Oxygen carrier materials and methods of making and using same

Abstract

According to one or more embodiments described herein, the oxygen carrier material may include a redox-active metal oxide and an alkali-containing composition. The alkali-containing composition may have the formula Na u K v Li w (Si x Al y O z ) r wherein the sum of u, v, and w can be equal to 1, the sum of x and y can be equal to 1, z can be greater than 1.5, and r can be from 0.02 to 20. Methods of making the oxygen carrier material and methods of using the oxygen carrier material to produce olefinic compounds are also described herein.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of U.S. Provisional Application No. 63 / 489,573, filed March 10, 2023, the contents of which are incorporated herein in their entirety.

[0002] FIELD OF THE INVENTION FIELD OF THE DISCLOSURE Embodiments of the present disclosure relate generally to oxygen carrier materials, and more particularly to oxygen carrier materials and methods of making oxygen carrier materials. [Background technology]

[0003] Some chemical processes utilize oxygen carrier materials. In such processes, oxygen may be cyclically delivered or "carried" through the reduction and subsequent oxidation of the oxygen carrier material. Oxygen carrier materials may be used in chemical processes that require oxygen. In such processes, the oxygen carried by the oxygen carrier material may be utilized as an oxygen source. In particular, oxygen carrier materials may be utilized in cyclic chemical processes in which oxygen may be added to and removed from the oxygen carrier material as oxygen is used throughout the process. For example, a combustion reaction may utilize oxygen from the oxygen carrier material. Summary of the Invention

[0004] There is a continuing need for oxygen carrier materials suitable for use in particular chemical processes. It may be desirable to have oxygen carrier materials that can operate to selectively carry oxygen for particular chemical reactions. For example, the oxygen carrier material may be selective for the combustion of hydrogen over the combustion of hydrocarbons. In accordance with some embodiments, it has been discovered that certain oxygen carrier compositions can possess these desirable attributes. For example, as described herein, oxygen carrier materials comprising redox-active metal oxides and certain alkali-containing compositions may have beneficial performance over conventional oxygen carrier materials.

[0005] According to one or more embodiments of the present disclosure, the oxygen carrier material may include a redox-active metal oxide and an alkali-containing composition. The alkali-containing composition may be represented by the formula Na u K v Li w (Si x Al y O z ) r where the sum of u, v, and w may be equal to 1, the sum of x and y may be equal to 1, z may be greater than 1.5, and r may be between 0.02 and 20.

[0006] According to one or more additional embodiments of the present disclosure, a method of making an oxygen carrier material may include providing a redox-active metal oxide. The method may also include impregnating the redox-active metal oxide with an aqueous solution containing one or more water-soluble alkali silicates, alkali aluminates, or alkali aluminosilicates to produce the impregnated redox-active metal oxide. The method may also include drying the impregnated redox-active metal oxide and calcining the impregnated redox-active metal oxide to produce the oxygen carrier material. The oxygen carrier material may include a redox-active metal oxide and an alkali-containing composition. The alkali-containing composition may be a compound having the formula Na u K v Li w (Si x Al y O z ) r where the sum of u, v, and w may be equal to 1, the sum of x and y may be equal to 1, z may be greater than 1.5, and r may be between 0.02 and 20.

[0007] According to one or more additional embodiments of the present disclosure, a method for producing olefinic compounds may include contacting a feed stream containing one or more hydrocarbons with an oxygen carrier material in a reactor. In the reactor, the one or more hydrocarbons may be dehydrogenated to form hydrogen and one or more olefinic compounds, and at least a portion of the hydrogen may be reacted with oxygen from the oxygen carrier material to produce water. The method may also include passing at least a portion of the oxygen carrier material to a regeneration unit and passing at least a portion of the oxygen carrier material from the regeneration unit to the reactor. The oxygen carrier material may include a redox-active metal oxide and an alkali-containing composition. The alkali-containing composition may be a compound having the formula Na u K v Li w (Si x Al y O z ) r where the sum of u, v, and w may be equal to 1, the sum of x and y may be equal to 1, z may be greater than 1.5, and r may be between 0.02 and 20.

[0008] Additional features and advantages of the present disclosure will be set forth in the detailed description that follows, and will in part become apparent to those skilled in the art from that description, or may be learned by practicing the embodiments described herein, including the detailed description, the following claims, and the accompanying drawings. [Brief explanation of the drawings]

[0009] 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] FIG. 1 is a schematic diagram of a reactor system suitable for use with an oxygen carrier material according to one or more embodiments described herein. [Figure 2] 1 is a powder X-ray diffraction pattern of an oxygen carrier material according to one or more embodiments described herein.

[0010] Additional features and advantages of the present disclosure will be set forth in the detailed description that follows, and will in part become apparent to those skilled in the art from that description, or may be learned by practicing the embodiments described herein, including the detailed description, the following claims, and the accompanying drawings.

[0011] It is to be understood that both the foregoing general description and the following detailed description are intended to describe various embodiments and provide an overview or framework for understanding the nature and features of the claimed subject matter. The accompanying drawings are included to provide a further understanding of the various embodiments, and are incorporated into and constitute a part of this specification. The drawings illustrate various embodiments described herein and, together with the description, explain the principles and operation of the claimed subject matter. DETAILED DESCRIPTION OF THE INVENTION

[0012] Specific embodiments of the present application will now be described. However, this disclosure may be embodied in different forms and should not be construed as limited to the embodiments set forth in this disclosure. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0013] Generally, the present disclosure describes various embodiments of oxygen carrier materials, embodiments of methods of making oxygen carrier materials, and embodiments of methods of using oxygen carrier materials.

[0014] According to one or more embodiments, the oxygen carrier material may comprise a redox-active metal oxide and an alkali-containing composition. As used herein, the term "redox-active metal oxide" refers to a metal oxide that can undergo reduction in the presence of a reducing agent, such as hydrogen, and oxidation in the presence of an oxidizing agent, such as oxygen or air. The alkali-containing composition generally has the formula Na u K v Li w (Si x Al y Oz ) r : (wherein u+v+w=1, x+y=1, z is greater than 1.5, and r is 0.02 to 20). Without being bound by theory, it is believed that the redox active metal oxide and the compound of the formula Na u K v Li w (Si x Al y O z ) r It is believed that combination of an alkali-containing composition having the formula (I) with an alkali-containing composition having the formula (I) can form an oxygen carrier material that can be selective for the combustion of hydrogen in the presence of hydrocarbons.

[0015] As described herein, the oxygen carrier material may comprise a redox-active metal oxide and an alkali-containing composition. In some embodiments, at least 90 wt.%, at least 95 wt.%, at least 99 wt.%, at least 99.5 wt.%, or even at least 99.9 wt.% of the oxygen carrier material comprises a combination of the redox-active metal oxide and the alkali-containing composition. In some embodiments, the oxygen carrier material may consist of the redox-active metal oxide and the alkali-containing composition.

[0016] In one or more embodiments, the ratio of the weight of redox active metal oxide to the weight of alkali-containing composition in the oxygen carrier material can be 5:1 or greater, e.g., 10:1 or greater, 15:1 or greater, 20:1 or greater, 25:1 or greater, 30:1 or greater, 35:1 or greater, 40:1 or greater, 45:1 or greater, or even 50:1 or greater. In some embodiments, the ratio of the weight of redox active metal oxide to the weight of alkali-containing composition can be from 5:1 to 95:1. For example, the ratio of the weight of the redox active metal oxide to the weight of the alkali-containing composition is from 5:1 to 90:1, e.g., from 5:1 to 80:1, from 5:1 to 70:1, from 5:1 to 60:1, from 5:1 to 50:1, from 5:1 to 40:1, from 5:1 to 30:1, from 5:1 to 20:1, from 5:1 to 10:1, from 10:1 to 95:1, from 10:1 to 90:1, from 10:1 to 100:1, from 10:1 to 105 ... 0:1~80:1, 10:1~70:1, 10:1~60:1, 10:1~50:1, 10:1~40:1, 10:1~30:1, 10:1~20:1, 20:1~95:1, 20:1~90:1, 20:1~80:1, 20:1~70:1, 20:1~60:1, 20:1~50:1, 20:1~40:1, 20:1~30 :1, 30:1~95:1, 30:1~90:1, 30:1~80:1, 30:1~70:1, 30:1~60:1, 30:1~50:1, 30:1~40:1, 40:1~95:1, 40:1~90:1, 40:1~80:1, 40:1~70:1, 40:1~60:1, 40:1~50:1, 50:1~95:1, 50 The ratio may be 5:1 to 90:1, 50:1 to 80:1, 50:1 to 70:1, 50:1 to 60:1, 60:1 to 95:1, 60:1 to 90:1, 60:1 to 80:1, 60:1 to 70:1, 70:1 to 95:1, 70:1 to 90:1, 70:1 to 80:1, 80:1 to 95:1, 80:1 to 90:1, or 90:1 to 95:1. Without being bound by theory, it is believed that a ratio of the weight of redox-active metal oxide to the weight of alkali-containing composition in the oxygen carrier material of less than 5:1 may reduce the total oxygen capacity of the oxygen carrier material because the alkali-containing composition is believed to be less redox-active. It is also believed that the alkali-containing composition may beneficially affect the selectivity of the oxygen carrier material.Furthermore, it is believed that a ratio of the weight of redox-active metal oxide to the weight of the alkali-containing composition in the oxygen carrier material greater than 5:1 balances the non-redox-active nature of the alkali-containing composition with its beneficial effect on selectivity.

[0017] As described herein, the oxygen carrier material may include a redox-active metal oxide. In one or more embodiments, the redox-active metal oxide includes 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 may be a metal oxide of an IUPAC Group 6, 7, 8, 9, 10, 11, or 12 metal. In some embodiments, the redox-active metal oxide may be an oxide of a metal selected from Fe, Mn, Cu, Ni, Co, or Ce. In some embodiments, the redox-active metal oxide may be an oxide of a metal selected from Fe and Mn. In some embodiments, the redox-active metal oxide may be Fe2O3, FeO, Fe3O4, Mn2O3, MnO, Mn3O4, MnO 2、 (Ca 1-x Sr x )MnO3, Mg6MnO8, LaSrMnO3, LaSrFeO3, FeTiO 3、 Fe2TiO5, FeTi3O 10, BaMnO3, or combinations thereof. For example, other suitable redox-active metal oxides are disclosed in "Chemical Looping Combustion: Status and Development Challenges," Energy Fuels 2020, 34, 9077-9093, "On the Attrition Evaluation of Oxygen Carriers in Chemical Looping Combustion," Fuel Processing Technology 148 (2016) 188-197, and LSFan, "Chemical Looping Systems for Fossil Energy Conversions," John Wiley & Sons (2010), which are incorporated herein by reference in their entireties.

[0018] As described herein, the oxygen carrier material has the formula Na u K v Li w (Si x Al y O z ) r (wherein u+v+w=1, x+y=1, z is greater than 1.5, and r is 0.02 to 20). Without being bound by theory, it is believed that the alkali-containing composition may have the formula Na u K v Li w (Si x Al y O z ) r and a redox-active metal oxide, resulting in improved selectivity for hydrogen combustion over hydrocarbons, as demonstrated in this example, when compared to an oxygen carrier material that does not include an alkali-containing composition. x It is thought that the amount of formation will be reduced.

[0019] In the oxygen carrier material, the alkali-containing composition may act as a surface dopant, a bulk dopant, or both. When the alkali-containing composition acts as a surface dopant, it may partially or completely coat the surface of the redox-active metal oxide. When the alkali-containing composition acts as a bulk dopant, it may be distributed throughout the interior of the redox-active metal oxide. When the alkali-containing composition acts as both a surface dopant and a bulk dopant, it may partially or completely coat the surface of the redox-active metal oxide and may be distributed throughout the interior of the redox-active metal oxide.

[0020] where u+v+w=1 indicates that the alkali-containing composition includes at least some amount of one or more of sodium, potassium, and lithium. In some embodiments, one of u, v, or w is equal to 1. In such embodiments, the alkali-containing composition may include sodium but not potassium or lithium, may include potassium but not sodium or lithium, or may include lithium but not sodium or potassium. In other embodiments, the alkali-containing composition may include sodium and potassium but not lithium, may include sodium and lithium but not potassium, may include potassium and lithium but not sodium, or the alkali-containing composition may include sodium, potassium, and lithium.

[0021] Formula Na u K v Li w (Si x Al y O z ) rwherein x + y may be equal to 1. Thus, the alkali-containing composition includes at least some amount of one or both of silicon and aluminum. In some embodiments, x may be equal to 1, and the alkali-containing composition may include silicon but not aluminum. In other embodiments, y may be equal to 1, and the alkali-containing composition may include aluminum but not silicon. In yet other embodiments, the alkali-containing composition may include both silicon and aluminum. In the formula, x and y may be equal to any number between 0 and 1, including 0 and 1, respectively, so long as the sum of x and y is equal to 1. For example, both x and y may be equal to 0.5, or x may be equal to 0.75 and y may be equal to 0.25, or x may be equal to 0.25 and y may be equal to 0.75.

[0022] The alkali-containing composition may contain oxygen. u K v Li w (Si x Al y O z ) r wherein z may be 1.5 or greater, indicating that at least some oxygen is present in the alkali-containing composition. In one or more embodiments, z may be 1.5 or greater, e.g., 2 or greater, 2.5 or greater, 3 or greater, 3.5 or greater, 4 or greater, 4.5 or greater, or even 5 or greater. In some embodiments, z may be from 1.5 to 5, e.g., from 1.5 to 4.5, from 1.5 to 4, from 1.5 to 3.5, from 1.5 to 3, from 1.5 to 2.5, from 1.5 to 2, from 2 to 5, from 2 to 4.5, from 2 to 4, from 2 to 3.5, from 2 to 3, from 2 to 2.5, from 2.5 to 5, from 2.5 to 4.5, from 2.5 to 4, from 2.5 to 3.5, from 2.5 to 3, from 3 to 5, from 3 to 4.5, from 3 to 4, from 3 to 3.5, from 3.5 to 5, from 3.5 to 4.5, from 3.5 to 4, from 4 to 5, from 4 to 4.5, or from 4.5 to 5.

[0023] In one or more embodiments, the formula Na u K v Li w (Si x Al y O z ) rIn the formula, r may be 0.02 to 20. For example, r may be 0.02 to 15, 0.02 to 10, 0.02 to 5, 0.02 to 1, 0.02 to 0.5, 0.02 to 0.1, 0.02 to 0.05, 0.05 to 20, 0.05 to 15, 0.05 to 10, 0.05 to 5, 0.05 to 1, 0.05 to 0.5, 0.05 to 0.1, or 0.1 to 20. , 0.1 to 15, 0.1 to 10, 0.1 to 5, 0.1 to 1, 0.1 to 0.5, 0.5 to 20, 0.5 to 15, 0.5 to 10, 0.5 to 5, 0.5 to 1, 1 to 20, 1 to 15, 1 to 10, 1 to 5, 5 to 20, 5 to 15, 5 to 20, 10 to 20, 10 to 15, or 15 to 20.

[0024] In one or more embodiments, the alkali-containing composition may be free of boron. In further embodiments, the alkali-containing composition may be any of NaAlO2, KAlO2, Na4SiO4, Na6Si2O7, Na2SiO3, Na2SiO5, Na6Si6O 19 , K2SiO3, K2Si2O5, or K2Si4O9.

[0025] In one or more embodiments, the oxygen carrier material can be fluidizable. In some embodiments, the oxygen carrier material can have a median particle size (D50) of 50 μm to 300 μm, e.g., 50 μm to 250 μm, 50 μm to 200 μm, 50 μm to 150 μm, 50 μm to 100 μm, 100 μm to 300 μm, 100 μm to 250 μm, 100 μm to 200 μm, 100 μm to 150 μm, 150 μm to 300 μm, 150 μm to 250 μm, 150 μm to 200 μm, 200 μm to 300 μm, 200 μm to 250 μm, or 250 μm to 300 μm.

[0026] In some embodiments, oxygen carrier materials may exhibit properties known in the industry as "Geldart A" or "Geldart B" properties. Particles 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.

[0027] Group A is understood by those skilled in the art to represent aerated powders with bubble-free fluidization; high bed expansion; slow, linear degassing rate; bubble characteristics where splitting / re-coalescing bubbles may predominate, with maximum bubble size and large wake; high levels of solids mixing and gas backmixing assuming equal U-Umf (where U is the carrier gas velocity and Umf is the minimum fluidization velocity, but typically but not necessarily measured in meters per second, m / s, i.e., excess gas velocity exists); axisymmetric slug characteristics; and no eruptions except in very shallow beds. Assuming equal cfp, the listed properties tend to improve as the average particle size decreases; or as the fraction less than 45 micrometers (μm) increases; or as the gas pressure, temperature, viscosity, and density increase. Generally, particles with small average particle size and / or low particle density (1.4 grams per cubic centimeter, g / cm) 3 They exhibit a viscosity of less than 1000 psi, are easily fluidized with smooth fluidization at low gas velocities, and may exhibit controlled foaming with small bubbles at higher gas velocities.

[0028] Group B starts to foam at Umf; shows moderate bed expansion; has rapid degassing; has no limitation on bubble size; assuming U-Umf is equal, the levels of solid mixing and gas backmixing are moderate; both axisymmetric slag and asymmetric slag; and jets only in shallow beds; and is understood by those skilled in the art as representing a "sand-like" powder. 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 appear to contribute much to the improvement of the above characteristics. Generally, most of the particles have a particle size (cfp) of 40 μm < cfp < 500 μm when the density (ρp) is 1.4 < pp < 4 g / cm 3 in the case of 4 g / cm 3 in the case of 60 μm < cfp < 500 μm, and a particle size (cfp) of 250 μm < cfp < 100 μm when the density (ρp) is 1 g / cm 3 in the case of

[0029] In one or more embodiments, a method of making an oxygen carrier material described herein may include providing a redox-active metal oxide, impregnating an aqueous solution containing one or more water-soluble alkali silicates, alkali aluminates, or alkali aluminosilicates into the redox-active metal oxide to produce an impregnated redox-active metal oxide, drying the impregnated redox-active metal oxide, and calcining the impregnated redox-active metal oxide to produce the oxygen carrier material.

[0030] Providing a redox-active metal oxide may include any conventional technique for preparing a redox-active metal oxide, including spray drying, granulation, and solid-phase synthesis followed by drying and calcining. In some embodiments, the redox-active metal oxide may be Geldart group A or group B particles before impregnation. In other embodiments, the redox-active metal oxide may not be Geldart group A or group B particles before impregnation.

[0031] As described above, a method for making an oxygen carrier material may include impregnating a redox-active metal oxide with an aqueous solution. The aqueous solution may include one or more water-soluble alkali silicates, alkali aluminates, or alkali aluminosilicates. In some embodiments, the aqueous solution may include one or more of sodium silicate, potassium silicate, lithium silicate, sodium aluminate, potassium aluminate, lithium aluminate, or combinations thereof. In one or more embodiments, the aqueous solution may have a pH greater than 7. For example, the aqueous solution may have a pH greater than 7.5, greater than 8, greater than 8.5, greater than 9, greater than 9.5, greater than 10, greater than 10.5, greater than 11, or even greater than 11.5.

[0032] In one or more embodiments, the redox active metal oxide may be impregnated by dry impregnation, also known as incipient wetness impregnation. In one or more embodiments, the redox active metal oxide may be impregnated by wet impregnation. In some embodiments, the redox active metal oxide may be impregnated with an aqueous solution two or more times.

[0033] The impregnated redox-active metal oxide may then be dried after impregnation. In some embodiments, the impregnated redox-active metal oxide may be dried under air. In one or more embodiments, the impregnated redox-active metal oxide may be dried at a temperature less than 200°C, e.g., less than 175°C, less than 150°C, less than 125°C, less than 100°C, less than 75°C, or even less than 50°C. In embodiments in which the redox-active metal oxide is impregnated with an aqueous solution more than once, the impregnated redox-active metal oxide may be dried between impregnations.

[0034] The dried, impregnated, redox-active metal oxide may then be calcined to produce the oxygen carrier material. In one or more embodiments, the dried, impregnated, redox-active metal oxide may be calcined at a temperature less than 1200° C., e.g., less than 1100° C., less than 1000° C., less than 900° C., less than 800° C., less than 700° C., less than 600° C., or even less than 500° C. In one or more embodiments, the dried, impregnated, redox-active metal oxide may be calcined under air.

[0035] According to one or more embodiments of the present disclosure, a method for producing olefinic compounds using the oxygen carrier materials described herein is provided. As used herein, the term "olefinic compound" refers to a hydrocarbon having one or more carbon-carbon double bonds, separate from the formal double bonds in aromatic compounds. For example, ethylene and styrene are olefinic compounds, while ethylbenzene is not an olefinic compound because the only double bond present in ethylbenzene is a formal double bond present as part of the aromatic structure. Referring now to FIG. 1 , a reactor system 100 that may be used with the method of the present disclosure is shown, although other reactor systems known to those skilled in the art are also contemplated herein. For example, the oxygen carrier materials of the present disclosure may be utilized in the systems and methods disclosed in WO 2020 / 046978, the teachings of which are incorporated herein by reference in their entirety.

[0036] Returning to FIG. 1 , reactor system 100 may include reactor 110 and regeneration unit 120. In one or more embodiments, reactor 110 may be a fluidized bed reactor. Feed stream 101 may be fed into reactor 110. In one or more embodiments, feed stream 101 may include one or more hydrocarbons. In one or more embodiments, the one or more hydrocarbons may include one or more of ethane, propane, butane, or ethylbenzene. According to one or more embodiments, the one or more hydrocarbons 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% ethane by weight. In additional embodiments, the one or more hydrocarbons 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% propane by weight. In additional embodiments, the one or more hydrocarbons 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% butane by weight. In additional embodiments, the one or more hydrocarbons 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% ethylbenzene by weight. In additional embodiments, the one or more hydrocarbons may comprise a total of at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or even at least 99% ethane, propane, butane, and ethylbenzene by weight.

[0037] In reactor 110, feed stream 101 may be contacted with an oxygen carrier material, and one or more hydrocarbons may be dehydrogenated to form hydrogen and one or more olefinic compounds. At least a portion of the hydrogen may react with oxygen from the oxygen carrier material to form water. Reacting the hydrogen with oxygen from the oxygen carrier material may reduce the oxygen carrier material. The dehydrogenation reaction in fluidized bed reactor 110 may be thermally driven or catalytically driven.

[0038] In one or more embodiments, the dehydrogenation reaction may utilize a dehydrogenation catalyst. The dehydrogenation catalyst may be any suitable catalyst known to those skilled in the art. For example, suitable catalysts are described in Chem. Rev. 2014, 114, 20, 10613-10653, the entire contents of which are incorporated herein by reference, and U.S. Patent No. 8,669,406, the entire contents of which are incorporated herein by reference. Alternatively, no catalyst may be utilized to carry out the dehydrogenation reaction.

[0039] The reduced oxygen carrier material may need to be reoxidized before being used again in reactor 110. The reduced oxygen carrier material may be sent from reactor 110 to regeneration unit 120 via stream 103. In regeneration unit 120, the reduced oxygen carrier material may be reoxidized. In some embodiments, the oxygen carrier material is reoxidized by exposure to an oxygen-containing gas, such as air or oxygen. The reoxidized oxygen carrier material may then be returned from regeneration unit 120 to reactor 110 via stream 104. Thus, the oxygen carrier material may be looped or circulated through reactor system 100. In some embodiments, the reoxidized oxygen carrier material may be partially reduced before being sent to reactor 110.

[0040] The one or more olefinic compounds produced in reactor 110 may exit reactor 110 via product stream 102. In one or more embodiments, the olefinic compounds may include one or more of ethylene, propylene, butylene, or styrene. The term butylene includes any isomer of butylene, such as α-butylene, cis-β-butylene, trans-β-butylene, and isobutylene. In some embodiments, the olefin-containing effluent may include at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, or even at least 60 wt% ethylene. In additional embodiments, the olefin-containing effluent may include at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, or even at least 60 wt% propylene. In additional embodiments, the olefin-containing effluent may include at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, or even at least 60 wt% butylene. In additional embodiments, the olefin-containing effluent may comprise at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, or even at least 60 wt% styrene. In additional embodiments, the olefin-containing effluent may comprise at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, or even at least 60 wt% of the sum of one or more of ethylene, propylene, butylene, and styrene. The product stream 102 may further comprise unreacted components of the feed stream and other reaction products that are not considered olefinic compounds. The olefinic compounds can be separated from the unreacted components in a subsequent separation step. [Example]

[0041] Various embodiments of the present disclosure will be further clarified by the following examples, which are illustrative in nature and should not be construed as limiting the subject matter of the present disclosure.

[0042] Table 1 - Sample preparation Comparative Example A was a non-redox active inert quartz chip used as received. Comparative Example B was calcium manganese oxide (CaMnO), Comparative Example C was manganese oxide (MnO), Comparative Example D was copper oxide (CuO), Comparative Example E was cerium oxide (CeO), and Comparative Example F was iron oxide (FeO). Comparative Examples A-F were all commercially produced and used as received.

[0043] Comparative Examples C1-C4 were prepared by impregnating Comparative Example D with an aqueous solution of sodium nitrate. The impregnated material was dried at a temperature below 200°C and subsequently calcined in air at below 1000°C for 6 hours. The resulting compositions of the comparative examples are tabulated in Table 2.

[0044] Comparative Examples C5-C6 were prepared by impregnating Comparative Example E with SiO2 and calcining the mixture in air at a temperature below 1000° C. The resulting compositions of the comparative examples are tabulated in Table 3.

[0045] Samples 1-3 were prepared by impregnating Comparative Example B. First, commercially available sodium aluminate (#13404) from Sigma Aldrich was dissolved in water to form an impregnation solution. The impregnation solution was then added to a given amount of Comparative Example B to form an impregnated material. The impregnated material was then dried at a temperature below 200°C and subsequently calcined in air at below 1000°C for 6 hours. The compositions of the resulting samples are listed in Table 1. Additionally, Figure 1 shows the powder X-ray diffraction patterns of Sample 1 and Sample 3, with Sample 3 having a higher sodium aluminate loading.

[0046] Samples 4 to 7 were prepared by impregnating Comparative Example B. First, a potassium silicate solution was commercially available from Zaclon (Zacsil 30 or Zacsil 865) and used as the impregnation solution. A given amount of the impregnation solution was added to a given amount of Comparative Example B to form an impregnated material. The impregnated material was then dried at a temperature below 200°C and subsequently calcined in air at below 1000°C for 6 hours. The compositions of the resulting samples are listed in Table 1.

[0047] Samples 8-10 were prepared by impregnating Comparative Example B. First, a sodium silicate solution was commercially obtained from Sigma Aldrich (#338443) and used as the impregnation solution. The impregnation solution was added to a given amount of Comparative Example B to form the impregnated material. The impregnated material was dried at a temperature below 200°C and subsequently calcined in air at below 1000°C for 6 hours. The compositions of the resulting samples are listed in Table 1.

[0048] Samples 11-13 were prepared by impregnating Comparative Example B. First, sodium silicate and sodium aluminate were commercially obtained and combined to form an aqueous impregnation solution. The impregnation solution was then added to a given amount of Comparative Example B to form the impregnated material. The impregnated material was dried at a temperature below 200°C and subsequently calcined in air at below 1000°C for 6 hours. The compositions of the resulting samples are listed in Table 1.

[0049] Samples 14-17 were prepared by impregnating Comparative Example C. First, a commercially available sodium silicate solution was used as the impregnation solution. The impregnation solution was then added to a given amount of Comparative Example C to form the impregnated material. The impregnated material was dried at a temperature below 200°C and subsequently calcined in air at below 1000°C for 6 hours. The compositions of the resulting samples are listed in Table 2.

[0050] Samples 18-19 were prepared by impregnating Comparative Example C. First, a sodium silicate solution and sodium hydroxide were commercially obtained and combined to form an aqueous impregnation solution. The impregnation solution was then added to a given amount of Comparative Example C to form the impregnated material. The impregnated material was dried at a temperature below 200°C and subsequently calcined in air at below 1000°C for 6 hours. The compositions of the resulting samples are listed in Table 2.

[0051] Samples 20-22 were prepared by impregnating Comparative Example D. First, a potassium silicate solution was obtained commercially from Zaclon (Zacsil 30) and combined with potassium hydroxide to form an impregnation solution. The impregnation solution was then added to a given amount of Comparative Example D to form the impregnated material. The impregnated material was dried at a temperature below 200°C and subsequently calcined in air at below 1000°C for 6 hours. The compositions of the resulting samples are shown in Table 2.

[0052] Samples 23-25 ​​were prepared by impregnating Comparative Example C. First, commercially available sodium aluminate was dissolved in water to form an impregnation solution. Then, the impregnation solution was added to a given amount of Comparative Example C to form the impregnated material. The impregnated material was dried at a temperature below 200°C and then calcined in air at below 1000°C for 6 hours. The compositions of the resulting samples are listed in Table 2.

[0053] Sample 26 was prepared by impregnating Comparative Example D. First, a commercially available sodium silicate solution was used as the impregnation solution. The impregnation solution was then added to a given amount of Comparative Example E to form an impregnated material. The impregnated material was dried at a temperature below 200°C and then calcined in air at below 1000°C for 6 hours. The composition of the resulting sample is listed in Table 3.

[0054] Sample 27 was prepared by impregnating Comparative Example E. First, a commercially available sodium silicate solution was used as the impregnation solution. The impregnation solution was then added to a given amount of Comparative Example E to form an impregnated material. The impregnated material was dried at a temperature below 200°C and then calcined in air at below 1000°C for 6 hours. The composition of the resulting sample is listed in Table 4.

[0055] Samples 28-30 were prepared by impregnating Comparative Example F. First, a commercially available sodium silicate solution was used as the impregnation solution. The impregnation solution was then added to a given amount of Comparative Example E to form the impregnated material. The impregnated material was dried at a temperature below 200°C and subsequently calcined in air at below 1000°C for 6 hours. The compositions of the resulting samples are listed in Table 5.

[0056] Example 2 - Ethane dehydrogenation performance Testing of oxygen carrier materials was performed in a fixed-bed laboratory reactor. A 0.5 g portion of the sample was placed in a 0.5-inch OD quartz sphere connected to a 6.5 mm OD quartz tube. The sample bed was supported on a layer of quartz wool pills and 0.5-1.0 mm quartz chips. The empty space in the quartz sphere above the sample bed was filled with 0.5-1.0 mm quartz chips. The reactor was placed in a clamshell furnace, and 50 sccm of helium was started to flow through the reactor tube. The reactor was then heated from room temperature to 780 °C under a 40 standard cubic centimeter (sccm) air flow. The oxygen carrier material was subjected to a sequence of several cycles, each cycle comprising ethane dehydrogenation (reduction) and air regeneration (oxidation), with an inert nitrogen purge, if present, between the reduction and oxidation pulses. The ethane dehydrogenation step lasted for 7 hours. -1 The experiments were carried out at a weight hourly space velocity (WHSV) of 1000 kJ / s. Specifically, 52.72 sccm of a gas mixture containing 90 mol% ethane and 10 mol% helium was fed through the reactor for 60 seconds while the reactor was held at 780°C. Analysis of the product gas composition was carried out 30 seconds after the dehydrogenation reaction pulse. During the air regeneration step, 40 sccm of air was fed through the reactor for 10 minutes. Between each ethane dehydrogenation step and the air regeneration step, the reactor tube was purged with 40 sccm of nitrogen for 2 minutes. The product gas composition was analyzed using a Siemens Maxim Process Gas Chromatograph. For each oxygen carrier material, multiple repeated reduction-oxidation cycles were carried out to determine the average ethane conversion, ethylene selectivity, and CO2. x Selectivities and hydrogen:ethylene ratios are reported.

[0057] [Table 1]

[0058] As shown in Table 1, the presence of an oxygen carrier (Comparative Example B) improves ethane conversion and the hydrogen-to-ethylene ratio when compared to the reaction without an oxygen carrier (Comparative Example A). However, the oxygen carrier without a promoter (Comparative Example B) is not selective for the combustion of hydrogen over the combustion of hydrocarbons in the reactor, resulting in less CO than any of the samples with a promoter present (Samples 1-13). x The selectivity was significantly higher, indicating that combustion of hydrocarbons with oxygen from the oxygen carrier occurred at a higher rate relative to the unpromoted oxygen carrier.

[0059] [Table 2]

[0060] As shown in Table 2, the samples containing promoters, Comparative Examples C1-C6 and Samples 14-25, all had significantly lower CO values ​​than the sample without promoter, Comparative Example C. x Table 2 also shows the selectivity of the Na u K v Li w (Si x Al y O z ) r The samples containing the accelerator (e.g., samples 14 to 25) were treated with the formula Na u K v Li w (Si x Al y O z ) r Compared to Comparative Examples C1-C7, which have promoters without CO x It is also shown that the catalyst had one or more of improved selectivity or improved hydrogen to ethylene ratio.

[0061] [Table 3]

[0062] As shown in Table 3, samples containing promoters (e.g., Sample 26) had significantly higher C2H4 selectivity and significantly lower CO2 selectivity than Comparative Example D, which did not contain a promoter. x It had selectivity.

[0063] [Table 4]

[0064] As shown in Table 4, samples containing promoters (e.g., Sample 27) had significantly higher C2H4 selectivity and significantly lower CO2 selectivity than Comparative Example E, which did not contain a promoter. x It had selectivity.

[0065] [Table 5]

[0066] As shown in Table 5, samples containing a promoter (e.g., Samples 29-30) had a higher hydrogen to ethylene ratio and CO2 when compared to Comparative Example D, which contained the same oxygen carrier but no promoter. x The selectivity was significantly improved.

[0067] Example 3 - Powder X-ray diffraction patterns of sample oxygen carrier materials Figure 2 shows the powder X-ray diffraction patterns of Sample 1 and Sample 3. As shown in Figure 2, the peaks associated with sodium aluminate are only detectable at higher loadings than Sample 3. The presence of the sodium aluminate peak in the pattern of Sample 3 indicates that sodium aluminate as a promoter was successfully impregnated into the oxygen carrier. The low promoter level in Sample 1 means that even though the sodium aluminate peak is not visible, it can be inferred from the peak of Sample 3 that Sample 1 was also successfully impregnated into the oxygen carrier with sodium aluminate.

[0068] According to a first aspect of the present disclosure, an oxygen carrier material can include a redox-active metal oxide and an alkali-containing composition. The alkali-containing composition can be represented by the formula Na u K vLi w (Si x Al y O z ) r where the sum of u, v, and w may be equal to 1, the sum of x and y may be equal to 1, z may be greater than 1.5, and r may be between 0.02 and 20.

[0069] A second aspect of the present disclosure may include the first aspect, wherein the weight ratio of the redox-active metal oxide to the alkali-containing composition is 5:1 or greater.

[0070] A third aspect of the present disclosure may include any preceding aspect or combination of aspects, wherein the redox active metal oxide is an oxide of a metal selected from Fe, Mn, Cu, Ni, Co, or Ce.

[0071] A fourth aspect of the present disclosure can include any preceding aspect or combination of aspects, wherein the redox active metal oxide is an oxide of a metal selected from Fe and Mn.

[0072] A fifth aspect of the present disclosure is a method for preparing a redox active metal oxide, comprising the steps of: preparing a redox active metal oxide from Fe2O3, FeO, Mn2O3, MnO, CaMnO3, Mg6MnO8, LaSrMnO3, LaSrFeO3, FeTiO3, Fe2TiO5, Fe3Ti3O 10 or BaMnO3.

[0073] A sixth aspect of the present disclosure may include any of the preceding aspects or combinations of aspects, wherein r is 0.1-10.

[0074] A seventh aspect of the present disclosure may include any preceding aspect or combination of aspects, wherein x or y is equal to 1.

[0075] An eighth aspect of the present disclosure may include any preceding aspect or combination of aspects, wherein one of u, v, or w is equal to 1.

[0076] A ninth aspect of the present disclosure can include any preceding aspect or combination of aspects, wherein the alkali-containing composition does not include boron.

[0077] A tenth aspect of the present disclosure is a method for preparing an alkali-containing composition comprising the steps of: NaAlO2, KAlO2, Na4SiO4, Na6Si2O7, Na2SiO3, Na2SiO5, Na6Si6O 19 , K2SiO3, K2Si2O5, or K2Si4O9, and may include any of the foregoing aspects or combinations of aspects.

[0078] An eleventh aspect of the present disclosure can include any preceding aspect or combination of aspects, wherein at least 95% by weight of the oxygen carrier material comprises a combination of a redox-active metal oxide and an alkali-containing composition.

[0079] In a twelfth aspect of the present disclosure, a method of making an oxygen carrier material may include providing a redox-active metal oxide, impregnating the redox-active metal oxide with an aqueous solution containing one or more water-soluble alkali silicates, alkali aluminates, or alkali aluminosilicates to form an impregnated redox-active metal oxide, drying the impregnated redox-active metal oxide, and calcining the impregnated redox-active metal oxide to form an oxygen carrier material. The oxygen carrier material may include a redox-active metal oxide and an alkali-containing composition. The alkali-containing composition may be a redox-active metal oxide having a formula Na u K v Li w (Si x Al y O z ) r where the sum of u, v, and w may be equal to 1, the sum of x and y may be equal to 1, z may be greater than 1.5, and r may be between 0.02 and 20.

[0080] A thirteenth aspect of the present disclosure may include the twelfth aspect, wherein the aqueous solution has a pH greater than 7.

[0081] In a fourteenth aspect of the present disclosure, a method for producing olefinic compounds may include contacting a feed stream containing one or more hydrocarbons with an oxygen carrier material in a reactor. In the reactor, the one or more hydrocarbons may be dehydrogenated to form hydrogen and one or more olefinic compounds, and at least a portion of the hydrogen may be reacted with oxygen from the oxygen carrier material to produce water. The method may also include passing at least a portion of the oxygen carrier material to a regeneration unit and passing at least a portion of the oxygen carrier material from the regeneration unit to the reactor. The oxygen carrier material may include a redox-active metal oxide and an alkali-containing composition. The alkali-containing composition may be a compound having the formula Na u K v Li w (Si x Al y O z ) r where the sum of u, v, and w may be equal to 1, the sum of x and y may be equal to 1, z may be greater than 1.5, and r may be between 0.02 and 20.

[0082] A fifteenth aspect of the present disclosure may include the fourteenth aspect, wherein the one or more hydrocarbons include ethane and the one or more olefinic compounds include ethylene.

[0083] 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.

[0084] 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 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 technology include those that include some or all of the features of the appended claims.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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 art, this term is introduced in the claims as an open-ended transitional phrase used to introduce the recitation of a series of features of structure, and should be interpreted in a similar manner to the more commonly used open-ended preamble term "comprising."

[0089] 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 the 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.

[0090] As understood in the context of the term as used herein, the term "passing" can include passing a substance directly between two portions of the disclosed system, and in some other instances, can mean passing a substance indirectly between two portions of the disclosed system. For example, indirect passing can include passing the specified substance through an intermediate operating unit, valve, sensor, etc.

Claims

1. 1. An oxygen carrier material comprising: a redox active metal oxide; Formula Na ｕ K ｖ Li ｗ (Si ｘ Al ｙ O ｚ ) ｒ (wherein, u+v+w=1, x+y=1, z is greater than 1.5, r is 0.02 to 20. an alkali-containing composition having Including, The oxygen carrier material, wherein the weight ratio of the redox active metal oxide to the alkali-containing composition is 5:1 or greater.

2. 2. The oxygen carrier material of claim 1, wherein the redox active metal oxide is an oxide of a metal selected from Fe, Mn, Cu, Ni, Co, or Ce.

3. 3. The oxygen carrier material according to claim 1 or 2, wherein the redox active metal oxide is an oxide of a metal selected from Fe and Mn.

4. The redox active metal oxide is Fe ２ O ３ , FeO, Mn ２ O ３ , MnO, CaMnO ３ , Mg ６ MnO ８ , LaSrMnO ３ , LaSrFeO ３ , FeTiO ３ , Fe ２ TiO ５ , Fe ３ Ti ３ O １０ , or BaMnO ３ 2. The oxygen carrier material of claim 1, selected from:

5. 5. The oxygen carrier material according to claim 1, wherein r is 0.1 to 10.

6. 6. The oxygen carrier material according to claim 1, wherein one of x or y is equal to 1.

7. The oxygen carrier material of any of claims 1 to 6, wherein one of u, v, or w is equal to 1.

8. The oxygen carrier material of any of claims 1 to 7, wherein the alkali-containing composition does not contain boron.

9. The alkali-containing composition is NaAlO ２ , KAlO ２ , Na ４ SiO ４ , Na ６ Si ２ O ７ , Na ２ SiO ３ , Na ２ SiO ５ , Na ６ Si ６ O １９ , K. ２ SiO ３ , K. ２ Si ２ O ５ , or K ２ Si ４ O ９ 10. The oxygen carrier material of claim 1 selected from the group consisting of:

10. 10. The oxygen carrier material of any of claims 1 to 9, wherein at least 95% by weight of the oxygen carrier material comprises the redox active metal oxide in combination with the alkali-containing composition.

11. 1. A method of making an oxygen carrier material, comprising: providing a redox active metal oxide; impregnating the redox-active metal oxide with an aqueous solution comprising one or more water-soluble alkali silicates, alkali aluminates, or alkali aluminosilicates to form an impregnated redox-active metal oxide; drying the impregnated redox active metal oxide; calcining the impregnated redox active metal oxide to form the oxygen carrier material; Including, the oxygen carrier material a redox active metal oxide; Formula Na ｕ K ｖ Li ｗ (Si ｘ Al ｙ O ｚ ) ｒ (In the formula, u+v+w=1, x+y=1, z is greater than 1.5, r is 0.02 to 20. an alkali-containing composition having Including, The method wherein the weight ratio of the redox active metal oxide to the alkali-containing composition is 5:1 or greater.

12. 12. The method of claim 11, wherein the aqueous solution has a pH greater than 7.

13. 1. A process for producing an olefin compound, comprising: contacting a feed stream comprising one or more hydrocarbons with an oxygen carrier material in a reactor, the one or more hydrocarbons are dehydrogenated to form hydrogen and one or more olefinic compounds; contacting, wherein at least a portion of the hydrogen reacts with oxygen from the oxygen carrier material to produce water; directing at least a portion of the oxygen carrier material to a regeneration unit; Passing at least a portion of the oxygen carrier material from the regeneration unit to the reactor; Including, the oxygen carrier material a redox active metal oxide; Formula Na ｕ K ｖ Li ｗ (Si ｘ Al ｙ O ｚ ) ｒ (In the formula, u+v+w=1, x+y=1, z is greater than 1.5, r is 0.02 to 20. an alkali-containing composition having A method comprising:

14. 14. The method of claim 13, wherein the one or more hydrocarbons comprise ethane and the one or more olefinic compounds comprise ethylene.

Images