Method for dehydrogenating hydrocarbons using combustion unit

Abstract

In accordance with one or more embodiments described herein, a method for dehydrogenating hydrocarbons may include contacting a feed stream comprising one or more hydrocarbons with a particulate solid that may comprise an oxygen carrier material to form hydrogen and one or more products. At least a portion of the hydrogen may react with oxygen from the oxygen carrier material to form water and reduce the oxygen content in the oxygen carrier material. The particulate solids may be passed from the dehydrogenation reactor to a combustion unit. The combustion unit may include a first gas inlet and a second gas inlet that may be above the first gas inlet. An oxygen-containing gas may enter the combustion unit through the first gas inlet, and a fuel may enter the combustion unit through the second gas inlet.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Application Serial No. 63 / 406,447, filed on September 14, 2022, which is hereby incorporated by reference in its entirety. Technical Field

[0003] Embodiments described herein relate generally to chemical processing, and more particularly, to methods and systems for dehydrogenating chemical species. Background Art

[0004] Olefin compounds can be used as basic 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 product packaging, construction, textiles, etc. Therefore, olefin compounds such as ethylene, propylene, butylene and styrene are needed in industry. Summary of the invention

[0005] A method for producing olefin compounds can be carried out by dehydrogenating hydrocarbons. The dehydrogenation reaction can reduce or remove the hydrogen formed during dehydrogenation by reacting hydrogen with oxygen to form water to promote, which pushes the balance to the olefin compound product. In such embodiments, oxygen carrier materials can be utilized to provide oxygen reacting with hydrogen. The oxygen carrier material can be contained in a granular solid. This oxygen carrier material can be circulated through a reactor and a combustion unit, wherein a fuel can be burned to at least heat the oxygen carrier material.

[0006] As described herein, it has been found that utilizing a co-current flow pattern for particulate solids and gas in a combustion unit may be beneficial.Especially, embodiments described herein include flow patterns, wherein particulate solids generally move upward through the combustion unit, and gas (comprising fuel and oxygen-containing gas) moves in a generally upward direction.In addition, oxygen-containing gas and fuel can enter the combustion unit by the first gas inlet and the second gas inlet respectively.The first gas inlet (for oxygen-containing gas) can be below the second gas inlet (for fuel) so that the oxygen carrier material contacts oxygen-containing gas in the upstream of its initial contact with the fuel.This arrangement allows the oxygen carrier material to be at least partially oxidized before being exposed to the fuel in the combustion unit.

[0007] According to one or more embodiments described herein, hydrocarbons can be dehydrogenated by a method including contacting a feed stream containing one or more hydrocarbons with a particulate solid in a dehydrogenation reactor. The particulate solid may include an oxygen carrier material. In the dehydrogenation reactor, 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 and reduce the oxygen content in the oxygen carrier material. The method may also include transferring the particulate solid from the dehydrogenation reactor to a combustion unit. The particulate solid can move through the combustion unit in a generally upward direction, and the gas can move through the combustion unit in a generally upward direction, so that the particulate solid and the gas move through the combustion unit in a co-current flow mode. The combustion unit may include a first gas inlet and a second gas inlet. The first gas inlet may be below the second gas inlet. An oxygen-containing gas may enter the combustion unit through the first gas inlet. Fuel may enter the combustion unit through the second gas inlet. In the region of the combustion unit above the first gas inlet and below the second gas inlet, the oxygen content in at least a portion of the oxygen carrier material of the particulate solid may increase. In the region of the combustion unit above the second gas inlet, at least a portion of the fuel may react with oxygen from one or both of the oxygen-containing gas and the oxygen carrier material of the particulate solid. The method may also include transferring at least a portion of the particulate solid from the combustion unit to a dehydrogenation reactor.

[0008] 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 characteristics of the claimed subject matter. Additional features and advantages of the embodiments will be set forth in the specific embodiments, and in part, will be readily apparent to those of ordinary skill in the art from the description including the drawings and claims, or may be recognized by practicing the described embodiments. The drawings are included to provide a further understanding of the embodiments, and together with the specific embodiments, to explain the principles and operation of the claimed subject matter. However, the embodiments depicted in the drawings are illustrative and exemplary in nature, and are not intended to limit the claimed subject matter. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] Reference will now be made in more detail to various embodiments, some of which are illustrated in the accompanying drawings, in which:

[0010] Figure 1 schematically depicts a reactor system according to one or more embodiments of the present disclosure;

[0011] Figure 2 Another reactor system according to additional embodiments of the present disclosure is schematically depicted.

[0012] When describing Figure 1 and Figure 2While the simplified schematic illustration of FIG. 1 does not include the many valves, temperature sensors, electronic controllers, etc. that may be used and are well known to those of ordinary skill in the art, are not included. In addition, the accompanying components that are typically included in such reactor systems, such as, air supply sources, heat exchangers, buffer tanks, etc., are also not included. However, it should be understood that these components are within the scope of the present disclosure. DETAILED DESCRIPTION

[0013] The specific embodiments of the application will now be described. However, the present disclosure can be implemented in different forms and should not be construed as being limited to the embodiments set forth in the present disclosure. On the contrary, these embodiments are provided so that the present disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0014] Now in this article we will Figure 1 and Figure 2 Embodiments of the presently disclosed methods are described in detail in the context of a reactor system that operates as a circulating fluidized bed process to dehydrogenate hydrocarbons. However, it should be understood that the principles disclosed and taught herein can be applied to other systems that utilize different system components oriented in different ways. For example, the concepts described herein are equally applicable to other systems having alternative reactor units and combustion units, such as those operating under non-fluidized conditions, or those systems that include downcomers instead of risers, or vice versa. It should also be understood that not all systems are fluidized. Figure 1 and Figure 2 All parts of the reactor system should be interpreted as being essential to the claimed subject matter. In addition, although the method steps listed in the attached claims are Figure 1 and Figure 2 Although the present invention is described in the context of a reactor system of the present invention, such enumerated method steps should be understood to be applicable to other systems, as understood by those skilled in the art.

[0015] Reference now Figure 1 , schematically depicts an exemplary reactor system 100 that may be suitable for use with the methods described herein. The reactor system 100 may include a dehydrogenation reactor 110 and a combustion unit 150. A feed stream 102 may be passed into the dehydrogenation reactor 110. A particulate solid 180 may be passed into the dehydrogenation reactor 110 via stream 152. The particulate solid 180 may contact the feed stream 102 in the dehydrogenation reactor 110. The particulate solid 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 leave the dehydrogenation reactor 110 via a product stream 114.

[0016] The particulate solids 180 may exit the dehydrogenation reactor 110 and may be passed to the combustion unit 150 via stream 112. The combustion unit 150 may include a first gas inlet 160 and a second gas inlet 170. The first gas inlet 160 may be below the second gas inlet 170. An oxygen-containing gas 162 may enter the combustion unit 150 through the first gas inlet 160, and a fuel 172 may enter the combustion unit 150 through the second gas inlet 170. The particulate solids 180 may travel through the combustion unit 150 in a generally upward direction, first through the first gas inlet 160, and then through the second gas inlet 170. The gases within the combustion unit 150, such as the oxygen-containing gas 162 and the fuel 172, may travel through the combustion unit 150 in a generally upward direction, such that the particulate solids 180 and the gases move through the combustion unit 150 in a generally co-current flow pattern. The particulate solids 180 may then exit the combustion unit 150 via stream 152 and be passed back to the dehydrogenation reactor 110.

[0017] In some embodiments, the reactor system 100 is operable to perform a circulating fluidized bed (CFB) dehydrogenation process. The CFB dehydrogenation process may include a dehydrogenation reactor 110 and a combustion unit 150, both of which are based on a fluidized bed.

[0018] As previously discussed, in one or more embodiments, feed stream 102 can be passed into dehydrogenation reactor 110. In one or more embodiments, feed stream 102 may include one or more hydrocarbons. In one or more embodiments, one or more hydrocarbons may include an alkyl moiety. As used in the present disclosure, if a molecule has at least one carbon-carbon single bond that can be dehydrogenated to form a carbon-carbon double bond, the hydrocarbon includes an "alkyl moiety". In one or more embodiments, one or more hydrocarbons may include one or more of ethane, propane, butane or ethylbenzene. According to one or more embodiments, one or more hydrocarbons may include at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight or even at least 99% by weight of ethane. In other embodiments, one or more hydrocarbons may include at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight or even at least 99% by weight of propane. In other embodiments, one or more hydrocarbons may comprise 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% of butane. In other embodiments, one or more hydrocarbons may comprise 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% of ethylbenzene. In other embodiments, one or more hydrocarbons may comprise 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% of the sum of ethane, propane, butane and ethylbenzene.

[0019] According to other embodiments, the dehydrogenation reactor 110 can be operated in a "backmixed" mode, wherein the feed stream 102 enters the reactor so as to closely approach isothermal conditions. Thus, the fluid velocity at this region can be sufficiently low and the flux of particulate solids 180 can be sufficiently large that a dense bed can be formed at or around the location where the feed stream 102 is injected. In some embodiments, the superficial velocity of the reactor can be from 3 ft / sec to 80 ft / sec, such as from 3 ft / sec to 40 ft / sec or from 10 ft / sec to 30 ft / sec. The flux of particulate solids 180 in the reactor can be 1 lb / ft 2 -s to 300lb / ft 2 -s, such as 40lb / ft 2 -s to 200lb / ft 2 -s, or 60lb / ft 2 -s to 160lb / ft 2-s. The reactor may include multiple diameters and may include one or more frustums to increase or decrease the velocity of the particulate solids 180 and / or the gaseous reactants. The reactor may be operated at a gas residence time of 0.1 seconds to 10 seconds, such as 0.5 seconds to 6 seconds.

[0020] The granular solid 180 can be used in the general operation of the reactor system 100. As used herein, the term "granular solid" may refer to one or more solid particles suitable for fluidization. In one or more embodiments, the granular solid 180 may include an oxygen carrier material and a dehydrogenation catalyst material. In some embodiments, the granular solid 180 may be substantially composed of an oxygen carrier material. As described herein, "substantially composed of..." refers to a material having less than 1% by weight of an unlisted material (i.e., substantially composed of A means that A accounts for at least 99% by weight of the composition). In some embodiments, the granular solid 180 may not include a dehydrogenation catalyst material. In some embodiments, the oxygen carrier material and the dehydrogenation catalyst material may be separate particles of the granular solid 180. In some embodiments, the oxygen carrier material and the dehydrogenation catalyst may be contained in the same particles of the granular solid 180.

[0021] In embodiments where the particulate solid 180 comprises a dehydrogenation catalyst, the dehydrogenation of the one or more hydrocarbons may be performed at least in part by catalytic dehydrogenation. Catalytic dehydrogenation is the dehydrogenation of hydrocarbons facilitated by the use of a dehydrogenation catalyst. In embodiments where the particulate solid 180 does not comprise a dehydrogenation catalyst, the dehydrogenation of the one or more hydrocarbons may be performed by non-catalytic thermal dehydrogenation. Non-catalytic thermal dehydrogenation refers to the dehydrogenation of hydrocarbons that occurs due to high temperature, pressure, or a combination thereof without the use of a dehydrogenation catalyst.

[0022] In some embodiments, particulate solid 180 may comprise a "dual use material" that can serve as both a dehydrogenation catalyst and an oxygen carrier material. It should be understood that in at least the embodiments described herein, the oxygen carrier material and the dehydrogenation catalyst are used in the same reaction vessel (such as Figure 1 In embodiments in which the reaction vessel is used, this dual-purpose material can be used to replace the oxygen carrier material of the particulate solid 180 and the dehydrogenation catalyst of the particulate solid 180, or in combination with them.

[0023] Unless specified herein, "oxygen carrier material" may generally refer to an oxygen-enriched oxygen carrier material or an oxygen-deficient oxygen carrier material. Unless specified herein, "dual-purpose material" may generally refer to an oxygen-enriched dual-purpose material or an oxygen-deficient dual-purpose material. For example, an oxygen-deficient state may occur after some oxygen is used for combustion, and after regeneration of the oxygen-deficient state material before combustion may be oxygen-enriched. The reaction may occur in one or more fluidized bed reactors, such as a circulating fluidized bed reactor. The reactor may be, for example, a riser or a downcomer.

[0024] As described herein, in one or more embodiments, the dehydrogenation catalyst and the oxygen carrier material can be separate particles of the granular solid 180. An expected advantage of this type of system is that the functionality of the system can be changed even when the system is online by adding, removing or replacing one or both of the dehydrogenation catalyst and the oxygen carrier material. For example, the reaction heat load can be adjusted by adding or removing one or both of the dehydrogenation catalyst and the oxygen carrier material. In some embodiments, this can be advantageous compared to dual-purpose materials because the thermal balance of dual-purpose particles must be determined before the reaction and cannot be easily adjusted by changing the amount of the dehydrogenation catalyst relative to the oxygen carrier material. Controlling the ratio of the dehydrogenation catalyst relative to the oxygen carrier material can be more advantageous because the reaction selectivity can be better adjusted. 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 the downstream separation process.

[0025] In some embodiments, the dehydrogenation reactor 110 may include 1 wt% to 100 wt%, such as 5 wt% to 95 wt%, or 75 wt% to 25 wt%, of 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 50 wt% to 75 wt% of 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 oxygen carrier material (e.g., at least 80 wt%, at least 85 wt%, or even at least 90 wt%) may be present, particularly if the oxygen release of the oxygen carrier material is relatively slow compared to the dehydrogenation rate. In some embodiments, the dehydrogenation reactor 110 may include 0 wt% to 99 wt%, such as 5 wt% to 95 wt%, or 25 wt% to 75 wt% of dehydrogenation catalyst based on the total weight of the particulate solids 180 in the dehydrogenation reactor 110. In other embodiments, the dehydrogenation reactor 110 may include 25% to 50% by weight of dehydrogenation catalyst based on the total weight of the particulate solids 180 in the dehydrogenation reactor 110. In some embodiments, the dehydrogenation reactor 110 may include up to 95%, 99%, or even 100% by weight of dual use materials based on the total weight of the particulate solids 180 in the dehydrogenation reactor 110. For example, when utilized, all or a majority of the particulate solids 180 may be dual use materials. In embodiments, the particulate solids 180 materials may include all solids in the system except coke.

[0026] As previously described, within the dehydrogenation reactor 110, hydrogen may be contacted with an oxygen-rich oxygen carrier material of the particulate solid 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 a redox-active metal oxide or a mixture of redox-active metal oxides. Redox-active metal oxides include binary, ternary, or other mixed metal oxides that are capable of being reduced in the presence of a reducing agent (e.g., hydrogen) and oxidized in the presence of an oxidizing agent (e.g., oxygen or air). In some embodiments, the redox-active metal oxide may be a metal MO x , where M can be one or more metals of IUPAC Group 6, 7, 8, 9, 10, 11 or 12, and "x" is the number of associated 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 to Group 12 metal oxides. In some embodiments, the redox-active metal oxide can be cerium oxide. For example, the redox-active metal oxide can be Ce - O2, 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 specific embodiments, the oxygen carrier material may be a crushed solid or powder. In other embodiments, the oxygen carrier material may be formulated using redox-active metal oxides and binders and / or support materials to produce a fluidizable material with desired physical properties (e.g., particle size distribution, density and wear resistance). The binder and / or support material may include alumina, silica, titania, magnesia, zirconium oxide or a combination thereof.

[0027] 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. Adding a promoter may result in the formation of a core-shell morphology. The promoter may include an alkali metal or alkaline earth metal oxide from IUPAC Groups 1 and 2 and / or a compound comprising an alkali metal-transition metal oxide or an alkaline earth metal-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 metals or alkaline earth transition metal oxides may be Na2WO4, K2MoO4, Na2MoO4, K2WO4, Li2WO4, CsWO4, Li2MoO4, CaWO4, CaMoO4, MgWO4, MgMoO4, SrWO4, SrMoO4, BaWO4 and BaMoO4. In some embodiments, the promoter may include one or more of an alkali metal salt or alkaline earth metal salt selected from Group 1 and 2 metal cations and counterions. 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 counterions may include carbonates, sulfates, sulfites, sulfides, phosphates, phosphites, and borates. 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 a combination thereof.

[0028] For example, oxygen carrier materials such as those disclosed in U.S. Application No. 62 / 725,504, filed on August 31, 2018, entitled "METHODS OF PRODUCING HYDROGEN-SELECTIVE OXYGEN CARRIER MATERIALS" and U.S. Application No. 62 / 725,508, filed on August 31, 2018, entitled "HYDROGEN-SELECTIVE OXYGEN CARRIER MATERIALS AND METHODS OF USE" are considered suitable for use in the processes disclosed herein, and the teachings of these references are incorporated herein by reference. In one or more additional embodiments, the oxygen carrier material may include those of U.S. Pat. No. 5,430,209, U.S. Pat. No. 7,122,495, and / or WO 2018 / 232133, each of which is incorporated herein by reference in its entirety.

[0029] The oxygen-enriched oxygen carrier material can be reduced by releasing oxygen that is selective for burning hydrogen. For example, the oxygen carrier material can be selectively used for burning hydrogen, rather than hydrocarbons. In some embodiments, based on the gross weight of the oxygen-enriched oxygen carrier material, the oxygen-enriched oxygen carrier material comprises about 1 wt % to about 20 wt % of releasable oxygen. In other embodiments, the oxygen-enriched oxygen carrier material comprises about 1 wt % to about 10 wt %, about 1 wt % to about 5 wt %, about 5 wt % to about 20 wt % or about 5 wt % to about 10 wt % of releasable oxygen. As described herein, "releasable oxygen" may refer to oxygen that can be released by oxidation-reduction by the oxygen carrier material. Other oxygen that cannot be released by oxidation-reduction may be present in the oxygen carrier material. It should be understood that in some embodiments, oxygen can be released from the surface of the oxygen carrier material while burning with hydrogen at the surface of the oxygen carrier material.

[0030] As previously described, the releasable oxygen of the oxygen-enriched oxygen carrier material can be selectively used to burn hydrogen rather than 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.

[0031] In embodiments, when hydrogen is contacted with the oxygen-enriched oxygen carrier material, some of the releasable oxygen is removed from the oxygen-enriched oxygen carrier material. In some embodiments, contacting hydrogen with the oxygen-enriched oxygen carrier material may remove from about 1 wt % to 50 wt % of the releasable oxygen from the oxygen-enriched oxygen carrier material. In other embodiments, contacting hydrogen with the oxygen-enriched oxygen carrier material may remove from about 10 wt % to about 50 wt %, from about 10 wt % to about 25 wt %, or from about 25 wt % to about 50 wt % of the releasable oxygen from the oxygen-enriched oxygen carrier material.

[0032] In further embodiments, when hydrogen contacts the oxygen-enriched oxygen carrier material, the oxygen-enriched oxygen carrier material burns greater than about 50% of the hydrogen. In other embodiments, when hydrogen contacts the oxygen-enriched oxygen carrier material, the oxygen-enriched oxygen carrier material burns about 50% to about 90%, or about 75% to about 90% of the hydrogen produced.

[0033] Contact of the oxygen-enriched oxygen carrier material with hydrogen can combust the hydrogen and form an oxygen-reduced oxygen carrier material. To form the oxygen-reduced oxygen carrier material, at least a portion of the oxygen-enriched oxygen carrier material can be reduced to a lower oxidation state. Once the oxygen carrier material has been reduced to form the oxygen-reduced oxygen carrier material, the oxygen-reduced oxygen carrier material can be discharged from the dehydrogenation reactor 110 in the lower oxidation state.

[0034] 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 carried by an alumina or alumina silica carrier, 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 those including Ga, Cr and / or Fe-based catalysts. According to another embodiment, a Pt-based catalyst may be utilized. In one or more embodiments, those catalysts disclosed in EP 0948475B1 and / or WO 2010 / 133565 may be utilized, each of which is incorporated herein by reference in its entirety. It is contemplated that other catalyst embodiments suitable for use in the systems and methods described herein include those in U.S. Pat. No. 8,669,406, which are incorporated herein by reference in their entirety. Such catalysts may contain relatively small amounts of Cr, such as less than 6%, or approximately 1.5%. However, it should be understood that other suitable dehydrogenation catalysts may be used to perform the dehydrogenation reaction.

[0035] In one or more embodiments, when there is steam, the dehydrogenation catalyst may show suitable stability. As described herein, the combustion of hydrogen may form steam, which may be in direct contact with the dehydrogenation catalyst. It is expected that not all dehydrogenation catalysts are equally effective in a steam environment. In one or more embodiments, a dehydrogenation catalyst is utilized, which maintains a large amount of reactivity and / or selectivity for the dehydrogenation of light alkanes. For example, one or more of the dehydrogenation catalysts utilized in the system and method disclosed by the present invention may not deteriorate more than 25%, more than 20%, more than 15%, more than 10%, more than 5% in terms of alkane conversion and / or dehydrogenation selectivity, or when there is steam in an amount consistent with the operation of the system disclosed by the present invention, even improved alkane conversion and / or dehydrogenation selectivity may be provided. In some embodiments, when exposed to at least 10 mol.% of water (such as 10 mol.% to 50 mol.%) for a period of, for example, 120 seconds (according to some embodiments of the currently disclosed system, the catalyst may be exposed to the time of such conditions), the dehydrogenation catalyst may work with such conversion and / or selectivity.

[0036] Suitable examples of dehydrogenation catalysts can be prepared so that they meet the Geldart A definition. In some embodiments, the dehydrogenation catalyst comprises gallium and platinum supported on silica-modified alumina in the form of delta or theta phase, or in the form of a mixture of delta + theta phase, or theta + alpha phase, or delta + theta + alpha phase, and has a preferably less than about 100 square meters / gram (m2) as determined by the BET method. 2 / g) of surface area. In other embodiments, the dehydrogenation catalyst comprises: 0.1 wt% to 34 wt%, preferably 0.2 wt% to 3.8 wt% of gallium oxide (Ga2O3); 1 part per million (ppm) to 300 ppm, preferably 50 ppm to 300 ppm of platinum by weight; 0 wt% to 5 wt%, preferably 0.01 wt% to 1 wt% of alkali and / or alkaline earth, such as potassium; 0.08 wt% to 3 wt% of silicon dioxide; the balance 100 wt% is aluminum oxide.

[0037] In one or more embodiments, heat (i.e., exothermic or endothermic) can be generated or used by heat gained or lost by dehydrogenation reaction, reoxidation of oxygen-reduced oxygen carrier material, and reduction of oxygen-enriched oxygen carrier material. In one or more embodiments, the contact of hydrocarbon feed with dehydrogenation catalyst can be endothermic and result in dehydrogenation heat loss. In some embodiments, the contact of hydrogen with oxygen-enriched oxygen carrier material can be exothermic and result in combustion heat gain. The reoxidation of oxygen-reduced oxygen carrier material can be exothermic and result in oxygenation heat gain. Thus, by incorporating hydrogen combustion during catalytic dehydrogenation, in some embodiments, sufficient heat can be generated during the reoxidation of oxygen-reduced oxygen carrier material to serve as a heat source for alkane to olefin reaction. Thus, embodiments of the disclosed process can allow higher alkane conversion while reducing or eliminating the fuel gas demand required for conventional cracking, because the heat gained by reoxidation of oxygen carrier material, combustion of hydrogen, or both during the whole process can generate the heat required for alkane or alkyl aromatic compound to olefin reaction.

[0038] As described herein, "dehydrogenation heat loss" refers to the amount of heat lost by 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 carrier material reduced by oxygen. In one or more embodiments, the combustion heat gain can contribute heat to the system, which accounts for at least a portion of the dehydrogenation heat loss. In other embodiments, the fuel 172 can be burned to heat one or more of the dehydrogenation catalyst or the oxygen carrier material. The fuel 172 can make up for any shortcomings in the 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 fuel 172 required can be substantially less than the amount of fuel that would be required in a system that does not incorporate an oxygen carrier material.

[0039] Due to the high heat load and / or downstream separation steps required for the endothermic dehydrogenation reaction, it is sometimes necessary to separate the unreacted hydrocarbons and remove the hydrogen produced in the dehydrogenation reaction, so it is relatively expensive to produce olefin compounds by conventional dehydrogenation processes (e.g., processes that do not incorporate hydrogen combustion). With regard to the reduced heat input, the catalytic dehydrogenation process is generally endothermic and requires heat. However, the exothermic combustion of hydrogen can offset the heat input demand to a certain extent. In addition, the oxygen carrier material can be regenerated to restore its oxygen once the oxygen content is reduced after combustion, which can be exothermic. This exothermic regeneration step can additionally offset the heat input demand to maintain the dehydrogenation reaction. In some embodiments, the heat generated by the oxygen carrier regeneration and combustion reaction can completely cover the heat and other heat requirements required for the endothermic dehydrogenation reaction, such as heating the feed gas (air, hydrocarbons, etc.) or balancing heat losses, or at least reducing any fuel 172 requirements of the system. For additional summary information on the dehydrogenation reaction incorporated with hydrogen combustion, those skilled in the art refer to, for example, U.S. Patent Publication 2021 / 0292259A1, which teaches that it is incorporated herein by reference in its entirety.

[0040] Still reference Figure 1 , during operation of the dehydrogenation reactor 110 of the reactor system 100, the feed stream 102 can enter a riser within the dehydrogenation reactor 110, and a product stream 114 can exit the reactor system 100 via stream 114. According to one or more embodiments, the reactor system 100 can be operated by feeding a chemical feed (e.g., in a feed stream 102 such as feed stream 102) into the dehydrogenation reactor 110.

[0041] According to one or more embodiments, particulate solids 180 can be fed into the dehydrogenation reactor 110 via stream 152. The particulate solids 180 can include an oxygen-enriched oxygen carrier material. The particulate solids 180 can also include a dehydrogenation catalyst. The feed stream 102 can contact the particulate solids 180 in the dehydrogenation reactor 110. The feed stream 102 and the particulate solids 180 can each flow upward into and through the dehydrogenation reactor 110 to produce one or more products, oxygen-reduced oxygen carrier materials, and hydrogen. In the dehydrogenation reactor 110, one or more hydrocarbons in the feed stream 102 can be dehydrogenated to form one or more products and hydrogen. In addition, within the dehydrogenation reactor 110, hydrogen can contact the oxygen-enriched oxygen carrier material in the dehydrogenation reactor 110. The oxygen-enriched oxygen carrier material can be reducible. The contact of the oxygen-enriched oxygen carrier material with hydrogen can burn hydrogen and reduce the oxygen carrier material to form oxygen-reduced oxygen carrier material and water.

[0042] In one or more embodiments, one or more products can leave the dehydrogenation reactor 110 via a product stream 114. The stream 114 can be further processed or further reacted, such as by one or more subsequent separation steps. It is contemplated that the stream 114 can be used as a feed to another reactor system 100 or sold as a chemical product. In an embodiment, the one or more products in the stream 114 can be mixed with water produced by the reaction of hydrogen produced during the dehydrogenation of the one or more hydrocarbons with oxygen from the oxygen carrier material. In some embodiments, a condenser can be used to remove water from the stream 114 and the one or more products.

[0043] As described above, in some embodiments, stream 114 may include one or more products. In one or more embodiments, one or more products may include one or more olefin compounds. As used herein, the term "olefin compound" refers to a hydrocarbon with one or more carbon-carbon double bonds except the formal double bonds in aromatic compounds. For example, ethylene and styrene are olefin compounds, but ethylbenzene is not an olefin compound because the only double bond present in ethylbenzene is a formal double bond present as a part of an aromatic structure. In one or more embodiments, one or more olefin compounds may include one or more of ethylene, propylene, butylene or styrene. In some embodiments, product stream 114 may include at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight or even at least 99% by weight of ethylene. In other embodiments, stream 114 may include at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight or even at least 99% by weight of propylene. In other embodiments, stream 114 may comprise 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% of butene. In other embodiments, stream 114 may comprise 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% of styrene. In other embodiments, stream 114 may comprise 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% of the sum of one or more of ethylene, propylene, butene and styrene.

[0044] In some embodiments, the one or more products and the particulate solids 180 may be passed to a separation device in a separation section within the dehydrogenation reactor 110. The particulate solids 180 may be in a separation device such as a stripping column ( Figure 1The one or more products may then be transported out of the separation section of the dehydrogenation reactor 110. For example, the separated vapor may be removed from the dehydrogenation reactor 110 via a conduit at a gas outlet port of a separation section within the 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 cyclone separation stages.

[0045] In one or more embodiments, the dehydrogenation reactor 110 can be operated with a residence time of the vapor in the fluidized bed reactor 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.

[0046] In one or more embodiments, the dehydrogenation reactor 110 may be operated at a temperature greater than or equal to 550°C and less than or equal to 800°C. In some embodiments, the temperature in the dehydrogenation reactor 110 may be 625°C or 650°C to 770°C. In other embodiments, the temperature in the dehydrogenation reactor 110 may be 700°C to 750°C. Without being bound by any particular theory, it is believed that too low a temperature (e.g., 550°C or less) may limit the maximum conversion of hydrocarbons due to equilibrium constraints and reduced dehydrogenation rates of heat and catalytic components. Too low a temperature may also result in a slow oxygen release rate in the oxygen carrier material and low hydrogen combustion. On the other hand, high temperatures (e.g., greater than 800°C) may result in thermal degradation of the products produced and may result in product selectivity that is less than economically feasible. In some embodiments, one or more of the main feed components may be propane, ethylbenzene and / or butane, and the dehydrogenation reactor 110 may be operated at a temperature greater than 600°C. In other embodiments, the main feed component may be ethane, and the dehydrogenation reactor 110 may be operated at a temperature of at least 625°C.

[0047] In some embodiments, the dehydrogenation reactor 110 may be operated at a pressure of at least atmospheric pressure (about 14.7 psia). In some embodiments, the dehydrogenation reactor 110 may be operated at a pressure of about 500 psia. In other embodiments, the dehydrogenation reactor 110 may be operated 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, the combustion unit 150 and the regeneration unit 210 may be operated at a pressure within 30 psi of the dehydrogenation reactor 110.

[0048] The residence time of the particles in the dehydrogenation reactor 110 can generally vary from 0.5 seconds (sec) to 360 sec. In other embodiments, the residence time of the particulate solids 180 can be from about 0.5 sec to about 200 sec, from about 0.5 sec to about 100 sec, from about 0.5 sec to about 50 sec, or from about 0.5 sec to about 20 sec.

[0049] In other embodiments, the ratio of particulate solids 180 to feed stream 102 in dehydrogenation reactor 110 on a weight / weight (w / w) basis may be in the range of 5 to 150. In some embodiments, the ratio may be in the range of 10 to 40, such as 12 to 36 or 12 to 24.

[0050] In other embodiments, the flux of particulate solids 180 in the upstream reactor section may be 1 lb / ft2-sec (lb / ft 2 -s)(about 4.89kg / m 2 -s) to 300lb / ft 2 -s(to about 97.7kg / m 2 -s), such as 1lb / ft 2 -s to 20lb / ft 2 -s, and the flux in the downstream reactor section may be 1 lb / ft 2 -s(about 48.9kg / m 2 -s) to 300lb / ft 2 -s(about 489kg / m 2 -s), such as 10 lb / ft 2 -s to 100lb / ft 2 -s.

[0051] In one or more embodiments, the granular solid 180 may be capable of fluidization. In some embodiments, the granular solid 180 may exhibit characteristics known in the industry as "Geldart A" or "Geldart B" characteristics. According to D. Geldart, Gas Fluidization Technology, John Wiley & Sons (New York, 1986), pp. 34-37; and D. Geldart, "Types of Gas Fluidization", Powder Technol. 7 (1973) 285-292, the entire contents of which are incorporated herein by reference, solids can be classified as "Class A" or "Class B".

[0052] Class A is understood by those skilled in the art to represent an aeratable powder having fluidization in a bubble-free regime; high bed expansion; slow and linear rate of degassing; bubble characteristics which may include the advantage of splitting / recoalescing bubbles, having a maximum bubble size and large wake; high levels of solid mixing and gas backmixing, assuming U - umf is equal (U is the velocity of the carrier gas and Umf is the minimum fluidization velocity, typically but not necessarily measured in meters per second (m / s), i.e., there is an excessive gas velocity); axisymmetric slug characteristics; and no spouting except in very shallow beds. The listed characteristics tend to improve with decreasing mean particle size, assuming cfp is equal; or with increasing proportion < 45 microns (μm); or with increasing pressure, temperature, viscosity, and density of the gas. Generally, the particles may exhibit a small mean particle size and / or low particle density (< 1.4 grams per cubic centimeter, g / cm 3 ); are easily fluidized, where smooth fluidization occurs at low gas velocities; and may exhibit controlled bubbling with small bubbles at higher gas velocities.

[0053] Class B is understood by those skilled in the art to represent a "sand-like" powder which begins to bubble at Umf; which exhibits moderate bed expansion; rapid degassing; no limitation on bubble size; moderate levels of solid mixing and gas backmixing, assuming U - umf is equal; both axisymmetric and non-axisymmetric slugs; and spouting only in shallow beds. These characteristics tend to improve with decreasing mean particle size, but the particle size distribution and certain uncertainties in the gas, pressure, temperature, viscosity, or density do not seem to have much effect on improving these characteristics. Generally, when the density (pp) is 1.4 < pp < 4 g / cm 3 , the particle size (cfp) of most particles is 40 μm < cfp < 500 μm, and preferably, when the density (pp) is 4 g / cm 3 , the particle size of most particles is 60 μm < cfp < 500 μm, and when the density (pp) is 1 g / cm 3 , the particle size of most particles is 250 μm < cfp < 100 μm.

[0054] Still referring to Figure 1 , in one or more embodiments, the particulate solid 180 and the gas product may pass through an efficient cyclone separator in the stripping section of the reactor system 100 within the dehydrogenation reactor 110 ( Figure 1The stripping section may be separated from the reactor 110 or may be a separate container. In the described embodiment, the granular solid 180 may be transferred to the combustion unit 150 via stream 112. In some embodiments, the dehydrogenation catalyst, the oxygen carrier material, or both may be stripped with a replacement gas (such as nitrogen, steam, methane, natural gas, or other suitable gas) in the stripping section before being sent to the combustion unit 150. In some embodiments, a portion of the granular solid 180 may be transferred from the stripping section via stream 116 to stream 152 for reuse in the reactor 110 without first passing through the regeneration unit 150. Without being bound by theory, it is believed that by recycling a portion of the granular solid 180 back to the reactor 110, the oxygen content of the oxygen carrier material may be better controlled because the oxygen carrier material may be given more time to react its oxygen so that the oxygen carrier material may 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 control over the temperature of the material entering the reactor 110 , thereby improving the temperature profile of the reactor 110 .

[0055] 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 the reaction in the dehydrogenation reactor 110. As used herein, "deactivated" may refer to a catalyst that is contaminated with substances such as coke, whose temperature is below the temperature required to promote the reaction of the feed, or may refer to an oxygen carrier material that is oxygen-deficient. In some embodiments, contaminants such as coke may be deposited on the particulate solids 180 that are passed from the dehydrogenation reactor 110 to the combustion unit 150.

[0056] The particulate solid 180 may enter the combustion unit 150 via stream 112. The particulate solid 180 may pass through a first gas inlet 160, through which an oxygen-containing gas 162 may enter the combustion unit 150, and then through an air zone 164. The air zone 164 is so named for simplicity because air may be used as the oxygen-containing gas. The particulate solid 180 may then pass through a second gas inlet 170, through which a fuel 172 may enter the combustion unit 150. Above the second gas inlet 170 may be a fuel zone 174, which includes the fuel and any oxygen that is not reacted in the air zone 164. The particulate solid 180 may then leave the combustion unit 150 via stream 152 and be passed back to the dehydrogenation reactor 110. Typically, in the air zone 164, the oxygen carrier material may be oxidized, and in the fuel zone, the fuel may be burned together with any remaining oxygen that is not reacted in the air zone and oxygen from the oxygen carrier material.

[0057] In the combustion unit 150, the conditions can remove pollutants (such as coke), increase the temperature of the particulate solid 180, increase the oxygen content of the oxygen carrier material of the particulate solid 180, reduce the oxygen content of the oxygen carrier material of the particulate solid 180, or a combination thereof. In some embodiments, the coke on the particulate solid 180 can be removed by burning in an oxygen-containing environment in the combustion unit 150. In further embodiments, the particulate solid 180 can be heated to a target temperature by the fuel 172. The particulate solid 180 can then be recycled back to the dehydrogenation reactor 110, carrying the heat required for the dehydrogenation reaction. For additional general information on dehydrogenation performed in a fluidized bed, those skilled in the art refer to, for example, U.S. Patent Publication 2005 / 0177016A1; International Patent Publication WO 2005 / 077867 A1 (corresponding to U.S. Patent Publication 2008 / 0194891A1); and International Patent Publication WO 20107591 A1.

[0058] The oxygen carrier may be oxidized or reduced when it is used 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 burn hydrogen as effectively within the dehydrogenation reaction as an oxygen carrier with a relatively higher oxidation state. Conversely, an oxygen carrier with a relatively higher oxidation state may be more likely to oxidize hydrocarbons during the dehydrogenation reaction when compared to an oxygen carrier with a relatively lower oxidation state, thereby potentially impairing olefin production by the method. Passing the oxygen carrier to and through the combustion unit 150 may help control the oxidation state of the oxygen carrier material.

[0059] In some embodiments, the oxygen-reduced oxygen carrier material of the particulate solid 180 can be reoxidized to an oxidation state higher than the oxidation state of the oxygen-reduced oxygen carrier material by burning in an oxygen-containing environment in the combustion unit 150. In some embodiments, the oxygen-containing environment can be air. In some embodiments of forming an oxygen-enriched oxygen carrier material, the oxygen-reduced oxygen carrier material can be restored to its original oxidation state. In some embodiments, the oxygen-reduced oxygen carrier material can have an oxidation state of +2, +3 or +4. The oxygen-enriched oxygen carrier material can then be circulated 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-enriched oxygen carrier material to the dehydrogenation reactor 110.

[0060] In one or more embodiments, the fuel 172 can be combusted in the combustion unit 150 to generate heat and increase the temperature of the particulate solids 180. The heat generated by the oxidation of the oxygen-reduced oxygen carrier material and the combustion of the fuel 172 can be sufficient to maintain the temperature of the dehydrogenation reactor 110 at a desired temperature. The desired temperature can depend on the minimum temperature required for operation of the dehydrogenation reactor 110 because the particulate solids 180 can enter the dehydrogenation reactor 110 and apply their temperature to the dehydrogenation reactor 110.

[0061] In one or more embodiments, the combustion unit 150 can be operated 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. Typically, the temperature of the combustion unit 150 can be at least 50° C. higher than the temperature of the dehydrogenation reactor 110. Such a temperature range can be utilized so that the temperature of the dehydrogenation reactor 110 can be maintained with a limited amount of dehydrogenation catalyst and / or oxygen support material. Additionally, if a dehydrogenation catalyst is utilized, such temperatures can be required to activate the dehydrogenation catalyst.

[0062] The residence time of the particulate solid 180 in the combustion unit 150 can generally vary from 0.5 seconds (sec) to 240 sec. In other embodiments, the residence time of the particulate solid 180 can be from about 0.5 sec to about 200 sec, from about 0.5 sec to about 100 sec, from about 0.5 sec to about 50 sec, or from about 0.5 sec to about 20 sec.

[0063] As described herein, in one or more embodiments, particulate solids 180 may be transferred from dehydrogenation reactor 110 to combustion unit 150 via stream 112. According to embodiments, particulate solids 180 and gases in combustion unit 150 may move in a generally upward direction. As used in the present disclosure, the term "generally upward direction" means that the average velocity of particulate solids 180 and gases in this section of reactor system 100 is in an upward direction, wherein the upward direction is opposite to the pull of gravity. Since it is an average value, the velocity of a single particle of gas molecules or particulate solids 180 in this section of reactor system 100 may have a distribution and may not be equal to the average value, but as a whole, the velocity of gas and / or particulate solids 180 will be averaged to be generally upward. In embodiments, particulate solids 180 and gases may move through combustion unit 150 in a co-current flow mode.

[0064] In one or more embodiments, the combustion unit 150 may include a first gas inlet 160 and a second gas inlet 170 above the first gas inlet 160. As used herein, "gas inlet" refers to any component that can be operated to inject gas into the combustion unit 150. For example, the gas inlet can be a blower or a distributor. In addition, as will be appreciated by those skilled in the art, other suitable gas suppliers are contemplated herein. According to an embodiment, the oxygen-containing gas 162 may enter the combustion unit 150 via the first gas inlet 160. In some embodiments, the oxygen-containing gas 162 may be air, high oxygen air, air mixed with steam, or flue gas. High oxygen air is air to which oxygen has been added. In some embodiments, the oxygen-containing gas 162 may include at least 28 mol.% of oxygen. In other embodiments, the oxygen-containing gas 162 may include about 2 mol.% to about 28 mol.% oxygen, about 2 mol.% to about 25 mol.%, about 2 mol.% to about 20 mol.%, about 2 mol.% to about 15 mol.%, about 2 mol.% to about 10 mol.%, about 2 mol.% to about 5 mol.%, about 5 mol.% to about 28 mol.%, about 5 mol.% to about 25 mol.%, about 5 mol.% to about 20 mol.%, about 5 mol.% to about 15 mol.%, about 5 ...25 mol.%, about 5 mol.% to about 20 mol.%, about 5 mol.% to about 15 mol.%, about 5 mol.% to about 10 mol.%, about 2 mol.% to about 5 mol.%, about 5 mol.% to about 25 mol.%, about 5 mol.% to about 20 mol.%, about 5 mol.% to about 15 mol.%, about 5 mol.% to about 10 mol.%, about 2 mol.% to about 5 mol.%, about 2 mol.% to about 5 mol.%, about 2 mol.% to about 25 mol.%, about 2 mol.% to about 20 mol.%, about 2 mol.% to about 15 mol.%, about 2 mol.% to about 10 mol.%, about 2 % 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%.

[0065] In embodiments, the oxygen-containing gas 162 may enter the combustion unit 150 in a generally upward direction. In some embodiments, the oxygen-containing gas 162 may enter the combustion unit 150 in an initially downward direction and then flow generally upward following other gases within the combustion unit 150. In some embodiments, the area above the first gas inlet 160 may be an air zone 164 because the directional flow of the oxygen-containing gas 162 into the combustion unit 150 may result in a higher oxygen concentration in the area above the first gas inlet 160 than in other areas of the combustion unit 150. In one or more embodiments, the oxygen concentration in the air zone 164 may be greater than 25 mol.%. In other embodiments, the oxygen concentration in the air zone 164 may be about 4 mol.% to about 28 mol.% oxygen, about 4 mol.% to about 21 mol.%, about 4 mol.% to about 10 mol.%, about 10 mol.% to about 28 mol.%, about 10 mol.% to about 21 mol.%, or about 21 mol.% to about 28 mol.% oxygen. The name air is used here simply to indicate the presence of oxygen, as air is generally the least expensive oxygen-containing gas.

[0066] In one or more embodiments, the oxygen content in at least a portion of the oxygen carrier material of the particulate solid 180 can increase in a region above the first gas inlet 160 but below the second gas inlet 170. For example, the oxygen content in at least a portion of the oxygen carrier material of the particulate solid 180 can increase in the air zone 164.

[0067] In one or more embodiments, the fuel 172 may enter the combustion unit 150 via the second gas inlet 170. In some embodiments, the fuel 172 may enter the combustion unit 150 in an initially downward direction and then flow generally upward following other gases within the combustion unit 150. In some embodiments, the fuel 172 may include hydrogen, methane, ethane, propane, natural gas, or a combination thereof. According to the embodiment, the fuel 172 may enter the combustion unit 150 in a generally upward direction. In an embodiment, at least a portion of the fuel 172 in the region above the second gas inlet 170 may react with oxygen from the oxygen carrier material of the particulate solid 180, the oxygen-containing gas 162, or both to generate heat and increase the temperature of the particulate solid 180. The region above the second gas inlet 170 may be a fuel zone 174 because the directional flow of the fuel 172 into the combustion unit 150 may result in a higher concentration of the fuel 172 in the region above the second gas inlet 170 than in the region below the first gas inlet 160 or in the region below the second gas inlet 170.

[0068] In some embodiments, the concentration of the fuel 172 in the fuel zone 174 may be less than 20 mol%. In some embodiments, the concentration of the fuel 172 in the fuel zone 174 may be about 0.1 mol.% to about 15 mol.%, about 0.1 mol.% to about 10 mol.%, about 0.1 mol.% to about 5 mol.%, about 0.1 mol.% to about 1 mol.%, about 0.1 mol.% to about 0.5 mol.%, about 0.5 mol.% to about 20 mol.%, about 0.5 mol.% to about 15 mol.%, about 0.5 mol.% to about 10 mol.%, about 0.5 mol.% to about 5 mol.%. .%, about 0.5 mol.% to about 1 mol.%, about 1 mol.% to about 20 mol.%, about 1 mol.% to about 15 mol.%, about 1 mol.% to about 10 mol.%, about 1 mol.% to about 5 mol.%, about 5 mol.% to about 20 mol.%, about 5 mol.% to about 15 mol.%, about 5 mol.% to about 10 mol.%, about 10 mol.% to about 20 mol.%, about 10 mol.% to about 15 mol.%, or about 15 mol.% to about 20 mol.%.

[0069] In one or more embodiments, at least a portion of the particulate solids 180 can exit the combustion unit 150 via stream 152 and can be passed back to the dehydrogenation reactor 110. In some embodiments, passing at least a portion of the particulate solids 180 from the combustion unit 150 to the dehydrogenation reactor 110 can include separating the particulate solids 180 from the flue gas produced in the combustion unit 150 and then passing the particulate solids 180 to the dehydrogenation reactor 110. In one or more embodiments, at least a portion of the oxygen carrier material of the particulate solids 180 can exit the combustion unit 150 at least partially reoxidized. In one or more embodiments, at least a portion of the oxygen carrier material of the particulate solids 180 can exit the combustion unit 150 at least partially reduced.

[0070] Without being bound by theory, according to one or more embodiments, it is believed that the combustion unit 150 can be most efficiently utilized when the oxygen carrier material of the particulate solid 180 has a sufficient fuel burn rate in a reduced form. For example, if the oxygen carrier material, when reduced, can sufficiently burn the fuel 172 in the combustion zone to heat the particulate solid 180 for use in the dehydrogenation reactor 110. A material that does not have a sufficient fuel burn rate in a reduced form may not be able to sufficiently burn the fuel 172 within the combustion unit 150 to heat the particulate solid 180 for use in the dehydrogenation reactor 110. It is believed that performing fuel combustion in the combustion zone can better prevent the fuel 172 and combustion products (such as carbon dioxide and water) from entering downstream processes including the oxidation zone or the dehydrogenation reactor 110, and can allow for easier handling of the combustion products and unburned fuel by allowing all combustion of the fuel 172 that needs to be performed in a single isolated unit of the reactor system 100.

[0071] It is also believed that the use of the combustion unit 150 can help control the oxidation state of the oxygen carrier material. The co-current flow of gas and particulate solids 180 combined with the specific arrangement of the gas inlet within the combustion unit 150 allows at least a portion of the oxygen carrier material to be reoxidized before flowing into the area of ​​the combustion unit 150 with a higher fuel concentration. By adjusting the concentrations of oxygen and fuel in the combustion unit 150, the oxidation state of the oxygen carrier material when leaving the combustion unit 150 can be higher or lower than the oxidation state of the oxygen carrier material when entering the combustion unit 150. Compared to a reactor system that does not include the combustion unit 150, this flexibility can allow the reactor system 100 using the combustion unit 150 to be more easily adjusted to adapt to changing conditions within the dehydrogenation reactor 110 to maintain the selectivity and productivity of the dehydrogenation reaction.

[0072] Reference now Figure 2200, a reactor system according to another embodiment of the present disclosure is shown. The particulate solids 180 may be transferred from the dehydrogenation reactor 110 to the combustion unit 150 via stream 112. The particulate solids 180 may then be transferred from the combustion unit 150 to the regeneration unit 210 via stream 152. The particulate solids 180 may then enter the gas / solid separator 218 within the regeneration unit 210. The particulate solids 180 may be separated from the flue gas produced in the combustion unit 150 by the gas / solid separator 218. The flue gas may then exit the regeneration unit 210 via stream 214. The particulate solids 180 may then travel downward through the regeneration unit 210, passing through the third gas inlet 220, through which the oxygen-containing gas 222 may enter the regeneration unit 210. The particulate solids 180 may then travel through the fourth gas inlet 230, through which the stripping gas 232 may enter the regeneration unit 210. The particulate solids 180 may then exit the regeneration unit 210 and pass back to the dehydrogenation reactor 110 via stream 212 .

[0073] As described herein, in one or more embodiments, the particulate solids 180 may be transferred from the combustion unit 150 to the regeneration unit 210 via the stream 152. In the regeneration unit 210, the particulate solids 180 may pass through the gas / solid separator 218. According to one or more embodiments, the separator 218 may be a riser terminal system, which may include a cyclone separation system. In embodiments where the riser terminal system includes a cyclone separation system, some of the particulate solids 180 may leave the riser terminal system without first passing through the cyclone separation system. The cyclone separation system may include two or more cyclone separation stages. In embodiments where the separator 218 includes more than one cyclone separation stage, the first separation device into which the fluidized stream enters is referred to as a primary cyclone separation device. The fluidized effluent from the primary cyclone separation device may enter a secondary cyclone separation device for further separation. The primary cyclone separation device may include, for example, a primary cyclone separator and a system commercially available under the names VSS (commercially available from UOP), LD2 (commercially available from Stone and Webster), and RS2 (commercially available from Stone and Webster). Primary cyclone separators 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 separator as a primary cyclone separation device, one or more additional cyclone separators, for example, a secondary cyclone separator and a tertiary cyclone separator, are used to further separate particulate solids from the product gas. It should be understood that any primary cyclone separation device may be used in embodiments of the present invention. Particulate solids 180 may be separated from waste gas, such as flue gas. The gases separated from the particulate solids 180 may be combined with the gases from the regeneration unit 210 and exit the regeneration unit 150 via the exhaust gas stream 214 .

[0074] According to an embodiment, the granular solid 180 may move through the regeneration unit 210 in a generally downward direction. As used in the present disclosure, the term "generally downward direction" means that the average velocity of the granular solid 180 is in a downward direction, where the downward direction is under the pull of gravity. Since it is an average value, the velocity of individual particles of the granular solid 180 may have a distribution and may not be equal to the average value, but as a whole, the velocity of the granular solid 180 will average generally downward. According to an embodiment, the gas within the regeneration unit 210 may move through the regeneration unit 210 in a generally upward direction. According to an embodiment, the granular solid 180 and the gas may move through the regeneration unit 210 in a countercurrent flow mode.

[0075] In one or more embodiments, the regeneration unit 210 may include a third gas inlet 220 and a fourth gas inlet 230 below the third gas inlet 220. According to the embodiment, the oxygen-containing gas 222 may enter the regeneration unit 210 via the third gas inlet 220. In some embodiments, the oxygen-containing gas 222 may be air, enriched air, air mixed with steam, or flue gas. Enriched air is air with oxygen added. In some embodiments, the oxygen-containing gas 222 may contain less than 28 mol.% oxygen. In other embodiments, the oxygen-containing gas 222 may include about 2 mol.% to about 28 mol.% oxygen, about 2 mol.% to about 25 mol.% oxygen, about 2 mol.% to about 20 mol.% oxygen, about 2 mol.% to about 15 mol.% oxygen, about 2 mol.% to about 10 mol.% oxygen, about 2 mol.% to about 5 mol.% oxygen, about 5 mol.% to about 28 mol.% oxygen, about 5 mol.% to about 25 mol.% oxygen, about 5 mol.% to about 20 mol.% oxygen, about 5 mol.% to about 15 mol.% oxygen, about 5 mol.% to about 10 mol.% oxygen. % to about 10 mol. % oxygen, about 10 mol. % to about 28 mol. % oxygen, about 10 mol. % to about 25 mol. % oxygen, about 10 mol. % to about 20 mol. % oxygen, about 10 mol. % to about 15 mol. % oxygen, about 15 mol. % to about 28 mol. % oxygen, about 15 mol. % to about 25 mol. % oxygen, about 15 mol. % to about 20 mol. % oxygen, about 20 mol. % to about 28 mol. % oxygen, about 20 mol. % to about 25 mol. % oxygen, or about 25 mol. % to about 28 mol. % oxygen.

[0076] In an embodiment, the oxygen-containing gas 222 can enter the regeneration unit 210 in a generally upward direction. In some embodiments, the area above the third gas inlet 220 can be an air zone 224 because the directional flow of the oxygen-containing gas 222 into the regeneration unit 210 can result in a higher oxygen concentration in the area above the third gas inlet 220 than in other areas of the regeneration unit 210. In one or more embodiments, the oxygen concentration in the air zone 224 can be greater than 25 mol.%. In some embodiments, the oxygen concentration in the air zone 224 can be about 4 mol.% to about 28 mol.% oxygen, about 4 mol.% to about 21 mol.%, about 4 mol.% to about 10 mol.%, about 10 mol.% to about 28 mol.%, about 10 mol.% to about 21 mol.%, or about 21 mol.% to about 28 mol.% oxygen. The name air is used here to simply show the presence of oxygen because air is generally the lowest cost oxygen-containing gas.

[0077] In one or more embodiments, the regeneration unit 210 can include a fourth gas inlet 230. In an embodiment, a stripping gas 232 can enter the regeneration unit 210 through the fourth gas inlet 230. In an embodiment, the fourth gas inlet 230 can be below the third gas inlet 220. In an embodiment, the stripping gas 232 can exit the fourth gas inlet 230 in a generally upward direction. Thus, in an embodiment, the area above the fourth gas inlet 230 and below the third gas inlet 220 can be a stripping zone 234 because the directional flow of the stripping gas 232 into the regeneration unit 210 can result in a higher concentration of the stripping gas 232 in the area above the fourth gas inlet 230 and below the third gas inlet 220. In some embodiments, the stripping gas 232 can include nitrogen, steam, or a combination thereof.

[0078] In one or more embodiments, the stripping gas 232 may include a reducing agent. In one or more embodiments, the reducing agent may include hydrogen, methane, or a combination thereof. In some embodiments, the particulate solid 180 may be exposed to the reducing agent in the stripping gas 232 in the stripping zone 234, and the oxygen content in at least a portion of the oxygen carrier material of the particulate solid 180 may be reduced. In some embodiments, the concentration of the reducing agent in the stripping gas 232 may be greater than 10 mol.%. In some embodiments, the concentration of the reducing agent in the stripping gas 232 may even be greater than 90 mol.%. In some embodiments, the concentration of the reducing agent in the stripping gas 232 can be from about 1 mol.% to about 100 mol.%, such as from about 1 mol.% to about 90 mol.%, from about 1 mol.% to about 80 mol.%, from about 1 mol.% to about 70 mol.%, from about 1 mol.% to about 60 mol.%, from about 1 mol.% to about 50 mol.%, from about 1 mol.% to about 40 mol.%, from about 1 mol.% to about 30 mol.%, from about 1 mol.% to about 20 mol.%, from about 1 mol.% to about 10 mol.%, about 10 mol.% to about 100 mol.%, about 10 mol.% to about 90 mol.%, about 10 mol.% to about 80 mol.%, about 10 mol.% to about 70 mol.%, about 10 mol.% to about 60 mol.%, about 10 mol.% to about 50 mol.%, about 10 mol.% to about 40 mol.%, about 10 mol.% to about 30 mol.%, about 10 mol.% to about 20 mol.%, about 20 mol.% to about 100 mol.%, about 20 mol.% to about 90 mol.% %, about 20 mol.% to about 80 mol.%, about 20 mol.% to about 70 mol.%, about 20 mol.% to about 60 mol.%, about 20 mol.% to about 50 mol.%, about 20 mol.% to about 40 mol.%, about 20 mol.% to about 30 mol.%, about 30 mol.% to about 100 mol.%, about 30 mol.% to about 90 mol.%, about 30 mol.% to about 80 mol.%, about 30 mol.% to about 70 mol.%, about 30 mol.% to about 60 mol.% %, about 30 mol.% to about 50 mol.%, about 30 mol.% to about 40 mol.%, about 40 mol.% to about 100 mol.%, about 40 mol.% to about 90 mol.%, about 40 mol.% to about 80 mol.%, about 40 mol.% to about 70 mol.%, about 40 mol.% to about 60 mol.%, about 40 mol.% to about 50 mol.%, about 50 mol.% to about 100 mol.%, about 50 mol.% to about 90 mol.%, about 50 mol.% to about 80 mol.%, about 50 mol.% to about 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.% of the reducing agent in the stripping gas 232.

[0079] In one or more embodiments, at least a portion of the particulate solids 180 can be withdrawn from the regeneration unit 210 and passed through at least a portion of the regeneration unit 210 a second time before being delivered to the dehydrogenation reactor 110. Thus, in some embodiments, at least a portion of the particulate solids 180 can be withdrawn from the stripping zone 234 and delivered to the air zone 224. In some embodiments, at least a portion of the particulate solids 180 can be withdrawn from the regeneration unit 210 via stream 216 and delivered back to the combustion unit 150. At least a portion of the particulate solids 180 can be withdrawn from any point of the regeneration unit 210, such as from an area above the third gas inlet 220, from an area above the fourth gas inlet 230 and below the third gas inlet 220, from an area below the fourth gas inlet 230, or from a combination thereof.

[0080] In a first aspect of the present disclosure, hydrocarbons may be dehydrogenated by a method comprising contacting a feed stream comprising one or more hydrocarbons with a particulate solid in a dehydrogenation reactor. The particulate solid may comprise an oxygen carrier material. In the dehydrogenation reactor, one or more hydrocarbons may be dehydrogenated to form hydrogen and one or more products. At least a portion of the hydrogen may react with oxygen from the oxygen carrier material to form water and reduce the oxygen content in the oxygen carrier material. The method may also include transferring the particulate solid from the dehydrogenation reactor to a combustion unit. The particulate solid may move through the combustion unit in a generally upward direction, and the gas may move through the combustion unit in a generally upward direction, so that the particulate solid and the gas move through the combustion unit in a co-current flow pattern. The combustion unit may comprise a first gas inlet and a second gas inlet. The first gas inlet may be below the second gas inlet. An oxygen-containing gas may enter the combustion unit through the first gas inlet. A fuel may enter the combustion unit through the second gas inlet. In the region of the combustion unit above the first gas inlet and below the second gas inlet, the oxygen content in at least a portion of the oxygen carrier material of the particulate solid may increase. In the region of the combustion unit above the second gas inlet, at least a portion of the fuel may react with oxygen from one or both of the oxygen-containing gas and the oxygen carrier material of the particulate solid. The method may also include transferring at least a portion of the particulate solid from the combustion unit to a dehydrogenation reactor.

[0081] A second aspect of the present disclosure may include the first aspect, wherein transferring at least a portion of the particulate solids from the combustion unit to the dehydrogenation reactor includes separating the particulate solids from the flue gas.

[0082] A third aspect includes any of the preceding aspects or combinations of aspects, wherein the one or more hydrocarbons comprise an alkyl moiety and the one or more products comprise one or more olefin compounds.

[0083] A fourth aspect includes any of the preceding aspects or combinations of aspects, wherein the one or more hydrocarbons comprise ethane and the one or more products comprise ethylene.

[0084] A fifth aspect includes any of the preceding aspects or combinations of aspects, wherein the fuel comprises hydrogen.

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

[0086] A seventh aspect of the present disclosure includes any of the preceding aspects or combinations of aspects, wherein transferring at least a portion of the particulate solids from the combustion unit to the dehydrogenation reactor includes passing the particulate solids through a regeneration unit, wherein the particulate solids are exposed to an oxygen-containing gas in the regeneration unit such that the oxygen content in at least a portion of the oxygen carrier material of the particulate solids is increased.

[0087] An eighth aspect of the present disclosure includes any of the preceding aspects or combinations of aspects, wherein the particulate solids and the oxygen-containing gas in the regeneration unit move in a countercurrent flow pattern.

[0088] A ninth aspect of the present disclosure includes any of the preceding aspects or combinations of aspects, wherein the regeneration unit comprises a third gas inlet and a fourth gas inlet, and wherein the oxygen-containing gas enters the regeneration unit through the third gas inlet, and the stripping gas enters the regeneration unit through the fourth gas inlet, wherein the stripping gas comprises a reducing agent in an amount ranging from 0 mol.% to 100 mol.%.

[0089] A tenth aspect of the present disclosure includes any of the preceding aspects or combinations of aspects, wherein a portion of the particulate solids is withdrawn 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] An eleventh aspect of the present disclosure includes any of the preceding aspects or combinations of aspects, wherein the particulate solid consists essentially of the oxygen carrier material.

[0091] A twelfth aspect of the present disclosure includes any of the preceding aspects or combinations of aspects, wherein the dehydrogenation of the one or more alkanes is performed by non-catalytic thermal dehydrogenation.

[0092] A thirteenth aspect of the present disclosure includes any of the preceding aspects or combinations of aspects, wherein the particulate solid further comprises a dehydrogenation catalyst material, and the dehydrogenation of the one or more alkanes is at least partially performed by catalytic dehydrogenation.

[0093] A fourteenth aspect of the present disclosure includes any of the preceding aspects or combinations of aspects, wherein the dehydrogenation catalyst material and the oxygen support material are separate particles of a particulate solid or contained in the same particle of a particulate solid.

[0094] A fifteenth aspect of the present disclosure includes any of the preceding aspects or combinations of aspects, wherein the particulate solid is a Geldart Type A or Geldart Type B particle.

[0095] It will be apparent to those skilled in the art that various modifications and variations may be made to the technology disclosed in the present invention without departing from the spirit and scope of the technology. Because those skilled in the art may make modifications, combinations, sub-combinations and variations of the disclosed embodiments that incorporate the spirit and essence of the technology disclosed in the present invention, the technology should be interpreted as including everything within the scope of the attached claims and their equivalents. In addition, although some aspects of the present disclosure may be identified herein as preferred or particularly advantageous, it is contemplated that the present disclosure is not limited to these aspects.

[0096] It should be noted that the various details described in the present disclosure should not be considered to imply that these details relate to elements that are essential components of the various embodiments described in the present disclosure, even in the case where specific elements are shown in each of the drawings attached to this specification. Unless so explicitly stated, the features disclosed and described herein should not be interpreted as "essential". Contemplated embodiments of the present technology include those that include some or all of the features of the appended claims.

[0097] For purposes of describing and defining the present disclosure, it is noted that the term "about" is used herein to represent the inherent degree of uncertainty that may be attributed to any quantitative comparison, value, measurement, or other representation. The term "about" is also utilized herein to represent the degree by which a quantitative representation may vary from a stated reference without resulting in a change in the basic function of the subject matter at issue.

[0098] Where relevant, where a composition is described as “comprising” one or more elements, embodiments of the composition “consisting of” or “consisting essentially of” those one or more elements are contemplated herein.

[0099] It should be understood that in some embodiments, the composition range of a chemical composition in a stream or reactor should be understood as a mixture of isomers containing the composition. For example, a composition range of butenes may include a mixture of various isomers of butenes. It should be understood that examples provide composition ranges for various streams, and the total amount of isomers of a particular chemical composition may constitute a range.

[0100] It should be noted that one or more of the following claims and detailed description utilize the term "wherein" or "wherein" as a transition phrase. For purposes of defining the present technology, it should be noted that this term is introduced in the claims as an open transition phrase that is used to introduce a recitation of a series of features of a structure and should be interpreted in a manner similar to the more commonly used open-ended preamble term "comprising."

[0101] In some embodiments, a chemical or chemical stream is described as being "transferred" from one system unit or a portion of a system unit to another system unit or a portion of a system unit. As described herein, such transfer may include direct transfer or indirect transfer. For example, in the case of transfer from "unit A" to "unit B", direct transfer has no intermediate destinations between unit A and unit B (i.e., directly through a pipeline or other transport channel), and indirect transfer may include one or more intermediate destinations between unit A and unit B. For example, a stream transferred from unit A to unit B may pass through, but is not limited to, a heat exchanger, a processing device, etc.

[0102] It should be understood that any two quantitative values ​​assigned to a characteristic may constitute a range for that characteristic, and all combinations of ranges formed by all of the quantitative values ​​for a given characteristic are considered in the present disclosure. Where multiple ranges of quantitative values ​​are provided, these ranges may be combined to form a wider range, which is contemplated in the embodiments described herein.

Claims

1. A method for dehydrogenating hydrocarbons, the method comprising: A feed stream comprising one or more hydrocarbons is contacted with a particulate solid in a dehydrogenation reactor, wherein the particulate solid comprises an oxygen carrier material, and wherein in the dehydrogenation reactor: dehydrogenating the one or more hydrocarbons to form hydrogen and one or more products; and reacting at least a portion of the hydrogen with oxygen from the oxygen carrier material to form water and reduce the oxygen content of the oxygen carrier material; The particulate solids are transferred from the dehydrogenation reactor to a combustion unit, wherein: the particulate solids move through the combustion unit in a generally upward direction and the gas moves through the combustion unit in a generally upward direction such that the particulate solids and the gas move through the combustion unit in a co-current flow pattern; The combustion unit comprises a first gas inlet and a second gas inlet, the first gas inlet is below the second gas inlet, the oxygen-containing gas enters the combustion unit through the first gas inlet, and the fuel enters the combustion unit through the second gas inlet; In the region of the combustion unit above the first gas inlet and below the second gas inlet, the oxygen content in at least a portion of the oxygen carrier material of the particulate solid increases; and in a region of the combustion unit above the second gas inlet, at least a portion of the fuel reacts with oxygen from one or both of the oxygen-containing gas or the oxygen carrier material of the particulate solid; and At least a portion of the particulate solids is transferred from the combustion unit to the dehydrogenation reactor.

2. The method of claim 1, wherein transferring at least a portion of the particulate solids from the combustion unit to the dehydrogenation reactor comprises separating the particulate solids from flue gas.

3. A process according to any preceding claim, wherein the one or more hydrocarbons comprise alkyl moieties and the one or more products comprise one or more olefin compounds.

4. A process according to any preceding claim, wherein the one or more hydrocarbons comprises ethane and the one or more products comprises ethylene.

5. A method according to any preceding claim, wherein the fuel comprises hydrogen.

6. A method according to any preceding claim, wherein coke is deposited on the particulate solids passed from the dehydrogenation reactor to the combustion unit, and at least a portion of the coke reacts with oxygen in the combustion unit.

7. A method according to any preceding claim, wherein transferring at least a portion of the particulate solids from the combustion unit to the dehydrogenation reactor comprises passing the particulate solids through a regeneration unit, wherein the particulate solids are exposed to an oxygen-containing gas in the regeneration unit such that the oxygen content in at least a portion of the oxygen carrier material of the particulate solids is increased.

8. The process of claim 7, wherein the particulate solid and the oxygen-containing gas in the regeneration unit move in a countercurrent mode.

9. The method according to claim 7 or 8, wherein the regeneration unit comprises a third gas inlet and a fourth gas inlet, and wherein the oxygen-containing gas enters the regeneration unit through the third gas inlet, and the stripping gas enters the regeneration unit through the fourth gas inlet, wherein the stripping gas comprises the reducing agent in an amount of 0 mol.% to 100 mol.%.

10. A process according to claims 7 to 9, wherein a portion of the particulate solids is withdrawn from the regeneration unit and passed a second time through at least a portion of the regeneration unit before being passed to the dehydrogenation reactor.

11. A method according to any preceding claim, wherein the particulate solid consists essentially of the oxygen carrier material.

12. A process according to any preceding claim, wherein the dehydrogenation of the one or more alkanes is carried out by non-catalytic thermal dehydrogenation.

13. The process of claims 1 to 10, wherein the particulate solid further comprises a dehydrogenation catalyst material and the dehydrogenation of the one or more alkanes is at least partially performed by catalytic dehydrogenation.

14. The method of claim 13, wherein the dehydrogenation catalyst material and the oxygen support material are separate particles of the particulate solid or are contained in the same particle of the particulate solid.

15. A method according to any preceding claim, wherein the particulate solid is a Geldart type A or Geldart type B particle.

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