CN119654304A - Process for dehydrogenating hydrocarbons by thermal dehydrogenation - Google Patents

Abstract

The present invention relates to a method for dehydrogenating hydrocarbons, which may include passing a hydrocarbon feed containing one or more alkanes or alkyl aromatic compounds into a fluidized bed reactor. In the fluidized bed reactor, at least 95wt% of the hydrocarbon feed may have an atmospheric boiling point less than or equal to 300°C. The method may include thermally cracking the hydrocarbon feed in the fluidized bed reactor to produce a dehydrogenated product and hydrogen. The fluidized bed reactor may be operated at a temperature of at least 600°C. The fluidized bed reactor may be free of a dehydrogenation catalyst. The method may include contacting the hydrogen with an oxygen carrier material in the fluidized bed reactor to burn the hydrogen and form an oxygen-reduced oxygen carrier material. The oxygen carrier material may be reducible.

Description

Process for dehydrogenating hydrocarbons by thermal dehydrogenation

Cross Reference to Related Applications

The present application claims priority from U.S. provisional application Ser. No. 63/406,449 filed on 9/14 of 2022, which is hereby incorporated by reference in its entirety.

Technical Field

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

Background

Light olefins and aromatic olefins are useful as base materials for the production of many types of goods and materials. For example, ethylene may be used to make polyethylene, ethylene chloride or ethylene oxide. In addition, styrene can be used to produce polystyrene. Such products are useful in product packaging, construction, textiles, and the like. These base chemicals may be formed by dehydrogenation of hydrocarbon feeds. Accordingly, there is a need in the industry for new dehydrogenation processes to form materials such as ethylene, propylene, butylene, and styrene.

Disclosure of Invention

One method of producing light olefins and/or aromatic olefins is to thermally dehydrogenate a feed stream comprising one or more alkanes (such as ethane, propane, n-butane, and/or isobutane) or alkylaromatic compounds (such as ethylbenzene). By thermal dehydrogenation, the chemicals can be dehydrogenated without the use of a dehydrogenation catalyst. Such thermal dehydrogenation reactions produce hydrogen. According to embodiments disclosed herein, such hydrogen formed by thermal (i.e., non-catalytic) dehydrogenation reacts with oxygen from the oxygen carrier material to form water, which can be separated from the product olefins. Furthermore, while thermal dehydrogenation reactions require relatively more heat input to the system, the reaction of hydrogen with oxygen from the oxygen carrier material is exothermic and thus can offset at least a portion of the heat input load required for thermal dehydrogenation. The oxygen carrier material may be recycled to the regeneration unit where oxygen is replenished, which may be exothermic, and may offset some of the additional heat input into the system. Thus, the processes described herein can efficiently produce light olefins without the need for a dehydrogenation catalyst.

Further, as described herein, embodiments may include combusting the supplemental fuel in a regeneration unit. It has been found that methods that fail to utilize supplemental fuel may not properly include sufficient heat balance to maintain thermal dehydrogenation. Advantageously, the combustion of such supplementary fuel can be carried out in the same zone as the oxidation of the oxygen carrier material (each using the oxygen present in the regeneration unit). The heat generated by the combustion of the supplemental fuel may raise the temperature of the oxygen carrier material in the regeneration unit, which may be a major source of heat transfer to the reactor where thermal dehydrogenation occurs.

In accordance with at least one embodiment of the present disclosure, a process for dehydrogenating hydrocarbons may comprise passing a hydrocarbon feed comprising one or more alkanes or alkylaromatic compounds to a fluidized bed reactor. In the fluidized bed reactor, at least 95wt% of the hydrocarbon feed may have an atmospheric boiling point of less than or equal to 300 ℃. The method may further include thermally cracking the hydrocarbon feed in a fluidized bed reactor to produce a dehydrogenation product and hydrogen. The fluidized bed reactor may be operated at a temperature of at least 600 ℃. The fluidized bed reactor may be free of dehydrogenation catalyst. The method may further include contacting the hydrogen with an oxygen carrier material in a fluidized bed reactor to combust the hydrogen and form an oxygen reduced oxygen carrier material. The oxygen carrier material may be reducible. The method may further include transferring the oxygen-reduced oxygen carrier material to a regeneration unit, oxidizing the oxygen-reduced oxygen carrier material in the regeneration unit to form an oxygen-enriched oxygen carrier material, combusting a supplemental fuel in the regeneration unit to generate heat and raise a temperature of the oxygen carrier material, and transferring the oxygen-enriched oxygen carrier material to the fluidized bed reactor.

These and other embodiments are described in more detail in the following detailed description in conjunction with the accompanying drawings.

Drawings

The following detailed description of certain embodiments of the present disclosure can be best understood when read in conjunction with the following drawings, where like structure is indicated with like reference numerals and in which:

FIG. 1 schematically depicts a catalytic dehydrogenation system according to one or more embodiments described herein, and

FIG. 2 schematically depicts a catalytic dehydrogenation system with recycling according to one or more embodiments described herein.

It should be understood that the figures are schematic in nature and do not include some components of reactor systems commonly employed in the art, such as, but not limited to, temperature transmitters, pressure transmitters, flow meters, pumps, valves, etc. Such components are well known to be within the spirit and scope of the disclosed embodiments. However, operational components (such as those described in the present disclosure) may be added to the embodiments described in the present disclosure.

Reference will now be made in detail to various embodiments, some of which are illustrated in the accompanying drawings. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts.

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.

Embodiments are disclosed herein that relate to a method of treating a chemical stream to form a product by thermal dehydrogenation. In various embodiments, the process may include the use of thermal dehydrogenation as well as oxygen carrier materials. The method can include thermally dehydrogenating an alkane or alkylaromatic to form hydrogen and an alkene or olefinic aromatic, and then combusting the hydrogen with oxygen from an oxygen carrier material, as described herein.

As described herein, the process does not include a dehydrogenation catalyst. Dehydrogenation catalysts include materials that catalyze dehydrogenation reactions. Oxygen carrier materials are not considered dehydrogenation catalysts herein if they are only minimally capable of catalyzing dehydrogenation reactions. That is, the oxygen carrier materials used herein have little or no catalytic function as compared to their oxygen-introducing activity.

There are many advantages to using a process that does not include a dehydrogenation catalyst. For example, the increased cost of dehydrogenation catalysts that may often need replacement or regeneration is eliminated. Furthermore, in one or more embodiments, the complexity of the reaction system is reduced, as catalytic reactions are eliminated, and therefore only thermal dehydrogenation and combustion of hydrogen need be considered in the design.

Unless specified herein, "oxygen carrier material" may generally refer to oxygen-enriched oxygen carrier material or oxygen-deficient oxygen carrier material. The anoxic state may exist after some oxygen is released and used for hydrogen combustion, and may be oxygen enriched prior to hydrogen combustion. Typically, the oxygen carrier material enters the regeneration unit in an anoxic state and exits the regeneration unit in an oxygen-enriched state. The reaction to convert the oxygen carrier material from an oxygen-rich state to an oxygen-deficient state may be carried out in one or more fluidized bed reactors, such as circulating fluidized bed reactors. The reactor may be, for example, a riser or a downcomer. It should be appreciated that the oxygen-rich state of the oxygen carrier material may not be fully oxidized and that the oxygen-depleted state of the oxygen carrier may still include some releasable oxygen. However, the oxygen content of the oxygen carrier material in the oxygen-rich state is typically greater than the oxygen content in the oxygen-deficient state.

Referring now to fig. 1, a reactor system 100 is depicted that can be used to perform the methods of the present disclosure. The reactor system 100 may include a fluidized bed reactor 110 and a regeneration unit 120. The hydrocarbon feed 101 may be passed to a fluidized bed reactor 110. Oxygen carrier material may be circulated between fluidized bed reactor 110 and regeneration unit 120 via streams 103 and 104 as shown. The product may exit the fluidized bed reactor 110 via stream 102.

In one or more embodiments, the hydrocarbon feed 101 can comprise one or more alkanes or alkylaromatic compounds. For example, the hydrocarbon feed 101 may comprise one or more of ethane, propane, butane, or ethylbenzene. According to one or more embodiments, the hydrocarbon feed 101 may comprise at least 50wt%, at least 60wt%, at least 70wt%, at least 80wt%, at least 90wt%, at least 95wt%, or even at least 99wt% ethane. In additional embodiments, hydrocarbon feed 101 may comprise at least 50wt%, at least 60wt%, at least 70wt%, at least 80wt%, at least 90wt%, at least 95wt%, or even at least 99wt% propane. In additional embodiments, the hydrocarbon feed 101 may comprise at least 50wt%, at least 60wt%, at least 70wt%, at least 80wt%, at least 90wt%, at least 95wt%, or even at least 99wt% butane. In additional embodiments, the hydrocarbon feed 101 can comprise at least 50wt%, at least 60wt%, at least 70wt%, at least 80wt%, at least 90wt%, at least 95wt%, or even at least 99wt% ethylbenzene. In additional embodiments, the hydrocarbon feed 101 may comprise at least 50wt%, at least 60wt%, at least 70wt%, at least 80wt%, at least 90wt%, at least 95wt%, or even at least 99wt% of the sum of ethane, propane, butane, and ethylbenzene.

According to one or more embodiments, at least 95wt% of the hydrocarbon feed 101 may have an atmospheric boiling point less than or equal to 300 ℃. According to additional embodiments, at least 95wt% of the hydrocarbon feed 101 may have an atmospheric boiling point less than or equal to 275 ℃, less than or equal to 250 ℃, less than or equal to 225 ℃, less than or equal to 200 ℃, less than or equal to 175 ℃, less than or equal to 150 ℃, less than or equal to 125 ℃, or even less than or equal to 100 ℃. For example, hydrocarbon feed 101 may not be crude oil or a heavy fraction of crude oil. In further embodiments, at least 99wt% of the hydrocarbon feed 101 may have an atmospheric boiling point less than or equal to 300 ℃.

Still referring to fig. 1, the reactor system 100 may include a fluidized bed reactor 110 and a regeneration unit 120, both of which may be fluidized bed-based and have the same or different fluidization mechanisms. According to some embodiments, the fluidized bed reactor 110 may be operated in a "back-mixed" mode, wherein the feed hydrocarbons enter the fluidized bed reactor 110 to approximate substantially isothermal conditions. Thus, the fluid velocity at this region may be sufficiently low and the solids flux may be sufficiently large that a dense bed may be formed at or around the location of injection of the hydrocarbon. In some embodiments, the apparent velocity in the zone may be 3 to 80 feet/second, such as 3 to 40 feet/second or 10 to 30 feet/second. The solids 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. Fluidized bed reactor 110 may include a plurality of diameters and may include one or more frustums to increase or decrease the velocity of the solid and/or gaseous reactants. The fluidized bed reactor 110 may operate at a gas residence time of 0.1 seconds to 10 seconds, such as 0.5 seconds to 6 seconds.

An embodiment of the general operation of the fluidized bed reactor 110 to perform a continuous reaction will now be described. As used herein, "solids" in the fluidized bed reactor 110 may include oxygen carrier material. In some embodiments, the fluidized bed reactor 110 may include from 1wt% to 100wt%, such as from 95wt% to 100wt% of the oxygen carrier material, based on the total weight of all solids in the fluidized bed reactor.

During operation of the fluidized bed reactor 110 of the reactor system 100, the hydrocarbon feed 101 may enter the fluidized bed reactor 110 and the product stream may exit the reactor system 100 via stream 102. According to one or more embodiments, the reactor system 100 can be operated by feeding a chemical feed (e.g., in a feed stream such as hydrocarbon feed 101) into the fluidized bed reactor 110.

According to one or more embodiments, oxygen-enriched oxygen carrier material can also be fed from the regeneration unit 120 to the fluidized bed reactor 110 via stream 104. The chemical feed of stream 101 may be contacted with oxygen-enriched oxygen carrier material in fluidized bed reactor 110. Each of the chemical feed and oxygen-enriched oxygen carrier material may flow upward into and through the fluidized bed reactor 110 and produce chemical products and oxygen-reduced oxygen carrier material.

According to embodiments, exposure of the feedstock to elevated temperatures in the fluidized bed reactor 110 may cause thermal dehydrogenation to form olefinic chemicals and hydrogen. Additionally, within the fluidized bed reactor 110, the hydrogen may be contacted with an oxygen-enriched oxygen carrier material. The oxygen-enriched oxygen carrier material may be reducible and contact of the oxygen-enriched oxygen carrier material with hydrogen combusts the hydrogen and forms an oxygen-reduced oxygen carrier material.

In some embodiments, the chemical product and oxygen-reduced oxygen carrier material may be transferred to a separation device in a separation section within the fluidized bed reactor 110. The oxygen-reduced oxygen carrier material may be separated from the chemical products (and any unreacted feed) in a separation device within the fluidized bed reactor 110. The chemical product (and unreacted feed) may then be transferred out of the separation section of fluidized bed reactor 110. For example, the separated vapor may be removed from the fluidized bed reactor 110 via a conduit at the gas outlet end of the separation section within the fluidized bed 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 fluidized bed reactor 110 can be operated with a residence time of the gas in the fluidized bed reactor 110 of less than 10 seconds (such as less than 9 seconds, less than 8 seconds, less than 7 seconds, less than 6 seconds, less than 5 seconds, less than 4 seconds, or even less than 3 seconds). As will be appreciated by those skilled in the art, the thermal dehydrogenation rate may vary with temperature and thus the residence time.

In one or more embodiments, the fluidized bed reactor 110 can be operated at a temperature greater than 600 ℃ and less than or equal to 800 ℃. In some embodiments, the temperature in the fluidized bed reactor 110 may be 625 ℃, or 650 ℃ to 770 ℃. In other embodiments, the temperature in the fluidized bed reactor 110 may be 700 ℃ to 750 ℃. Without being bound by any particular theory, it is believed that too low a temperature (e.g., 600 ℃ or less) may limit the maximum conversion of hydrocarbons due to equilibrium constraints. 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 desired 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 fluidized bed reactor 110 may be operated at temperatures above 600 ℃. In additional embodiments, the primary feed component may be ethane, and the fluidized bed reactor 110 may be operated at a temperature of at least 625 ℃.

In some embodiments, the fluidized bed reactor 110 may be operated at a pressure of at least atmospheric pressure (about 14.7 psia). In some embodiments, the fluidized bed reactor 110 may operate at a pressure of about 500 psia. In other embodiments, fluidized bed reactor 110 may be operated at a pressure of about 4psia to about 160psia, about 20psia to about 100psia, or about 30psia to about 60 psia. In some embodiments, the regeneration unit 120 may be operated at a pressure within 30psi of the fluidized bed reactor 110.

In some embodiments, the hydrocarbon feed may contact oxygen-enriched oxygen carrier material in an upstream reactor section of the fluidized bed reactor 110. Each of the chemical feed and oxygen-enriched oxygen carrier material may flow upward and through a downstream reactor section of the fluidized bed reactor 110 to produce chemical products and an oxygen-reduced oxygen carrier material, wherein hydrogen is formed by thermal dehydrogenation and is combusted by oxygen from the oxygen carrier material to form the oxygen carrier material in an oxygen-reduced state. In one or more embodiments, the feed distributor within the fluidized bed reactor 110 is operable to distribute the hydrocarbon feed stream at all shroud distributor velocities of 200 feet per second to 50 feet per second. In such embodiments, various feed streams may be utilized while maintaining desired reactor characteristics, such as operating as a fast fluidization, turbulent, or bubbling bed reactor in the upstream reactor section of the fluidized bed reactor 110 and as a dilute phase riser reactor in the downstream reactor section of the fluidized bed reactor 110. For example, a suitable dispenser is disclosed in U.S. patent No. 9,370,759, the teachings of which are incorporated herein by reference in their entirety. The chemical product and the oxygen-reduced oxygen carrier material may be transferred from a reactor section downstream of the fluidized bed reactor 110 to a separation device within the fluidized bed reactor 110, wherein the oxygen-reduced oxygen carrier material may be separated from the chemical product.

In additional embodiments, the Weight Hourly Space Velocity (WHSV) for the disclosed process may range from 0.1 pounds (lb) to 100lb of chemical feed per hour (h) per lb of solids (lb feed per hour per lb of solids) in the reactor. In some embodiments, where the fluidized bed reactor 110 comprises an upstream reactor section operating as a fast fluidized, turbulent, or bubble bed reactor and a downstream reactor section operating as a dilute phase riser reactor, the superficial gas velocity in the upstream reactor section may range from 2 feet per second (about 0.61 meters per second) to 10 feet per second (about 3.05 meters per second), and the superficial gas velocity in the downstream reactor section may range from 30 feet per second (about 9.14 meters per second) to 70 feet per second (about 21.31 meters per second). In additional embodiments, a reactor configuration that is entirely riser-type may operate at a single high superficial gas velocity, for example, at least 30 feet per second (about 9.15 meters per second) at all times in some embodiments.

The residence time of the solids in the fluidized bed reactor 110 typically can vary from 0.5 seconds (sec) to 240 seconds. In other embodiments, the residence time of the solids may be from about 0.5 seconds to about 200 seconds, from about 0.5 seconds to about 100 seconds, from about 0.5 seconds to about 50 seconds, or from about 0.5 seconds to about 20 seconds.

In additional embodiments, the ratio of solids to hydrocarbon feed 101 in fluidized bed reactor 110 may 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 flux of solids (e.g., oxygen carrier material) 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 (about 97.7kg/m ² -s), such as from 1lb/ft ² -s to 20lb/ft ² -s, and the flux in the downstream reactor section may be from 1lb/ft ² -s (about 48.9kg/m ² -s) to 300lb/ft2-s (about 489kg/m ² -s), such as from 10lb/ft ² -s to 100lb/ft ² -s.

In one or more embodiments, the solid (e.g., oxygen carrier material) can include solid particles capable of fluidization. In some embodiments, the solid may exhibit a characteristic referred to in the industry as a "Geldart a" characteristic. Solids can be classified as either "class A" or "class B" according to D.Geldart, gas Fluidization Technology, john Wiley & Sons (New York, 1986), 34-37 and D.Geldart, "Types of Gas Fluidization," Powder technology.7 (1973) 285-292, the entire contents of which are incorporated herein by reference. In one or more embodiments, the oxygen carrier material may exhibit a characteristic referred to in the industry as a "Geldart a" characteristic. In other embodiments, the oxygen carrier material may exhibit a characteristic referred to in the industry as a "Geldart B" characteristic.

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 as the average particle size decreases, assumingEqual, or with an increase in the <45 micrometer (μm) ratio, or with an increase in the 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, when the density (ρp) is 1.4< ρp <4g/cm3, the particle size of most particlesIs thatAnd preferably when the density (ρp) is 4g/cm3And when the density (. Rho.p) is 1g/cm3

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 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 group1 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 "METHODS OF PRODUCING HYDROGEN-SELECTIVE OXYGEN CARRIER MATERIALS" filed on Ser. No. 31 at 2018 and U.S. application Ser. No. 62/725,508 entitled "HYDROGEN-SELECTIVE OXYGEN CARRIER MATERIALS AND METHDS OF USE" filed on Ser. No. 31 at 2018 are considered suitable for USE in the disclosed processes OF the present invention, 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 1wt% to about 20wt% releasable oxygen based on the total weight of the oxygen-enriched oxygen carrier material. In other embodiments, the oxygen-enriched oxygen carrier material comprises about 1wt% to about 10wt%, about 1wt% to about 5wt%, about 5wt% to about 20wt%, or about 5wt% to about 10wt% 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 1wt% to 50wt% 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 about 10wt% to about 50wt%, about 10wt% to about 25wt%, or about 25wt% to about 50wt% of the releasable oxygen.

In further embodiments, 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 fluidized bed reactor 110 in a lower oxidation state.

By way of example, ethane may be thermally dehydrogenated to form ethylene and hydrogen. By thermal dehydrogenation, the chemicals can be dehydrogenated without the use of a dehydrogenation catalyst. Such a thermal dehydrogenation reaction scheme for converting ethane to ethylene is shown in chemical formula 1:

ΔH_o=+137kJ/mol(1)

the dehydrogenation reaction can be promoted by reducing or removing hydrogen produced by thermal dehydrogenation, which pushes the reaction equilibrium toward the product. That is, in chemical formula 1, the removal of hydrogen pushes the equilibrium to the right, thereby allowing the reaction to reach a higher conversion level or to operate at a lower temperature.

The disclosed process for producing light olefins and aromatic olefins may combine thermal dehydrogenation and hydrogen combustion. According to one or more embodiments, the disclosed process can be operated at higher pressures and lower temperatures relative to conventional processes, yet still achieve comparable conversion levels, due to the removal of hydrogen by combustion with oxygen. As a result, in some embodiments, the disclosed process in combination with hydrogen combustion may allow for relatively smaller process units and thus reduce capital costs. It has been found that incorporating an oxygen carrier material in the dehydrogenation reaction can reduce the amount of heat input required and/or can reduce the cost of subsequent separation of unreacted alkane, alkylaromatic, and hydrogen. Incorporation of oxygen carrier material and recycling in the process, as described herein, may promote combustion of hydrogen to form water.

On the other hand, some conventional processes for producing light olefins may require relatively high reaction temperatures. For example, some conventional processes may require reactor temperatures above 850 ℃. The high temperatures can lead to expensive conventional processes. For example, because these conventional processes require higher temperatures, the reactors utilized in such processes may not have the ability to incorporate reactor internals or other design features. Alternatively, such processes may require that the reactor internals and other process units be manufactured from specialty materials, which increases capital costs.

It is contemplated that in some embodiments, hydrogen formed by combustion in the disclosed process may simultaneously reduce downstream separation costs. For example, in a downstream process, the product stream may need to be liquefied. Thus, a reduction in hydrogen in the product stream may reduce the volume of gas that needs to be liquefied or change the desired temperature for liquefying the hydrocarbon due to lower hydrogen content. Thus, complete or partial removal of hydrogen from the product stream may reduce the energy requirements of the downstream liquefaction process. In addition, complete or partial removal of hydrogen from the product stream may then reduce other downstream separation costs by eliminating the need for other process units that may be used to separate hydrogen from the product stream (either before or after liquefaction).

Because of the high heat load and/or downstream separation steps required for the endothermic dehydrogenation reaction, it is sometimes necessary to separate unreacted alkane or alkylaromatic compounds and remove hydrogen produced in the dehydrogenation reaction, producing light olefins 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 losses, or at least reducing any supplemental fuel requirements of the system.

Still referring to fig. 1, the oxygen-reduced oxygen carrier material and the gaseous products may be separated within the fluidized bed reactor 110 by a high efficiency cyclone. In such embodiments, the oxygen-reduced oxygen carrier material may be transferred to regeneration unit 120 via stream 103. In further embodiments, the oxygen carrier material may be stripped with a displacement gas such as nitrogen, steam, methane, natural gas, or other suitable gas before being passed to the regeneration unit 120.

According to an embodiment, the oxygen carrier material may be transferred via stream 103 to regeneration unit 120 where regeneration takes place. Regeneration may remove contaminants such as coke, raise the temperature of the oxygen carrier material, or both. In some embodiments, the oxygen-reduced oxygen carrier material 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 the regeneration unit 120. 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 carrying the heat required for the dehydrogenation reaction may then be recycled back to the fluidized bed reactor 110. In other embodiments, nitrogen or steam may also be used to deliver oxygen-enriched oxygen carrier material to the fluidized bed reactor 110. The resulting gas stream from the regeneration unit 120 is comprised of depleted or lower concentration O ₂ containing air.

In one or more embodiments, the supplemental fuel may be combusted in the regeneration unit 120 to generate heat and raise the temperature of the oxygen carrier material. The heat generated by the oxidation of the oxygen-reduced oxygen carrier material and the combustion of the supplemental fuel may be sufficient to maintain the temperature of the fluidized bed reactor 110 at a desired temperature. The desired temperature may depend on the minimum temperature required for operation of the fluidized bed reactor 110, as the oxygen carrier material may enter the fluidized bed reactor 110 and its temperature is applied to the fluidized bed reactor 110.

In some embodiments, the supplemental fuel may comprise one or more of hydrogen, methane, ethane, propane, natural gas, or a combination thereof. The supplemental fuel may be gaseous. However, it should be understood that other fuel types are also contemplated and within the scope of the disclosed embodiments. The supplemental fuel may be combusted by exposure to oxygen at elevated temperatures. For example, air, oxygen enriched air, or oxygen may be present in the regeneration unit 120. Advantageously, in one or more embodiments, the same gas may be used to oxidize the oxygen-reduced oxygen carrier material and burn the supplemental fuel.

Without being bound by theory, the amount of fuel combusted may generally be an amount sufficient to supply the necessary to heat the fluidized bed reactor 110 in which thermal dehydrogenation occurs. While oxidation of the oxygen reduced oxygen carrier material may provide some heat, it may not be sufficient to heat the oxygen carrier material to a degree sufficient to heat the fluidized bed reactor 110. Thus, the combustion of the supplemental fuel may compensate for the difference between the heat required for the thermal dehydrogenation reaction and the oxidation of the oxygen-reduced oxygen carrier material (as well as other reactions described herein, such as the formation of water by hydrogen combustion).

In one or more embodiments, the regeneration unit 120 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 120 may be at least 50 ℃ higher than the temperature of the fluidized bed reactor 110. Such a temperature range may be utilized such that a limited amount of oxygen carrier material may be used to maintain the temperature of the fluidized bed reactor 110.

Still referring to fig. 1, oxygen-enriched oxygen carrier material may be transferred from regeneration unit 120 to fluidized bed reactor 110 via stream 104. Thus, the oxygen carrier material may be recycled or re-circulated through the reactor system 100.

Fig. 2 depicts a system that is similar in many respects to the system of fig. 1, with differences described below. Referring now to fig. 2, in one or more embodiments of the invention, reoxidation of the oxygen reduced oxygen carrier material may be controlled by the depicted system. For example, according to one embodiment, the flue gas may be transferred via stream 108 into the regeneration unit 120. In some embodiments, the flue gas may be a recycle stream from an adjacent chemical process. In some embodiments, the oxygen-reduced oxygen carrier material may be reoxidized to an oxidation state that is higher than the oxidation state of the oxygen-reduced oxygen carrier material by at least a portion of the flue gas recycled to the regeneration unit 120 via stream 112 exiting the regeneration unit 120 via stream 109. Stream 109 exiting regeneration unit 120 may include oxygen depleted or air containing a lower concentration of oxygen. In some embodiments, stream 112 may be mixed with fresh air via stream 107 to form stream 108. In some embodiments, stream 108 may comprise at least 25 mole% (mol%) oxygen. In other embodiments, stream 108 may comprise from about 4mol% to about 25mol% oxygen, from about 4mol% to about 21mol%, from 4mol% to about 10mol% oxygen, from 10mol% to about 25mol% oxygen, or from 10mol% to about 21mol% oxygen.

In embodiments, some of the releasable oxygen is removed from the oxygen-enriched oxygen carrier material by contacting the flue gas with the oxygen-enriched oxygen carrier material. In some embodiments, contacting the flue gas with the oxygen-enriched oxygen carrier material may remove from about 0wt% to 15wt% 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 0wt% to about 10wt%, from about 0wt% to about 5wt%, or from about 5wt% to about 10wt% of the releasable oxygen.

In other embodiments, the oxygen-reduced oxygen carrier material may be partially reoxidized in the regeneration unit 120 to an oxidation state that is higher than the oxidation state of the oxygen-reduced oxygen carrier material. In some embodiments, the oxygen-enriched oxygen carrier material comprises less releasable oxygen than the maximum releasable oxygen capacity of the oxygen carrier material.

In another embodiment, the oxygen-enriched oxygen carrier material may also be reduced to a lower oxidation state ("at least partially reduced") by combusting the oxygen-enriched oxygen carrier material with a reducing gas. Without being bound by theory, in some embodiments, at least partially reducing the oxygen-enriched oxygen carrier material may pretreat the oxygen carrier material to maximize the selectivity of the fluidized bed reactor 110. The releasable oxygen bound to the surface of the oxygen carrier material may burn less selectively to hydrogen than the remaining bulk oxygen. In further embodiments, the oxygen-enriched oxygen carrier material may be at least partially reduced after transfer from the regeneration unit 120 and prior to transfer to the fluidized bed reactor 110 in the reducer. In some embodiments, the fuel source may be used to at least partially reduce an oxygen-rich oxygen carrier material, wherein the fuel source pre-combusts oxygen that is chemically absorbed during reoxidation of the oxygen-reduced oxygen carrier material in the regeneration unit 120. Depending on the configuration of the reducer, the products formed from the pre-combustion may exit the reactor system 100 via stream 102, or alternatively, the products formed from the pre-combustion may exit the regenerator unit 120 (e.g., via line 111 in fig. 2) or at any location along line 104. In some embodiments, the product formed by pre-combustion may be stripped from one of the process streams by, for example, nitrogen, steam, or air. In some embodiments, pre-combustion may reduce the amount of reducible and free oxygen on the oxygen carrier by between 0.01% and 10%. Without being bound by any particular theory, this oxygen is expected to be the least selective for hydrogen combustion.

Referring now to fig. 1 and 2, in some embodiments, product gas from the fluidized bed reactor 110 may exit the fluidized bed reactor 110 via stream 102. Stream 102 may be further processed or otherwise reacted, such as by one or more subsequent separation steps. It is contemplated that stream 102 may be used as a feed to another reactor system or sold as a chemical product.

In one or more embodiments, the reactor system 100 can be used to dehydrogenate hydrocarbons to produce olefins and other products (e.g., styrene from ethylbenzene), which can exit the fluidized bed reactor 110 via stream 102. In one or more embodiments, stream 102 can comprise one or more olefins and other products. Stream 102 may comprise one or more of ethylene, propylene, butene, or styrene. According to one or more embodiments, stream 102 can comprise at least 50wt%, at least 60wt%, at least 70wt%, at least 80wt%, at least 90wt%, at least 95wt%, or even at least 99wt% ethylene. In additional embodiments, stream 102 may comprise at least 50wt%, at least 60wt%, at least 70wt%, at least 80wt%, at least 90wt%, at least 95wt%, or even at least 99wt% propylene. In additional embodiments, stream 102 may comprise at least 50wt%, at least 60wt%, at least 70wt%, at least 80wt%, at least 90wt%, at least 95wt%, or even at least 99wt% of the sum of ethylene and propylene.

In one or more embodiments, the heat gained or lost by the thermal dehydrogenation reaction, reoxidation of the oxygen-reduced oxygen carrier material, and reduction of the oxygen-enriched oxygen carrier material can generate or use heat (i.e., exothermic or endothermic). In one or more embodiments, thermal dehydrogenation 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 combining hydrogen combustion during thermal dehydrogenation, in some embodiments, sufficient heat can 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 fuel gas requirements that may be required for conventional cracking and/or dehydrogenation, as heat gained by reoxidation of the oxygen carrier material, combustion of hydrogen, or both may generate the heat required for alkane or alkylaromatic to alkene reactions throughout the process.

Referring now to the embodiment of the process depicted in fig. 2, stream 102 or a portion of stream 102 may be transferred back to fluidized bed reactor 110 via product recycle stream 105. In some embodiments, stream 102 may include one or more unreacted alkanes or alkylaromatic compounds. In further embodiments, one or more unreacted alkanes or alkylaromatic compounds may pass from the fluidized bed reactor 110 to a separation unit (not depicted) via stream 102. A separation unit may be used to separate one or more unreacted alkanes or alkylaromatic compounds from the remaining dehydrogenation effluent. In some embodiments, one or more unreacted alkanes or alkylaromatic compounds may then be transferred out of the separation unit and transferred to the fluidized bed reactor 110 via the product recycle stream 105. In some embodiments, from about 10% to about 90% of the one or more unreacted alkanes or alkylaromatic compounds may be transferred to the fluidized bed reactor 110 via the product recycle stream 105. In other embodiments, from about 20% to about 90%, from about 30% to about 90%, from about 40% to about 90%, from about 50% to about 90%, from about 60% to about 90%, from about 70% to about 90%, or from about 80% to about 90% of the one or more unreacted alkanes or alkylaromatic compounds may be transferred to the fluidized bed reactor 110 via the product recycle stream 105.

The present disclosure includes several aspects. In a first aspect of the present disclosure, a method of dehydrogenating hydrocarbons may include passing a hydrocarbon feed comprising one or more alkanes or alkylaromatic compounds into a fluidized bed reactor. In the fluidized bed reactor, at least 95wt% of the hydrocarbon feed has an atmospheric boiling point of less than or equal to 300 ℃. The method further includes thermally cracking the hydrocarbon feed in the fluidized bed reactor to produce a dehydrogenation product and hydrogen. The fluidized bed reactor is operated at a temperature of at least 600 ℃. The fluidized bed reactor is free of dehydrogenation catalyst. The method further includes contacting the hydrogen with an oxygen carrier material in the fluidized bed reactor to combust the hydrogen and form an oxygen reduced oxygen carrier material. The oxygen carrier material is reducible. The method further includes transferring the oxygen-reduced oxygen carrier material to a regeneration unit, oxidizing the oxygen-reduced oxygen carrier material in the regeneration unit to form an oxygen-enriched oxygen carrier material, combusting a supplemental fuel in the regeneration unit to generate heat and raise a temperature of the oxygen carrier material, and transferring the oxygen-enriched oxygen carrier material to the fluidized bed reactor.

A second aspect of the present disclosure includes the first aspect, further comprising partially reducing the oxygen-enriched oxygen carrier material prior to contacting the hydrogen with the oxygen-enriched oxygen carrier material in the fluidized bed reactor.

A third aspect of the present disclosure includes any one of the preceding aspects, wherein the fluidized bed reactor is operated at a temperature of at least 600 ℃ and less than 850 ℃.

A fourth aspect of the present disclosure includes any one of the preceding aspects, wherein the supplemental fuel is selected from hydrogen, methane, ethane, propane, natural gas, or a combination thereof.

A fifth aspect of the present disclosure includes any one of the preceding aspects, wherein all solid particulate material in the fluidized bed reactor is an oxygen carrier material.

A sixth aspect of the present disclosure includes any one of the preceding aspects, wherein the oxygen-enriched oxygen carrier material comprises from 1wt% to 20wt% releasable oxygen based on the total weight of the oxygen-enriched oxygen carrier material.

A seventh aspect of the present disclosure includes any one of the preceding aspects, wherein contacting the hydrogen with the oxygen-enriched oxygen carrier material removes from 1wt% to 50wt% of the releasable oxygen from the oxygen-enriched oxygen carrier material.

An eighth aspect of the present disclosure includes any one of the preceding aspects, wherein the hydrogen is combusted greater than 50% of the hydrogen in contact with the oxygen-enriched oxygen carrier material.

A ninth aspect of the present disclosure includes any one of the preceding aspects, wherein the oxygen carrier material comprises one or more metal oxides.

A tenth aspect of the present disclosure includes any one of the preceding aspects, wherein the oxygen carrier material exhibits Geldart a or Geldart B characteristics.

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 and 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 (10)

1. A method for dehydrogenating hydrocarbons, the method comprising: Passing a hydrocarbon feed comprising one or more alkanes or alkyl aromatic compounds into a fluidized bed reactor, wherein at least 95 wt% of the hydrocarbon feed has an atmospheric boiling point less than or equal to 300° C.; thermally cracking the hydrocarbon feed in the fluidized bed reactor to produce a dehydrogenated product and hydrogen, wherein the fluidized bed reactor is operated at a temperature of at least 600° C., and wherein the fluidized bed reactor is free of a dehydrogenation catalyst; and contacting the hydrogen with an oxygen-enriched oxygen carrier material in the fluidized bed reactor to combust the hydrogen and form an oxygen-reduced oxygen carrier material, wherein the oxygen-enriched oxygen carrier material is reducible; delivering the oxygen-reduced oxygen carrier material to a regeneration unit; oxidizing the oxygen-reduced oxygen carrier material in the regeneration unit to form the oxygen-enriched oxygen carrier material; combusting supplemental fuel in the regeneration unit to generate heat and increase the temperature of the oxygen carrier material; and The oxygen-rich oxygen carrier material is delivered to the fluidized bed reactor. 2. The method of claim 1, further comprising partially reducing the oxygen-enriched oxygen carrier material prior to contacting the hydrogen with the oxygen-enriched oxygen carrier material in the fluidized bed reactor. 3. A process according to any one of the preceding claims, wherein the fluidised bed reactor is operated at a temperature of at least 600°C and below 850°C. 4. The method according to any one of the preceding claims, wherein the supplemental fuel is selected from hydrogen, methane, ethane, propane, natural gas or combinations thereof. 5. A process according to any one of the preceding claims, wherein all solid particulate material in the fluidised bed reactor is oxygen carrier material. 6. The method according to any one of the preceding claims, wherein the oxygen-rich oxygen carrier material comprises from 1 wt% to 20 wt% of releasable oxygen, based on the total weight of the oxygen-rich oxygen carrier material. 7. The method of any one of the preceding claims, wherein contacting the hydrogen with the oxygen-enriched oxygen carrier material removes from the oxygen-enriched oxygen carrier material from 1 wt% to 50 wt% of the releasable oxygen. 8. The method of any one of the preceding claims, wherein contacting the hydrogen with the oxygen-enriched oxygen carrier material combusts greater than 50% of the hydrogen. 9. A method according to any one of the preceding claims, wherein the oxygen carrier material comprises one or more metal oxides. 10. The method according to any one of the preceding claims, wherein the oxygen carrier material exhibits Geldart A or Geldart B properties.