Process for dehydrogenation of hydrocarbons by thermal dehydrogenation

Abstract

A method for dehydrogenating hydrocarbons may include passing a hydrocarbon feed containing one or more alkanes or alkylaromatics into a fluidized bed reactor. In the fluidized bed reactor, at least 95 wt.% of the hydrocarbon feed may have an atmospheric boiling point of 300°C or less. The method may include pyrolyzing the hydrocarbon feed in the fluidized bed reactor to produce a dehydrogenated product and hydrogen. The fluidized bed reactor may operate at a temperature of at least 600°C. The fluidized bed reactor may not include a dehydrogenation catalyst. The method may include contacting hydrogen with an oxygen carrier material in the fluidized bed reactor to combust the hydrogen and form an oxygen-depleted oxygen carrier material. The oxygen carrier material may be reducible.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Provisional Patent Application No. 63 / 406,449, filed September 14, 2022, which is incorporated herein by reference in its entirety.

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

[0003] Light olefins and aromatic olefins can be used as base materials to produce many types of goods and materials. For example, ethylene can be used to make polyethylene, ethylene chloride, or ethylene oxide. Additionally, styrene can be used to produce polystyrene. Such products can be used in product packaging, construction, textiles, and the like. These base chemicals can be formed by the dehydrogenation of hydrocarbon feeds. Therefore, there is an industry need for new dehydrogenation processes to form materials such as ethylene, propylene, butene, and styrene. Summary of the Invention

[0004] One method for producing light olefins and / or aromatic olefins is by thermal dehydrogenation of a feed stream containing one or more alkanes, such as ethane, propane, n-butane, and / or i-butane, or alkylaromatics, such as ethylbenzene. Thermal dehydrogenation allows chemicals to be dehydrogenated without the use of a dehydrogenation catalyst. Hydrogen is produced by such a thermal dehydrogenation reaction. According to embodiments disclosed herein, this hydrogen formed by thermal (i.e., non-catalytic) dehydrogenation is reacted with oxygen from an oxygen carrier material to form water, which can be separated from the product olefins. Furthermore, while the thermal dehydrogenation reaction requires a relatively large heat input to the system, the reaction of hydrogen with oxygen from the oxygen carrier material is exothermic and can therefore offset at least a portion of the heat input load required for thermal dehydrogenation. The oxygen carrier material may be recycled to a regeneration unit where oxygen is supplemented, which may be exothermic and offset some additional heat input to the system. Thus, the methods described herein can efficiently produce light olefins without the need for a dehydrogenation catalyst.

[0005] Furthermore, as described herein, embodiments may include the combustion of an auxiliary fuel in the regeneration unit. It has been discovered that processes that do not utilize an auxiliary fuel may not adequately include a heat balance sufficient to sustain thermal dehydrogenation. Advantageously, such combustion of the auxiliary fuel may be carried out in the same area as the oxidation of the oxygen carrier material (each using oxygen present in the regeneration unit). Heat from the combustion of the auxiliary fuel may increase the temperature of the oxygen carrier material in the regeneration unit, which may be the primary source of heat transport into the reactor where thermal dehydrogenation occurs.

[0006] According to at least one embodiment of the present disclosure, a method for dehydrogenating hydrocarbons may include passing a hydrocarbon feed containing one or more alkanes or alkylaromatics into a fluidized-bed reactor. In the fluidized-bed reactor, at least 95 wt.% of the hydrocarbon feed may have an atmospheric boiling point of 300°C or less. The method may further include pyrolyzing the hydrocarbon feed in the fluidized-bed reactor to produce a dehydrogenated product and hydrogen. The fluidized-bed reactor may operate at a temperature of at least 600°C. The fluidized-bed reactor may not include a dehydrogenation catalyst. The method may further include contacting hydrogen with an oxygen carrier material in the fluidized-bed reactor to combust the hydrogen and form an oxygen-depleted oxygen carrier material. The oxygen carrier material may be reducible. The method may further include passing the oxygen-depleted oxygen carrier material to a regeneration unit, oxidizing the oxygen-depleted oxygen carrier material in the regeneration unit to form an oxygen-rich oxygen carrier material, burning a supplemental fuel in the regeneration unit to generate heat and increase the temperature of the oxygen carrier material, and passing the oxygen-rich oxygen carrier material to a fluidized bed reactor.

[0007] These and other embodiments are described in more detail below in the Detailed Description of the Invention, taken in conjunction with the accompanying drawings. [Brief explanation of the drawings]

[0008] The following detailed description of certain embodiments of the present disclosure can be best understood when read in conjunction with the following drawings, in which like structure is indicated with like reference numerals and in which: [Figure 1] 1 illustrates a schematic of a catalytic dehydrogenation system according to one or more embodiments described herein. [Figure 2] 1 illustrates a schematic of a catalytic dehydrogenation system with recycle according to one or more embodiments described herein.

[0009] It should be understood that the drawings are schematic in nature and do not include some components of reactor systems commonly used in the art, such as, without limitation, temperature transmitters, pressure transmitters, flow meters, pumps, valves, etc. It will be appreciated that these components are within the spirit and scope of the disclosed embodiments. However, operating components such as those described in this disclosure may be added to the embodiments described in this disclosure.

[0010] Reference will now be made in more 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 OF THE INVENTION

[0011] Specific embodiments of the present application will now be described. However, the present disclosure may be embodied in different forms and should not be construed as limited to the embodiments set forth in this disclosure.

[0012] Disclosed herein are embodiments relating to methods for treating a chemical stream to form products by thermal dehydrogenation. In various embodiments, the process can include using thermal dehydrogenation with an oxygen carrier material. The method can include thermally dehydrogenating an alkane or alkyl aromatic to form hydrogen and an olefin or olefin aromatic, and then combusting the hydrogen with oxygen from the oxygen carrier material described herein.

[0013] As described herein, the process does not include a dehydrogenation catalyst. A dehydrogenation catalyst includes a material that catalyzes a dehydrogenation reaction. If an oxygen carrier material can only minimally catalyze a dehydrogenation reaction, such oxygen carrier material is not considered a dehydrogenation catalyst as contemplated herein. That is, the oxygen carrier material utilized herein has little or no catalytic function compared to the activity of the oxygen carrier material in introducing oxygen.

[0014] Utilizing a process that does not include a dehydrogenation catalyst has many advantages. For example, it eliminates the added cost of a dehydrogenation catalyst, which may need to be replaced or rejuvenated frequently. Furthermore, in one or more embodiments, the catalytic reaction is eliminated, thus reducing the complexity of the reaction system, as only the thermal dehydrogenation and hydrogen combustion need be considered in the design.

[0015] Unless otherwise specified herein, the term "oxygen carrier material" may generally refer to an oxygen-rich or oxygen-depleted oxygen carrier material. The oxygen-depleted state may exist after some oxygen has been released and utilized in the combustion of hydrogen, and may be oxygen-rich before the combustion of hydrogen. Generally, the oxygen carrier material may enter the regeneration unit in an oxygen-depleted state and exit the regeneration unit in an oxygen-rich state. The reaction converting the oxygen carrier material from an oxygen-rich state to an oxygen-depleted state may occur in one or more fluidized bed reactors, such as a circulating fluidized bed reactor. The reactor may be, for example, a riser or a downer. It should be understood that the oxygen-rich state of the oxygen carrier material may not be completely oxidized, and the oxygen-depleted state of the oxygen carrier may still contain some releasable oxygen. However, the oxygen content of the oxygen carrier material in the oxygen-rich state is typically higher than the oxygen content in the oxygen-depleted state.

[0016] Referring now to Figure 1, there is shown a reactor system 100 that may be used to practice the method of the present disclosure. The reactor system 100 may include a fluidized bed reactor 110 and a regeneration unit 120. A hydrocarbon feed 101 may be fed into the fluidized bed reactor 110. An oxygen carrier material may be circulated between the fluidized bed reactor 110 and the regeneration unit 120 via streams 103 and 104, as shown. A product may be fed from the fluidized bed reactor 110 via stream 102.

[0017] In one or more embodiments, the hydrocarbon feed 101 may include one or more alkanes or alkylaromatics. For example, the hydrocarbon feed 101 may include one or more of ethane, propane, butane, or ethylbenzene. According to one or more embodiments, the hydrocarbon feed 101 may include at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, or even at least 99 wt% ethane. In additional embodiments, the hydrocarbon feed 101 may include at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, or even at least 99 wt% propane. In additional embodiments, the hydrocarbon feed 101 may include at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, or even at least 99 wt% butane. In additional embodiments, the hydrocarbon feed 101 may comprise at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or even at least 99% by weight of ethylbenzene. In additional embodiments, the hydrocarbon feed 101 may comprise at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or even at least 99% by weight of the sum of ethane, propane, butane, and ethylbenzene.

[0018] According to one or more embodiments, at least 95 wt. % of the hydrocarbon feed 101 may have an atmospheric boiling point of 300° C. or less. According to additional embodiments, at least 95 wt. % of the hydrocarbon feed 101 may have an atmospheric boiling point of 275° C. or less, 250° C. or less, 225° C. or less, 200° C. or less, 175° C. or less, 150° C. or less, 125° C. or less, or even 100° C. or less. For example, the hydrocarbon feed 101 may not be crude oil or a heavy fraction of crude oil. In additional embodiments, at least 99 wt. % of the hydrocarbon feed 101 may have an atmospheric boiling point of 300° C. or less.

[0019] 1, the reactor system 100 can include a fluidized bed reactor 110 and a regeneration unit 120, both of which may be fluidized bed-based and may have the same or different fluidization regimes. According to some embodiments, the fluidized bed reactor 110 can be operated in a "backmixed" mode, where the feed hydrocarbons enter the fluidized bed reactor 110 in a manner that is very close to isothermal. Thus, the fluid velocity in this region can be sufficiently low and the solids flow velocity can be sufficiently high so that a dense bed can form at or around where the hydrocarbons are injected. In some embodiments, the superficial velocity in this region can be 3-80 ft / s, such as 3-40 ft / s, or 10-30 ft / s. The solids flow velocity in the reactor can be 40-200 lb / ft 2 -s, or 60-160 lb / ft 2 -s etc. 1 to 300 lb / ft 2 The fluidized bed reactor 110 may be a fluidized bed reactor having a gas residence time of 0.1 to 10 seconds, such as 0.5 to 6 seconds. The fluidized bed reactor 110 may include multiple diameters and may include one or more frustum to increase or decrease solid and / or gas reactant velocities. The fluidized bed reactor 110 may be operated at a gas residence time of 0.1 to 10 seconds, such as 0.5 to 6 seconds.

[0020] A general operational embodiment of the fluidized bed reactor 110 for conducting 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 1% to 100%, such as 95% to 100%, by weight of oxygen carrier material, based on the total weight of all solids in the fluidized bed reactor.

[0021] During operation of the fluidized bed reactor 110 of the reactor system 100, a hydrocarbon feed 101 may enter the fluidized bed reactor 110 and a product stream may exit the reactor system 100 via stream 102. According to one or more embodiments, the reactor system 100 may be operated by feeding a chemical feed (e.g., in a feed stream such as the hydrocarbon feed 101) into the fluidized bed reactor 110.

[0022] According to one or more embodiments, an oxygen-rich oxygen carrier material may also be fed from regeneration unit 120 to fluidized bed reactor 110 via stream 104. The chemical feed in stream 101 may contact the oxygen-rich oxygen carrier material in fluidized bed reactor 110. The chemical feed and the oxygen-rich oxygen carrier material may each flow upwardly through fluidized bed reactor 110 to produce chemical products and oxygen-depleted oxygen carrier material.

[0023] According to embodiments, exposing the feed to high temperatures in the fluidized bed reactor 110 may cause thermal dehydrogenation to form olefinic chemicals and hydrogen gas. Additionally, the hydrogen may be contacted with an oxygen-rich oxygen carrier material in the fluidized bed reactor 110. The oxygen-rich oxygen carrier material may be reducible, and contacting the oxygen-rich oxygen carrier material with hydrogen may result in combustion of the hydrogen and formation of an oxygen-depleted oxygen carrier material.

[0024] In some embodiments, the chemical product and the oxygen-depleted oxygen carrier material may be sent to a separation device within a separation section within the fluidized-bed reactor 110. The oxygen-depleted oxygen carrier material may be separated from the chemical product (and any unreacted feed) in the separation device within the fluidized-bed reactor 110. The chemical product (along with the unreacted feed) may then be transported from the separation section of the fluidized-bed reactor 110. For example, the separated vapor may be removed from the fluidized-bed reactor 110 through a pipe at a gas outlet port of the separation section within the fluidized-bed reactor 110. According to one or more embodiments, the separation device may be a cyclone separation system. The cyclone separation system may include two or more stages of cyclone separation.

[0025] In one or more embodiments, the fluidized bed reactor 110 may be operated with a gas residence time 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 the fluidized bed reactor 110. As will be appreciated by those skilled in the art, just as residence time may vary, the rate of thermal dehydrogenation may vary with temperature.

[0026] In one or more embodiments, the fluidized-bed reactor 110 can operate at temperatures greater than 600°C and less than or equal to 800°C. In some embodiments, the temperature in the fluidized-bed reactor 110 can be 625°C or between 650°C and 770°C. In other embodiments, the temperature in the fluidized-bed reactor 110 can be between 700°C and 750°C. Without being bound by any particular theory, it is believed that if the temperature is too low (e.g., below 600°C), equilibrium constraints may limit the maximum hydrocarbon conversion rate. If the temperature is too low, the oxygen release rate from the oxygen carrier material may also be slow, and hydrogen combustion may also be reduced. On the other hand, high temperatures (e.g., above 800°C) may lead to thermal degradation of the desired products produced, leading to lower product selectivities than are economically feasible. In some embodiments, the primary feed component(s) may be propane, ethylbenzene, and / or butane, and the fluidized-bed reactor 110 may operate at temperatures greater than 600°C. In an additional embodiment, the primary feed component may be ethane and the fluidized bed reactor 110 may operate at a temperature of at least 625°C.

[0027] In some embodiments, the fluidized bed reactor 110 may operate 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, the fluidized bed reactor 110 may operate at a pressure of about 4 psia to about 160 psia, about 20 psia to about 100 psia, or about 30 psia to about 60 psia. In some embodiments, the regeneration unit 120 may operate within 30 psia of the pressure of the fluidized bed reactor 110.

[0028] In some embodiments, the hydrocarbon feed may contact an oxygen-rich oxygen carrier material in an upstream reactor section of the fluidized-bed reactor 110. The chemical feed and the oxygen-rich oxygen carrier material may each flow upwardly through a downstream reactor section of the fluidized-bed reactor 110 to produce a chemical product and an oxygen-depleted oxygen carrier material, where hydrogen is formed by thermal dehydrogenation and combusted with oxygen from the oxygen carrier material to form the oxygen-depleted oxygen carrier material. In one or more embodiments, the feed distributor in the fluidized-bed reactor 110 may be operable to discharge the hydrocarbon feed stream at shroud distributor velocities ranging from 200 ft / s to 50 ft / s. Such embodiments may utilize a variety of feed streams while maintaining desired reactor characteristics, such as operating as a fast fluidized-bed reactor, a turbulent-bed reactor, or a 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 distributor 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 oxygen-depleted oxygen carrier material may be passed from the downstream reactor section of the fluidized bed reactor 110 to a separation device within the fluidized bed reactor 110, where the oxygen-depleted oxygen carrier material may be separated from the chemical product.

[0029] In additional embodiments, the weight hourly space velocity (WHSV) of the disclosed processes can range from 0.1 lb to 100 lb of chemical feed per pound (lb) of solids in the reactor per hour (h) (lb feed / hr / lb solids). In some embodiments, when the fluidized bed reactor 110 includes an upstream reactor section operating as a fast fluidized bed reactor, a turbulent bed reactor, or a bubbling bed reactor, and a downstream reactor section operating as a dilute-phase riser reactor, the superficial gas velocity can range from 2 ft / s (about 0.61 m / s) to 10 ft / s (about 3.05 m / s) in the upstream reactor section and from 30 ft / s (about 9.14 m / s) to 70 ft / s (about 21.31 m / s) in the downstream reactor section. In additional embodiments, a fully riser reactor configuration may operate at a single high superficial gas velocity, for example, in some embodiments, at least 30 ft / s (about 9.15 m / s) throughout.

[0030] The residence time of the solids in the fluidized bed reactor 110 can typically vary from 0.5 seconds (sec) to 240 seconds. In other embodiments, the residence time of the solids can be from about 0.5 seconds to about 200 seconds, from about 0.5 seconds to about 100 seconds, from about 0.5 seconds to about 50 seconds, or from about 0.5 seconds to about 20 seconds.

[0031] In additional embodiments, the ratio of solids to hydrocarbon feed 101 in the fluidized bed reactor 110 can range from 5 to 150 on a weight-to-weight (w / w) basis. In some embodiments, the ratio can range from 10 to 40, such as from 12 to 36, or from 12 to 24.

[0032] In additional embodiments, the flow rate of the solids (e.g., oxygen carrier material) is between 1 and 20 pounds per square foot second (lb / ft ) in the upstream reactor section. 2 -s), 1 lb / ft 2 -s(about 4.89kg / m2-s)~300lb / ft 2 -s(~97.7kg / m 2-s), and in the downstream reactor section, 10 to 100 lb / ft 2 -s, etc., 1 lb / ft 2 -s(about 48.9kg / m 2 -s)~300lb / ft2-s(approximately 489kg / m 2 -s).

[0033] In one or more embodiments, the solid (e.g., oxygen carrier material) may comprise solid particles that can be fluidized. In some embodiments, the solid may exhibit what is known in the industry as "Geldart A" properties. Solids may be classified as "Group A" or "Group B" according to D. Geldart, Gas Fluidization Technology, John Wiley & Sons (New York, 1986), 34-37, and D. Geldart, "Types of Gas Fluidization," Powder Technol. 7 (1973) 285-292, which are incorporated herein by reference in their entireties. In one or more embodiments, the oxygen carrier material may exhibit what is known in the industry as "Geldart A" properties. In other embodiments, the oxygen carrier material may exhibit what is known in the industry as "Geldart B" properties.

[0034] Group A is understood by those skilled in the art to represent a powder that can contain air and has the following characteristics: fluidization in a bubble-free range, high bed expansion, a slow and linear degassing rate, where divided / recombined bubbles can be dominant, bubble characteristics with a maximum bubble size and a large wake, a high level of solid mixing and gas backmixing assuming equal U-Umf (where U is the velocity of the carrier gas and Umf is the minimum fluidization velocity, typically not necessarily measured in meters per second, m / s, i.e., there is an excess gas velocity), axisymmetric slug characteristics, and no ejection except for a very shallow bed. Assuming dp is equal, as the average particle size decreases, or as the proportion above 45 micrometers (μm) increases, or as the pressure, temperature, viscosity, and density of the gas increase, the listed characteristics tend to improve. Generally, the particles exhibit a small average particle size and / or a low particle density (less than 1.4 grams per cubic centimeter, g / cm 3 ³) and can be easily fluidized to have smooth fluidization at low gas velocities and can exhibit bubbling with controlled small bubbles even at higher gas velocities.

[0035] Group B is understood by those skilled in the art to represent a "sand-like" powder that starts foaming at Umf, exhibits moderate bed expansion, rapid degassing, no limitation on bubble size, and assuming equal U-Umf, has a moderate level of solid mixing and gas backmixing, both axisymmetric and asymmetric slugs, and ejects only from a shallow bed. These characteristics tend to improve as the average particle size decreases, but the particle size distribution and, with some uncertainty, the gas pressure, temperature, viscosity, or density do not seem to contribute much to the improvement of the above characteristics. Generally, most of the particles have a particle size (dp) of 40 μm < dp < 500 μm when the density (pp) is 1.4 < pp < 4 g / cm³, preferably 60 μm < dp < 500 μm when the density (pp) is 4 g / cm³, and 250 μm < dp < 100 μm when the density (pp) is 1 g / cm³.

[0036] The oxygen carrier material may include one or more metal oxides. According to one or more embodiments, the one or more metal oxides may be redox-active metal oxides or mixtures of redox-active metal oxides. Redox-active metal oxides include binary, ternary, or other mixed metal oxides that can undergo reduction in the presence of a reducing agent (e.g., hydrogen) and oxidation in the presence of an oxidizing agent (e.g., oxygen or air). In some embodiments, the redox-active metal oxide is a metal MO x where M can be one or more metals from IUPAC Groups 6, 7, 8, 9, 10, 11, or 12, and "x" is the number of bonded oxygen atoms in the structure. For example, the redox-active metal oxide can be Mn2O3, Fe2O3, Co3O4, CuO, (LaSr)CoO3, (LaSr)MnO3, Mg6MnO8, MgMnO3, MnO2, Fe3O4, Mn3O4, Cu2O, NiO, Ni2O3, CrO, Cr2O3, CrO2, ZnO, or any combination of other IUPAC Group 6-12 metal oxides. In some embodiments, the redox-active metal oxide can be cerium oxide. For example, the redox-active metal oxide can be CeO2, Ce2O3, or any other mixed metal oxide containing cerium. In further embodiments, the oxygen carrier material may include lanthanum oxide, La2O3, in combination with other reducible metal oxides. In some embodiments, the redox-active metal oxide may be selected from Mn2O3, Fe2O3, Co3O4, CuO, (LaSr)CoO3, (LaSr)MnO3, Mg6MnO8, MgMnO3, MnO2, Fe3O4, Mn3O4, and Cu2O. In some embodiments, the oxygen carrier material may be a solid. In certain embodiments, the oxygen carrier material may be a pulverized solid or powder. In other embodiments, the oxygen carrier material may be formulated using redox-active metal oxides and binder and / or support materials to produce a flowable material with required physical properties, such as particle size distribution, density, and wear resistance. The binder and / or support material may include alumina, silica, titania, magnesia, zirconia, or a combination thereof.

[0037] In one or more embodiments, the oxygen carrier material may include a hydrogen-selective oxygen carrier material, which may include a promoter or a combination of various promoters. The addition of promoter(s) may result in the formation of a core-shell morphology. The promoter(s) may include compounds containing alkali or alkaline earth metal oxides and / or alkali or alkaline earth transition metal oxides from IUPAC Groups 1 and 2. In some embodiments, the alkali elements may include one or more of sodium, lithium, potassium, and cesium. In some embodiments, the alkaline earth elements may include one or more of calcium, magnesium, strontium, and barium. In some embodiments, the transition metal may include one or more of tungsten and molybdenum. For example, the one or more alkali transition metal oxides or alkaline earth transition metal oxides can be Na2WO4, K2MoO4, Na2MoO4, K2WO4, Li2WO4, CsWO4, Li2MoO4, CaWO4, CaMoO4, MgWO4, MgMoO4, SrWO4, SrMoO4, BaWO4, and BaMoO4. In some embodiments, the promoter can include one or more alkali metal or alkaline earth metal salts selected from Group 1 and Group 2 metal cations and a counterion. In some embodiments, the alkali element can include one or more of sodium, lithium, potassium, and cesium. In some embodiments, the alkaline earth element can include one or more of calcium, magnesium, strontium, and barium. In some embodiments, the counterion can include carbonate, sulfate, sulfite, sulfide, phosphate, phosphite, and borate.For example, the alkali metal salt or alkaline earth metal salt can be Na2CO3, Na2SO4, Na3PO4, Li2CO3, Li2SO4, Li3PO4, K2CO3, K2SO4, K3PO4, Cs2CO3, Cs2SO4, Cs3PO4, CaCO3, CaSO4, Ca3(PO4)2, SrCO3, SrSO4, Sr3(PO4)2, MgCO3, MgSO4, Mg3(PO4)2, BaCO3, BaSO4, Ba3(PO4)2, Na2HPO4, KHSO4, Na2SO3, K2B4O7, Na3BO3, or combinations thereof.

[0038] For example, oxygen carrier materials such as those disclosed in U.S. Patent Application No. 62 / 725,504, filed August 31, 2018, entitled "METHODS OF PRODUCING HYDROGEN-SELECTIVE OXYGEN CARRIER MATERIALS," and U.S. Patent Application No. 62 / 725,508, filed August 31, 2018, entitled "HYDROGEN-SELECTIVE OXYGEN CARRIER MATERIALS AND METHODS OF USE," are contemplated as suitable for the processes of the present disclosure, the teachings of which are incorporated herein by reference. In one or more additional embodiments, the oxygen carrier material may include the oxygen carrier materials of U.S. Patent No. 5,430,209, U.S. Patent No. 7,122,495, and / or WO 2018 / 232133, each of which is incorporated by reference in its entirety.

[0039] The oxygen-rich oxygen carrier material may be reducible by releasing oxygen, which may be selective for the combustion of hydrogen. For example, the oxygen carrier material may be selective for the combustion of hydrogen over hydrocarbons. In some embodiments, the oxygen-rich oxygen carrier material comprises about 1% to about 20% by weight of releasable oxygen, based on the total weight of the oxygen-rich oxygen carrier material. In other embodiments, the oxygen-rich oxygen carrier material comprises about 1% to about 10% by weight, about 1% to about 5% by weight, about 5% to about 20% by weight, or about 5% to about 10% by weight of releasable oxygen. As used herein, "releasable oxygen" may refer to oxygen that can be released via redox by the oxygen carrier material. Other oxygen may be present in the oxygen carrier material that is not releasable via redox. It should be understood that in some embodiments, oxygen may be released from the surface of the oxygen carrier material simultaneously with the combustion of hydrogen on the surface of the oxygen carrier material.

[0040] As previously mentioned, the releasable oxygen of an oxygen-rich oxygen carrier material can be selective for the combustion of hydrogen over hydrocarbons. In some embodiments, at least about 60% of the releasable oxygen of the oxygen carrier material is selective for hydrogen combustion. In other embodiments, at least about 55% of the releasable oxygen of the oxygen carrier material is selective for hydrogen combustion.

[0041] In embodiments, contacting hydrogen with the oxygen-rich oxygen carrier material removes a portion of the releasable oxygen from the oxygen-rich oxygen carrier material. In some embodiments, contacting hydrogen with the oxygen-rich oxygen carrier material removes between about 1% and 50% by weight of the releasable oxygen from the oxygen-rich oxygen carrier material. In other embodiments, contacting hydrogen with the oxygen-rich oxygen carrier material removes between about 10% and about 50% by weight, between about 10% and about 25% by weight, or between about 25% and about 50% by weight of the releasable oxygen from the oxygen-rich oxygen carrier material.

[0042] In further embodiments, when hydrogen contacts the oxygen-rich oxygen carrier material, the oxygen-rich oxygen carrier material combusts greater than about 50% of the hydrogen. In other embodiments, when hydrogen contacts the oxygen-rich oxygen carrier material, the oxygen-rich oxygen carrier material combusts about 50% to about 90%, or about 75% to about 90%, of the hydrogen produced.

[0043] When the oxygen-rich oxygen carrier material is contacted with hydrogen, the hydrogen may combust to form an oxygen-depleted oxygen carrier material. At least a portion of the oxygen-rich oxygen carrier material may be reduced to a lower oxidation state to form the oxygen-depleted oxygen carrier material. Once the oxygen carrier material is reduced to form the oxygen-depleted oxygen carrier material, the oxygen-depleted oxygen carrier material may be discharged from the fluidized bed reactor 110 in the lower oxidation state.

[0044] As an example, ethane may be thermally dehydrogenated to form ethylene and hydrogen gas. Thermal dehydrogenation allows chemicals to be dehydrogenated without the use of a dehydrogenation catalyst. Such a thermal dehydrogenation reaction scheme for converting ethane to ethylene is shown in Equation 1.

[0045]

number

[0046] The dehydrogenation reaction may be facilitated by removing hydrogen produced by reduction or thermal dehydrogenation, which pushes the reaction equilibrium toward the product. That is, in Equation 1, removing hydrogen pushes the equilibrium to the right, which may allow the reaction to achieve increased levels of conversion or operate at a lower temperature.

[0047] The disclosed process for producing light olefins and aromatic olefins may incorporate thermal dehydrogenation and hydrogen combustion. Due to the removal of hydrogen by combustion with oxygen, according to one or more embodiments, the disclosed process may operate at higher pressures and lower temperatures compared to conventional processes while achieving comparable conversion levels. As a result, in some embodiments, the disclosed process incorporating hydrogen combustion may enable a relatively smaller process unit, thus reducing capital costs. It has been found that incorporating an oxygen carrier material in the dehydrogenation reaction may reduce the required input heat and / or reduce the subsequent separation costs of unreacted alkanes, alkylaromatics, and hydrogen. As described herein, incorporating and recycling an oxygen carrier material through the process may facilitate the combustion of hydrogen to form water.

[0048] 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 in excess of 850°C. High temperatures may make conventional processes expensive. For example, due to the higher temperatures required by these conventional processes, the reactors utilized in such processes may not be capable of incorporating reactor structures or other design features. Alternatively, such processes may require that reactor structures and other process units be made from specialized materials, which increases capital costs.

[0049] In some embodiments, it is contemplated that combusting the hydrogen formed in the disclosed processes may simultaneously reduce downstream separation costs. For example, in downstream processes, the product stream may need to be liquefied. Thus, reducing the hydrogen in the product stream may reduce the volume of gas that needs to be liquefied due to the lower hydrogen content, or may change the temperature required for hydrocarbon liquefaction. Thus, completely or partially removing hydrogen in the product stream may reduce the energy requirements for downstream liquefaction processes. Additionally, completely or partially removing hydrogen in the product stream may subsequently reduce other downstream separation costs by eliminating the need for other process units that may be utilized to separate hydrogen from the product stream (before or after liquefaction).

[0050] The production of light olefins by conventional dehydrogenation processes (e.g., those that do not incorporate hydrogen combustion) can be relatively expensive due to the high heat load required for the endothermic dehydrogenation reaction and / or the downstream separation steps sometimes required to separate unreacted alkanes or alkylaromatics and remove the hydrogen produced in the dehydrogenation reaction. Regarding heat input reduction, catalytic dehydrogenation processes are generally endothermic and require heat. However, the exothermic combustion of hydrogen can offset that heat input requirement to some extent. Furthermore, if the oxygen content of the oxygen carrier material is reduced after combustion, it may be regenerated to regain oxygen for the oxygen carrier material, and the regeneration may be exothermic. This exothermic regeneration step may further offset the heat input requirement to sustain the dehydrogenation reaction. In some embodiments, the heat generated by the oxygen carrier regeneration and combustion reaction may completely cover the heat required for the endothermic dehydrogenation reaction and other heat demands, such as heating the feed gas (air, hydrocarbons, etc.) or balancing heat losses, or may at least reduce the need for any auxiliary fuel in the system.

[0051] 1 , the oxygen-depleted oxygen carrier material and gas product may be separated by high-efficiency cyclones within fluidized bed reactor 110. In the described embodiment, the oxygen-depleted oxygen carrier material may be sent to regeneration unit 120 via stream 103. In a further embodiment, the oxygen carrier material may be stripped with a displacement gas, such as nitrogen, steam, methane, natural gas, or other suitable gas, before being sent to regeneration unit 120.

[0052] According to embodiments, the oxygen carrier material may be sent via stream 103 to a regeneration unit 120 where regeneration occurs. Regeneration may remove contaminants such as coke, increase the temperature of the oxygen carrier material, or both. In some embodiments, the oxygen-depleted oxygen carrier material may be reoxidized to a higher oxidation state than the oxygen-depleted 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-rich oxygen carrier material, the oxygen-depleted oxygen carrier material may be restored to its original oxidation state. In some embodiments, the oxygen-depleted oxygen carrier material may have an oxidation state of +2, +3, or +4. The oxygen-rich oxygen carrier material may then be circulated back to the fluidized-bed reactor 110, carrying the heat required for the dehydrogenation reaction. In other embodiments, nitrogen or steam may be used to transport the oxygen-rich oxygen carrier material to the fluidized-bed reactor 110. The gas stream obtained from the regeneration unit 120 consists of air that is O2 depleted or contains a lower concentration of O2.

[0053] In one or more embodiments, the supplemental fuel may be combusted in the regeneration unit 120 to generate heat and increase the temperature of the oxygen carrier material. The heat generated by the oxidation of the oxygen-depleted 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 to operate the fluidized bed reactor 110, as the oxygen carrier material enters the fluidized bed reactor 110 and may impart the temperature of the oxygen carrier material to the fluidized bed reactor 110.

[0054] In some embodiments, the supplemental fuel may include one or more of hydrogen, methane, ethane, propane, natural gas, or combinations thereof. The supplemental fuel may be gaseous. However, it should be understood that other fuel types are contemplated and within the scope of embodiments of the present disclosure. The supplemental fuel may be combusted by exposure to oxygen at elevated temperatures. For example, air, oxygen-enriched air, or oxygen gas may be present in the regeneration unit 120. Advantageously, in one or more embodiments, the same gas may be utilized to oxidize the oxygen-depleted oxygen-carrying material and combust the supplemental fuel.

[0055] Without being bound by theory, the amount of fuel combusted may generally be sufficient to provide the heat necessary to heat the fluidized bed reactor 110 in which the thermal dehydrogenation is occurring. The oxidation of the oxygen-depleted oxygen carrier material may provide some heat, but may not be sufficient to heat the oxygen carrier material sufficiently to heat the fluidized bed reactor 110. Thus, the combustion of a supplemental fuel can make up the heat difference between the heat available for the thermal dehydrogenation reaction and the oxidation of the oxygen-depleted oxygen carrier material (as well as other reactions described herein, such as water formation by hydrogen combustion).

[0056] In one or more embodiments, the regeneration unit 120 may operate at a temperature of 650°C, or even 700°C to 900°C, such as 725°C to 875°C, or 750°C to 850°C. Generally, the regeneration unit 120 may have a temperature at least 50°C higher than the temperature of the fluidized bed reactor 110. Such a temperature range may be utilized such that the temperature of the fluidized bed reactor 110 can be maintained with a limited amount of oxygen carrier material.

[0057] 1, the oxygen-rich oxygen carrier material may be sent from the regeneration unit 120 to the fluidized bed reactor 110 via stream 104. Thus, the oxygen carrier may be looped or recycled through the reactor system 100.

[0058] FIG. 2 illustrates a system similar in many respects to the system of FIG. 1, with the differences described below. Referring now to FIG. 2, in one or more embodiments described herein, reoxidation of an oxygen-depleted oxygen carrier material can be controlled by the illustrated system. For example, according to one embodiment, flue gas can be sent to regeneration unit 120 via stream 108. In some embodiments, the flue gas can be a recycle stream from an adjacent chemical process. In some embodiments, the oxygen-depleted oxygen carrier material can be reoxidized to an oxidation state higher than that of the oxygen-depleted oxygen carrier material by at least a portion of the flue gas exiting regeneration unit 120 via stream 109, which is recycled to regeneration unit 120 via stream 112. Stream 109 exiting regeneration unit 120 can include air that is oxygen-depleted or contains a lower concentration of oxygen. In some embodiments, stream 112 can be mixed with fresh air via stream 107 to form stream 108. In some embodiments, stream 108 can include at least 25 mole percent (mol%) oxygen. In other embodiments, stream 108 can contain between about 4 mol% and about 25 mol% oxygen, between about 4 mol% and about 21 mol%, between 4 mol% and about 10 mol% oxygen, between 10 mol% and about 25 mol% oxygen, or between 10 mol% and about 21 mol% oxygen.

[0059] In embodiments, contacting the flue gas with the oxygen-rich oxygen carrier material removes a portion of the releasable oxygen from the oxygen-rich oxygen carrier material. In some embodiments, contacting the flue gas with the oxygen-rich oxygen carrier material removes between about 0% and 15% by weight of the releasable oxygen from the oxygen-rich oxygen carrier material. In other embodiments, contacting hydrogen with the oxygen-rich oxygen carrier material removes between about 0% and about 10% by weight, between about 0% and about 5% by weight, or between about 5% and about 10% by weight of the releasable oxygen from the oxygen-rich oxygen carrier material.

[0060] In other embodiments, the oxygen-depleted oxygen carrier material may be partially reoxidized to an oxidation state higher than the oxidation state of the oxygen-depleted oxygen carrier material in the regeneration unit 120. In some embodiments, the oxygen-rich oxygen carrier material comprises less releasable oxygen than the maximum releasable oxygen capacity of the oxygen carrier material.

[0061] In another embodiment, the oxygen-rich oxygen carrier material may also be reduced (“at least partially reduced”) to a lower oxidation state by combusting the oxygen-rich oxygen carrier material with a reducing gas. Without being bound by theory, in some embodiments, at least partially reducing the oxygen-rich oxygen carrier material may precondition the oxygen carrier material to maximize selectivity in the fluidized-bed reactor 110. Releasable oxygen bound to the surface of the oxygen carrier material may be less selective for hydrogen combustion than the remaining bulk oxygen. In further embodiments, the oxygen-rich oxygen carrier material may be at least partially reduced in a reducer after being routed from the regeneration unit 120 and before being routed to the fluidized-bed reactor 110. In some embodiments, a fuel source may be used to at least partially reduce the oxygen-rich oxygen carrier material, where the fuel source pre-combusts oxygen chemically absorbed during reoxidation of the oxygen-depleted oxygen carrier material in the regeneration unit 120. Depending on the reducer configuration, the products formed by pre-combustion may exit reactor system 100 via stream 102, or the products formed by pre-combustion can exit regenerator unit 120 (e.g., via line 111 in FIG. 2 ) or anywhere along line 104. In some embodiments, the products formed by pre-combustion can be stripped from one of the process streams, for example, with nitrogen, steam, or air. In some embodiments, pre-combustion can reduce the amount of reducible and free oxygen on the oxygen carrier by 0.01 to 10%. Without being bound by theory, this oxygen is expected to be the least selective for hydrogen combustion.

[0062] 1 and 2, in some embodiments, product gas from the fluidized bed reactor 110 may be sent from the fluidized bed reactor 110 via stream 102. Stream 102 may be further processed, such as by one or more subsequent separation steps, or may be further reacted. It is contemplated that stream 102 may be utilized as a feed for another reactor system or may be sold as a chemical product.

[0063] In one or more embodiments, reactor system 100 may be used to dehydrogenate hydrocarbons to produce olefins and other products (e.g., styrene from ethylbenzene), which may exit fluidized bed reactor 110 via Stream 102. In one or more embodiments, Stream 102 may include one or more olefins and other products. Stream 102 may include one or more of ethylene, propylene, butylene, or styrene. According to one or more embodiments, Stream 102 may include at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or even at least 99% ethylene by weight. In additional embodiments, Stream 102 may include at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or even at least 99% propylene by weight. In additional embodiments, stream 102 may comprise at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight, or even at least 99% by weight of the sum of ethylene and propylene.

[0064] In one or more embodiments, heat gained or lost through the thermal dehydrogenation reaction, the reoxidation of the oxygen-depleted oxygen carrier material, and the reduction of the oxygen-rich oxygen carrier material may produce or use heat (i.e., may be exothermic or endothermic). In one or more embodiments, the thermal dehydrogenation may be endothermic, resulting in a dehydrogenation heat loss. In some embodiments, contact of hydrogen with the oxygen-rich oxygen carrier material may be exothermic, resulting in a combustion heat gain. The reoxidation of the oxygen-depleted oxygen carrier material may be exothermic, resulting in an oxygenation heat gain. Thus, by incorporating hydrogen combustion during thermal dehydrogenation, in some embodiments, sufficient heat may be generated during the reoxidation of the oxygen-depleted oxygen carrier material to act as a heat source for the alkane-to-olefins reaction. Thus, because the heat gained throughout the process by the reoxidation of the oxygen carrier material, the combustion of hydrogen, or both, can generate the amount of heat necessary for the alkane or alkylaromatics-to-olefins reaction, embodiments of the disclosed process may enable higher alkane conversion rates while reducing or eliminating the need for fuel gas, which may be required for conventional cracking and / or dehydrogenation.

[0065] Referring now to the process embodiment shown in FIG. 2 , stream 102, or a portion of stream 102, may be sent back to fluidized bed reactor 110 via product recycle stream 105. In some embodiments, stream 102 may contain one or more unreacted alkanes or alkylaromatics. In further embodiments, the one or more unreacted alkanes or alkylaromatics may be sent from fluidized bed reactor 110 via stream 102 to a separation unit (not shown). The one or more unreacted alkanes or alkylaromatics may be separated from the remainder of the dehydrogenation effluent using a separation unit. In some embodiments, the one or more unreacted alkanes or alkylaromatics may then be transported from the separation unit and sent to fluidized bed reactor 110 via product recycle stream 105. In some embodiments, from about 10% to about 90% of the one or more unreacted alkanes or alkylaromatics may be sent to fluidized bed reactor 110 via product recycle stream 105. In other embodiments, about 20% to about 90%, about 30% to about 90%, about 40% to about 90%, about 50% to about 90%, about 60% to about 90%, about 70% to about 90%, or about 80% to about 90% of the one or more unreacted alkanes or alkylaromatics may be sent to fluidized bed reactor 110 via product recycle stream 105.

[0066] The present disclosure includes several embodiments. In a first embodiment of the present disclosure, a method for dehydrogenating hydrocarbons can include passing a hydrocarbon feed containing one or more alkanes or alkylaromatics into a fluidized bed reactor. In the fluidized bed reactor, at least 95 wt.% of the hydrocarbon feed has an atmospheric boiling point of 300°C or less. The method further includes pyrolyzing the hydrocarbon feed in the fluidized bed reactor to produce a dehydrogenated product and hydrogen. The fluidized bed reactor operates at a temperature of at least 600°C. The fluidized bed reactor does not include a 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 passing the oxygen-depleted oxygen carrier material to a regeneration unit, oxidizing the oxygen-depleted oxygen carrier material in the regeneration unit to form an oxygen-rich oxygen carrier material, burning a supplemental fuel in the regeneration unit to generate heat and increase the temperature of the oxygen carrier material, and passing the oxygen-rich oxygen carrier material to a fluidized bed reactor.

[0067] A second aspect of the present disclosure includes the first aspect, further comprising partially reducing the oxygen-rich oxygen carrier material prior to contacting the hydrogen with the oxygen-rich oxygen carrier material in the fluidized bed reactor.

[0068] A third aspect of the present disclosure includes any of the preceding aspects, wherein the fluidized bed reactor operates at a temperature of at least 600°C and less than 850°C.

[0069] A fourth aspect of the present disclosure includes any of the preceding aspects, wherein the supplemental fuel is selected from hydrogen, methane, ethane, propane, natural gas, or combinations thereof.

[0070] A fifth aspect of the present disclosure includes any of the preceding aspects, wherein all of the solid particulate material in the fluidized bed reactor is the oxygen carrier material.

[0071] A sixth aspect of the present disclosure includes any of the preceding aspects, wherein the oxygen-rich oxygen carrier material comprises 1% to 20% by weight of releasable oxygen, based on the total weight of the oxygen-rich oxygen carrier material.

[0072] A seventh aspect of the present disclosure includes any of the preceding aspects, wherein contacting the hydrogen with the oxygen-rich oxygen carrier material removes between 1% and 50% by weight of the releasable oxygen from the oxygen-rich oxygen carrier material.

[0073] An eighth embodiment of the present disclosure includes any of the preceding embodiments, wherein contacting the hydrogen with the oxygen-rich oxygen carrier material combusts more than 50% of the hydrogen.

[0074] A ninth aspect of the present disclosure includes any of the preceding aspects, wherein the oxygen carrier material includes one or more metal oxides.

[0075] A tenth aspect of the present disclosure includes any of the preceding aspects, wherein the oxygen carrier material exhibits properties of Geldart A or Geldart B.

[0076] It will be apparent to those skilled in the art that various modifications and variations can be made to the technology of the present disclosure without departing from the spirit and scope of the technology. Since combinations, subcombinations, and variations of the disclosed embodiments incorporating the spirit and substance of the technology of the present disclosure may occur to those skilled in the art, the technology should be construed as including all within the scope of the appended claims and their equivalents. Furthermore, although some aspects of the present disclosure may be identified herein as preferred or particularly advantageous, it is intended that the present disclosure is not limited to these aspects.

[0077] It should be noted that the various details described in this disclosure should not be construed as implying that these details relate to elements that are essential components of the various embodiments described in this disclosure, even if a particular element is illustrated in each of the drawings accompanying this specification. Unless specifically identified as such, features disclosed and described herein should not be construed as "essential." Contemplated embodiments of the present technology include those that include some or all of the features of the appended claims.

[0078] It should be noted that for purposes of describing and defining this disclosure, the term "about" is utilized in this disclosure to express the inherent degree of uncertainty that may result from any quantitative comparison, value, measurement, or other representation. The term "about" is also utilized in this disclosure to express the degree to which a quantitative representation may vary from the basis of description without resulting in a change in the basic functionality of the subject matter in question.

[0079] Where relevant, when a composition is described as "comprising" one or more elements, embodiments of the composition that "consist" or "consist essentially of" those one or more elements are contemplated herein.

[0080] In some embodiments, a chemical or chemical stream is described as being "fed" from one system unit or portion of a system unit to another system unit or portion of a system unit. As described herein, such a feed may include a direct feed or an indirect feed. For example, when feeding from "unit A" to "unit B," a direct feed would have no intermediate destination between unit A and unit B (i.e., directly through a pipe or other transport passageway), while an indirect feed would include one or more intermediate destinations between unit A and unit B. For example, a stream fed from unit A to unit B may pass through, without limitation, a heat exchanger, a processing device, etc.

[0081] It is understood that the compositional ranges of chemical components in a stream or reactor should, in some embodiments, be understood to contain a mixture of isomers of that component. For example, a compositional range specifying butene may include a mixture of various isomers of butene. It is understood that the examples provide compositional ranges for various streams, and that the total amount of isomers of a particular chemical composition may constitute a range.

[0082] It should be noted that one or more of the following claims utilize the term "where" or "wherein" as a transitional phrase. It should be noted that for purposes of defining the present technology, this term is introduced in the claims as an open-ended transitional phrase used to introduce the recitation of a series of features of a structure, and should be interpreted in a similar manner to the more commonly used open-ended preamble term "comprising."

[0083] It should be understood that any two quantitative values ​​assigned to a property may constitute a range for that property, and all combinations of ranges formed from all stated quantitative values ​​for a given property are contemplated in this application. When multiple ranges are given for quantitative values, these ranges may be combined to form larger ranges, which are contemplated in the embodiments described herein.

Claims

1. 1. A process for dehydrogenating hydrocarbons, comprising: passing a hydrocarbon feed comprising one or more alkanes or alkylaromatics into a fluidized bed reactor, wherein at least 95 wt.% of the hydrocarbon feed has an atmospheric boiling point of 300°C or less; pyrolyzing the hydrocarbon feed in the fluidized bed reactor, the fluidized bed reactor operating at a temperature of at least 600°C and not containing a dehydrogenation catalyst, to produce dehydrogenated products and hydrogen; contacting the hydrogen with a reducible oxygen-rich oxygen carrier material in the fluidized bed reactor to combust the hydrogen and form an oxygen-depleted oxygen carrier material; passing the oxygen-depleted oxygen carrier material to a regeneration unit; oxidizing the oxygen-depleted oxygen carrier material in the regeneration unit to form the oxygen-enriched oxygen carrier material; burning a supplemental fuel in the regeneration unit to generate heat and increase the temperature of the oxygen carrier material; and passing the oxygen-enriched oxygen carrier material to the fluidized bed reactor.

2. 10. The method of claim 1, further comprising partially reducing the oxygen-rich oxygen carrier material prior to contacting the hydrogen with the oxygen-rich oxygen carrier material in the fluidized bed reactor.

3. 3. The method of claim 1 or 2, wherein the fluidized bed reactor operates at a temperature of at least 600°C and less than 850°C.

4. The method of any one of claims 1 to 3, wherein the supplemental fuel is selected from hydrogen, methane, ethane, propane, natural gas, or combinations thereof.

5. 5. The process of any one of claims 1 to 4, wherein all of the solid particulate material in the fluidized bed reactor is oxygen carrier material.

6. 6. The method of any one of claims 1 to 5, wherein the oxygen-rich oxygen carrier material comprises 1% to 20% by weight of releasable oxygen based on the total weight of the oxygen-rich oxygen carrier material.

7. 7. The method of any one of claims 1 to 6, wherein contacting the hydrogen with the oxygen-rich oxygen carrier material removes from 1% to 50% by weight of the releasable oxygen from the oxygen-rich oxygen carrier material.

8. 8. The method of any one of claims 1 to 7, wherein contacting the hydrogen with the oxygen-rich oxygen carrier material combusts more than 50% of the hydrogen.

9. The method of any one of claims 1 to 8, wherein the oxygen carrier material comprises one or more metal oxides.

10. The method of any preceding claim, wherein the oxygen carrier material exhibits the properties of Geldart A or Geldart B.

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