Method for dehydrogenating hydrocarbons using regenerator

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. The regeneration unit may include a first gas inlet and a second gas inlet, which may be below the first inlet. Fuel may enter the regeneration unit through the first gas inlet and an oxygen-containing gas may enter the regeneration unit through the second gas inlet. In a region of the regeneration unit above the first gas inlet, at least a portion of the fuel may react with oxygen from one or both of the oxygen-containing gas or the oxygen carrier material.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 406,439, filed on September 14, 2023, the entire disclosure of which is hereby incorporated by reference into this document. 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. In some embodiments, the dehydrogenation reaction can be promoted by reducing or removing the hydrogen formed during dehydrogenation by reacting hydrogen with oxygen to form water, 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 included in a granular solid. This oxygen carrier material can be circulated through a 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 at least heat the oxygen carrier material.

[0006] As described herein, it has been found that utilizing a specific countercurrent flow pattern for particulate solids and gas in a regenerator may be beneficial.Embodiments described herein include flow patterns, wherein particulate solids move generally downward through the regenerator, and gas (comprising fuel and oxygen-containing gas) moves in a generally upward direction.In addition, fuel and oxygen-containing gas enter the regeneration unit through the first gas inlet and the second gas inlet respectively, wherein the second gas inlet is below the first gas inlet.This arrangement can allow the oxygen carrier material to be fully oxidized and heated to perform dehydrogenation reaction.During fuel combustion, oxygen from the oxygen carrier material can be utilized, which reduces the oxygen content of the oxygen carrier material.Exposing the oxygen carrier material to the oxygen-containing gas after fuel combustion can help ensure that the oxygen carrier material fully oxidizes and leaves the regeneration 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 contain 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 at least a portion of the particulate solid from the dehydrogenation reactor to a regeneration unit. The particulate solid can move through the regeneration unit in a generally downward direction, and the gas can move through the regeneration unit in a generally upward direction, so that the particulate solid and the gas move through the regeneration unit in a countercurrent flow mode. The regeneration unit may include a first gas inlet and a second gas inlet, and the second gas inlet may be below the first gas inlet. The fuel may enter the regeneration unit through the first gas inlet. The oxygen-containing gas may enter the regeneration unit through the second gas inlet. In the region of the regeneration unit above the first gas inlet, at least a portion of the fuel may react with oxygen from one or both of the oxygen-containing gas or the oxygen carrier material of the particulate solid. The method may further include transferring at least a portion of the particulate solids from the regeneration 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; and

[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 regeneration 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 regeneration 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 regeneration unit 150 via stream 112. The regeneration unit 150 may include a gas / solid separator 190, a first gas inlet 160, and a second gas inlet 170. The first gas inlet 160 may be above the second gas inlet 170. The fuel 162 may enter the regeneration unit 150 through the first gas inlet 160, and the oxygen-containing gas 172 may enter the regeneration unit 150 through the second gas inlet 170. The particulate solids 180 may travel through the regeneration unit 150 in a generally downward direction, first through the separator 190, then through the first gas inlet 160, and then through the second gas inlet 170. The gas within the regeneration unit 150, such as the fuel 162 and the oxygen-containing gas 172, may travel through the regeneration unit 150 in a generally upward direction, such that the particulate solids 180 and the gas move through the regeneration unit 150 in a countercurrent flow pattern. The particulate solids 180 may then exit the regeneration unit 150 and pass back to the dehydrogenation reactor 110 via stream 152 .

[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 regeneration 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 some 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 CeO2, Ce2O3, or any other mixed metal oxide containing cerium. In further embodiments, the oxygen carrier material can include a combination of lanthanum oxide La2O3 and other reducible metal oxides. In some embodiments, the redox-active metal oxide can 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 can be a solid. In specific embodiments, the oxygen carrier material can be a crushed solid or a powder. In other embodiments, the oxygen carrier material can be formulated using a redox-active metal oxide and a binder and / or a support material to produce a fluidizable material having desired physical properties (e.g., particle size distribution, density, and wear resistance). The binder and / or support material can include alumina, silica, titania, magnesia, zirconia, 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 supplemental fuel 162 can be burned to heat one or more of the dehydrogenation catalyst or the oxygen carrier material. The supplemental fuel 162 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 supplemental fuel 162 required can be substantially less than the amount of supplemental fuel 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 unreacted alkanes or alkyl aromatic compounds and remove the hydrogen produced in the dehydrogenation reaction, and 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 supplementary fuel 162 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 550°C or 600°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 regeneration unit 150 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 240 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 a fluidization with a range of no bubbles; high bed expansion; slow and linear degassing rate; bubble characteristics, which may include the advantage of splitting / recoalescing bubbles, having a maximum bubble size and a large wake; a high level 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 average particle size, assuming cfp is equal; or with an increasing proportion of <45 micrometers (μm); or with increasing gas pressure, temperature, viscosity, and density. Generally, the particles may exhibit a small average particle size and / or a low particle density (<1.4 grams per cubic centimeter, g / cm 3 ); are easily fluidized, where they fluidize smoothly 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 that starts to bubble at Umf; exhibits moderate bed expansion; rapid degassing; no limitation on bubble size; a moderate level of solid mixing and gas backmixing, assuming U - umf is equal; both axisymmetric and asymmetric slugs; and spouting only in shallow beds. These characteristics tend to improve with decreasing average particle size, but the particle size distribution and certain uncertainties of the gas, pressure, temperature, viscosity, or density seem to have little 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 vessel. In the described embodiment, the granular solid 180 may be transferred to the 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 the regeneration 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 solid 180 may be slightly deactivated after contacting the feed stream 102. In other embodiments, the dehydrogenation catalyst of the particulate solid 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 a substance 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 solid 180 that is passed from the dehydrogenation reactor 110 to the regeneration unit 150.

[0056] The particulate solids 180 may enter the regeneration unit 150 via stream 112. The particulate solids 180 may then enter the gas / solid separator 190 within the regeneration unit 150. Exiting the separator 190, the particulate solids 180 may pass through the fuel zone 164 and through the first gas inlet 160 through which the fuel 162 may enter the regeneration unit 150. The particulate solids 180 may then pass through the air zone 174 and through the second gas inlet 170 through which the oxygen-containing gas 172 may enter the regeneration unit 150. The particulate solids 180 may then exit the regeneration unit 150 via stream 152 and be passed back to the dehydrogenation reactor 110.

[0057] Regeneration can remove contaminants (such as coke), increase the temperature of the particulate solids 180, increase the oxygen content of the oxygen carrier material of the particulate solids 180, or a combination thereof. In some embodiments, the coke on the particulate solids 180 can be removed by combustion in an oxygen-containing environment in the regeneration unit 150. In further embodiments, the particulate solids 180 can be heated to a target temperature by the fuel 162. The particulate solids 180 can then be circulated 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 / 077867A1 (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 regeneration 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 regeneration 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. The resulting gas stream 154 from the regeneration unit 150 can be composed of air depleted of O2 or containing a lower concentration of O2.

[0060] In one or more embodiments, the supplemental fuel 162 can 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-reduced oxygen carrier material and the combustion of the supplemental fuel 162 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 regeneration 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 regeneration 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 regeneration unit 150 can generally vary from 0.5 seconds (sec) to 360 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 the dehydrogenation reactor 110 to the regeneration unit 150 via stream 112. In the regeneration unit 150, the particulate solids 180 may pass through a gas / solid separator 190. According to one or more embodiments, the separator 190 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 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 190 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. Gas separated from the particulate solids 180 may be combined with gas from the regeneration unit 150 and exit the regeneration unit 150 via the exhaust gas stream 154 .

[0064] According to an embodiment, the granular solid 180 may move through the regeneration unit 150 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, wherein the downward direction is under the pull of gravity. Since it is an average value, the velocity of a single particle 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 to be generally downward. According to an embodiment, the gas within the regeneration unit 150 may move through the regeneration unit 150 in a generally upward direction. As used in the present disclosure, the term "generally upward direction" means that the average velocity of the gas within the regeneration unit 150 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 the gas molecules within the regeneration unit 150 may have a distribution and may not be equal to the average value, but as a whole, the velocity of the gas will average to be generally upward. According to an embodiment, the granular solid 180 and the gas may move through the regeneration unit 150 in a countercurrent flow mode.

[0065] 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 that can be operated to inject gas into the regeneration 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 fuel 162 may enter the regeneration unit 150 via the first gas inlet 160. In one or more embodiments, the oxygen-containing gas 172 may enter the regeneration unit 150 via the second gas inlet 170. In some embodiments, the fuel 162 may include hydrogen, methane, ethane, propane, natural gas, or a combination thereof. According to an embodiment, the fuel 162 may enter the regeneration unit 150 in a generally upward direction. In some embodiments, the fuel 162 may enter the regeneration unit in an initially downward direction and then flow generally upward following other gases within the regeneration unit 150. In an embodiment, at least a portion of the fuel 162 in the region above the first gas inlet 160 may react with oxygen from one or both of the oxygen-containing gas 172 or the oxygen carrier material of the particulate solid 180 to generate heat and increase the temperature of the particulate solid 180. In an embodiment, the region above the first gas inlet 160 may be a fuel zone 164 because the directional flow of the fuel 162 into the regeneration unit 150 may result in a higher concentration of the fuel 162 in the region above the first gas inlet 160 than in the region below the first gas inlet 160.

[0066] In some embodiments, the concentration of the fuel 162 in the fuel zone 164 may be less than 20 mol%. In some embodiments, the concentration of the fuel 162 in the fuel zone 164 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.%.

[0067] In one or more embodiments, at least a portion of the fuel 162 in the fuel zone 164 can react with oxygen from the oxygen-enriched oxygen carrier material of the particulate solid 180, and the oxygen content of at least a portion of the oxygen-enriched oxygen carrier material of the particulate solid 180 can be reduced to form an oxygen-reduced oxygen carrier material. In other embodiments, at least a portion of the fuel 162 in the fuel zone 164 can react with oxygen from the oxygen-containing gas 172, and the oxygen from the oxygen-containing gas 172 can oxidize the oxygen-reduced oxygen carrier material of the particulate solid 180 to form an oxygen-enriched oxygen carrier material.

[0068] As described herein, in one or more embodiments, the oxygen-containing gas 172 can enter the regeneration unit 150 via the second gas inlet 170. In some embodiments, the oxygen-containing gas 172 can be air, enriched air, air mixed with steam, or flue gas. Enriched air is air to which oxygen has been added. In some embodiments, the oxygen-containing gas 172 can contain at least 28 mol.% oxygen. In other embodiments, the oxygen-containing gas 172 can contain 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 1 ...5 mol.% oxygen, about 5 mol.% to about 20 mol.% oxygen, about 5 mol.% to about 15 mol.% oxygen, about 5 mol.% to about % 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.

[0069] In embodiments, the oxygen-containing gas 172 may enter the regeneration unit 150 in a generally upward direction. In some embodiments, the oxygen-containing gas 172 may enter the regeneration unit 150 in an initially downward direction and then flow generally upward following other gases within the regeneration unit 150. In some embodiments, the area above the second gas inlet 170 and below the first gas inlet 160 may be an air zone 174 because the directional flow of the oxygen-containing gas 172 into the regeneration unit 150 may result in a higher oxygen concentration in the area between the first gas inlet and the second gas inlet than in other areas of the regeneration unit 150. In one or more embodiments, the oxygen concentration in the air zone 174 may be greater than 25 mol.%. In some embodiments, the oxygen concentration in the air zone 174 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.

[0070] In embodiments, at least a portion of the oxygen-reduced oxygen carrier material of the particulate solid 180 can react with oxygen from the oxygen-containing gas 172 in the air zone 174, and the oxygen content of at least a portion of the oxygen carrier material of the particulate solid 180 can be increased to form an oxygen-enriched oxygen carrier material of the particulate solid 180. In one or more embodiments, at least a portion of the particulate solid 180 can be transferred from the regeneration unit 150 back to the dehydrogenation reactor 110 via stream 152.

[0071] Without being bound by theory, it is believed that after exposing the oxygen carrier material to the fuel 162, by exposing the oxygen carrier material to the oxygen-containing gas 172 in the region of the regeneration unit 150, the oxygen carrier material may be oxidized by the oxygen-containing gas 172, thereby replacing at least a portion of the oxygen that may have been released during the combustion of the fuel 162. This may result in the oxygen carrier material exiting the regeneration unit 150 being in a higher oxidation state than the oxygen carrier material that was not exposed to the oxygen-containing gas 172 after exposure to the fuel 162. For example, if the regeneration unit 150 allows the fuel 162 to enter through the second gas inlet 170 instead of the first gas inlet 160, and the oxygen-containing gas 172 enters through the first gas inlet 160 instead of the second gas inlet 170, the oxygen carrier material may be reduced by the fuel 162 and may not be fully reoxidized before being passed back to the dehydrogenation reactor 110. Because different materials used for the oxygen carrier material may have higher or lower oxidation state requirements for their ideal performance in the dehydrogenation reaction, this situation may negatively affect the selectivity and activity of the oxygen carrier material in the dehydrogenation reaction, potentially reducing the overall performance of the reactor system 100. In other words, contacting the oxygen carrier material with oxygen (in the lower portion of the regeneration unit 150 ) after the fuel 162 is combusted with oxygen from the oxygen carrier material (in the upper portion of the regeneration unit 150 ) ensures that the oxygen carrier material is fully oxidized upon exiting the regeneration unit 150 .

[0072] It is also believed that by adding the oxygen-containing gas 172 below the fuel 162, the oxygen-containing gas 172 can mix with the fuel 162 in the fuel zone 164. The additional oxygen that can be added to the fuel zone 164 in this case can help the fuel 162 burn and can reoxidize at least a portion of the oxygen carrier material. For example, it is believed that for some oxygen carrier materials, reoxidation can occur completely in the fuel zone 164 because the oxygen from the oxygen-containing gas 172 that has traveled to the fuel zone 164 completely oxidizes the oxygen carrier material of the particulate solid 180. It is believed that placing the air zone 174 below the fuel zone 164 in the regeneration unit 150 can allow the oxygen carrier material of the particulate solid 180 to leave the regeneration unit 150 in a higher oxidation state than it might in other regeneration unit 150 configurations.

[0073] Reference now Figure 2, a reactor system according to another embodiment of the present disclosure is shown. The particulate solids 180 can be first transferred from the dehydrogenation reactor 110 to the pre-oxidation unit 210 via stream 112 before being transferred to the regeneration unit 150. The oxygen-containing gas 212 can enter the pre-oxidation unit 210, and the particulate solids 180 can be exposed to the oxygen-containing gas 172. The oxygen-containing gas 212 and the particulate solids 180 can flow through the pre-oxidation unit 210 generally in an upward direction and can exit the pre-oxidation unit 210 via stream 222 and can be transferred to the regeneration unit 150. The particulate solids 180 can flow through the regeneration unit 150 generally in a downward direction, first through the fuel zone 164, then through the air zone 174, and finally through the third gas inlet 140 below the second gas inlet 170, through which the stripping gas 142 can enter the regeneration unit 150. The particulate solids 180 may then exit the regeneration unit 150 via stream 152 and be passed back to the dehydrogenation reactor 110. The preoxidation unit 210 and the third gas inlet 140 are optional additions to the reactor system 200. It is contemplated that the reactor system 200 may include only the preoxidation unit 210, but not the third gas inlet 140, or only the third gas inlet 140, but not the preoxidation unit 210.

[0074] As described herein, in one or more embodiments, the particulate solids 180 can be passed from the dehydrogenation reactor 110 to the pre-oxidation unit 210 prior to being passed to the regeneration unit 150. In one or more embodiments, the oxygen-containing gas 212 can be passed through the oxidizing gas inlet ( Figure 2% 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 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 mol. % to about 15 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 ...8 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 % 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.% oxygen.

[0075] In an embodiment, the oxygen carrier material of the particulate solid 180 may be exposed to the oxygen-containing gas 212 in the pre-oxidation unit 210. In some embodiments, the oxygen content in at least a portion of the oxygen carrier material of the particulate solid 180 may be increased in the pre-oxidation unit 210. In some embodiments, the oxygen-containing gas 212 and the particulate solid 180 may flow through the pre-oxidation unit 210 in a generally co-current flow in an upward direction. As used herein, "generally co-current" means that the average velocity of the particulate solid 180 and the oxygen-containing gas 212 is in the same direction. Because it is an average value, the velocity of a single particle of the particulate solid 180 or a single gas molecule of the oxygen-containing gas 212 may have a distribution and may not be equal to the average value, but as a whole, the velocity of the two components will be averaged to be generally in the same direction. In some embodiments, coke that may be formed on the particulate solid 180 in the dehydrogenation reactor 110 may be burned in the pre-oxidation unit 210, thereby heating at least a portion of the particulate solid 180.

[0076] In one or more embodiments, the particulate solids 180 can be transferred from the pre-oxidation unit 210 to the regeneration unit 150 via stream 222. In some embodiments, the particulate solids 180 can be mixed with a gas as it is transferred 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, a carrier gas from the dehydrogenation reactor 110, or a combination thereof.

[0077] In one or more embodiments, the particulate solids 180 may be passed from the regeneration unit 150 to the pre-oxidation unit 210. For example, the particulate solids 180 may be passed back to the pre-oxidation unit 210 to achieve a desired oxidation level of the oxygen carrier material of the particulate solids 180. In some embodiments, the particulate solids 180 may be passed from the regeneration unit 150 to the pre-oxidation unit 210 from the fuel zone 164 to pass again through the pre-oxidation unit 210 and the regeneration unit 150. In other embodiments, the particulate solids 180 may be passed from the regeneration unit 150 to the pre-oxidation unit 210 from the air zone 174 to pass again through the pre-oxidation unit 210 and the regeneration unit 150. In further embodiments, the particulate solids 180 may be passed from the regeneration unit 150 to the pre-oxidation unit 210 from both the air zone 174 and the fuel zone 164.

[0078] Still reference Figure 2 In one or more embodiments, the regeneration unit 150 may include a third gas inlet 140. In an embodiment, a stripping gas 142 may enter the regeneration unit 150 through the third gas inlet 140. In an embodiment, the third gas inlet 140 may be below the second gas inlet 170. In an embodiment, the stripping gas 142 may exit the third gas inlet 140 in a generally upward direction. In some embodiments, the stripping gas 142 may enter the regeneration unit 150 in an initially downward direction and then flow generally upward following other gases within the regeneration unit 150. Thus, in an embodiment, the area above the third gas inlet 140 and below the second gas inlet 170 may be a stripping zone 144, because the directional flow of the stripping gas 142 into the regeneration unit 150 may result in a higher concentration of the stripping gas 142 in the area above the third gas inlet 140 and below the second gas inlet 170. In some embodiments, the stripping gas 142 may include air, nitrogen, steam, or a combination thereof.

[0079] In one or more embodiments, the stripping gas 142 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 142 in the stripping zone 144, 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 142 may be greater than 10 mol.%. In some embodiments, the concentration of the reducing agent in the stripping gas 142 may even be greater than 90 mol.%. In some embodiments, the concentration of the reducing agent in the stripping gas 142 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 142.

[0080] In one or more embodiments, at least a portion of the particulate solids 180 can be withdrawn from the regeneration unit 150 and passed through at least a portion of the regeneration unit 150 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 air zone 174 and delivered to the fuel zone 164. In other embodiments, at least a portion of the particulate solids 180 can be withdrawn from the stripping zone 144 and delivered to the fuel zone 164, the air zone 174, or both.

[0081] 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 comprises an oxygen carrier material. In the dehydrogenation reactor, 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 and reduce the oxygen content in the oxygen carrier material. The method also includes transferring at least a portion of 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, so that the particulate solid and the gas move through the regeneration unit in a countercurrent flow pattern. The regeneration unit includes a first gas inlet and a second gas inlet. The second gas inlet is below the first gas inlet. The fuel enters the regeneration unit through the first gas inlet. The oxygen-containing gas enters the regeneration unit through the second gas inlet. In the region of the regeneration unit above the first 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. The method may also include transferring at least a portion of the particulate solid from the regeneration unit to the dehydrogenation reactor.

[0082] A second aspect of the present disclosure may include the first aspect, wherein the oxygen content in at least a portion of the oxygen carrier material of the particulate solid is increased in a region of the regeneration unit above the second gas inlet and below the first gas inlet.

[0083] A third aspect of the present disclosure may include the first aspect, wherein in a region of the regeneration unit above the first gas inlet, at least a portion of the fuel reacts with oxygen from the oxygen carrier material of the particulate solid and the oxygen content of at least a portion of the oxygen carrier material is reduced.

[0084] A fourth aspect of the present disclosure may include the first aspect, wherein in a 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 and the oxygen content of at least a portion of the oxygen carrier material increases.

[0085] A fifth aspect of the present disclosure may include the first aspect, wherein at least a portion of the particulate solids are passed back to the dehydrogenation reactor without being passed to the regeneration unit.

[0086] A sixth aspect of the present disclosure may include any of the preceding aspects, wherein the one or more hydrocarbons comprise an alkyl moiety and the one or more products comprise one or more olefin compounds.

[0087] A seventh aspect of the present disclosure may include any of the preceding aspects, wherein the fuel comprises hydrogen.

[0088] An eighth aspect of the present disclosure may include any of the preceding aspects, wherein the coke is deposited on particulate solids transferred from the dehydrogenation reactor to the regeneration unit, and at least a portion of the coke is reacted in the regeneration unit.

[0089] A ninth aspect of the present disclosure may include any of the preceding aspects, wherein transferring 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 such that the oxygen content in at least a portion of the oxygen carrier material of the solid particles in the pre-oxidation unit is increased.

[0090] A tenth aspect of the present disclosure may include the ninth aspect, wherein the particulate solid and the oxygen-containing gas flow through the pre-oxidation unit in a generally co-current flow in an upward direction.

[0091] An eleventh aspect of the present disclosure may include any of the preceding aspects, wherein the regeneration unit comprises a third gas inlet below the second gas inlet, and the stripping gas enters the regeneration unit through the third gas inlet, and wherein the stripping gas comprises 0 mol.% to 100 mol.% of the reducing agent.

[0092] A twelfth aspect of the present disclosure may include any of the preceding aspects, 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.

[0093] A thirteenth aspect of the present disclosure may include any of the preceding aspects, wherein the solid particles consist essentially of an oxygen carrier material, and the dehydrogenation of the one or more hydrocarbons is performed by non-catalytic thermal dehydrogenation.

[0094] A fourteenth aspect of the present disclosure may include the first aspect, wherein the particulate solid may further comprise a dehydrogenation catalyst material, and wherein the dehydrogenation of the one or more hydrocarbons is at least partially performed by catalytic dehydrogenation.

[0095] A fifteenth aspect of the present disclosure may include the fourteenth aspect, wherein the dehydrogenation catalyst material and the oxygen support material are separate particles of the particulate solid, or the dehydrogenation catalyst material and the oxygen support material are contained in the same particle of the particulate solid.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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.

[0101] 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.

[0102] 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."

[0103] 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; transferring at least a portion of the particulate solids from the dehydrogenation reactor to a regeneration unit, wherein: the particulate solids move 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 solids and gas move through the regeneration unit in a countercurrent flow pattern; The regeneration unit comprises a first gas inlet and a second gas inlet, the second gas inlet is below the first gas inlet, fuel enters the regeneration unit through the first gas inlet, and oxygen-containing gas enters the regeneration unit through the second gas inlet; reacting at least a portion of the fuel with oxygen from one or both of the oxygen-containing gas or the oxygen carrier material of the particulate solid in a region of the regeneration unit above the first gas inlet; as well as At least a portion of the particulate solids is transferred from the regeneration unit to the dehydrogenation reactor. 2 . The method according to claim 1 , wherein the oxygen content in at least a portion of the oxygen carrier material of the particulate solid increases in the region of the regeneration unit above the second gas inlet and below the first gas inlet.

3. The method according to claim 1, wherein 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 carrier material of the particulate solid and the oxygen content of at least a portion of the oxygen carrier material is reduced.

4. The method of claim 1, wherein 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 and the oxygen content of at least a portion of the oxygen carrier material increases.

5. The process of claim 1 wherein at least a portion of the particulate solids are passed back to the dehydrogenation reactor without being passed to the regeneration unit.

6. 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 olefinic compounds.

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

8. A process according to any preceding claim, wherein coke is deposited on the particulate solids passed from the dehydrogenation reactor to the regeneration unit, and at least a portion of the coke is reacted in the regeneration unit.

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

10. The process of claim 9 wherein the particulate solid and the oxygen-containing gas flow through the pre-oxidation unit in a generally co-current upward direction.

11. A method according to any preceding claim, wherein the regeneration unit comprises a third gas inlet below the second gas inlet and a stripping gas enters the regeneration unit through the third gas inlet, and wherein the stripping gas comprises 0 mol.% to 100 mol.% of reducing agent.

12. A process according to any preceding claim, 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.

13. A process according to any preceding claim, wherein said solid particles consist essentially of said oxygen carrier material and said dehydrogenation of said one or more hydrocarbons is carried out by non-catalytic thermal dehydrogenation.

14. The method of claim 1, wherein the particulate solid further comprises a dehydrogenation catalyst material, and wherein the dehydrogenation of the one or more hydrocarbons is at least partially performed by catalytic dehydrogenation.

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

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