on the minimum temperature required to operate the dehydrogenation reactor 110, as the particulate solids 180 may enter and impart its temperature to the dehydrogenation reactor 110.

[0058] In one or more embodiments, the regeneration unit 150 may operate at a temperature of 650°C or even 700°C to 900°C, such as 725°C to 875°C, or 750°C to 850°C. Generally, the regeneration unit 150 may have a temperature at least 50°C higher than the temperature of the dehydrogenation reactor 110. Such a temperature range may be utilized such that the temperature of the dehydrogenation reactor 110 can be maintained with a limited amount of dehydrogenation catalyst and / or oxygen carrier material. Furthermore, such temperatures may be necessary to activate the dehydrogenation catalyst, if utilized.

[0059] The residence time of particulate solids 180 within regeneration unit 150 can typically vary from 0.5 seconds (s) to 240 seconds. In other embodiments, the residence time of particulate solids 180 can be from about 0.5 seconds to about 200 seconds, from about 0.5 seconds to about 100 seconds, from about 0.5 seconds to about 50 seconds, or from about 0.5 seconds to about 20 seconds.

[0060] Continuing with reference to FIG. 1 , in one or more embodiments, particulate solids 180 may be sent from dehydrogenation reactor 110 to regeneration unit 150 via stream 112. In regeneration unit 150, particulate solids 180 may pass through gas / solid separator 158. According to one or more embodiments, separator 158 may be a riser end system, which may include a cyclone separation system. In embodiments in which the riser end system includes a cyclone separation system, a portion of particulate solids 180 may be discharged from the riser end system without first passing through the cyclone separation system. The cyclone separation system may include two or more stages of cyclone separation. In embodiments in which separator 158 includes two or more cyclone separation stages, the first separator into which the fluidized stream enters is referred to as the primary cyclone separator. The fluidized effluent from the primary cyclone separator may enter a secondary cyclone separator for further separation. Primary cyclone separators may include, for example, primary cyclones and systems commercially available under the designations VSS (available from UOP), LD2 (available from Stone and Webster), and RS2 (available from Stone and Webster). Primary cyclones are described, for example, in U.S. Pat. Nos. 4,579,716, 5,190,650, and 5,275,641, each of which is incorporated herein by reference in its entirety. In some separation systems utilizing a primary cyclone as the primary cyclone separator, one or more sets of additional cyclones, such as secondary and tertiary cyclones, are used to further separate the particulate solids from the product gas. It should be understood that any primary cyclone separator may be used in embodiments of the present invention. The particulate solids 180 may be separated from an exhaust gas, such as a flue gas. The gas separated from the particulate solids 180 may be mixed with the gas from the regeneration unit 150 and exit the regeneration unit 150 via exhaust stream 154 .

[0061] According to embodiments, the particulate solids 180 may move in a generally downward direction through the regeneration unit 150. As used herein, the term "generally downward direction" means that the average velocity of the particulate solids 180 is a downward direction, where the downward direction is due to gravity. As an average, the velocities of individual particles of the particulate solids 180 may have a distribution and may not equal the average, but overall, the velocity of the particulate solids 180 is generally downward on average. According to embodiments, the gas within the regeneration unit 150 may move in a generally upward direction through the regeneration unit 150. As used herein, the term "generally upward direction" means that the average velocity of the gas is an upward direction, where the upward direction opposes the attractive force of gravity. As an average, the velocities of the gas molecules within the regeneration unit 150 may have a distribution and may not equal the average, but overall, the velocity of the gas is generally upward on average. According to an embodiment, the particulate solids 180 and gas may move through the regeneration unit 150 in a countercurrent pattern.

[0062] In one or more embodiments, the regeneration unit 150 may include a first gas inlet 160 and a second gas inlet 170 below the first gas inlet 160. As used herein, "gas inlet" refers to any component operable to inject gas into the regeneration unit 150. For example, the gas inlet may be a blower or a distributor. Additionally, other suitable gas suppliers are contemplated herein, as known to those skilled in the art.

[0063] According to embodiments, oxygen-containing gas 162 may enter regeneration unit 150 via first gas inlet 160. In some embodiments, oxygen-containing gas 162 may be air, enriched air, air mixed with steam, or flue gas. Enriched air is air with added oxygen gas. In some embodiments, oxygen-containing gas 162 may contain at least 28 mol% oxygen. In other embodiments, oxygen-containing gas 162 may contain between about 2 mol% and about 28 mol% oxygen, between about 2 mol% and about 25 mol%, between about 2 mol% and about 20 mol%, between about 2 mol% and about 15 mol%, between about 2 mol% and about 10 mol%, between about 2 mol% and about 5 mol%, between about 5 mol% and about 28 mol%, between about 5 mol% and about 25 mol%, between about 5 mol% and about 20 mol%, between about 5 mol% and about 15 mol%, or between about 5 mol% and about 28 mol%. % to about 10 mol%, about 10 mol% to about 28 mol%, about 10 mol% to about 25 mol%, about 10 mol% to about 20 mol%, about 10 mol% to about 15 mol%, about 15 mol% to about 28 mol%, about 15 mol% to about 25 mol%, about 15 mol% to about 20 mol%, about 20 mol% to about 28 mol%, about 20 mol% to about 25 mol%, or about 25 mol% to about 28 mol% of oxygen.

[0064] In embodiments, the oxygen-containing gas 162 may enter the regeneration unit 150 in a generally upward direction. In some embodiments, the oxygen-containing gas 162 may initially enter the regeneration unit 150 in a generally downward direction before following the generally upward flow of other gases in the regeneration unit 150. In some embodiments, the region above the first gas inlet 160 may be an air zone 164 because the directional flow of the oxygen-containing gas 162 into the regeneration unit 150 may cause the oxygen concentration in the region above the first gas inlet 160 to be higher than other regions of the regeneration unit 150. In one or more embodiments, the oxygen concentration in the air zone 164 may be greater than 25 mole %. In other embodiments, the oxygen concentration in air zone 164 can be between about 4 mol% and about 28 mol% oxygen, between about 4 mol% and about 21 mol%, between about 4 mol% and about 10 mol%, between about 10 mol% and about 28 mol%, between about 10 mol% and about 21 mol%, or between about 21 mol% and about 28 mol% oxygen. Because air is often the least costly oxygen-containing gas available, the name air is used herein simply to indicate the presence of oxygen.

[0065] In one or more embodiments, fuel 172 may enter regeneration unit 150 via second gas inlet 170. In some embodiments, fuel 172 may include hydrogen, methane, ethane, propane, natural gas, or combinations thereof. According to embodiments, fuel 172 may enter regeneration unit 150 in a generally upward direction. In some embodiments, fuel 172 may initially enter regeneration unit 150 in a generally downward direction before following the generally upward flow of other gases in regeneration unit 150. In embodiments, at least a portion of fuel 172 in the region above second gas inlet 170 and below first gas inlet 160 may react with oxygen from the oxygen-carrying material of particulate solids 180 to generate heat, increasing the temperature of particulate solids 180 and reducing the oxygen content. In an embodiment, the region above the second gas inlet 170 and below the first gas inlet 160 may be a fuel zone 174 because the directional flow of fuel 172 into the regeneration unit 150 may cause the concentration of fuel 172 in the region above the second gas inlet 170 and below the first gas inlet 160 to be higher than the concentration of fuel 172 in the region above the first gas inlet 160 or the region below the second gas inlet 170.

[0066] In some embodiments, the concentration of fuel 172 in fuel zone 174 can be greater than 20 mol%, greater than 50 mol%, or even greater than 90 mol%. In some embodiments, the concentration of fuel 172 in fuel zone 174 can be between about 40 mol% and about 100 mol%, between about 40 mol% and about 90 mol%, between about 40 mol% and about 80 mol%, between about 40 mol% and about 70 mol%, between about 40 mol% and about 60 mol%, between about 40 mol% and about 50 mol%, between about 50 mol% and about 100 mol%, between about 50 mol% and about 90 mol%, between about 50 mol% and about 80 mol%, or between about 50 mol% and about It may be 70 mol%, about 50 mol% to about 60 mol%, about 60 mol% to about 100 mol%, about 60 mol% to about 90 mol%, about 60 mol% to about 80 mol%, about 60 mol% to about 70 mol%, about 70 mol% to about 100 mol%, about 70 mol% to about 90 mol%, about 70 mol% to about 80 mol%, about 80 mol% to about 100 mol%, about 80 mol% to about 90 mol%, or about 90 mol% to about 100 mol%.

[0067] In embodiments, at least a portion of the oxygen-depleted oxygen-carrying material of the particulate solids 180 may react with oxygen from the oxygen-containing gas 162 in the air zone 164, and the oxygen content of at least a portion of the oxygen-carrying material of the particulate solids 180 may increase to form oxygen-enriched oxygen-carrying material of the particulate solids 180. In some embodiments, at least a portion of the fuel 172 may travel upward through the regeneration unit 150 to the air zone 164 without being combusted in the fuel zone 174. In some embodiments, at least a portion of the fuel 172 may react with oxygen from the oxygen-containing gas 162 in a region above the first gas inlet 162. In some embodiments, any fuel 172 remaining in the regeneration unit 150 after combustion of the fuel 172 in the fuel zone 174 may be combusted in the air zone 164, such that a majority of the fuel 172 entering the regeneration unit 150 through the second gas inlet 170 is combusted within the regeneration unit 150. For example, it may be desirable to ensure that a majority of the fuel 172 is combusted within the regeneration unit 150 to sufficiently heat the particulate solids 180 using a minimal amount of fuel 172, or to ensure that only a minimal amount of fuel 172 exits the regeneration unit 150 to downstream processes, which may improve the safety of those processes. In one or more embodiments, at least a portion of the particulate solids 180 may be sent back from the regeneration unit 150 to the dehydrogenation reactor 110 via stream 152.

[0068] Without being bound by theory, it is believed that by exposing the oxygen carrier material to fuel 172 in the region of the regeneration unit 150 after exposing the oxygen carrier material to oxygen-containing gas 162, the oxygen content of at least a portion of the oxygen carrier material may be reduced as oxygen from the oxygen carrier material reacts with fuel 172. The oxygen carrier material may then exit the regeneration unit 150 without replacing oxygen released during combustion of fuel 172 and return to the dehydrogenation reactor 110 in a pre-reduced state. A portion of the oxygen carrier material may have desired activity and selectivity for particular reaction conditions in a reduced state that is less than the maximum oxidation level of the material. Therefore, it may be desirable to pre-reduce the material before it exits the regeneration unit 150. For example, by exposing the oxygen carrier material to fuel 172 below oxygen-containing gas 162 in a countercurrent pattern, the regeneration unit 150 may allow the oxygen carrier material to be sufficiently pre-reduced before exiting the regeneration unit 150, so that further reduction may not be required.

[0069] It is also believed that pre-reduction using supplemental fuel 172 in regeneration unit 150 may utilize sufficient fuel 172 combustion to heat particulate solids 180 sufficiently for use in the dehydrogenation reaction. Additionally, pre-reduction using fuel 172 may produce exhaust gases such as carbon dioxide and water. It may be beneficial to produce these gases in regeneration unit 150 and allow them to be vented along with other combustion gases produced in regeneration, for example, from the combustion of coke on particulate solids 180.

[0070] 2 , reactor system 200 according to an additional embodiment of the present disclosure is shown. Particulate solids 180 may first be sent from dehydrogenation reactor 110 to pre-oxidation unit 210 via stream 112 before being sent to regeneration unit 150. Oxygen-containing gas 212 may enter pre-oxidation unit 210, and particulate solids 180 may be exposed to oxygen-containing gas 212. Oxygen-containing gas 212 and particulate solids 180 may flow generally co-currently in an upward direction through pre-oxidation unit 210, exit pre-oxidation unit 210 via stream 222, and then be sent to regeneration unit 150. The particulate solids 180 may flow through the regeneration unit 150 in a generally downward direction, first through the air zone 164, then through a third gas inlet 140 below the first gas inlet 160 and above the second gas inlet 170, through which the stripping gas 142 enters the regeneration unit 150. The particulate solids 180 may flow through the fuel zone 174, then through a fourth gas inlet 130 below the second gas inlet 170, through which the stripping gas 132 enters the regeneration unit 150. The particulate solids 180 may then exit the regeneration unit 150 via stream 152 and be sent back to the dehydrogenation reactor 110. The pre-oxidation unit 210 and the third gas inlet 140 are optional additions to the reactor system 200. In one or more embodiments, the reactor system 200 may include a pre-oxidation unit 210 but may not include the third gas inlet 140 or the fourth gas inlet 130. In some embodiments, the reactor system 200 may include the third gas inlet 140 but may not include the pre-oxidation unit 210 or the fourth gas inlet 130. In some embodiments, the reactor system 200 may include the fourth gas inlet 130 but may not include the pre-oxidation unit 210 or the third gas inlet 140. In some embodiments, the reactor system 200 may include the pre-oxidation unit 210 and the third gas inlet 140 but may not include the fourth gas inlet 130. In some embodiments, the reactor system 200 may include the pre-oxidation unit 210 and the fourth gas inlet 130 but may not include the third gas inlet 140.In some embodiments, the reactor system 200 may include a third gas inlet 140 and a fourth gas inlet 130 , but may not include a pre-oxidation unit 210 .

[0071] 2, in one or more embodiments, the particulate solids 180 may be sent from the dehydrogenation reactor 110 to a pre-oxidation unit 210 before being sent to the regeneration unit 150. In one or more embodiments, an oxygen-containing gas 212 may enter the pre-oxidation unit 210. In some embodiments, the oxygen-containing gas 212 may be air, enriched air, air mixed with steam, or flue gas. Enriched air is air with oxygen gas added. In some embodiments, the oxygen-containing gas 212 may include at least 28 mole percent oxygen. In other embodiments, the oxygen-containing gas 212 is between about 2 mol% and about 28 mol% oxygen, between about 2 mol% and about 25 mol%, between about 2 mol% and about 20 mol%, between about 2 mol% and about 15 mol%, between about 2 mol% and about 10 mol%, between about 2 mol% and about 5 mol%, between about 5 mol% and about 28 mol%, between about 5 mol% and about 25 mol%, between about 5 mol% and about 20 mol%, between about 5 mol% and about 1 ...8 mol%, % to about 10 mol%, about 10 mol% to about 28 mol%, about 10 mol% to about 25 mol%, about 10 mol% to about 20 mol%, about 10 mol% to about 15 mol%, about 15 mol% to about 28 mol%, about 15 mol% to about 25 mol%, about 15 mol% to about 20 mol%, about 20 mol% to about 28 mol%, about 20 mol% to about 25 mol%, or about 25 mol% to about 28 mol% of oxygen.

[0072] In embodiments, the oxygen-carrying material of the particulate solids 180 may be exposed to the oxygen-containing gas 212 in the pre-oxidation unit 210. In some embodiments, the oxygen content of at least a portion of the oxygen-carrying material of the particulate solids 180 may be increased in the pre-oxidation unit 210. In some embodiments, the oxygen-containing gas 162 and the particulate solids 180 may flow generally co-currently in an upward direction through the pre-oxidation unit 210. As used herein, "generally co-currently" means that the average velocities of the particulate solids 180 and the oxygen-containing gas 162 are in the same direction. As an average, the velocities of individual particles of the particulate solids 180 or individual gas molecules of the oxygen-containing gas 162 may have a distribution and may not be equal to the average, but overall, the velocities of both components are, on average, generally in the same direction. In some embodiments, coke that may form on the particulate solids 180 in the dehydrogenation reactor 110 may be combusted in the pre-oxidation unit 210, which heats at least a portion of the particulate solids 180. In some embodiments, carryover fuel 172 from the regeneration unit 150 , the reactor 110 , or both may react in the pre-oxidation unit 210 to heat at least a portion of the particulate solids 180 .

[0073] In one or more embodiments, the particulate solids 180 may be sent from the pre-oxidation unit 210 to the regeneration unit 150 via path 222. In some embodiments, the particulate solids 180 may be mixed with gases as they are sent to the regeneration unit 150, such as the oxygen-containing gas 212 from the pre-oxidation unit 210, combustion gases from the combustion of coke in the pre-oxidation unit 210, carryover gases from the dehydrogenation reactor 110, or combinations thereof. In one or more embodiments, the particulate solids 180 may be returned from the regeneration unit 150 to the pre-oxidation unit 210 via stream 156, thereby allowing the particulate solids 180 to be passed through the pre-oxidation unit 210 and the regeneration unit 150 at least one additional time.

[0074] In one or more embodiments, the particulate solids 180 may be sent from the regeneration unit 150 to the pre-oxidation unit 210. For example, the particulate solids 180 may be sent back to the pre-oxidation unit 210 to achieve a desired level of oxidation of the oxygen-carrying material of the particulate solids 180 or to remove coke from the particulate solids 180. In some embodiments, the particulate solids 180 may exit the regeneration unit 150 from the fuel zone 174 and be sent to the pre-oxidation unit 210, and be passed again through the pre-oxidation unit 210 and the regeneration unit 150. In other embodiments, the particulate solids 180 may exit the regeneration unit 150 from the air zone 164 and be sent to the pre-oxidation unit 210, and be passed again through the pre-oxidation unit 210 and the regeneration unit 150. In further embodiments, the particulate solids 180 may exit the regeneration unit 150 from both the air zone 164 and the fuel zone 174 and be sent to the pre-oxidation unit 210.

[0075] 2 , in one or more embodiments, the regeneration unit 150 may include a third gas inlet 140. In embodiments, the stripping gas 142 may enter the regeneration unit 150 through the third gas inlet 140. In embodiments, the third gas inlet 140 may be located below the first gas inlet 160 and above the second gas inlet 170. In embodiments, the stripping gas 142 may exit the third gas inlet 140 in a generally upward direction. In some embodiments, the stripping gas 142 may initially exit the third gas inlet in a downward direction before following the generally upward flow of other gases within the regeneration unit 150. Thus, in embodiments, the directional flow of stripping gas 142 into regeneration unit 150 may cause the concentration of stripping gas 132 to be higher in the region above third gas inlet 140 and below first gas inlet 160, such that the region above third gas inlet 140 and below first gas inlet 160 may be first strip zone 144. In some embodiments, stripping gas 142 may include nitrogen, steam, or a combination thereof. Without being bound by theory, it is believed that the use of first strip zone 144 may limit or prevent gas phase oxygen from oxygen-containing gas 162 from entering fuel zone 174. It is believed that gas phase oxygen in fuel zone 174 may oxidize the oxygen carrier material or limit the amount of oxygen from the oxygen carrier material used to react fuel 172, thereby reducing the reduction of the oxygen carrier material in fuel zone 174.

[0076] In one or more embodiments, the regeneration unit 150 may include a fourth gas inlet 130. In embodiments, the fourth gas inlet 130 may be located below the second gas inlet 170. In one or more embodiments, the stripping gas 132 may enter the regeneration unit 150 through the fourth gas inlet 130. In embodiments, the stripping gas 132 may exit the fourth gas inlet 130 in a generally upward direction. Thus, in embodiments, the directional flow of the stripping gas 132 into the regeneration unit 150 may cause the concentration of the stripping gas 132 to be higher in the region above the fourth gas inlet 130 and below the second gas inlet 170, such that the region above the fourth gas inlet 130 and below the second gas inlet 170 may be the second strip zone 134. In some embodiments, the stripping gas 132 may include nitrogen, steam, or a combination thereof. Without being bound by theory, it is believed that the use of the second strip zone 134 below the fuel zone 174 may limit or prevent carryover of fuel 172 from the fuel zone 174 to the reactor 110. Carryover fuel 172 entering the reactor 110 may prevent the reactor 110 from operating efficiently, for example, by burning within the reactor 110 and increasing the temperature within the reactor 110, or by utilizing oxygen from an oxygen carrier material to burn within the reactor 110 and limit the amount of oxygen available to convert hydrogen to water within the reactor 110.

[0077] In one or more embodiments, the regeneration unit 150 may include both the third gas inlet 140 and the fourth gas inlet 130. In other embodiments, the regeneration unit 150 may include the third gas inlet 140 but not the fourth gas inlet 130. In other embodiments, the regeneration unit 150 may include the fourth gas inlet 130 but not the third gas inlet 140. Thus, in one or more embodiments, the regeneration unit 150 may include the first strip zone 144 but not the second strip zone 134, the second strip zone 134 but not the first strip zone 144, or both the first strip zone 144 and the second strip zone 134.

[0078] In one or more embodiments, at least a portion of the particulate solids 180 may be removed from the regeneration unit 150 and passed through at least a portion of the regeneration unit 150 a second time before being passed through the dehydrogenation reactor 110. Thus, in some embodiments, at least a portion of the particulate solids 180 may be removed from a region above the fuel zone 174, from a region above the first strip zone 144, from a region below the second strip zone 134, from the air zone 164, or a combination thereof. In embodiments, the removed particulate solids 180 may be returned to the regeneration unit 150 at any location above the location from which the removed particulate solids 180 were removed. For example, if a portion of the particulate solids 180 were removed from the fuel zone 174, they may be returned to the regeneration unit 150 at any location above the fuel zone 174, such as the air zone 164, the first strip zone 144, or both.

[0079] In a first aspect of the present disclosure, hydrocarbons can be dehydrogenated by a method comprising contacting a feed stream containing one or more hydrocarbons with a particulate solid in a dehydrogenation reactor. The particulate solid comprises an oxygen carrier material. In the dehydrogenation reactor, the one or more hydrocarbons are dehydrogenated to form hydrogen and one or more products. At least a portion of the hydrogen reacts with oxygen from the oxygen carrier material to form water, reducing the oxygen content in the oxygen carrier material. The process further comprises passing the particulate solid from the dehydrogenation reactor to a regeneration unit. The particulate solid moves through the regeneration unit in a generally downward direction, and the gas moves through the regeneration unit in a generally upward direction, such that the particulate solid and the gas move through the regeneration unit in a countercurrent pattern. The regeneration unit comprises a first gas inlet and a second gas inlet. The second gas inlet is located below the first gas inlet. An oxygen-containing gas enters the regeneration unit through the first gas inlet. The fuel enters the regeneration unit through the second gas inlet. In a region of the regeneration unit above the second gas inlet and below the first gas inlet, at least a portion of the fuel reacts with oxygen from the particulate solid oxygen carrier material. The method further includes passing at least a portion of the particulate solids from the regeneration unit to a dehydrogenation unit.

[0080] A second aspect of the present disclosure may include the first aspect, wherein the oxygen content of at least a portion of the particulate solid oxygen carrier material is increased in a region of the regeneration unit above the first gas inlet.

[0081] A third aspect of the present disclosure includes any of the aforementioned aspects or combinations thereof, wherein at least a portion of the fuel moves to a region of the regeneration unit above the first gas inlet, and in the region of the regeneration unit above the first gas inlet, at least a portion of the fuel reacts with oxygen from the oxygen-containing gas.

[0082] A fourth aspect of the present disclosure includes any of the preceding aspects or combinations of those aspects, wherein the one or more hydrocarbons include an alkyl moiety and the one or more products include one or more olefinic compounds.

[0083] A fifth aspect of the present disclosure includes any of the preceding aspects or combinations of those aspects, wherein the one or more hydrocarbons include ethane and the one or more products include ethylene.

[0084] A sixth aspect of the present disclosure includes any of the preceding aspects or combinations of those aspects, wherein the fuel includes hydrogen.

[0085] A seventh aspect of the present disclosure includes any of the preceding aspects or combinations of those aspects, wherein coke is deposited on particulate solids passed from the dehydrogenation reactor to a regeneration unit, and at least a portion of the coke is reacted with oxygen in the regeneration unit.

[0086] An eighth aspect of the present disclosure includes any of the preceding aspects or combinations of those aspects, wherein passing the particulate solids from the dehydrogenation reactor to the regeneration unit includes passing the particulate solids through a pre-oxidation unit, wherein the particulate solids are exposed to an oxygen-containing gas in the pre-oxidation unit, whereby the oxygen content in the oxygen carrier material of the particulate solids is increased in the pre-oxidation unit.

[0087] A ninth aspect of the present disclosure includes any of the preceding aspects or combinations of those aspects, wherein the particulate solids and the oxygen-containing gas flow generally co-currently in an upward direction through the pre-oxidation unit.

[0088] A tenth aspect of the present disclosure includes any of the preceding aspects or combinations thereof, wherein the regeneration unit further comprises a third gas inlet below the first gas inlet and above the second gas inlet, and a fourth gas inlet below the second gas inlet, and wherein the stripping gas enters the regeneration unit through the third gas inlet and the fourth gas inlet.

[0089] An eleventh aspect of the present disclosure includes any of the preceding aspects or combinations of those aspects, wherein a portion of the particulate solids is removed from the regeneration unit and passed through at least a portion of the regeneration unit a second time before being passed to the dehydrogenation reactor.

[0090] A twelfth aspect of the present disclosure includes any of the preceding aspects or combinations of those aspects, wherein a portion of the removed particulate solids is removed from the regeneration unit from the fuel zone, the first strip zone, the air zone, the second strip zone, or a combination thereof.

[0091] A thirteenth aspect of the present disclosure includes any of the preceding aspects or combinations of those aspects, wherein the solid particulate consists essentially of an oxygen carrier material, and the dehydrogenation of the one or more hydrocarbons is effected by non-catalytic thermal dehydrogenation.

[0092] A fourteenth aspect of the present disclosure includes any of the preceding aspects or combinations of those aspects, wherein the particulate solid further comprises a dehydrogenation catalyst material, and wherein the dehydrogenation of the one or more hydrocarbons is effected at least in part by catalytic dehydrogenation.

[0093] A fifteenth aspect of the present disclosure includes any of the preceding aspects or combinations of those aspects, wherein the dehydrogenation catalyst material and the oxygen carrier material are separate particles of the particulate solid or are contained within the same particle of the particulate solid.

[0094] It will be apparent to those skilled in the art that various modifications and variations can be made to the technology of the present disclosure without departing from the spirit and scope of the technology. Since combinations, subcombinations, and variations of the disclosed embodiments incorporating the spirit and substance of the technology of the present disclosure may occur to those skilled in the art, the technology should be construed as including all within the scope of the appended claims and their equivalents. Furthermore, although some aspects of the present disclosure may be identified herein as preferred or particularly advantageous, it is intended that the present disclosure is not limited to these aspects.

[0095] It should be noted that various details described in this disclosure should not be construed as implying that these details relate to elements that are essential components of the various embodiments described in this disclosure, even if a particular element is illustrated in each of the drawings accompanying this specification. Unless specifically identified as such, features disclosed and described herein should not be construed as "essential." Contemplated embodiments of the present technology include subject matter that includes some or all of the features of the appended claims.

[0096] It should be noted that for purposes of describing and defining this disclosure, the term "about" is utilized in this disclosure to express the inherent degree of uncertainty that may result from any quantitative comparison, value, measurement, or other representation. The term "about" is also utilized in this disclosure to express the degree to which a quantitative representation may vary from the basis of description without resulting in a change in the basic functionality of the subject matter in question.

[0097] Where relevant, when a composition is described as "comprising" one or more elements, embodiments of the composition that "consist" or "consist essentially of" those one or more elements are contemplated herein.

[0098] It is understood that the compositional ranges of chemical components in a stream or reactor should, in some embodiments, be understood to contain a mixture of isomers of that component. For example, a compositional range specifying butene may include a mixture of various isomers of butene. It is understood that the examples provide compositional ranges for various streams, and that the total amount of isomers of a particular chemical composition may constitute a range.

[0099] It should be noted that one or more of the following claims utilize the term "where" or "wherein" as a transitional phrase. It should be noted that for purposes of defining the present technology, this term is introduced in the claims as an open-ended transitional phrase used to introduce the recitation of a series of features of a structure, and should be interpreted in a similar manner to the more commonly used open-ended preamble term "comprising."

[0100] In some embodiments, a chemical or chemical stream is described as being "fed" from one system unit or portion of a system unit to another system unit or portion of a system unit. As described herein, such a feed may include a direct feed or an indirect feed. For example, when feeding from "unit A" to "unit B," a direct feed would have no intermediate destination between unit A and unit B (i.e., directly through a pipe or other transport passageway), while an indirect feed may include one or more intermediate destinations between unit A and unit B. For example, a stream fed from unit A to unit B may pass through, without limitation, a heat exchanger, a processing device, etc.

[0101] It should be understood that any two quantitative values ​​assigned to a property may constitute a range for that property, and all combinations of ranges formed from all stated quantitative values ​​for a given property are contemplated in this application. When multiple ranges are given for quantitative values, these ranges may be combined to form larger ranges, which are contemplated in the embodiments described herein.

Claims

1. A method for dehydrogenating hydrocarbons, A feed stream containing one or more hydrocarbons is brought into contact with particulate solids in a dehydrogenation reactor, wherein the particulate solids contain an oxygen carrier material, and in the dehydrogenation reactor, The aforementioned one or more hydrocarbons are dehydrogenated to form hydrogen and one or more products. At least a portion of the hydrogen reacts with oxygen derived from the oxygen carrier material to form water, thereby reducing the oxygen content in the oxygen carrier material. Making contact, The process involves sending the particulate solid from the dehydrogenation reactor to the regeneration unit, The particulate solid moves through the regeneration unit in a generally downward direction, and the gas moves through the regeneration unit in a generally upward direction, thereby causing the particulate solid and the gas to move through the regeneration unit in a countercurrent pattern. The regeneration unit comprises a first gas inlet and a second gas inlet, the second gas inlet being located below the first gas inlet, oxygen-containing gas entering the regeneration unit through the first gas inlet, and fuel entering the regeneration unit through the second gas inlet. In the region of the regeneration unit above the second gas inlet and below the first gas inlet, at least a portion of the fuel reacts with oxygen derived from the particulate solid oxygen carrier material. Sending, Sending at least a portion of the particulate solid from the regeneration unit to the dehydrogenation reactor, A method that includes this.

2. The method according to claim 1, wherein the oxygen content in at least a portion of the particulate solid oxygen carrier material is increased in the region of the regeneration unit above the first gas inlet.

3. The method according to claim 1, wherein at least a portion of the fuel moves to the region of the regeneration unit above the first gas inlet, and in the region of the regeneration unit above the first gas inlet, at least a portion of the fuel reacts with oxygen derived from the oxygen-containing gas.

4. The method according to claim 1, wherein the one or more hydrocarbons include an alkyl moiety, and the one or more products include one or more olefin compounds.

5. The method according to claim 1, wherein the one or more hydrocarbons include ethane, and the one or more products include ethylene.

6. The method according to claim 1, wherein the fuel includes hydrogen.

7. The method according to claim 1, wherein coke is deposited on particulate solid sent from the dehydrogenation reactor to the regeneration unit, and at least a portion of the coke reacts with oxygen in the regeneration unit.

8. The method according to claim 1, wherein sending the particulate solid from the dehydrogenation reactor to the regeneration unit includes passing the particulate solid through a pre-oxidation unit, the particulate solid being exposed to an oxygen-containing gas in the pre-oxidation unit, thereby increasing the oxygen content in the oxygen carrier material of the particulate solid in the pre-oxidation unit.

9. The method according to claim 8, wherein the particulate solid and the oxygen-containing gas flow through the pre-oxidation unit in an upward direction in a generally parallel flow.

10. The aforementioned regeneration unit A third gas inlet located below the first gas inlet and above the second gas inlet, A fourth gas inlet located below the second gas inlet, Furthermore, The stripping gas enters the regeneration unit through the third gas inlet and the fourth gas inlet. The method according to claim 1.

11. The method according to claim 1, wherein a portion of the particulate solid is removed from the regeneration unit and passes through at least a portion of the regeneration unit a second time before being sent to the dehydrogenation reactor.

12. The method according to claim 11, wherein a portion of the extracted particulate solid is extracted from the regeneration unit from the fuel zone, the first strip zone, the air zone, the second strip zone, or a combination thereof.

13. The method according to claim 1, wherein the particulate solid essentially consists of the oxygen carrier material, and the dehydrogenation of the one or more hydrocarbons is carried out by non-catalytic thermal dehydrogenation.

14. The method according to any one of claims 1 to 13, wherein the particulate solid further comprises a dehydrogenation catalyst material, and the dehydrogenation of the one or more hydrocarbons is carried out at least partially by catalytic dehydrogenation.

15. The method according to claim 14, wherein the dehydrogenation catalyst material and the oxygen carrier material are separate particles of the particulate solid or are contained within the same particle of the particulate solid.

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