CN119630626A

CN119630626A - Method for dehydrogenating hydrocarbons using a regenerator

Info

Publication number: CN119630626A
Application number: CN202380056956.0A
Authority: CN
Inventors: M·T·普雷茨; C·班尼特; K·布朗; J·基思; D·尼斯肯斯; A·普拉琦
Original assignee: Dow Global Technologies LLC
Current assignee: Dow Global Technologies LLC
Priority date: 2022-09-14
Filing date: 2023-09-13
Publication date: 2025-03-14
Also published as: WO2024059600A1; CA3263435A1; KR20250068596A; EP4540210A1; JP2025531003A

Abstract

In accordance with one or more embodiments described herein, a process 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 that may be below the first inlet. Fuel may enter the regeneration unit through the first gas inlet and oxygen-containing gas may enter 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.

Description

Method for dehydrogenating hydrocarbons using a regenerator

Cross Reference to Related Applications

The present application claims the benefit of U.S. provisional application Ser. No. 63/406,439, filed on 9/14 of 2023, the entire disclosure of which is hereby incorporated by reference.

Technical Field

Embodiments described herein relate generally to chemical processing, and more particularly, to methods and systems for dehydrogenating chemicals.

Background

Olefin compounds can be used as a base material to produce many types of goods and materials. For example, ethylene may be used to make polyethylene, ethylene chloride or ethylene oxide. Such products may be used in product packaging, construction, textiles, and the like. Thus, there is a need in the industry for olefinic compounds such as ethylene, propylene, butylene, and styrene.

Disclosure of Invention

One method for producing olefin compounds is by dehydrogenating the hydrocarbon. In some embodiments, the dehydrogenation reaction may be facilitated by reacting hydrogen with oxygen to form water to reduce or remove hydrogen formed during dehydrogenation, which pushes the equilibrium toward the olefin compound product. In such embodiments, oxygen carrier materials may be utilized to provide oxygen that reacts with hydrogen. The oxygen carrier material may be contained in a particulate solid. Such oxygen carrier material may be circulated through the reactor and the regeneration unit, wherein the oxygen content of the oxygen carrier material may be increased in the regeneration unit. In some embodiments, fuel is additionally utilized in the regeneration unit to heat at least the oxygen carrier material.

As described herein, it has been found that utilizing a particular countercurrent flow pattern for particulate solids and gases in a regenerator may be beneficial. Embodiments described herein include flow modes in which particulate solids move generally downward through a regenerator and gases (including fuel and oxygen-containing gases) move in a generally upward direction. In addition, the fuel and the oxygen-containing gas enter the regeneration unit through a first gas inlet and a second gas inlet, respectively, wherein the second gas inlet is below the first gas inlet. This arrangement may allow the oxygen carrier material to be sufficiently oxidized and heated to perform the dehydrogenation reaction. Oxygen from the oxygen carrier material may be utilized during combustion of the fuel, which reduces the oxygen content of the oxygen carrier material. Exposing the oxygen carrier material to the oxygen-containing gas after combustion of the fuel may help ensure that the oxygen carrier material leaves the regeneration unit sufficiently oxidized.

According to one or more embodiments described herein, the hydrocarbons may be dehydrogenated by a process comprising contacting a feed stream comprising one or more hydrocarbons with a particulate solid in a dehydrogenation reactor. The particulate solid 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 further include passing at least a portion of the particulate solids from the dehydrogenation reactor to a regeneration unit. The particulate solids may move in a generally downward direction through the regeneration unit and the gas may move in a generally upward direction through the regeneration unit such that the particulate solids and gas move in a countercurrent flow pattern through the regeneration unit. The regeneration unit may include a first gas inlet and a second gas inlet, which may be below the first gas inlet. 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 particulate solid oxygen carrier material. The method may further include transferring at least a portion of the particulate solids from the regeneration unit to the dehydrogenation reactor.

It is to 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 character of the claimed subject matter. Additional features and advantages of the embodiments will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description, including the drawings and claims, or may be learned by practice of the described embodiments. The drawings are included to provide a further understanding of the embodiments and together with the detailed description serve to explain the principles and operations of the claimed subject matter. However, the implementations depicted in the drawings are illustrative and exemplary in nature and are not intended to limit the claimed subject matter.

Drawings

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

FIG. 1 schematically depicts a reactor system according to one or more embodiments of the present disclosure, and

Fig. 2 schematically depicts another reactor system according to a further embodiment of the present disclosure.

While the simplified schematic illustrations of fig. 1 and 2 are described, 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. Furthermore, the accompanying components typically included in such reactor systems, such as air supplies, heat exchangers, buffer tanks, etc., are also not included. However, it should be understood that these components are within the scope of this disclosure.

Detailed Description

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

Embodiments of the presently disclosed method will now be described in detail herein in the context of the reactor system of fig. 1 and 2, which operates as a circulating fluidized bed process to dehydrogenate hydrocarbons. However, it should be understood that the principles disclosed and taught herein may be applied to other systems that utilize different system components oriented in different ways. For example, the concepts described herein may be equally applied to other systems having alternative reactor units and regeneration units, such as those operating under non-fluidized conditions, or those systems that include downcomers rather than risers, and vice versa. It should also be understood that not all portions of the reactor systems of fig. 1 and 2 should be construed as necessary for the claimed subject matter. Furthermore, while the method steps recited in the appended claims are described in the context of the reactor system of fig. 1 and 2, such recited method steps should be understood to be applicable to other systems as would be understood by one of skill in the art.

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

Particulate solids 180 may exit dehydrogenation reactor 110 and may be transferred to 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 a first gas inlet 160 and the oxygen-containing gas 172 may enter the regeneration unit 150 through a second gas inlet 170. The particulate solids 180 may travel in a generally downward direction through the regeneration unit 150, first through the separator 190, then through the first gas inlet 160, and then through the second gas inlet 170. Gases 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 gases move through the regeneration unit 150 in a counter-current flow pattern. The particulate solids 180 may then exit the regeneration unit 150 and pass back to the dehydrogenation reactor 110 via stream 152.

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 based on a fluidized bed.

As previously discussed, in one or more embodiments, the feed stream 102 can be passed to the dehydrogenation reactor 110. In one or more embodiments, the feed stream 102 can comprise one or more hydrocarbons. In one or more embodiments, the one or more hydrocarbons can include an alkyl moiety. As used in this disclosure, a hydrocarbon comprises an "alkyl moiety" if the molecule has at least one carbon-carbon single bond capable of dehydrogenation to form a carbon-carbon double bond. In one or more embodiments, the one or more hydrocarbons can include one or more of ethane, propane, butane, or ethylbenzene. According to one or more embodiments, the 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% ethane. In further embodiments, the 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% propane. In further embodiments, the 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% butane. In further embodiments, the 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% ethylbenzene. In further embodiments, the 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.

According to further embodiments, the dehydrogenation reactor 110 may be operated in a "back-mixed" mode, wherein the feed stream 102 enters the reactor so as to closely approximate isothermal conditions. Thus, the fluid velocity at this region may be sufficiently low and the particulate solids 180 flux may be sufficiently large that a dense bed may be formed at or around the location of injection of the feed stream 102. In some embodiments, the superficial velocity of the reactor may be from 3 feet/second to 80 feet/second, such as from 3 feet/second to 40 feet/second or from 10 feet/second to 30 feet/second. The particulate solids 180 flux in the reactor may be 1lb/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 a plurality of diameters and may include one or more frustums to increase or decrease the particulate solid 180 and/or gaseous reactant velocity. 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.

The granular solid 180 may be used in the general operation of the reactor system 100. As used herein, the term "particulate solid" may refer to one or more solid particles suitable for fluidization. In one or more embodiments, the particulate solid 180 may include an oxygen carrier material and a dehydrogenation catalyst material. In some embodiments, the particulate solid 180 may consist essentially of an oxygen carrier material. As described herein, "consisting essentially of" means a material having less than 1% by weight of the unrecited material (i.e., consisting essentially of a means a comprises at least 99% by weight of the composition). In some embodiments, the particulate solid 180 may not include a dehydrogenation catalyst material. In some embodiments, the oxygen carrier material and the dehydrogenation catalyst material can be separate particles of the particulate solid 180. In some embodiments, the oxygen carrier material and the dehydrogenation catalyst can be contained within the same particles of the particulate solid 180.

In embodiments where particulate solid 180 comprises a dehydrogenation catalyst, dehydrogenation of 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 include a dehydrogenation catalyst, dehydrogenation of one or more hydrocarbons may be performed by non-catalytic thermal dehydrogenation. Non-catalytic thermal dehydrogenation refers to dehydrogenation of hydrocarbons that occurs due to high temperature, pressure, or a combination thereof without the use of a dehydrogenation catalyst.

In some embodiments, the particulate solid 180 may comprise a "dual use material" that may serve as both a dehydrogenation catalyst as well as an oxygen carrier material. It should be appreciated that in at least the embodiments described herein wherein the oxygen carrier material and the dehydrogenation catalyst are used in the same reaction vessel (such as the reaction vessel of fig. 1), such dual-purpose materials may be used in place of, or in combination with, the oxygen carrier material of the particulate solid 180 and the dehydrogenation catalyst of the particulate solid 180.

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

In one or more embodiments, the dehydrogenation catalyst and the oxygen support material can be separate particles of the particulate solid 180, as described herein. One expected advantage of such a system is that by adding, removing, or replacing one or both of the dehydrogenation catalyst and the oxygen carrier material, the functionality of the system can be altered even when the system is online. For example, the reaction heat load may be adjusted by adding or removing one or both of the dehydrogenation catalyst and the oxygen carrier material. In some embodiments, this may be advantageous compared to dual-purpose materials because the thermal balance of the dual-purpose particles must be determined prior to the reaction and cannot be easily adjusted by varying the amount of dehydrogenation catalyst relative to the oxygen carrier material. Controlling the ratio of dehydrogenation catalyst to oxygen carrier material may be more advantageous because the reaction selectivity may be better adjusted. For example, the amount of hydrogen in the system may be used to control the degree of combustion, or the component balance may be used to optimize the downstream separation process.

In some embodiments, the dehydrogenation reactor 110 can include from 1 wt% to 100 wt%, such as from 5 wt% to 95 wt%, or from 75 wt% to 25 wt% of the oxygen carrier material, based on the total weight of the particulate solids 180 in the dehydrogenation reactor 110. In other embodiments, the dehydrogenation reactor 110 can include from 50 wt% to 75 wt% 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 can include from 0 wt% to 99 wt%, such as from 5 wt% to 95 wt%, or from 25 wt% to 75 wt% of the dehydrogenation catalyst, based on the total weight of the particulate solids 180 in the dehydrogenation reactor 110. In some embodiments, the dehydrogenation reactor 110 can include 25 wt.% to 50 wt.% dehydrogenation catalyst based on the total weight of the particulate solids 180 in the dehydrogenation reactor 110. In some embodiments, the dehydrogenation reactor 110 can include up to 95 wt%, 99 wt%, or even 100 wt% dual-purpose material 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 solid 180 may be a dual purpose material. In embodiments, the particulate solid 180 material may include all solids in the system except coke.

As previously described, within the dehydrogenation reactor 110, the hydrogen can be contacted with an oxygen-enriched oxygen carrier material of the particulate solid 180. The oxygen carrier material may comprise 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 capable of undergoing reduction in the presence of a reducing agent (e.g., hydrogen) and oxidation in the presence of an oxidizing agent (e.g., oxygen or air). In some embodiments, the redox-active metal oxide may be metal MO _x, where M may 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 may 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 may be cerium oxide. For example, the redox active metal oxide may be CeO ₂、Ce₂O₃ or any other mixed metal oxide containing cerium. In further embodiments, the oxygen carrier material may include lanthanum oxide La ₂O₃ 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 Cu ₂ O. In some embodiments, the oxygen carrier material may be a solid. In particular 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 fluidizable materials having desired physical characteristics (e.g., particle size distribution, density, and attrition resistance). The binder and/or support material may include alumina, silica, titania, magnesia, zirconia, or combinations thereof.

In one or more embodiments, the oxygen carrier material may include a hydrogen-selective oxygen carrier material, which may include an accelerator or a combination of various accelerators. The addition of the promoter may result in the formation of a core-shell morphology. The promoter may comprise 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 or alkaline earth transition metal oxides may be Na₂WO₄、K₂MoO₄、Na₂MoO₄、K₂WO₄、Li₂WO₄、CsWO₄、Li₂MoO₄、CaWO₄、CaMoO₄、MgWO₄、MgMoO₄、SrWO₄、SrMoO₄、BaWO₄ and BaMoO ₄. In some embodiments, the promoter may include one or more selected from alkali metal salts or alkaline earth metal salts of 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 counter ion may include carbonates, sulfates, sulfites, sulfides, phosphates, phosphites, and borates. For example, the alkali metal salt or alkaline earth metal salt may 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.

For example, oxygen carrier materials such as those disclosed in U.S. application Ser. No. 62/725,504 entitled "method OF producing Hydrogen-selective oxygen carrier materials (METHODS OF PRODUCING HYDROGEN-SELECTIVE OXYGEN CARRIER MATERIALS)" filed on month 31 OF 2018 and U.S. application Ser. No. 62/725,508 entitled "Hydrogen-selective oxygen carrier materials and METHODS OF USE thereof (HYDROGEN-SELECTIVE OXYGEN CARRIER MATERIALS AND METHODS OF USE)" filed on month 31 OF 2018 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. patent No. 5,430,209, U.S. patent No. 7,122,495, and/or WO 2018/232133, each of which is incorporated herein by reference in its entirety.

Oxygen-enriched oxygen carrier materials can be reduced by releasing oxygen that can be selective to the burning hydrogen. For example, oxygen carrier materials may be selectively used to combust hydrogen rather than hydrocarbons. In some embodiments, the oxygen-enriched oxygen carrier material comprises about 1 wt.% to about 20 wt.% releasable oxygen, based on the total weight of the oxygen-enriched oxygen carrier material. In other embodiments, the oxygen-enriched oxygen carrier material comprises from about 1 wt.% to about 10 wt.%, from about 1 wt.% to about 5 wt.%, from about 5 wt.% to about 20 wt.%, or from about 5 wt.% to about 10 wt.% of releasable oxygen. As used herein, "releasable oxygen" may refer to oxygen that may be released by oxidation-reduction from an oxygen carrier material. Other oxygen not releasable by redox may be present in the oxygen carrier material. It should be appreciated that in some embodiments, oxygen may be released from the surface of the oxygen carrier material at the same time that hydrogen is combusted at the surface of the oxygen carrier material.

As previously described, the releasable oxygen of the oxygen-enriched oxygen carrier material may be selectively used to combust hydrogen rather than hydrocarbons. In some embodiments, at least about 60% of the releasable oxygen of the oxygen carrier material is selective to hydrogen combustion. In other embodiments, at least about 55% of the releasable oxygen of the oxygen carrier material is selective to hydrogen combustion.

In embodiments, when hydrogen is contacted with an 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 the oxygen-enriched oxygen carrier material 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.

In a further embodiment, the oxygen-enriched oxygen carrier material burns greater than about 50% hydrogen when the hydrogen is contacted with the oxygen-enriched oxygen carrier material. In other embodiments, when hydrogen is contacted with the oxygen-enriched oxygen carrier material, the oxygen-enriched oxygen carrier material burns to produce about 50% to about 90%, or about 75% to about 90% hydrogen.

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

In one or more embodiments, the particulate solid 180 may comprise a dehydrogenation catalyst, as described herein. In one or more embodiments, the dehydrogenation catalyst can include gallium, chromium, and/or platinum. As described herein, the gallium and/or platinum dehydrogenation catalyst comprises gallium, platinum, or both. The dehydrogenation catalyst can be carried on an alumina or alumina silica support and can optionally comprise potassium. In one or more embodiments, the dehydrogenation catalyst can include catalysts disclosed in U.S. patent No. 8,669,406 (which is incorporated herein by reference in its entirety), such as those comprising Ga, cr, and/or Fe-based catalysts. According to further embodiments, pt-based catalysts may be utilized. In one or more embodiments, catalysts such as those disclosed in EP 0948475B1 and/or WO 2010/133565 may be utilized, each of which is incorporated herein by reference in its entirety. Additional catalyst embodiments contemplated as suitable for use in the systems and methods described herein include those in U.S. patent No. 8,669,406, which is incorporated by reference herein in its entirety. Such catalysts may contain relatively small amounts of Cr, such as less than 6%, or about 1.5%. However, it should be understood that other suitable dehydrogenation catalysts may be used to perform the dehydrogenation reaction.

In one or more embodiments, the dehydrogenation catalyst can exhibit suitable stability when steam is present. As described herein, the combustion of hydrogen may form steam, which may be in direct contact with the dehydrogenation catalyst. Not all dehydrogenation catalysts are expected to be equally effective in a steam environment. In one or more embodiments, a dehydrogenation catalyst is utilized that maintains a substantial amount of its reactivity and/or selectivity to the dehydrogenation of light alkanes. For example, one or more of the dehydrogenation catalysts utilized in the disclosed systems and methods may not degrade by 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 may even have improved alkane conversion and/or dehydrogenation selectivity when an amount of steam is present consistent with the operation of the disclosed systems. In some embodiments, the dehydrogenation catalyst may function at such conversions and/or selectivities when exposed to at least 10mol.% water (such as 10mol.% to 50mol.% water) for a period of, for example, 120 seconds (according to some embodiments of the presently disclosed systems, the catalyst may be exposed to such conditions).

Suitable examples of dehydrogenation catalysts may be prepared such that they conform to the Geldart a definition. In some embodiments, the dehydrogenation catalyst comprises gallium and platinum supported on silica-modified alumina in the form of a delta or theta phase, or in the form of a delta + theta phase, or a theta + alpha phase, or a mixture of delta + theta + alpha phases, and has a surface area, as determined by the BET method, preferably less than about 100 square meters per gram (m ²/g). In other embodiments, the dehydrogenation catalyst comprises from 0.1 to 34 wt%, preferably from 0.2 to 3.8 wt% gallium oxide (Ga ₂O₃), from 1 to 300ppm, preferably from 50 to 300ppm, of platinum by weight, from 0 to 5 wt%, preferably from 0.01 to 1 wt% of an alkali and/or alkaline earth, such as potassium, from 0.08 to 3 wt% of silica, the balance being alumina, 100 wt%.

In one or more embodiments, the heat gained or lost by the dehydrogenation reaction, the reoxidation of the oxygen-reduced oxygen carrier material, and the reduction of the oxygen-enriched oxygen carrier material may generate or use heat (i.e., exothermic or endothermic). In one or more embodiments, the contacting of the hydrocarbon feed with the dehydrogenation catalyst can be endothermic and result in dehydrogenation heat loss. In some embodiments, the contacting of hydrogen with the oxygen-enriched oxygen carrier material may be exothermic and result in a thermal gain of combustion. The reoxidation of the oxygen reduced oxygen carrier material may be exothermic and result in a thermal gain of oxygenation. Thus, by incorporating hydrogen combustion during catalytic dehydrogenation, in some embodiments, sufficient heat may be generated during reoxidation of the oxygen reduced oxygen carrier material to act as a heat source for alkane to alkene reactions. Thus, embodiments of the disclosed process may allow for higher alkane conversion while reducing or eliminating the fuel gas requirements required for conventional cracking, as the heat gained by reoxidation of the oxygen carrier material, combustion of hydrogen, or both may generate the amount of heat required for alkane or alkylaromatic to alkene reactions throughout the process.

As used herein, "dehydrogenation heat loss" refers to the amount of heat lost through dehydrogenation of the feed alkane, "combustion heat gain" refers to the amount of heat generated through combustion of hydrogen, and "oxygenation heat gain" refers to the amount of heat generated through oxidation of the oxygen-reduced oxygen carrier material. In one or more embodiments, the combustion heat gain may contribute heat to the system, which accounts for at least a portion of the dehydrogenation heat loss. In further embodiments, the supplemental fuel 162 may be combusted to heat one or more of the dehydrogenation catalyst or oxygen carrier material. The supplemental fuel 162 may offset any drawbacks of 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 necessary may be substantially less than the amount of supplemental fuel necessary in a system that does not incorporate an oxygen carrier material.

Because of the high heat load and/or downstream separation steps required for the endothermic dehydrogenation reactions, it is sometimes necessary to separate unreacted alkane or alkylaromatic compounds and remove hydrogen produced in the dehydrogenation reactions, the production of olefin compounds by conventional dehydrogenation processes (e.g., processes that do not incorporate hydrogen combustion) can be relatively expensive. With respect to reduced heat input, catalytic dehydrogenation processes are typically endothermic and require heat. However, exothermic combustion of hydrogen can offset the heat input requirements to some extent. In addition, the oxygen carrier material may be regenerated to recover its oxygen once the oxygen content has been reduced after combustion, which may be exothermic. This exothermic regeneration step may additionally offset the heat input requirement to maintain the dehydrogenation reaction. In some embodiments, the heat generated by the oxygen carrier regeneration and combustion reaction may completely cover the heat required for the endothermic dehydrogenation reaction and other heat requirements, such as heating the feed gas (air, hydrocarbons, etc.) or balancing heat loss, or at least reducing any supplemental fuel 162 requirements of the system. For additional general information regarding dehydrogenation reactions incorporating hydrogen combustion, those skilled in the art refer to, for example, U.S. patent publication 2021/0292259A1, the teachings of which are incorporated herein by reference in their entirety.

Still referring to fig. 1, during operation of the dehydrogenation reactor 110 of the reactor system 100, the feed stream 102 may enter a riser within the dehydrogenation reactor 110, and the product stream 114 may 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 the feed stream 102) into the dehydrogenation reactor 110.

According to one or more embodiments, the particulate solids 180 can be fed to the dehydrogenation reactor 110 via stream 152. The particulate solid 180 may comprise an oxygen-enriched oxygen carrier material. The particulate solid 180 may also contain a dehydrogenation catalyst. Feed stream 102 may contact particulate solids 180 in dehydrogenation reactor 110. Feed stream 102 and particulate solids 180 may each flow upward into and through dehydrogenation reactor 110 to produce one or more products, oxygen-reduced oxygen carrier material, and hydrogen. In dehydrogenation reactor 110, one or more hydrocarbons in feed stream 102 can be dehydrogenated to form one or more products and hydrogen. In addition, within the dehydrogenation reactor 110, hydrogen may be contacted with an oxygen-enriched oxygen carrier material in the dehydrogenation reactor 110. The oxygen-enriched oxygen carrier material may be reducible. Contact of the oxygen-enriched oxygen carrier material with hydrogen combusts the hydrogen and reduces the oxygen carrier material to form an oxygen-reduced oxygen carrier material and water.

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

As described above, in some embodiments, stream 114 may comprise one or more products. In one or more embodiments, the one or more products can comprise one or more olefin compounds. As used herein, the term "olefin compound" refers to a hydrocarbon having one or more carbon-carbon double bonds in addition to the formal double bonds in the aromatic compound. For example, ethylene and styrene are olefin compounds, but ethylbenzene is not an olefin compound because the only double bond present in ethylbenzene is the formal double bond present as part of the aromatic structure. In one or more embodiments, the one or more olefin compounds may include one or more of ethylene, propylene, butylene, or styrene. In some embodiments, the product stream 114 can 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% ethylene. In further 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% propylene. In further 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% butene. In further 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% styrene. In further 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.

In some embodiments, one or more products and particulate solids 180 may be passed to a separation device in a separation section within dehydrogenation reactor 110. The particulate solids 180 may be separated from the one or more products in a separation device, such as a stripper (not depicted in fig. 1) within the dehydrogenation reactor 110. One or more products may then be conveyed 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 cyclonic separation system. The cyclonic separation system may comprise two or more cyclonic separation stages.

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).

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

In some embodiments, dehydrogenation reactor 110 can be operated at a pressure of at least atmospheric (about 14.7 psia). In some embodiments, dehydrogenation reactor 110 can be operated at a pressure of about 500 psia. In other embodiments, dehydrogenation reactor 110 may be operated at a pressure of from about 4psia to about 160psia, from about 20psia to about 100psia, or from about 30psia to about 80 psia. In some embodiments, the regeneration unit 150 may be operated at a pressure within 30psi of the dehydrogenation reactor 110.

The residence time of the particles in the dehydrogenation reactor 110 can generally vary from 0.5 seconds (sec) to 240sec. In other embodiments, the residence time of the particulate solid 180 may be from about 0.5sec to about 200sec, from about 0.5sec to about 100sec, from about 0.5sec to about 50sec, or from about 0.5sec to about 20sec.

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

In further embodiments, the throughput of particulate solids 180 in the upstream reactor section may be from 1 pounds per square foot-second (lb/ft ² -s) (about 4.89kg/m ² -s) to 300lb/ft ² -s (to about 97.7kg/m ² -s), such as from 1lb/ft ² -s to 20lb/ft ² -s, and the throughput in the downstream reactor section may be from 1lb/ft ² -s (about 48.9kg/m ² -s) to 300lb/ft ² -s (about 489kg/m ² -s), such as from 10lb/ft ² -s to 100lb/ft ² -s.

In one or more embodiments, the particulate solids 180 may be capable of fluidization. In some embodiments, the particulate solid 180 may exhibit a characteristic referred to in the industry as a "Geldart a" or "Geldart B" characteristic. According to D.Geldart, gas fluidization techniques (Gas Fluidization Technology), john Wiley father & Sons (John Wiley & Sons) (New York, 1986), pages 34-37, and D.Geldart, gas fluidization types (Types of Gas Fluidization), powder techniques (Powder technologies) 7 (1973) 285-292, the entire contents of which are incorporated herein by reference, solids may be classified as "class A" or "class B".

Class a is understood by those skilled in the art to represent an inflatable powder with fluidization without bubble range, high bed expansion, slow and linear degassing rate, bubble characteristics, which may include advantages of splitting/re-coalescing bubbles, with maximum bubble size and large wake, high levels of solid mixing and gas back mixing 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 too high gas velocity), axisymmetric lump characteristics, and no spouting except in very shallow beds. The listed characteristics tend to improve with decreasing average particle size, assuming equal cfp, or with increasing <45 micrometer (μm) ratio, or with increasing pressure, temperature, viscosity and density of the gas. In general, particles may exhibit small average particle size and/or low particle density (< 1.4 grams/cc, g/cm ³), easy fluidization, where fluidization is smooth at low gas velocities, and controlled bubbling with small bubbles at higher gas velocities.

Class B is understood by those skilled in the art to represent a "sand-like" powder that begins to bubble at Umf, that exhibits moderate bed expansion, rapid degassing, no restriction on bubble size, moderate levels of solid mixing and gas back mixing, assuming U-Umf are equal, both axisymmetric and asymmetric slugs, and spouting in shallow beds only. These properties tend to improve as the average particle size decreases, but the particle size distribution and some uncertainty of the gas, pressure, temperature, viscosity or density appear to have little effect on improving these properties. In general, the majority of particles have a particle size (cfp) of 40 μm < cfp <500 μm when the density (pp) is 1.4< pp <4g/cm ³, and preferably 60 μm < cfp <500 μm when the density (pp) is 4g/cm ³, and 250 μm < cfp <100 μm when the density (pp) is 1g/cm ³.

Still referring to fig. 1, in one or more embodiments, the particulate solids 180 and the gaseous products may be separated within the dehydrogenation reactor 110 by a high efficiency cyclone (not shown in fig. 1) in the stripping section of the reactor system 100. The stripping section may be within the reactor 110 or may be a separate vessel. In the illustrated embodiment, the particulate solids 180 may be transferred to the regeneration unit 150 via stream 112. In some embodiments, the dehydrogenation catalyst, oxygen carrier material, or both may be stripped with a displacement gas (such as nitrogen, steam, methane, natural gas, or other suitable gas) in a stripping section before being sent to the regeneration unit 150. In some embodiments, a portion of the particulate solids 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 particulate solids 180 back to the reactor 110, the oxygen content of the oxygen carrier material may be better controlled because the oxygen carrier material may be given more time to react off its oxygen so that the oxygen carrier material may supply more oxygen to the reactor. It is also believed that recycling the granular solids 180 may allow for improved temperature control of the reactor 110, as recycling the granular solids 180 may improve control of the temperature of the material entering the reactor 110, thereby improving the temperature profile of the reactor 110.

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 reaction in the dehydrogenation reactor 110. As used herein, "deactivated" may refer to a catalyst contaminated with a substance such as coke that is at a temperature below that 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 transferred from the dehydrogenation reactor 110 to the regeneration unit 150.

Particulate solids 180 may enter regeneration unit 150 via stream 112. The particulate solids 180 may then enter a gas/solids separator 190 within the regeneration unit 150. From separator 190, particulate solids 180 may pass through fuel zone 164 and through first gas inlet 160, through which fuel 162 may enter 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 transferred back to the dehydrogenation reactor 110.

Regeneration may remove contaminants (such as coke), raise the temperature of particulate solid 180, increase the oxygen content of the oxygen carrier material of particulate solid 180, or a combination thereof. In some embodiments, coke on the particulate solids 180 may be removed by combustion in an oxygen-containing environment in the regeneration unit 150. In further embodiments, the particulate solid 180 may be heated to a target temperature by the fuel 162. The particulate solids 180 may then be recycled back to the dehydrogenation reactor 110, carrying the heat required for the dehydrogenation reaction. For further general information on dehydrogenation in a fluidized bed, the person skilled in the art is referred to, for example, U.S. patent publication 2005/0177016A1, international patent publication WO 2005/077867A1 (corresponding to U.S. patent publication 2008/0194891 A1), and International patent publication WO 20107591 A1.

The oxygen carrier may be oxidized or reduced when it is used in the dehydrogenation process. The different oxidation states of the oxygen carrier may behave differently during the dehydrogenation process. For example, oxygen carriers having a lower oxidation state may not burn hydrogen within the dehydrogenation reaction as efficiently as oxygen carriers having a relatively higher oxidation state. Conversely, oxygen carriers having a relatively higher oxidation state may be more likely to oxidize hydrocarbons during the dehydrogenation reaction when compared to oxygen carriers having a relatively lower oxidation state, potentially compromising olefin production by the process. Transferring the oxygen carrier to and through the regeneration unit 150 may help control the oxidation state of the oxygen carrier material.

In some embodiments, the oxygen-reduced oxygen carrier material of particulate solid 180 may be reoxidized to an oxidation state that is higher than the oxidation state of the oxygen-reduced oxygen carrier material by combustion in an oxygen-containing environment in regeneration unit 150. In some embodiments, the oxygen-containing environment may be air. In some embodiments that form an oxygen-enriched oxygen carrier material, the oxygen-reduced oxygen carrier material may revert to its original oxidized state. In some embodiments, the oxygen-reduced oxygen carrier material may have an oxidation state of +2, +3, or +4. The oxygen-enriched oxygen carrier material may then be recycled back to the dehydrogenation reactor 110, carrying the heat required for the dehydrogenation reaction. In other embodiments, nitrogen or steam may also be used to deliver oxygen-enriched oxygen carrier material to the dehydrogenation reactor 110. The resulting gas stream 154 from the regeneration unit 150 may consist of depleted O ₂ or air containing a lower concentration of O ₂.

In one or more embodiments, the supplemental fuel 162 may be combusted in the regeneration unit 150 to generate heat and raise 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 may be sufficient to maintain the temperature of the dehydrogenation reactor 110 at a desired temperature. The desired temperature may depend on the minimum temperature required for operation of the dehydrogenation reactor 110, as the particulate solids 180 may enter the dehydrogenation reactor 110 and the temperature thereof may be applied to the dehydrogenation reactor 110.

In one or more embodiments, the regeneration unit 150 can operate at a temperature of 650 ℃ or even 700 ℃ to 900 ℃ (such as 725 ℃ to 875 ℃ or 750 ℃ to 850 ℃). Typically, the temperature of the regeneration unit 150 may be at least 50 ℃ higher than the temperature of the dehydrogenation reactor 110. Such temperature ranges may be utilized such that a limited amount of dehydrogenation catalyst and/or oxygen support material may be utilized to maintain the temperature of the dehydrogenation reactor 110. In addition, if a dehydrogenation catalyst is utilized, such temperatures may be required to activate the dehydrogenation catalyst.

The residence time of the particulate solids 180 in the regeneration unit 150 may generally vary from 0.5 seconds (sec) to 360sec. In other embodiments, the residence time of the particulate solid 180 may be from about 0.5sec to about 200sec, from about 0.5sec to about 100sec, from about 0.5sec to about 50sec, or from about 0.5sec to about 20sec.

In one or more embodiments, the particulate solids 180 can be transferred from the dehydrogenation reactor 110 to the regeneration unit 150 via stream 112, as described herein. In the regeneration unit 150, the particulate solids 180 may pass through a gas/solids separator 190. According to one or more embodiments, the separator 190 can be a riser end system, which can include a cyclonic separation system. In embodiments where the riser end system includes a cyclone system, some of the particulate solids 180 may exit the riser end system without first passing through the cyclone system. The cyclonic separation system may comprise two or more cyclonic separation stages. In embodiments where the separator 190 comprises more than one cyclone stage, the first separation device into which the fluidised stream enters is referred to as the primary cyclone device. The fluidized effluent from the primary cyclone may enter a secondary cyclone for further separation. The primary cyclone device may include, for example, a primary cyclone and a system commercially available under the names VSS (commercially available from UOP corporation), LD2 (commercially available from Dan Wei corporation (Stone and Webster)) and RS2 (commercially available from literacy corporation). Primary cyclones are described, for example, in U.S. Pat. Nos. 4,579,716, 5,190,650 and 5,275,641, each of which is incorporated herein by reference in its entirety. In some separation systems utilizing a primary cyclone as the primary cyclone, one or more additional sets of cyclones, e.g., secondary cyclones and tertiary cyclones, are used to further separate particulate solids from the product gas. It should be appreciated that any primary cyclonic separating apparatus may be used in embodiments of the invention. The particulate solids 180 may be separated from an exhaust gas, such as flue gas. The gas separated from particulate solids 180 may be combined with the gas from regeneration unit 150 and exit regeneration unit 150 via exhaust flow 154.

According to an embodiment, the granular solid 180 may move in a generally downward direction through the regeneration unit 150. As used in this disclosure, the term "generally downward direction" means that the average velocity of the particulate 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 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 150 may move in a generally upward direction through the regeneration unit 150. As used in this disclosure, the term "generally upward direction" means that the average velocity of the gas within the regeneration unit 150 is in an upward direction, where the upward direction is opposite the pulling force 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 generally upward. According to an embodiment, the particulate solids 180 and gas may move through the regeneration unit 150 in a countercurrent flow pattern.

In one or more embodiments, the regeneration unit 150 may include a first gas inlet 160 and a second gas inlet 170 below the first gas inlet 160. As used herein, "gas inlet" refers to any component operable to inject gas into the regeneration unit 150. For example, the gas inlet may be a blower or a distributor. In addition, other suitable gas supplies are contemplated herein, as will be appreciated by those skilled in the art. 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 can 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 combinations 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 embodiments, 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 embodiments, the region above the first gas inlet 160 may be the fuel zone 164 because the directional flow of fuel 162 into the regeneration unit 150 may result in a higher concentration of fuel 162 in the region above the first gas inlet 160 than in the region below the first gas inlet 160.

In some embodiments, the concentration of fuel 162 in fuel zone 164 may be less than 20mol.%. In some embodiments, the concentration of fuel 162 in fuel zone 164 may be about 0.1 to about 15mol.%, about 0.1 to about 10mol.%, about 0.1 to about 5mol.%, about 0.1 to about 1mol.%, about 0.1 to about 0.5mol.%, about 0.5 to about 20mol.%, about 0.5 to about 15mol.%, about 0.5 to about 10mol.%, about 0.5 to about 5mol.%, about 0.5 to about 1mol.%, about 1 to about 20mol.%, about 1 to about 15mol.%, about 1 to about 10mol.%, about 1 to about 5mol.%, about 5 to about 20mol.%, about 5 to about 5mol.%, about 5 to about 15mol.%, about 10 to about 20mol.%, about 10 to about 15mol.%, or about 15 to about 20mol.%.

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 can reduce the oxygen content of at least a portion of the oxygen-enriched oxygen carrier material of the particulate solid 180 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.

In one or more embodiments, the oxygen-containing gas 172 can enter the regeneration unit 150 via the second gas inlet 170, as described herein. In some embodiments, the oxygen-containing gas 172 may be air, high oxygen air, air mixed with steam, or flue gas. The high oxygen air is air to which oxygen is added. In some embodiments, the oxygen-containing gas 172 may comprise at least 28mol.% oxygen. In other embodiments, the oxygen-containing gas 172 may include about 2 to about 28mol.% of oxygen, about 2 to about 25mol.% of oxygen, about 2 to about 20mol.% of oxygen, about 2 to about 15mol.% of oxygen, about 2 to about 10mol.% of oxygen, about 2 to about 5mol.% of oxygen, about 5 to about 28mol.% of oxygen, about 5 to about 25mol.% of oxygen, about 5 to about 20mol.% of oxygen, about 5 to about 15mol.% of oxygen, about 5 to about 10mol.% of oxygen, about 10 to about 28mol.% of oxygen, about 10 to about 25mol.% of oxygen, about 10 to about 20mol.% of oxygen, about 10 to about 15mol.% of oxygen, about 15 to about 28mol.% of oxygen, about 15 to about 25mol.% of oxygen, about 15 to about 20mol.% of oxygen, about 20 to about 28mol.% of oxygen, or about 25 to about 28mol.% of oxygen.

In an embodiment, 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 follow the generally upward flow of 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 the air zone 174, as the directional flow of the oxygen-containing gas 172 into the regeneration unit 150 may result in a higher concentration of oxygen 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 can be greater than 25mol.%. In some embodiments, the oxygen concentration in the air zone 174 may be about 4 to about 28mol.% oxygen, about 4 to about 21mol.%, about 4 to about 10mol.%, about 10 to about 28mol.%, about 10 to about 21mol.%, or about 21 to about 28mol.% oxygen. The name air is used here to simply show the presence of oxygen, as air is typically the least costly oxygen-containing gas.

In embodiments, at least a portion of the oxygen-reduced oxygen carrier material of the particulate solid 180 may 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 may 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 solids 180 can be transferred from the regeneration unit 150 back to the dehydrogenation reactor 110 via stream 152.

Without being bound by theory, it is believed that by exposing the oxygen carrier material to the oxygen-containing gas 172 in the region of the regeneration unit 150 after exposing the oxygen carrier material to the fuel 162, 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 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 being exposed to the fuel 162. For example, if the regeneration unit 150 enters the fuel 162 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 sufficiently reoxidized before being passed back to the dehydrogenation reactor 110. Because the different materials used for the oxygen carrier material may have higher or lower oxidation state requirements for their desired performance in the dehydrogenation reaction, this situation may negatively impact the selectivity and activity of the oxygen carrier material in the dehydrogenation reaction, possibly 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 sufficiently oxidized upon exiting the regeneration unit 150.

It is also believed that by adding the oxygen-containing gas 172 below the fuel 162, the oxygen-containing gas 172 may mix with the fuel 162 in the fuel zone 164. In which case additional oxygen that may be added to the fuel zone 164 may assist in the combustion of the fuel 162 and may reoxidize at least a portion of the oxygen carrier material. For example, it is believed that for some oxygen carrier materials, reoxidation may occur entirely in the fuel zone 164 because 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 may allow the oxygen carrier material of the particulate solid 180 to exit the regeneration unit 150 in a higher oxidation state than would be possible in other regeneration unit 150 configurations.

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

In one or more embodiments, the particulate solids 180 can be transferred from the dehydrogenation reactor 110 to the pre-oxidation unit 210 prior to being transferred to the regeneration unit 150, as described herein. In one or more embodiments, the oxygen-containing gas 212 can enter the pre-oxidation unit 210 via an oxidizing gas inlet (not shown in fig. 2). In some embodiments, the oxygen-containing gas 212 may be air, high oxygen air, air mixed with steam, or flue gas. The high oxygen air is air to which oxygen is added. In some embodiments, the oxygen-containing gas 212 may comprise less than 28mol.% oxygen. In other embodiments, the oxygen-containing gas 212 may include from about 2 to about 28mol.% oxygen, from about 2 to about 25mol.%, from about 2 to about 20mol.%, from about 2 to about 15mol.%, from about 2 to about 10mol.%, from about 2 to about 5mol.%, from about 5 to about 28mol.%, from about 5 to about 25mol.%, from about 5 to about 20mol.%, from about 5 to about 15mol.%, from about 5 to about 10mol.%, from about 10 to about 28mol.%, from about 10 to about 25mol.%, from about 10 to about 20mol.%, from about 10 to about 15mol.%, from about 15 to about 28mol.%, from about 15 to about 25mol.%, from about 15 to about 20mol.%, from about 20 to about 28mol.%, from about 20 to about 25mol.%, or from about 25 to about 28mol.% oxygen.

In embodiments, 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 solids 180 may flow co-currently through the pre-oxidation unit 210 in a generally upward direction. As used herein, "substantially co-current" means that the average velocities of particulate solid 180 and oxygen-containing gas 212 are in the same direction. Because it is an average value, the velocity of individual particles of the particulate solid 180 or individual gas molecules of the oxygen-containing gas 212 may have a distribution and may not be equal to the average value, but as a whole, the velocities of the two components will average to be approximately in the same direction. In some embodiments, coke that may form on the granular solids 180 in the dehydrogenation reactor 110 may be combusted in the pre-oxidation unit 210, thereby heating at least a portion of the granular solids 180.

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 may be mixed with a gas, such as an oxygen-containing gas 212 from the pre-oxidation unit 210, a combustion gas from the combustion of coke in the pre-oxidation unit 210, a carrier gas from the dehydrogenation reactor 110, or a combination thereof, as the gas is passed to the regeneration unit 150.

In one or more embodiments, the particulate solids 180 can be transferred 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 level of oxidation of the oxygen carrier material of the particulate solids 180. In some embodiments, the particulate solids 180 may exit the regeneration unit 150 from the fuel zone 164 to the pre-oxidation unit 210 to pass through the pre-oxidation unit 210 and the regeneration unit 150 again. In other embodiments, the particulate solids 180 may exit the regeneration unit 150 from the air zone 174 to the pre-oxidation unit 210 to pass through the pre-oxidation unit 210 and the regeneration unit 150 again. In further embodiments, the particulate solids 180 may pass from the regeneration unit 150 to the pre-oxidation unit 210 from both the air zone 174 and the fuel zone 164.

Still referring to fig. 2, in one or more embodiments, the regeneration unit 150 may include a third gas inlet 140. In an embodiment, the 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 follow the generally upward flow of other gases within the regeneration unit 150. Thus, in embodiments, the region above the third gas inlet 140 and below the second gas inlet 170 may be the stripping zone 144, as the directional flow of stripping gas 142 into the regeneration unit 150 may result in a higher concentration of stripping gas 142 in the region 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.

In one or more embodiments, the stripping gas 142 can 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 solids 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 solids 180 may be reduced. In some embodiments, the concentration of the reducing agent in the stripping gas 142 may be greater than 10mol.%. In some embodiments, the concentration of the reducing agent in the stripping gas 142 may be even greater than 90mol.%. In some embodiments, the concentration of the reducing agent in the stripping gas 142 may be from about 1mol.% to about 100mol.%, such as from about 1mol.% to about 90mol.%, from about 1mol.% to about 80mol.%, from about 1mol.% to about 70mol.%, from about 1mol.% to about 60mol.%, from about 1mol.% to about 50mol.%, from about 1mol.% to about 40mol.%, from about 1mol.% to about 30mol.%, from about 1mol.% to about 20mol.%, from about 1mol.% to about 10mol.%, from about 10mol.% to about 100mol.%, about 10 to about 90mol.%, about 10 to about 80mol.%, about 10 to about 70mol.%, about 10 to about 60mol.%, about 10 to about 50mol.%, about 10 to about 40mol.%, about 10 to about 30mol.%, about 10 to about 20mol.%, about 20 to about 100mol.%, about 20 to about 90mol.%, about 20 to about 80mol.%, about 20 to about 70mol.%, About 20 to about 60, about 20 to about 50, about 20 to about 40, about 20 to about 30, about 30 to about 100, about 30 to about 90, about about 30 to about 80 mol%, about 30 to about 70 mol%, about 30 to about 60 mol%, about 30 to about 50 mol%, about 30 to about 40 mol%, about 40 to about 100 mol%, About 40 to about 90 mol%, about 40 to about 80 mol%, about 40 to about 70 mol%, about 40 to about 60 mol%, about 40 to about 50 mol%, about 50 to about 100 mol%, about 50 to about 90 mol%, about 50 to about 80 mol%, about 50 to about 70 mol%, about 50 to about 60 mol%, about 60 to about 100 mol%, about 60 to about 90 mol%, About 60 to about 80, about 60 to about 70, about 70 to about 100, about 70 to about 90, about 70 to about 80, about 80 to about 100, about 80 to about 90, or about 90 to about 100) of the reducing agent in the stripping gas 142.

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 passed to the dehydrogenation reactor 110. Thus, in some embodiments, at least a portion of the particulate solids 180 may be withdrawn from the air zone 174 and transferred 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 passed to the fuel zone 164, the air zone 174, or both.

In a first aspect of the present disclosure, hydrocarbons may be dehydrogenated by a process comprising contacting a feed stream comprising one or more hydrocarbons with a particulate solid in a dehydrogenation reactor. The particulate solid 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 further includes passing at least a portion of the particulate solids from the dehydrogenation reactor to a regeneration unit. The particulate solids move in a generally downward direction through the regeneration unit and the gas moves in a generally upward direction through the regeneration unit such that the particulate solids and gas move in a countercurrent flow pattern through the regeneration unit. The regeneration unit includes 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. 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 particulate solid oxygen carrier material. The method may further include transferring at least a portion of the particulate solids from the regeneration unit to the dehydrogenation reactor.

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 increases in a region of the regeneration unit above the second gas inlet and below the first gas inlet.

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 an oxygen content of at least a portion of the oxygen carrier material is reduced.

A fourth aspect of the present disclosure may include the first aspect, wherein in the region of the regeneration unit above the first gas inlet, at least a portion of the fuel reacts with oxygen of the oxygen-containing gas, and the oxygen content of at least a portion of the oxygen carrier material increases.

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 and not passed to the regeneration unit.

A sixth aspect of the present disclosure may include any one 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.

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

An eighth aspect of the present disclosure may include any one of the preceding aspects, wherein the 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.

A ninth aspect of the present disclosure may include any one of the preceding aspects, wherein transferring the particulate solids from the dehydrogenation reactor to the regeneration unit comprises 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.

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 co-current flow in a generally upward direction.

An eleventh aspect of the present disclosure may include any one 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 from 0mol.% to 100mol.% of the reducing agent.

A twelfth aspect of the present disclosure may include any one of the preceding 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.

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.

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.

A fifteenth aspect of the present disclosure may include the fourteenth aspect, wherein the dehydrogenation catalyst material and the oxygen carrier material are separate particles of a particulate solid or the dehydrogenation catalyst material and the oxygen carrier material are contained in the same particles of the particulate solid.

It will be apparent to those skilled in the art that various modifications and variations can be made in the techniques disclosed herein without departing from the spirit or scope of the technology. Since modifications, combinations, sub-combinations and variations of the disclosed embodiments incorporating the spirit and substance of the disclosed technology may occur to persons skilled in the art, the technology should be construed to include everything within the scope of the appended claims and equivalents thereof. Additionally, 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.

It should be noted that the various details described in this disclosure should not be construed to imply that these details relate to elements that are essential components of the various embodiments described in this disclosure, even where specific elements are shown in each of the drawings accompanying this specification. Unless explicitly indicated as such, none of the features disclosed and described herein should be interpreted as "necessary". Contemplated embodiments of the present technology include those that include some or all of the features of the appended claims.

For the purposes of describing and defining the present disclosure it is noted that the term "about" is utilized in the present disclosure 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 in the present disclosure 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.

Where the composition is described as "comprising" one or more elements, embodiments of compositions "consisting of" or "consisting essentially of" those one or more elements are contemplated herein, where relevant.

In some embodiments, a chemical or chemical stream is described as being "transferred" from one system unit or portion of a system unit to another system unit or 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", the transfer directly has no intermediate destination between unit a and unit B (i.e., directly through a pipe or other conveyance channel), and the transfer indirectly may include one or more intermediate destinations between unit a and unit B. For example, the flow passing from unit a to unit B may pass through, but is not limited to, a heat exchanger, a processing device, and the like.

It should be understood that in some embodiments, the compositional range of a chemical component in a stream or reactor should be understood to be a mixture of isomers containing that component. For example, the compositional range of a given butene may include a mixture of various isomers of butene. It should be understood that the examples provide a range of compositions for the various streams, and that the total amount of isomers of a particular chemical composition may constitute a range.

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

It should be understood that any two quantitative values assigned to a characteristic may constitute a range for that characteristic, and that all combinations of ranges formed by all of the quantitative values for a given characteristic are contemplated in this disclosure. Where multiple ranges of quantitative values are provided, these ranges can 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, the fuel enters the regeneration unit through the first gas inlet, and the 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; and

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.