Oxygen carrier materials and methods of making and using same

Abstract

According to one or more embodiments described herein, an oxygen carrier material may comprise a redox active metal oxide and an alkali metal-containing composition. The alkali metal containing composition may have the formula NauKvLiw (SixAlyOz) r. In the formula, the sum of u, v, and w may be 1, the sum of x and y may be 1, z may be greater than 1.5, and r may be 0.02 to 20. Also described herein are methods of making oxygen carrier materials and methods of producing olefin compounds using oxygen carrier materials.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 489,573, filed on March 10, 2023, the contents of which are incorporated herein in their entirety. Technical Field

[0003] Embodiments of the present disclosure relate generally to oxygen carrier materials, and in particular, to oxygen carrier materials and methods of making oxygen carrier materials. Background Art

[0004] Some chemical processes utilize oxygen carrier materials. In such processes, oxygen can be delivered or "carried" in a cycle via the reduction and subsequent oxidation of the oxygen carrier material. Oxygen carrier materials can be used in chemical processes that require oxygen. In such processes, the oxygen carried by the oxygen carrier material can serve as an oxygen source. In particular, oxygen carrier materials can be used in cyclic chemical processes, where oxygen can be added to and removed from the oxygen carrier material as the oxygen carrier material is used throughout the process. For example, combustion reactions can utilize oxygen from the oxygen carrier material. Summary of the Invention

[0005] There is a continuing need for oxygen carrier materials suitable for use with specific chemical processes. It may be desirable to have oxygen carrier materials that are operable to selectively carry oxygen for a specific chemical reaction. For example, an oxygen carrier material may be selective for the combustion of hydrogen but not for the combustion of hydrocarbons. It has been discovered that, according to some embodiments, specific oxygen-carrying compositions can possess these desirable properties. For example, and as described herein, oxygen carrier materials comprising redox-active metal oxides and specific alkali metal-containing compositions can have beneficial properties over conventional oxygen carrier materials.

[0006] According to one or more embodiments of the present disclosure, the oxygen support material may include a redox active metal oxide and an alkali metal-containing composition. The alkali metal-containing composition may have the formula Na u K v Li w (Si x Al y O z ) r In the formula, 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 0.02 to 20.

[0007] According to one or more additional embodiments of the present disclosure, a method of preparing an oxygen support material may include providing a redox-active metal oxide. The method may further include impregnating the redox-active metal oxide with an aqueous solution comprising one or more water-soluble alkali metal silicates, alkali metal aluminates, or alkali metal aluminosilicates to produce an impregnated redox-active metal oxide; the method may further include drying the impregnated redox-active metal oxide and calcining the impregnated redox-active metal oxide to produce the oxygen support material. The oxygen support material may include a redox-active metal oxide and an alkali metal-containing composition. The alkali metal-containing composition may have the formula Na u K v Li w (Si x Al y O z ) r In the formula, 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 0.02 to 20.

[0008] According to one or more additional embodiments of the present disclosure, a method for producing olefin compounds may include contacting a feed stream comprising 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 olefin compounds, and at least a portion of the hydrogen may react with oxygen from the oxygen carrier material to produce water. The method may also include transferring at least a portion of the oxygen carrier material to a regeneration unit and transferring 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 metal-containing composition. The alkali metal-containing composition may have the formula Na u K v Li w (Si x Al y O z ) r In the formula, 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 0.02 to 20.

[0009] Additional features and advantages of the present disclosure will be set forth in the detailed description which follows, and in part will be apparent to those skilled in the art from that description or learned by practicing the embodiments described herein, including the following detailed description, claims, and drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] The following detailed description of certain embodiments of the present disclosure may be best understood when taken in conjunction with the following drawings, in which like reference numerals indicate like structures, and in which:

[0011] Figure 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; and

[0012] Figure 2 is a powder x-ray diffraction pattern of an oxygen carrier material according to one or more embodiments described herein.

[0013] Additional features and advantages of the present disclosure will be set forth in the detailed description which follows, and in part will be apparent to those skilled in the art from that description or learned by practicing the embodiments described herein, including the following detailed description, claims, and drawings.

[0014] It should be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character 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 the various embodiments described herein and, together with the description, explain the principles and operation of the claimed subject matter. DETAILED DESCRIPTION

[0015] The specific embodiments of the present application will now be described. However, the present disclosure can be implemented in different forms and should not be construed as being limited to the embodiments set forth in the present disclosure. On the contrary, these embodiments are provided so that the present disclosure will be thorough and complete, and the scope of this theme will be fully conveyed to those skilled in the art.

[0016] Generally, various embodiments of oxygen carrier materials, embodiments of methods of making oxygen carrier materials, and embodiments of methods of using oxygen carrier materials are described in this disclosure.

[0017] According to one or more embodiments, the oxygen carrier material may include a redox-active metal oxide and an alkali metal-containing composition. As used herein, the term "redox-active metal oxide" refers to a metal oxide that can be reduced in the presence of a reducing agent (e.g., hydrogen) and oxidized in the presence of an oxidizing agent (e.g., oxygen or air). The alkali metal-containing composition may generally have the formula Na u K v Li w (Si x Al y O z ) rwherein u+v+w=1, x+y=1, z is greater than 1.5, and r is from 0.02 to 20. Without being bound by theory, it is believed that the redox active metal oxide and the metal oxide having the formula Na u K v Li w (Si x Al y O z ) r The combination of the alkali metal-containing composition can form an oxygen carrier material that can be selective for the combustion of hydrogen in the presence of hydrocarbons.

[0018] As described herein, the oxygen support material can include a redox-active metal oxide and an alkali-containing composition. In some embodiments, at least 90%, at least 95%, at least 99%, at least 99.5%, or even at least 99.9% by weight of the oxygen support material comprises a combination of a redox-active metal oxide and an alkali-containing composition. In some embodiments, the oxygen support material can consist of a redox-active metal oxide and an alkali-containing composition.

[0019] In one or more embodiments, the ratio of the weight of the redox-active metal oxide in the oxygen support material to the weight of the alkali metal-containing composition can be greater than, or equal to, 5: 1, such as greater than, or equal to, 10: 1, greater than, or equal to, 15: 1, greater than, or equal to, 20: 1, greater than, or equal to, 25: 1, greater than, or equal to, 30: 1, greater than, or equal to, 35: 1, greater than, or equal to, 40: 1, greater than, or equal to, 45: 1, or even greater than, or equal to, 50: 1. In some embodiments, the ratio of the weight of the redox-active metal oxide to the weight of the alkali metal-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 metal-containing composition can be 5:1 to 90:1, such as 5:1 to 80:1, 5:1 to 70:1, 5:1 to 60:1, 5:1 to 50:1, 5:1 to 40:1, 5:1 to 30:1, 5:1 to 20:1, 5:1 to 10:1, 10:1 to 95:1, 10:1 to 90:1, 10:1 to 100:1. to 80:1, 10:1 to 70:1, 10:1 to 60:1, 10:1 to 50:1, 10:1 to 40:1, 10:1 to 30:1, 10:1 to 20:1, 20:1 to 95:1, 20:1 to 90:1, 20:1 to 80:1, 20:1 to 70:1, 20:1 to 60:1, 20:1 to 50:1, 20:1 to 40:1, 20:1 to 3 0:1, 30:1 to 95:1, 30:1 to 90:1, 30:1 to 80:1, 30:1 to 70:1, 30:1 to 60:1, 30:1 to 50:1, 30:1 to 40:1, 40:1 to 95:1, 40:1 to 90:1, 40:1 to 80:1, 40:1 to 70:1, 40:1 to 60:1, 40:1 to 50:1, 50:1 to 95:1 1, 50:1 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 the redox-active metal oxide to the weight of the alkali metal-containing composition in the oxygen support material of less than 5:1 can reduce the total oxygen capacity of the oxygen support material because the alkali metal-containing composition is not believed to be redox-active. It is also believed that the alkali metal-containing composition can beneficially affect the selectivity of the oxygen support material. It is also believed that a ratio of the weight of redox-active metal oxide to the weight of the alkali metal-containing composition in the oxygen support material of greater than 5:1 can balance the non-redox-active nature of the alkali metal-containing composition with its beneficial effect on selectivity.

[0020] 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 a binary, ternary or other mixed metal oxide that can be reduced in the presence of a reducing agent (e.g., hydrogen) and oxidized in the presence of an oxidizing agent (e.g., oxygen or air). In some embodiments, the redox active metal oxide may be a metal 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 selected from Fe2O3, FeO, Fe3O4, Mn2O3, MnO, Mn3O4, MnO2, (Ca 1-x Sr x )MnO3, Mg6MnO8, LaSrMnO3, LaSrFeO3, FeTiO3, Fe2TiO5, FeTi3O 10 , BaMnO 3 or a combination 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), the entire contents of which are incorporated herein by reference.

[0021] As described herein, the oxygen carrier material may include an oxygen carrier having 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 from 0.02 to 20. Without being bound by theory, it is believed that compared to oxygen carrier materials that do not include alkali metal-containing compositions, the oxygen carrier materials comprising the formula Nau K v Li w (Si x Al y O z ) r The composition of an alkali metal and a redox-active metal oxide oxygen support material has an improved selectivity for combustion of hydrogen relative to hydrocarbons, resulting in lower amounts of CO x Formed as shown in the embodiments of the present invention.

[0022] In the oxygen carrier material, the alkali metal-containing composition can act as a surface dopant, a bulk dopant, or both. If the alkali metal-containing composition acts as a surface dopant, it can partially or completely coat the surface of the redox-active metal oxide. If the alkali metal-containing composition acts as a bulk dopant, the alkali metal-containing composition can be distributed throughout the interior of the redox-active metal oxide. If the alkali metal-containing composition acts as both a surface dopant and a bulk dopant, the alkali metal-containing composition can partially or completely coat the surface of the redox-active metal oxide and can also be distributed throughout the interior of the redox-active metal oxide.

[0023] In this formula, u + v + w = ​​1 indicates that the alkali metal-containing composition contains 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 metal-containing composition may contain sodium but not potassium or lithium, contain potassium but not sodium or lithium, or contain lithium but not sodium or potassium. In other embodiments, the alkali metal-containing composition may contain sodium and potassium but not lithium, contain sodium and lithium but not potassium, contain potassium and lithium but not sodium, or contain sodium, potassium, and lithium.

[0024] In the formula Na u K v Li w (Si x Al y O z ) rIn this formula, x + y can be equal to 1. Thus, the alkali-containing composition contains at least some amount of one or both of silicon and aluminum. In some embodiments, x can be equal to 1, and the alkali-containing composition can contain silicon but not aluminum. In other embodiments, y can be equal to 1, and the alkali-containing composition can contain aluminum but not silicon. In more embodiments, the alkali-containing composition can contain both silicon and aluminum. In this formula, x and y can each be equal to any number from 0 to 1, inclusive, as long as the sum of x and y is equal to 1. For example, both x and y can be equal to 0.5, x can be equal to 0.75 and y can be equal to 0.25, or x can be equal to 0.25 and y can be equal to 0.75.

[0025] The base-containing component may contain oxygen. u K v Li w (Si x Al y O z ) r In the embodiment of the present invention, z can be greater than or equal to 1.5, indicating that at least some amount of oxygen is present in the alkali metal-containing composition. In one or more embodiments, z can be greater than or equal to 1.5, such as greater than or equal to 2, greater than or equal to 2.5, greater than or equal to 3, greater than or equal to 3.5, greater than or equal to 4, greater than or equal to 4.5, or even greater than or equal to 5. In some embodiments, z can be from 1.5 to 5, such as from 1.5 to 4.5, 1.5 to 4, 1.5 to 3.5, 1.5 to 3, 1.5 to 2.5, 1.5 to 2, 2 to 5, 2 to 4.5, 2 to 4, 2 to 3.5, 2 to 3, 2 to 2.5, 2.5 to 5, 2.5 to 4.5, 2.5 to 4, 2.5 to 3.5, 2.5 to 3, 3 to 5, 3 to 4.5, 3 to 4, 3 to 3.5, 3.5 to 5, 3.5 to 4.5, 3.5 to 4, 4 to 5, 4 to 4.5, or 4.5 to 5.

[0026] In one or more embodiments, the formula Na u K v Li w (Si x Al y O z ) rThe r in can be from 0.02 to 20. For example, r can 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, 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.

[0027] In one or more embodiments, the alkali metal-containing composition may be free of boron. In other embodiments, the alkali metal-containing composition may be selected from the group consisting of: NaAlO2, KAlO2, Na4SiO4, Na6Si2O7, Na2SiO3, Na2SiO5, Na6Si6O 19 , K2SiO3, K2Si2O5 or K2Si4O9.

[0028] In one or more embodiments, the oxygen carrier material may be fluidizable. In some embodiments, the oxygen carrier material may have a diameter of 50 μm to 300 μm, such as 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

[0029] A median particle size (D50) of 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.

[0030] In some embodiments, the oxygen carrier material can exhibit properties known industrially as “Geldart A” or “Geldart B” characteristics. According to D. Geldart, Gas Fluidization Technology, John Wiley & Sons (New York, 1986), pages 34 - 37; and D. Geldart, “Types of Gas Fluidization”, Powder Technol. 7 (1973) 285 - 292, which are hereby incorporated by reference in their entirety, particles can be classified as “Group A” or “Group B”.

[0031] Group A is understood by those skilled in the art to represent an aeratable powder, having a bubble - free range of fluidization; high bed expansion; slow and linear rate of degassing; bubble characteristics, which may include the advantage of splitting / re - coalescing bubbles, having a maximum bubble size and a large wake; a high level of solid mixing and gas back - mixing, assuming U - umf is equal (U is the velocity of the carrier gas, and Umf is the minimum fluidization velocity, typically but not necessarily measured in meters per second (m / s), i.e., there is an excessive gas velocity); axisymmetric slug characteristics; and no spouting except in very shallow beds. The listed characteristics tend to improve with decreasing mean particle size, assuming cfp is equal; or with increasing proportion of <45 micrometers (μm); or with increasing gas pressure, temperature, viscosity, and density. Generally, the particles can exhibit a small mean particle size and / or a low particle density (<1.4 grams per cubic centimeter, g / cm 3 ); are easily fluidized, where smooth fluidization occurs at low gas velocities; and can exhibit controlled bubbling with small bubbles at higher gas velocities.

[0032] Group B is understood by those skilled in the art to represent “sand - like” powders, which start to bubble at Umf; which exhibit moderate bed expansion; rapid degassing; no limitation on bubble size; a moderate level of solid mixing and gas back - mixing, assuming U - umf is equal; both axisymmetric and asymmetric slugs; and spouting only in shallow beds. These characteristics tend to improve with decreasing mean particle size, but the particle size distribution and certain uncertainties in the gas, pressure, temperature, viscosity, or density seem to have little effect on improving these characteristics. Generally, when the density (pp) is 1.4 < pp < 4 g / cm 3 most of the particle sizes (cfp) are 40 μm < cfp < 500 μm, and preferably, when the density (pp) is < 4 g / cm 3 most of the particle sizes are 60 μm < cfp < 500 μm, and when the density (pp) is 1 g / cm 3When the particle size of most particles is 250 μm <cfp<100μm。

[0033] In one or more embodiments, methods of preparing an oxygen support material as described herein can include providing a redox active metal oxide, impregnating the redox active metal oxide with an aqueous solution comprising one or more water-soluble alkali metal silicates, alkali metal aluminates, or alkali metal aluminosilicates 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 support material.

[0034] Providing the redox-active metal oxide can include any conventional technique for preparing redox-active metal oxides, including spray drying, granulation, and solid-state synthesis, followed by drying and calcining. In some embodiments, the redox-active metal oxide can be a Geldart Group A or Group B particle prior to impregnation. In other embodiments, the redox-active metal oxide can be a non-Geldart Group A or Group B particle prior to impregnation.

[0035] As described above, the method of preparing the oxygen support material can include impregnating the redox-active metal oxide with an aqueous solution. The aqueous solution can include one or more water-soluble alkali metal silicates, alkali metal aluminates, or alkali metal aluminosilicates. In some embodiments, the aqueous solution can 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 can have a pH greater than 7. For example, the aqueous solution can 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.

[0036] In one or more embodiments, the redox-active metal oxide can be impregnated via dry impregnation (also known as incipient wetness impregnation). In one or more embodiments, the redox-active metal oxide can be impregnated via wet impregnation. In some embodiments, the redox-active metal oxide can be impregnated more than once with the aqueous solution.

[0037] The impregnated redox-active metal oxide can then be dried after impregnation. In some embodiments, the impregnated redox-active metal oxide can be dried in air. In one or more embodiments, the impregnated redox-active metal oxide can be dried at a temperature below 200° C., such as below 175° C., below 150° C., below 125° C., below 100° C., below 75° C., or even below 50° C. In embodiments where the redox-active metal oxide is impregnated with the aqueous solution more than once, the impregnated redox-active metal oxide can be dried between each impregnation.

[0038] The dried impregnated redox-active metal oxide can then be calcined to produce the oxygen support material. In one or more embodiments, the dried impregnated redox-active metal oxide can be calcined at a temperature below 1200° C., such as below 1100° C., below 1000° C., below 900° C., below 800° C., below 700° C., below 600° C., or even below 500° C. In one or more embodiments, the dried impregnated redox-active metal oxide can be calcined under air.

[0039] According to one or more embodiments of the present disclosure, a method for producing olefin compounds using the oxygen carrier materials described herein is provided. As used herein, the term "olefin compound" refers to a hydrocarbon having one or more carbon-carbon double bonds in addition to the formal double bonds in aromatic compounds. For example, ethylene and styrene are olefin compounds, but ethylbenzene is not an olefin compound because the only double bond present in ethylbenzene is a formal double bond that exists as part of the aromatic structure. Now referring to Figure 1 , shows a reactor system 100 that can be used with the method of the present disclosure, but other reactor systems known to those skilled in the art are contemplated herein. For example, the oxygen carrier materials of the present disclosure can be used in the systems and methods disclosed in WO 2020 / 046978, the teachings of which are incorporated herein by reference in their entirety.

[0040] Re-reference Figure 1, reactor system 100 can include reactor 110 and regeneration unit 120. In one or more embodiments, reactor 110 can be a fluidized bed reactor. Feed stream 101 can be passed into reactor 110. In one or more embodiments, feed stream 101 can comprise one or more hydrocarbons. In one or more embodiments, one or more hydrocarbons can comprise one or more of ethane, propane, butane or ethylbenzene. According to one or more embodiments, one or more hydrocarbons can comprise at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt% or even at least 99 wt% ethane. In other embodiments, one or more hydrocarbons can comprise at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt% or even at least 99 wt% propane. In other 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% by weight of butane. In other 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% by weight of ethylbenzene. In other 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% by weight of the sum of ethane, propane, butane, and ethylbenzene.

[0041] 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 reacts 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.

[0042] In one or more embodiments, the dehydrogenation reaction can utilize a dehydrogenation catalyst. The dehydrogenation catalyst can 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 (incorporated herein in their entirety by reference) and U.S. Patent No. 8,669,406 (incorporated herein in its entirety by reference). Alternatively, the dehydrogenation reaction can be carried out without utilizing a catalyst.

[0043] The reduced oxygen carrier material may need to be reoxidized before being used again in the reactor 110. The reduced oxygen carrier material may be transferred from the reactor 110 to the regeneration unit 120 via stream 103. In the regeneration unit 120, the reduced oxygen carrier material may be reoxidized. In some embodiments, the oxygen carrier material is reoxidized by exposing it to an oxygen-containing gas (e.g., air or oxygen). The reoxidized oxygen carrier material may then be transferred from the regeneration unit 120 back to the reactor 110 via stream 104. Thus, the oxygen carrier material may be looped or cycled through the reactor system 100. In some embodiments, the reoxidized oxygen carrier material may be partially reduced before being transferred to the reactor 110.

[0044] One or more olefin compounds produced in reactor 110 can leave reactor 110 via product stream 102. In one or more embodiments, olefin compounds can include one or more of ethylene, propylene, butylene or styrene. The term butylene includes any butylene isomer, such as α-butylene, cis-β-butylene, trans-β-butylene and isobutylene. In some embodiments, olefin-containing effluent can include at least 20 weight %, at least 30 weight %, at least 40 weight %, at least 50 weight % or even at least 60 weight % ethylene. In other embodiments, olefin-containing effluent can include at least 20 weight %, at least 30 weight %, at least 40 weight %, at least 50 weight % or even at least 60 weight propylene. In other embodiments, olefin-containing effluent can include at least 20 weight %, at least 30 weight %, at least 40 weight %, at least 50 weight % or even at least 60 weight butylene. In other embodiments, contain the olefin effluent and can comprise at least 20 % by weight, at least 30 % by weight, at least 40 % by weight, at least 50 % by weight or even at least 60 % by weight of vinylbenzene.In other embodiments, contain the olefin effluent and can comprise at least 20 % by weight, at least 30 % by weight, at least 40 % by weight, at least 50 % by weight or even at least 60 % by weight of ethene, propylene, butylene and the vinylbenzene.Product stream 102 can also comprise the unreacted components of feed stream and is not considered to other reaction products of olefinic compounds.Olefinic compounds can be separated with unreacted components in subsequent separation steps.

[0045] Example

[0046] Various embodiments of the present disclosure will be further illustrated by the following examples. The examples are illustrative in nature and should not be construed as limiting the subject matter of the present disclosure.

[0047] Example 1 - Sample preparation

[0048] Comparative Example A is a non-redox-active inert quartz flake used as received. Comparative Example B is calcium manganese oxide (CaMnO), Comparative Example C is manganese oxide (MnO), Comparative Example D is copper oxide (CuO), Comparative Example E is cerium oxide (CeO), and Comparative Example F is iron oxide (FeO). Comparative Examples AF are all commercially available and used as received.

[0049] Comparative Examples C1-C4 were prepared by impregnating Comparative Example D with an aqueous sodium nitrate solution. The impregnated material was dried at a temperature below 200°C and then calcined in air at a temperature below 1000°C for 6 hours. The compositions of the resulting Comparative Examples are shown in Table 2.

[0050] 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 compositions of the resulting Comparative Examples are shown in Table 3.

[0051] Samples 1-3 were prepared by impregnating Comparative Example B. First, sodium aluminate (#13404), commercially available 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 then calcined in air at a temperature below 1000°C for 6 hours. The compositions of the resulting samples are listed in Table 1. In addition, Figure 1 Powder x-ray diffraction patterns are shown for Sample 1 and Sample 3, where Sample 3 has a higher amount of sodium aluminate loading.

[0052] Samples 4-7 were prepared by impregnating Comparative Example B. First, a commercially available potassium silicate solution (Zacsil 30 or Zacsil 865) was obtained from Zaclon 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 then calcined in air at a temperature below 1000°C for 6 hours. The compositions of the resulting samples are listed in Table 1.

[0053] Samples 8-10 were prepared by impregnating Comparative Example B. First, a commercially available sodium silicate solution (#338443) was obtained from Sigma Aldrich and used as the impregnation solution. The impregnation solution was added to a given amount of Comparative Example B to form an impregnated material. The impregnated material was dried at a temperature below 200°C and then calcined in air at a temperature below 1000°C for 6 hours. The compositions of the resulting samples are listed in Table 1.

[0054] Samples 11-13 were prepared by impregnating Comparative Example B. First, commercially available sodium silicate and sodium chlorate were mixed to form an aqueous 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 dried at a temperature below 200°C and then calcined in air at a temperature below 1000°C for 6 hours. The compositions of the resulting samples are listed in Table 1.

[0055] Samples 14-17 were prepared by impregnating Comparative Example C. First, a commercially available sodium silicate solution was used as the impregnation solution. This impregnation solution was then added to a given amount of Comparative Example C to form an impregnated material. The impregnated material was dried at a temperature below 200°C and then calcined in air at a temperature below 1000°C for 6 hours. The compositions of the resulting samples are listed in Table 2.

[0056] Samples 18-19 were prepared by impregnating Comparative Example C. First, commercially available sodium silicate solution and sodium hydroxide were mixed to form an aqueous impregnation solution. The impregnation solution was then added to a given amount of Comparative Example C to form an impregnated material. The impregnated material was dried at a temperature below 200°C and then calcined in air at a temperature below 1000°C for 6 hours. The compositions of the resulting samples are listed in Table 2.

[0057] Samples 20-22 were prepared by impregnating Comparative Example D. First, a commercially available potassium silicate solution (Zacsil 30) was obtained from Zaclon and mixed with potassium hydroxide to form an impregnation solution. The impregnation solution was then added to a given amount of Comparative Example D to form an impregnated material. The impregnated material was dried at a temperature below 200°C and then calcined in air at a temperature below 1000°C for 6 hours. The compositions of the resulting samples are listed in Table 2.

[0058] Samples 23-25 ​​were prepared by impregnating Comparative Example C. First, commercially available sodium aluminate was dissolved in water to form an impregnation solution. This impregnation solution was then added to a given amount of Comparative Example C to form an impregnated material. The impregnated material was dried at a temperature below 200°C and then calcined in air at a temperature below 1000°C for 6 hours. The compositions of the resulting samples are listed in Table 2.

[0059] Sample 26 was prepared by impregnating Comparative Example D. First, a commercially available sodium silicate solution was used as the impregnation solution. This 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 a temperature below 1000°C for 6 hours. The composition of the resulting sample is listed in Table 3.

[0060] Sample 27 was prepared by impregnating Comparative Example E. First, a commercially available sodium silicate solution was used as the impregnation solution. This 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 a temperature below 1000°C for 6 hours. The composition of the resulting sample is listed in Table 4.

[0061] Samples 28-30 were prepared by impregnating Comparative Example F. First, a commercially available sodium silicate solution was used as the impregnation solution. This 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 a temperature below 1000°C for 6 hours. The compositions of the resulting samples are listed in Table 5.

[0062] Example 2 - Ethane Dehydrogenation Performance

[0063] The tests of the oxygen carrying materials were carried out in a fixed bed laboratory reactor. A 0.5 g portion of the sample was loaded into a 0.5 inch OD quartz sphere connected to a 6.5 mm OD quartz tube. The sample bed was supported on a piece of quartz wool and a layer of 0.5 mm - 1.0 mm quartz flakes. The empty space in the quartz sphere above the sample bed was filled with 0.5 mm - 1.0 mm quartz flakes. The reactor was mounted 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 gas flow of 40 standard cubic centimeters (sccm). The oxygen carrying material was subjected to several sequences of cycles - each cycle consisting of ethane dehydrogenation (reduction) and air regeneration (oxidation), with an inert nitrogen purge if the reactor tube was in between reduction and oxidation pulses. The ethane dehydrogenation step was carried out over a 7 hour period. -1 The dehydrogenation reaction was carried out at a weight hourly space velocity (WHSV) of 1.5 mol / 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 maintained at 780°C. The product gas composition was analyzed when the dehydrogenation reaction pulse was 30 seconds (midway). During the air regeneration step, 40 sccm of air was fed through the reactor for 10 minutes. Between each of the ethane dehydrogenation and air regeneration steps, the reactor tube was purged with 40 sccm of nitrogen for 2 minutes. The product gas composition was analyzed by a Siemens Maxim process gas chromatograph. For each oxygen-carrying material, multiple repetitions of the reduction-oxidation cycle were performed and the average ethane conversion, ethylene selectivity, CO x Selectivity and hydrogen:ethylene ratio.

[0064] Table 1

[0065]

[0066] As shown in Table 1, the presence of an oxygen carrier (Comparative Example B) increased the ethane conversion percentage and the hydrogen to ethylene ratio compared to the reaction without an oxygen carrier (Comparative Example A). However, the oxygen carrier in the absence of a promoter (Comparative Example B) was less selective for combustion of hydrogen than for combustion of hydrocarbons in the reactor, resulting in significantly higher CO 2 emissions than any of the samples in the presence of a promoter (Samples 1-13). x The percent selectivity indicates that the combustion of hydrocarbons with oxygen from the oxygen carrier occurs at a higher rate for the unpromoted oxygen carrier.

[0067] Table 2

[0068]

[0069] As shown in Table 2, the samples with accelerators (Comparative Examples C1-C6 and Samples 14-25) all have significantly lower CO than the sample without accelerator (Comparative Example C). x Selectivity. Table 2 also shows that when compared with the above-mentioned formula Na u K v Li w (Si x Al y O z ) r Compared with the comparative examples C1-C7 of the accelerators, the accelerators having the formula Na u K v Li w (Si x Al y O z ) r The samples (e.g., samples 14-25) containing the promoters had improved ethane conversion, improved ethylene selectivity, improved CO x selectivity or an increased hydrogen to ethylene ratio.

[0070] Table 3

[0071]

[0072] As shown in Table 3, the samples with a promoter (e.g., Sample 26) have significantly higher C2H4 selectivity and significantly lower CO2 selectivity than Comparative Example D without a promoter. x Selective.

[0073] Table 4

[0074]

[0075] As shown in Table 4, the samples with a promoter (e.g., Sample 27) have significantly higher C2H4 selectivity and significantly lower CO2 selectivity than Comparative Example E without a promoter. x Selective.

[0076] Table 5

[0077]

[0078] As shown in Table 5, the samples with the promoter (e.g., samples 29-30) had significantly improved hydrogen to ethylene ratios and CO 2 2 3 4 5 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 29 30 31 32 33 x Selective.

[0079] Example 3 - Powder X-ray diffraction pattern of oxygen carrier material sample

[0080] Figure 2 is the powder X-ray diffraction pattern of samples 1 and 3. Figure 2 As shown, the peak associated with sodium aluminate is only detectable at the higher loading of Sample 3. The presence of the sodium aluminate peak in the pattern of Sample 3 indicates that the impregnation successfully incorporated sodium aluminate as a promoter into the oxygen carrier. The low level of promoter 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 the impregnation of Sample 1 also successfully incorporated sodium aluminate into the oxygen carrier.

[0081] According to a first aspect of the present disclosure, the oxygen support material may include a redox active metal oxide and an alkali metal-containing composition. The alkali metal-containing composition may have the formula Na u K v Li w (Si x Al y O z ) r In the formula, 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 0.02 to 20.

[0082] 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 metal-containing composition is greater than or equal to 5:1.

[0083] 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.

[0084] A fourth aspect of the present disclosure may include any one of the preceding aspects or combinations of aspects, wherein the redox active metal oxide is an oxide of a metal selected from Fe and Mn.

[0085] A fifth aspect of the present disclosure may include any of the preceding aspects or combinations thereof, wherein the redox active metal oxide is selected from the group consisting of Fe2O3, FeO, Mn2O3, MnO, CaMnO3, Mg6MnO8, LaSrMnO3, LaSrFeO3, FeTiO3, Fe2TiO5, Fe3Ti3O 10 or BaMnO3.

[0086] A sixth aspect of the present disclosure may include any one of the preceding aspects or combinations of aspects, wherein r is from 0.1 to 10.

[0087] A seventh aspect of the present disclosure may include any preceding aspect or combination of aspects, wherein x or y is equal to 1.

[0088] 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.

[0089] A ninth aspect of the present disclosure may include any one of the preceding aspects or combinations of aspects, wherein the alkali metal-containing composition is free of boron.

[0090] A tenth aspect of the present disclosure may include any preceding aspect or combination of aspects, wherein the alkali metal-containing composition is selected from the group consisting of: NaAlO2, KAlO2, Na4SiO4, Na6Si2O7, Na2SiO3, Na2SiO5, Na6Si6O 19 , K2SiO3, K2Si2O5 or K2Si4O9.

[0091] An eleventh aspect of the present disclosure can include any preceding aspect or combination of aspects, wherein at least 95 weight percent of the oxygen support material comprises a combination of a redox-active metal oxide and an alkali metal-containing composition.

[0092] In a twelfth aspect of the present disclosure, a method of preparing an oxygen support material may include providing a redox-active metal oxide, impregnating the redox-active metal oxide with an aqueous solution comprising one or more water-soluble alkali metal silicates, alkali metal aluminates, or alkali metal aluminosilicates 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 support material. The oxygen support material may include the redox-active metal oxide and an alkali metal-containing composition. The alkali metal-containing composition may have the formula Na u K v Li w (Si x Al y O z ) rIn the formula, 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 0.02 to 20.

[0093] A thirteenth aspect of the present disclosure may include the twelfth aspect, wherein the aqueous solution has a pH greater than 7.

[0094] In a fourteenth aspect of the present disclosure, a method for producing olefin compounds may include contacting a feed stream comprising 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 olefin compounds, and at least a portion of the hydrogen may react with oxygen from the oxygen carrier material to produce water. The method may also include transferring at least a portion of the oxygen carrier material to a regeneration unit and transferring 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 metal-containing composition. The alkali metal-containing composition may have the formula Na u K v Li w (Si x Al y O z ) r In the formula, 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 0.02 to 20.

[0095] 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 olefin compounds include ethylene.

[0096] It will be apparent to those skilled in the art that various modifications and variations may be made to the technology disclosed herein without departing from the spirit and scope of the technology. Because modifications, combinations, sub-combinations, and variations of the disclosed embodiments that incorporate the spirit and substance of the technology disclosed herein may be made by those skilled in the art, the technology should be interpreted as including everything within the scope of the appended claims and their equivalents. In addition, although some aspects of the disclosure may be identified herein as preferred or particularly advantageous, it is contemplated that the disclosure is not limited to these aspects.

[0097] It should be noted that the various details described in this disclosure should not be considered to imply that these details relate to elements that are essential components of the various embodiments described in this disclosure, even when specific elements are shown in each of the drawings accompanying this specification. Unless so explicitly stated, no feature disclosed and described herein should be construed as "essential." Contemplated embodiments of the present technology include those that include some or all of the features of the appended claims.

[0098] For the purposes of describing and defining the present disclosure, it is noted that the term "about" is utilized herein to represent the inherent degree of uncertainty that may be attributed to any quantitative comparison, value, measurement, or other representation. The term "about" is also utilized herein to represent the degree by which a quantitative representation may vary from a stated reference without resulting in a change in the basic function of the subject matter at issue.

[0099] Where relevant, where compositions are described as “comprising” one or more elements, embodiments of the compositions “consisting of” or “consisting essentially of” those one or more elements are contemplated herein.

[0100] It should be understood that in some embodiments, a composition range for a chemical composition in a stream or reactor should be understood to refer to a mixture of isomers containing that composition. For example, a composition range specifying butenes may include a mixture of various isomers of butenes. It should be understood that the examples provide composition ranges for various streams, and the total amount of isomers of a particular chemical composition may constitute a range.

[0101] It should be noted that one or more of the following claims and detailed description utilize the term "wherein" or "wherein" as a transition phrase. For purposes of defining the present technology, it should be noted that this term is introduced in the claims as an open transition phrase that is used to introduce a recitation of a series of features of a structure and should be interpreted in a manner similar to the more commonly used open-ended term "comprising."

[0102] 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 by all of the described quantitative values ​​for a given property are contemplated in this disclosure. Where multiple ranges of quantitative values ​​are provided, these ranges may be combined to form broader ranges, which is contemplated in the embodiments described herein.

[0103] As understood in the context of the terms used herein, the term "transfer" may include directly transferring a substance between two parts of the disclosed system, and in some cases, may mean indirectly transferring a substance between two parts of the disclosed system. For example, indirect transfer may include steps in which the substance is transferred through an intermediate operating unit, valve, sensor, etc.

Claims

1. An oxygen carrier material, comprising: redox-active metal oxides; and With the formula Na u K v Li w (Si x Al y O z ) r An alkali metal-containing composition, wherein: u+v+w=1; x+y=1; z is greater than 1.5; and r is 0.02 to 20.

2. The oxygen carrier material of claim 1, wherein the weight ratio of the redox-active metal oxide to the alkali metal-containing composition is greater than or equal to 5:

1.

3. The oxygen carrier material according to any preceding claim, wherein the redox-active metal oxide is an oxide of a metal selected from Fe, Mn, Cu, Ni, Co or Ce.

4. The oxygen carrier material according to any preceding claim, wherein the redox-active metal oxide is an oxide of a metal selected from Fe and Mn.

5. The oxygen carrier material according to claim 1, wherein the redox active metal oxide is selected from the group consisting of Fe2O3, FeO, Mn2O3, MnO, CaMnO3, Mg6MnO8, LaSrMnO3, LaSrFeO3, FeTiO3, Fe2TiO5, Fe3Ti3O 10 or BaMnO3.

6. An oxygen carrier material according to any preceding claim, wherein r is from 0.1 to 10.

7. An oxygen carrier material according to any preceding claim, wherein one of x or y is equal to 1.

8. An oxygen carrier material according to any preceding claim, wherein one of u, v or w is equal to 1.

9. The oxygen carrier material according to any preceding claim, wherein the alkali metal-containing composition is free of boron.

10. The oxygen carrier material according to claim 1, wherein the alkali metal-containing composition is selected from the group consisting of: NaAlO2, KAlO2, Na4SiO4, Na6Si2O7, Na2SiO3, Na2SiO5, Na6Si6O 19 , K2SiO3, K2Si2O5 or K2Si4O9.

11. The oxygen support material of any preceding claim, wherein at least 95 wt. % of the oxygen support material comprises a combination of the redox-active metal oxide and the alkali metal-containing composition.

12. A method for preparing an oxygen carrier material, the method comprising: providing a redox-active metal oxide; impregnating the redox-active metal oxide with an aqueous solution comprising one or more water-soluble alkali metal silicates, alkali metal aluminates, or alkali metal aluminosilicates 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 support material; wherein the oxygen carrier material comprises: redox-active metal oxides; and With the formula Na u K v Li w (Si x Al y O z ) r An alkali metal-containing composition, wherein: u+v+w=1; x+y=1; z is greater than 1.5; and r is 0.02 to 20.

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

14. A method for producing an olefin compound, the method comprising: A feed stream comprising one or more hydrocarbons is contacted with an oxygen carrier material in a reactor wherein: dehydrogenating the one or more hydrocarbons to form hydrogen and one or more olefinic compounds; as well as reacting at least a portion of the hydrogen with oxygen from the oxygen carrier material to produce water; transferring at least a portion of the oxygen carrier material to a regeneration unit; and transferring at least a portion of the oxygen carrier material from the regeneration unit to the reactor; wherein the oxygen carrier material comprises: redox-active metal oxides; and With the formula Na u K v Li w (Si x Al y O z ) r An alkali metal-containing composition, wherein: u+v+w=1; x+y=1; z is greater than 1.5; and r is 0.02 to 20.

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

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