Oxygen carrier material comprising iron and one or more additional metals and method for production thereof

Abstract

An oxygen carrier material is disclosed, which may include a first composition. At least 95% by weight of the first composition may consist of: 0.001 to 0.999 mole parts of iron; 0.001 to 0.999 mole parts of a combination of one or more of manganese, cerium, cobalt, copper, nickel, or zinc; 0.04 to 0.8 parts by mole of one or more alkali metals; from 0.02 mole part to 0.4 mole part of tungsten; 0 to 3 parts by mole of titanium; and 1 to 10 parts by mole of oxygen. The sum of the molar parts of iron and the molar parts of a combination of one or more of manganese, cerium, cobalt, copper, nickel, or zinc may be equal to 1 molar part.

Description

Cross-references to related applications

[0001] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 595,991, filed November 3, 2023, the contents of which are incorporated herein by reference in their entirety. Technical Field

[0002] The embodiments disclosed herein generally relate to chemical treatment, and particularly to oxygen carrier materials used in chemical treatment. Background Technology

[0003] Some chemical processes that utilize oxygen as a reactant employ oxygen carrier materials. In such processes, oxygen can be delivered or "carried" in a cycle via reduction and subsequent oxidation of the oxygen carrier material. In these processes, the oxygen carried by the oxygen carrier material can be used as an oxygen source. Specifically, oxygen carrier materials can be used in cyclic chemical processes where oxygen can be added to and removed from the oxygen carrier material as it is used throughout the process. Such materials can be used in a variety of chemical treatment methods. Summary of the Invention

[0004] There remains a need for oxygen carrier materials suitable for use with specific chemical processes. This document describes specific oxygen carrier materials comprising at least: iron; one or more of manganese, cerium, cobalt, copper, nickel, or zinc; or multiple alkali metals; tungsten; and oxygen; in specific amounts relative to each other. It has been found that, according to one or more embodiments, the oxygen carrier materials described herein can exhibit relatively high selectivity for the combustion of hydrogen relative to the combustion of hydrocarbons. As detailed herein, such oxygen carrier materials can be used in methods for forming olefin compounds, among other intended uses.

[0005] According to one or more embodiments of this disclosure, the oxygen carrier material may comprise a first composition. At least 95% by weight of the first composition may consist of: 0.001 to 0.999 moles of iron; 0.001 to 0.999 moles of one or more of manganese, cerium, cobalt, copper, nickel, or zinc; 0.04 to 0.8 moles of one or more alkali metals; 0.02 to 0.4 moles of tungsten; 0 to 3 moles of titanium; and 1 to 10 moles of oxygen. The sum of the moles of iron and the moles of one or more of manganese, cerium, cobalt, copper, nickel, or zinc may be equal to 1 mole.

[0006] Additional features and advantages of this disclosure will be set forth in the detailed description below, and will be partly apparent from the description or by practice of the embodiments described herein, including the detailed description below, the claims, and the drawings. Attached Figure Description

[0007] The following detailed description of specific embodiments of this disclosure is best understood in conjunction with the following drawings, in which similar reference numerals indicate similar structures and in the drawings:

[0008] Figure 1 This is a schematic diagram of a reactor system suitable for use with an oxygen carrier material according to one or more embodiments described herein.

[0009] Additional features and advantages of this disclosure will be set forth in the detailed description below, and will be partly apparent from the description or by practice of the embodiments described herein, including the detailed description below, the claims, and the drawings.

[0010] 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 characteristics of the claimed subject matter. Drawings are included to provide a further understanding of the various embodiments, and these drawings are incorporated in and form a part of this specification. The drawings illustrate the various embodiments described herein and, together with the specification, explain the principles and operation of the claimed subject matter. Detailed Implementation

[0011] Specific embodiments of this application will now be described. However, the technical aspects of this application may be implemented in different forms and should not be construed as limited to the embodiments described in this specific embodiment.

[0012] Generally, various embodiments of the oxygen carrier material are described in this disclosure. As described herein, the oxygen carrier material may comprise a first composition and optionally one or more other materials. In one or more embodiments, the first composition may comprise or consist of an active material that generally contributes to the oxygen-carrying function and / or hydrogen combustion selectivity of the oxygen carrier material described herein. Generally, in the embodiments described herein, at least 95% by weight of the first composition may consist of: iron (Fe); one or more of manganese (Mn), cerium (Ce), cobalt (Co), copper (Cu), nickel (Ni), or zinc (Zn); one or more alkali metals, tungsten (W), oxygen (O), and optionally titanium (Ti), the amounts of which are defined by specific ratios between these various components.

[0013] In embodiments, in addition to the first composition, the oxygen carrier material may further comprise one or more additional materials. In embodiments, one or more additional materials may serve as binders in the oxygen carrier material. In some embodiments, the binder may not substantially contribute to the oxygen-carrying and / or catalytic function of the oxygen carrier material. The binder generally enhances the physical properties of the oxygen carrier material. According to embodiments, one or more additional materials may be selected from oxides of silicon, aluminum, calcium, magnesium, zirconium, niobium, or combinations thereof. Generally, one or more additional materials may not contain elements other than oxygen present in the first composition. Mixtures of various oxides of the intended elements may be included in one or more additional materials. Without limitation, in one or more embodiments, the additional materials may be selected from those disclosed in "Progress in Chemical-Looping Combustion and Reforming technologies" Progress in Energy and Combustion Science 38 (2012) 215-282 and "Chemical Looping Systems for Fossil Energy Conversions" by WILEY, published in 2010, Liang-Shih Fan. For example, in some embodiments, suitable other materials that can be used as binders include, but are not limited to, silica (colloidal, calcined, crystalline, amorphous), alumina (α, θ, or γ crystalline phase), and CaAl. x O y MgAl2O4, zirconium oxide, inorganic clays (such as kaolin, other aluminum silicates) and glass materials (such as glass fiber).

[0014] According to one or more embodiments, the oxygen carrier material may comprise at least 75% by weight, at least 80% by weight, at least 85% by weight, at least 90% by weight, at least 95% by weight, at least 99% by weight, at least 99.9% by weight of a first composition and a combination of one or more other materials, or may consist of a combination of the first composition and one or more other materials. For example, the oxygen carrier material may consist of a combination of the first composition and one or more other materials, wherein the one or more other materials may act as a binder and fill the remainder of the oxygen carrier material that is not part of the first composition.

[0015] In one or more embodiments, the oxygen carrier material may comprise a first composition in amounts of 1% to 5% by weight, 5% to 10% by weight, 10% to 15% by weight, 15% to 20% by weight, 20% to 25% by weight, 25% to 30% by weight, 30% to 35% by weight, 35% to 40% by weight, 40% to 45% by weight, 45% to 50% by weight, 50% to 55% by weight, 55% to 60% by weight, 60% to 65% by weight, 65% to 70% by weight, 70% to 75% by weight, 75% to 80% by weight, 80% to 85% by weight, 85% to 90% by weight, 90% to 95% by weight, 95% to 100% by weight, or any combination of one or more of these ranges. For example, the oxygen carrier material may comprise at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 35% by weight, at least 40% by weight, at least 45% by weight, at least 50% by weight, at least 55% by weight, at least 60% by weight, at least 65% by weight, at least 70% by weight, at least 75% by weight, at least 80% by weight, at least 85% by weight, at least 90% by weight, or even at least 95% by weight of the first composition. In some embodiments, the oxygen carrier material may comprise at least 99% by weight or at least 99.9% by weight of the first composition. In some embodiments, the oxygen carrier material may consist of the first composition.

[0016] In another embodiment, the oxygen carrier material may comprise one or more additional materials. According to the embodiment, the oxygen carrier material may comprise 1% to 50% by weight of one or more additional materials. For example, one or more additional materials may be present in the oxygen carrier material in amounts of 1% to 5% by weight, 5% to 10% by weight, 10% to 15% by weight, 15% to 20% by weight, 20% to 25% by weight, 25% to 30% by weight, 30% to 35% by weight, 35% to 40% by weight, 40% to 45% by weight, 45% to 50% by weight, or any combination of one or more of these ranges. For example, the oxygen carrier material may comprise less than or equal to 50% by weight and at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 35% by weight, at least 40% by weight, or at least 45% by weight of one or more additional materials. In another embodiment, the oxygen carrier material may comprise one or more other materials in amounts of at least 1% by weight and less than or equal to 5% by weight, less than or equal to 10% by weight, less than or equal to 15% by weight, less than or equal to 20% by weight, less than or equal to 25% by weight, less than or equal to 30% by weight, less than or equal to 35% by weight, less than or equal to 40% by weight, or less than or equal to 45% by weight.

[0017] As described herein, the relative amounts of materials in the first composition are described based on the relative amounts of atoms of each element contained in the first composition. Furthermore, as described herein, the oxygen-supporting material component can be described relative to the amounts of other components. For example, components described herein are expressed in amounts described as “molar parts.” As used herein, molar parts describe the molar ratio of one component to another and do not limit the total number or moles of a particular substituent. For example, iron may be present in an amount of 1 molar part, and oxygen may be present in amounts from 1 molar part to 10 molar parts, meaning that all compositions satisfying this ratio of iron atoms to oxygen atoms fall within the embodiments described herein, regardless of the original amounts of these components. Generally, and unless otherwise indicated, when multiple elements or other materials are listed together in specific amounts, this refers to the total of all such combinations of elements or other materials, even if it is not explicitly stated that the “total” or “combination” of these elements refers to the specified amount. For example, when “one or more alkali metals” are listed in amounts, the amount refers to the combination of all alkali metals.

[0018] Turning now to the first composition of the oxygen carrier material, in one or more embodiments, at least 95% by weight of the first composition may consist of: iron; one or more of manganese, cerium, cobalt, copper, nickel, or zinc; one or more alkali metals; tungsten; oxygen; and optionally titanium. For example, at least 96% by weight, at least 97% by weight, at least 98% by weight, at least 99% by weight, at least 99.5% by weight, or at least 99.9% by weight of the first composition may consist of: iron; one or more of manganese, cerium, cobalt, copper, nickel, or zinc; tungsten; oxygen; and optionally titanium. In some embodiments, the first composition may consist of: iron; one or more of manganese, cerium, cobalt, copper, nickel, or zinc; one or more alkali metals; tungsten; oxygen; and optionally titanium.

[0019] In one or more embodiments, iron, along with one or more of manganese, cerium, cobalt, copper, nickel, or zinc, may be present in the first composition. For the sake of compactness in this disclosure, manganese, cerium, cobalt, copper, nickel, and zinc may be referred to as "doped metals," wherein reference to one or more "doped metals" refers to one or more of manganese, cerium, cobalt, copper, nickel, and zinc. As described herein, the sum of the molar parts of iron and the molar parts of the combination of one or more doped metals may be equal to 1 molar part. Without being bound by any particular theory, it is believed that iron, along with one or more doped metals, may serve as a major component that binds to and dissociates from oxygen in redox reactions by altering its oxidation state.

[0020] Furthermore, without being bound by any particular theory, it is believed that the presence of one or more of manganese, cerium, cobalt, copper, nickel, and zinc can promote the combustion of methane in the regeneration unit 120 when methane is used as a fuel gas. That is, embodiments excluding one or more of these dopant metals may not allow for the regeneration of methane in the presence of oxygen, or for combustion in the embodiments described herein.

[0021] In such embodiments, iron may be present in the first composition, wherein iron is present in the first composition in a relative amount from 0.001 moles to 0.999 moles. In one or more embodiments, the first composition may contain a relative amount of iron of 0.001 moles to 0.1 moles, 0.1 moles to 0.2 moles, 0.2 moles to 0.3 moles, 0.3 moles to 0.4 moles, 0.4 moles to 0.5 moles, 0.5 moles to 0.6 moles, 0.6 moles to 0.7 moles, 0.7 moles to 0.8 moles, 0.8 moles to 0.9 moles, 0.9 moles to 0.999 moles, or any combination of one or more of these ranges.

[0022] In another embodiment, the first composition may contain a relative amount of iron of less than or equal to 0.999 moles and at least 0.1 moles, at least 0.2 moles, at least 0.3 moles, at least 0.4 moles, at least 0.5 moles, at least 0.6 moles, at least 0.7 moles, at least 0.8 moles, or at least 0.9 moles.

[0023] In another embodiment, the first composition may contain a relative amount of iron of at least 0.001 moles and less than or equal to 0.1 moles, less than or equal to 0.2 moles, less than or equal to 0.3 moles, less than or equal to 0.4 moles, less than or equal to 0.5 moles, less than or equal to 0.6 moles, less than or equal to 0.7 moles, less than or equal to 0.8 moles, or less than or equal to 0.9 moles.

[0024] According to an embodiment, the first composition may comprise a combination of one or more dopant metals (i.e., manganese, cerium, cobalt, copper, nickel, and zinc) in a relative amount of 0.001 moles to 0.999 moles. In one or more embodiments, the first composition may comprise a combination of dopant metals in a relative amount of 0.001 moles to 0.1 moles, 0.1 moles to 0.2 moles, 0.2 moles to 0.3 moles, 0.3 moles to 0.4 moles, 0.4 moles to 0.5 moles, 0.5 moles to 0.6 moles, 0.6 moles to 0.7 moles, 0.7 moles to 0.8 moles, 0.8 moles to 0.9 moles, 0.9 moles to 0.999 moles, or any combination of one or more of these ranges.

[0025] In another embodiment, the first composition may comprise a combination of one or more dopant metals in a relative amount of at least 0.1 molar, at least 0.2 molar, at least 0.3 molar, at least 0.4 molar, at least 0.5 molar, at least 0.6 molar, at least 0.7 molar, at least 0.8 molar, or at least 0.9 molar and less than or equal to 0.999 molar. In another embodiment, the first composition may comprise a combination of one or more dopant metals in a relative amount of less than or equal to 0.1 molar, less than or equal to 0.2 molar, less than or equal to 0.3 molar, less than or equal to 0.4 molar, less than or equal to 0.5 molar, less than or equal to 0.6 molar, less than or equal to 0.7 molar, less than or equal to 0.8 molar, or less than or equal to 0.9 molar and at least 0.001 molar.

[0026] In some embodiments, it is anticipated that only a single dopant metal may be present in the first composition. That is, only one of manganese, cerium, cobalt, copper, nickel, or zinc may be present in the first composition. In other embodiments, any combination of two, three, four, or five or all of manganese, cerium, cobalt, copper, nickel, and zinc may be present in the first composition. For any of these embodiments, the aforementioned ranges of relative amounts of dopant metals may apply to single, two, three, four, five, or six elements selected from manganese, cerium, cobalt, copper, nickel, and zinc.

[0027] In one or more embodiments, one or more alkali metals may be present in the first composition, wherein the one or more alkali metals may be present in the first composition in a relative amount of 0.04 moles to 0.8 moles. Without being bound by any particular theory, it is believed that the presence of this amount of alkali metal can improve hydrogen combustion selectivity relative to hydrocarbon combustion.

[0028] According to embodiments, one or more alkali metals may be selected from lithium, sodium, and potassium, wherein the relative amounts of the combination of lithium, sodium, and potassium are from 0.04 molar parts to 0.8 molar parts. In some embodiments, lithium is present in the first composition but sodium and potassium are absent. In other embodiments, sodium is present in the first composition but lithium and potassium are absent. In yet other embodiments, lithium and sodium are present in the first composition but potassium is absent, sodium and potassium are present in the first composition but lithium is absent, or potassium and lithium are present in the first composition but sodium is absent. In some embodiments, lithium, sodium, and potassium are present in the first composition.

[0029] In some embodiments, one or more alkali metals may be present in the first composition in a relative amount of less than or equal to 0.8 moles and at least 0.08 moles, at least 0.12 moles, at least 0.16 moles, at least 0.20 moles, at least 0.24 moles, at least 0.28 moles, at least 0.32 moles, at least 0.36 moles, at least 0.40 moles, at least 0.44 moles, at least 0.48 moles, at least 0.52 moles, at least 0.56 moles, at least 0.60 moles, at least 0.64 moles, at least 0.68 moles, at least 0.72 moles, or at least 0.76 moles.

[0030] In another embodiment, one or more alkali metals may be present in the first composition in a relative amount of at least 0.04 moles and less than or equal to 0.76 moles, less than or equal to 0.72 moles, less than or equal to 0.68 moles, less than or equal to 0.64 moles, less than or equal to 0.60 moles, less than or equal to 0.56 moles, less than or equal to 0.52 moles, less than or equal to 0.48 moles, less than or equal to 0.44 moles, less than or equal to 0.40 moles, less than or equal to 0.36 moles, less than or equal to 0.32 moles, less than or equal to 0.28 moles, less than or equal to 0.24 moles, less than or equal to 0.20 moles, less than or equal to 0.16 moles, less than or equal to 0.12 moles, or less than or equal to 0.08 moles.

[0031] In another embodiment, one or more alkali metals may be present in quantities of 0.04 mol to 0.08 mol, 0.08 mol to 0.12 mol, 0.12 mol to 0.16 mol, 0.16 mol to 0.20 mol, 0.20 mol to 0.24 mol, 0.24 mol to 0.28 mol, 0.28 mol to 0.32 mol, 0.32 mol to 0.36 mol, 0.36 mol to 0.40 mol, or 0.40 mol to 0.44 mol. The relative amounts of 0.44 to 0.48 moles, 0.48 to 0.52 moles, 0.52 to 0.56 moles, 0.56 to 0.60 moles, 0.60 to 0.64 moles, 0.64 to 0.68 moles, 0.68 to 0.72 moles, 0.72 to 0.76 moles, 0.76 to 0.80 moles, or any combination of one or more of these ranges, are present in the first composition.

[0032] In one or more embodiments, tungsten may be present in the first composition, wherein tungsten may be present in a relative amount of 0.02 molar parts to 0.4 molar parts in the first composition. Without being bound by theory, it is believed that tungsten present in this amount can modulate the release of oxygen from iron, which can inhibit the oxidation of hydrocarbons.

[0033] In some embodiments, tungsten may be present in the first composition in a relative amount of less than or equal to 0.4 moles and at least 0.06 moles, at least 0.08 moles, at least 0.10 moles, at least 0.12 moles, at least 0.14 moles, at least 0.16 moles, at least 0.18 moles, at least 0.20 moles, at least 0.22 moles, at least 0.24 moles, at least 0.26 moles, at least 0.28 moles, at least 0.30 moles, at least 0.32 moles, at least 0.34 moles, at least 0.36 moles, or even at least 0.38 moles.

[0034] In another embodiment, tungsten may be present in the first composition in a relative amount of at least 0.02 moles and less than or equal to 0.38 moles, less than or equal to 0.36 moles, less than or equal to 0.34 moles, less than or equal to 0.32 moles, less than or equal to 0.30 moles, less than or equal to 0.28 moles, less than or equal to 0.26 moles, less than or equal to 0.24 moles, less than or equal to 0.22 moles, less than or equal to 0.20 moles, less than or equal to 0.18 moles, less than or equal to 0.16 moles, less than or equal to 0.14 moles, less than or equal to 0.12 moles, less than or equal to 0.10 moles, less than or equal to 0.08 moles, less than or equal to 0.06 moles, or even less than or equal to 0.04 moles and at least 0.02 moles.

[0035] In another embodiment, tungsten can be in the amounts of 0.02 mol parts to 0.04 mol parts, 0.04 mol parts to 0.06 mol parts, 0.06 mol parts to 0.08 mol parts, 0.08 mol parts to 0.10 mol parts, 0.10 mol parts to 0.12 mol parts, 0.12 mol parts to 0.14 mol parts, 0.14 mol parts to 0.16 mol parts, 0.16 mol parts to 0.18 mol parts, 0.18 mol parts to 0.20 mol parts, and 0.20 mol parts to 0.22 mol parts. The first composition contains relative amounts of 0.22 to 0.24 moles, 0.24 to 0.26 moles, 0.26 to 0.28 moles, 0.28 to 0.30 moles, 0.30 to 0.32 moles, 0.32 to 0.34 moles, 0.34 to 0.36 moles, 0.36 to 0.38 moles, 0.38 to 0.40 moles, or any combination of one or more of these ranges.

[0036] In one or more embodiments, oxygen may be present in the first composition in a relative amount from 1 mole to 10 moles. The amount of oxygen may depend on the oxidation state of the oxygen support material, wherein more oxygen may be present in embodiments when the oxygen support material is storing oxygen atoms, and less oxygen may be present once such oxygen has been provided for the reaction and prior to regeneration. Generally, as described herein, the amount of oxygen may vary at different points in the process of forming the olefin.

[0037] In some embodiments, oxygen may be present in amounts less than or equal to 10 moles and at least 1.25 moles, at least 1.5 moles, at least 1.75 moles, at least 2 moles, at least 2.25 moles, at least 2.5 moles, at least 2.75 moles, at least 3 moles, at least 3.25 moles, at least 3.5 moles, at least 3.75 moles, at least 4 moles, at least 4.25 moles, at least 4.5 moles, at least 4.75 moles, at least 5 moles, at least 5.25 moles. The relative amounts of at least 5.5 moles, at least 5.75 moles, at least 6 moles, at least 6.25 moles, at least 6.5 moles, at least 6.75 moles, at least 7 moles, at least 7 moles, at least 7.25 moles, at least 7.5 moles, at least 7.75 moles, at least 8 moles, at least 8.25 moles, at least 8.5 moles, at least 8.75 moles, at least 9 moles, at least 9.25 moles, at least 9.5 moles, or even at least 9.75 moles are present in the first composition.

[0038] In another embodiment, oxygen may be at least 1 mole and less than or equal to 1.25 moles, less than or equal to 1.5 moles, less than or equal to 1.75 moles, less than or equal to 2 moles, less than or equal to 2.25 moles, less than or equal to 2.5 moles, less than or equal to 2.75 moles, less than or equal to 3 moles, less than or equal to 3.25 moles, less than or equal to 3.5 moles, less than or equal to 3.75 moles, less than or equal to 4 moles, less than or equal to 4.25 moles, less than or equal to 4.5 moles, less than or equal to 4.75 moles, less than or equal to 5 moles, less than or equal to 5.25 moles, less than or equal to... The relative amounts of 5.5 moles or less than or equal to 5.75 moles, 6 moles or less than or equal to 6.25 moles, 6.5 moles or less than or equal to 6.75 moles, 7 moles or less than or equal to 7.25 moles, 7.5 moles or less than or equal to 7.75 moles, 8 moles or less than or equal to 8.25 moles, 8.5 moles or less than or equal to 8.75 moles, 9 moles or less than or equal to 9.25 moles, 9.5 moles or less than or equal to 9.75 moles are present in the first composition.

[0039] In another embodiment, oxygen may be 1 mole to 1.25 moles, 1.25 moles to 1.5 moles, 1.5 moles to 1.75 moles, 1.75 moles to 2 moles, 2 moles to 2.25 moles, 2.25 moles to 2.5 moles, 2.5 moles to 2.75 moles, 2.75 moles to 3 moles, 3 moles to 3.25 moles, 3.25 moles to 3.5 moles, 3.5 moles to 3.75 moles, 3.75 moles to 4 moles, 4 moles to 4.25 moles, 4.25 moles to 4.5 moles, 4.5 moles to 4.75 moles, 4.75 moles to 5 moles, 5 moles to 5.25 moles, 5.25 moles to 5.5 moles, and 5.5 moles to 5. The relative amounts of 75 moles, 5.75 moles to 6 moles, 6 moles to 6.25 moles, 6.25 moles to 6.5 moles, 6.5 moles to 6.75 moles, 6.75 moles to 7 moles, 7 moles to 7.25 moles, 7.25 moles to 7.5 moles, 7.5 moles to 7.75 moles, 7.75 moles to 8 moles, 8 moles to 8.25 moles, 8.25 moles to 8.5 moles, 8.5 moles to 8.75 moles, 8.75 moles to 9 moles, 9 moles to 9.25 moles, 9.25 moles to 9.5 moles, 9.5 moles to 9.75 moles, 9.75 moles to 10 moles, or any combination of one or more of these ranges, are present in the first composition.

[0040] In one or more embodiments, the first composition may optionally contain titanium. That is, in some embodiments, titanium may be present in the first composition, and in other embodiments, titanium may not be present in the first composition. In one or more embodiments, titanium may be present in the first composition in a relative amount of 0 to 3 moles. In some embodiments, titanium may be present in the first composition in a relative amount of 0.001 to 3 moles. Without being bound by theory, it is believed that the presence of titanium can improve the mechanical stability of the oxygen-supported material. Furthermore, unlike ilmenite, titanium combined with iron and alkali metals can form crystalline phases containing alkali metals, iron, and titanium (e.g., prederite and alkali manganese ore), which may adversely promote reduction.

[0041] In some embodiments, titanium may be present in the first composition in a relative amount of at least 0.25 moles, at least 0.5 moles, at least 0.75 moles, at least 1 mole, at least 1.25 moles, at least 1.5 moles, at least 1.75 moles, at least 2 moles, at least 2.25 moles, at least 2.5 moles, or at least 2.75 moles and less than or equal to 3 moles.

[0042] In another embodiment, titanium may be present in the first composition in a relative amount of less than or equal to 0.25 moles, less than or equal to 0.5 moles, less than or equal to 0.75 moles, less than or equal to 1 mole, less than or equal to 1.25 moles, less than or equal to 1.5 moles, less than or equal to 1.75 moles, less than or equal to 2 moles, less than or equal to 2.25 moles, less than or equal to 2.5 moles, or less than or equal to 2.75 moles and at least 0 moles or at least 0.001 moles.

[0043] In another embodiment, titanium may be present in the first composition in relative amounts of 0 to 0.25 moles, 0.001 to 0.25 moles, 0.25 to 0.5 moles, 0.5 to 0.75 moles, 0.75 to 1 mole, 1 to 1.25 moles, 1.25 to 1.5 moles, 1.5 to 1.75 moles, 1.75 to 2 moles, 2 to 2.25 moles, 2.25 to 2.5 moles, 2.5 to 2.75 moles, 2.75 to 3 moles, or any combination of one or more of these ranges.

[0044] In one or more embodiments, the oxygen carrier material may be fluidizable. In some embodiments, the oxygen carrier material may have a median particle size (D50) 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 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.

[0045] In some implementations, the oxygen carrier material may exhibit properties industrially known as “Geldart A” or “Geldart B” characteristics. The particles may be classified as “Group A” or “Group B” according to the following literature: D. Geldart, Gas Fluidization Technology, John Wiley & Sons (New York, 1986), 34-37; and D. Geldart, “Types of Gas Fluidization,” Powder Technology, 7 (1973) 285-292, the entire contents of which are incorporated herein by reference.

[0046] Group A is understood by those skilled in the art to represent an aeratable powder having a range of bubble-free fluidization; high bed expansion; slow and linear degassing rate; bubble characteristics which may include the advantage of splitting / coalescing bubbles, having a maximum bubble size and large wake; high levels of solids mixing and gas backmixing, 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 < 45 microns (μm); or with increasing gas pressure, temperature, viscosity, and density. Generally, the particles may 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 they fluidize smoothly at low gas velocities; and may exhibit controlled bubbling with small bubbles at higher gas velocities.

[0047] Group B is understood by those skilled in the art to represent a "sand-like" powder which begins to bubble at Umf; which exhibits moderate bed expansion; rapid degassing; no limit on bubble size; moderate levels of solids mixing and gas backmixing, 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 , the particle size (cfp) of most particles is 40 μm < cfp < 500 μm, and preferably, when the density (pp) is 4 g / cm 3 , the particle size of most particles is 60 μm < cfp < 500 μm, and when the density (pp) is 1 g / cm 3 , the particle size of most particles is 250 μm < cfp < 100 μm.

[0048] In one or more embodiments, the oxygen carrier material described herein can be prepared by a variety of synthetic techniques, including solid-state synthesis, or wet or dry impregnation followed by drying and high-temperature calcination, as known to those skilled in the art. Generally, the various components in the first composition can be added as solid powders in the form of their oxides, then thoroughly mixed or homogenized, followed by calcination in air at high temperature. Alternatively, some components in the first composition can be incorporated by completely (wet or dry impregnation) or partially (slurry impregnation) dissolving their precursors in water, and then combining them with the solid powders of the remaining components, followed by drying and high-temperature calcination in air. Optionally, small amounts of other materials described herein may be added during the synthesis of the oxygen carrier to provide physical strength and stability.

[0049] In some embodiments, as described above, the oxygen carrier can be prepared by impregnation. Impregnation can be performed using wet impregnation or dry impregnation (sometimes referred to as initial wetting impregnation). Impregnation can utilize an aqueous solution containing some components of the first composition; for example, in various embodiments, the aqueous solution may contain one or more precursors of alkali metals and / or tungsten. In some embodiments, the aqueous solution may contain potassium tungstate, potassium carbonate, potassium sulfate, potassium nitrate, potassium acetate, ammonium paratungstate, ammonium metatungstate, tungstic acid, 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. In some embodiments, multiple impregnation steps may occur to impregnate different materials.

[0050] The impregnated material can then be dried after impregnation. In some embodiments, the impregnated material can be dried in air. In one or more embodiments, the impregnated material can be dried at temperatures 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 some embodiments, impregnation can be performed more than once with an aqueous solution, and the impregnated material can be dried between each impregnation.

[0051] The dried impregnated material can then be calcined to produce an oxygen carrier material. In one or more embodiments, calcination can be carried out at temperatures greater than 600°C, such as greater than 700°C, greater than 800°C, greater than 900°C, greater than 1000°C, greater than 1100°C, or even greater than 1200°C. In one or more embodiments, the dried impregnated material can be calcined in air. In embodiments utilizing multiple impregnation steps, the impregnated material can be calcined between each impregnation. In embodiments, the dried impregnated material can be calcined in air for more than 1 hour. For example, the dried impregnated material can be calcined in air for more than 2 hours, more than 4 hours, more than 10 hours, or even more than 20 hours.

[0052] In some embodiments, the oxygen carrier material can be used in methods including fluidized beds, moving beds, or circulating fluidized beds (CFB). In such embodiments, it may be desirable to have the oxygen carrier as engineered microparticles with "Geldart A" or "Geldart B" properties. Without being theoretically limited, in one or more embodiments, it is believed that a selection of methods for manufacturing engineered microparticles of the oxygen carrier material, such as manufacturing techniques like spray drying, high-shear granulation, and fluidized bed granulation, followed by drying and high-temperature calcination, can be used to achieve fluidizable microparticles.

[0053] According to one or more embodiments of this disclosure, a method for producing olefin compounds using the oxygen-supported 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 found 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 an aromatic structure.

[0054] Now refer to Figure 1 The diagram shows a reactor system 100 that can be used with the methods of this disclosure, but other reactor systems that would be suitable for the methods of this disclosure are also contemplated. Figure 1 This is a simplified system, and other systems can be envisioned. Additionally, in... Figure 1The present invention envisions various reactor types that are also potentially applicable to the methods described herein. For example, the oxygen carrier material disclosed herein can be used in at least the systems and methods disclosed in PCT International Application No. PCT / US23 / 73963 entitled “Methods For Dehydrogenating Hydrocarbons By Thermal Dehydrogenation” and International Patent Publication WO 2020 / 046978 entitled “Methods for Dehydrogenating Hydrocarbons,” the teachings of each of which are incorporated herein by reference in their entirety. These disclosed technical aspects may be further described herein with respect to… Figure 1 The methods and systems described. Also note, Figure 1 The steps shown should not be construed as necessary steps, especially with respect to the methods of the appended claims.

[0055] Still refer to Figure 1 The reactor system 100 may include a reactor 110 and a regeneration unit 120. In one or more embodiments, the reactor 110 may be a fluidized bed reactor. Generally, a feed stream 101 may be passed to and processed in the reactor 110 to form a product stream 102 comprising one or more olefin compounds. As described in detail herein, according to one or more embodiments, an oxygen carrier material may be circulated between the reactor 110 and the regeneration unit 120, wherein the oxygen carrier material enters the reactor 110 in an oxygen-enriched state, is supplied with oxygen in the reactor 110, leaves the reactor 110 in an oxygen-deficient state, and may be regenerated in the regeneration unit 120 to an oxygen-enriched state.

[0056] In one or more embodiments, feed stream 101 may comprise one or more hydrocarbons. As described herein, feed stream 101 may be passed to reactor 110. In one or more embodiments, the one or more hydrocarbons may comprise one or more of ethane, propane, butane, or ethylbenzene. According to one or more embodiments, the one or more hydrocarbons may comprise any one of at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, or even at least 99 wt% of ethane. In another embodiment, the one or more hydrocarbons may comprise at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, or even at least 99 wt% of propane. In another embodiment, the one or more hydrocarbons may comprise at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, or even at least 99 wt% of butane. In another embodiment, one or more hydrocarbons may contain at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight, or even at least 99% by weight of ethylbenzene. In another embodiment, one or more hydrocarbons may contain at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight, or even at least 99% by weight of the sum of ethane, propane, butane, and ethylbenzene.

[0057] According to the embodiment, the oxygen carrier material can be delivered to reactor 110 in an oxygen-enriched state. In reactor 110, one or more hydrocarbons in the feed stream 101 can be dehydrogenated to form hydrogen (i.e., gaseous H2) and one or more olefin compounds. According to the embodiment, at least a portion of the hydrogen can react with oxygen from the oxygen carrier material to form water. Reacting hydrogen with oxygen from the oxygen carrier material reduces the oxygen carrier material and converts it to an oxygen-deficient state. As described herein, the oxygen-enriched oxygen carrier material has a greater amount of oxygen than the oxygen-deficient oxygen carrier material. However, it should be understood that some oxygen may still be contained in the oxygen-deficient oxygen carrier material.

[0058] According to some embodiments, the dehydrogenation reaction in reactor 110 can be thermally driven (i.e., non-catalytic), wherein in such embodiments, no dehydrogenation catalyst is used in reactor 110. While the temperature of reactor 110 is variable, in some embodiments, reactor 110 can be operated at temperatures from 600°C to 850°C, which may be suitable for promoting thermal dehydrogenation. In other embodiments, a dehydrogenation catalyst can be used to promote dehydrogenation in reactor 110. The dehydrogenation catalyst can be transferred together with the oxygen support material and circulated between reactor 110 and regeneration unit 120. In embodiments where a dehydrogenation catalyst is used, temperatures from 600°C to 850°C can also be utilized. Suitable dehydrogenation catalysts include, but are not limited to, those comprising platinum, platinum and gallium, platinum and tin, or chromium. 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).

[0059] One or more olefin compounds produced in reactor 110, along with unconverted hydrocarbons, water, and unconverted hydrogen, may exit reactor 110 via product stream 102. In one or more embodiments, the olefin compounds may include one or more of ethylene, propylene, butene, or styrene. The term butene includes any butene isomer, such as α-butene, cis-β-butene, trans-β-butene, and isobutene. In some embodiments, the olefin-containing effluent may contain at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, or even at least 60 wt% of ethylene. In other embodiments, the olefin-containing effluent may contain at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, or even at least 60 wt% of propylene. In other embodiments, the olefin-containing effluent may contain at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, or even at least 60 wt% of butene. In another embodiment, the olefin-containing effluent may contain at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, or even at least 60 wt% of styrene. In another embodiment, the olefin-containing effluent may contain at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, or even at least 60 wt% of one or more of ethylene, propylene, butene, and styrene. Product stream 102 may further contain unreacted components from feed stream 101 and other reaction products that are not considered olefin compounds. Olefin compounds may be separated from the unreacted components in a subsequent separation step.

[0060] As described herein, in reactor 110, one or more hydrocarbons (such as ethane) can be dehydrogenated to produce hydrogen, which can then react with oxygen via a combustion reaction to form water. Oxygen is supplied by an oxygen carrier material, and the reaction of hydrogen to water pushes the dehydrogenation equilibrium toward the product, such as ethylene. In such embodiments, it is advantageous that the oxygen carrier material promotes the combustion of hydrogen more than its reaction with hydrocarbons present in reactor 110. Such hydrocarbons may include feed hydrocarbons (such as ethane) and product olefin compounds (such as ethylene). The reaction of these hydrocarbons with oxygen from the oxygen carrier material may undesirably form carbon monoxide and / or carbon dioxide. Carbon dioxide and carbon monoxide in product stream 102 can cause several problems, such as difficulty in separating such components from other compounds in product stream 102, and the potential release of carbon dioxide into the environment or the need to contain such carbon dioxide. For example, carbon monoxide may be an undesirable inhibitor in some downstream unit operations such as acetylene hydrogenation reactors. With this in mind, it has been found that the oxygen carrier material of this disclosure can have a relatively high selectivity for promoting the combustion of hydrogen to form water, compared to the selectivity for promoting the combustion of undesirable hydrocarbons with feed alkanes (such as ethane) and / or product olefin compounds (such as ethylene).

[0061] According to one or more embodiments, and as described herein, the hydrogen formed by the dehydrogenation reaction is gaseous H2, which reacts with oxygen from the oxygen-supported material. This is the opposite of some other reaction mechanisms in which hydrogen is not formed, such as oxidative dehydrogenation. Instead, in such oxidative dehydrogenation reactions, the alkane is processed into an alkene in a single reaction step, where no hydrogen (H2) is formed as an intermediate. This concept is described in detail, for example, in “Oxidative Dehydrogenation of Ethane: Common Principles and Mechanistic Aspects,” Gartner et al., ChemCatChem 2013, 5, 3196-3217.

[0062] As described herein, the oxygen carrier material is transferred into reactor 110 and subsequently exits reactor 110. See again... Figure 1In some embodiments, the oxygen carrier material circulates between reactor 110 and regeneration unit 120. The oxygen carrier material can be transferred from reactor 110 to regeneration unit 120 via feed stream 103 and back from regeneration unit 120 to reactor 110 via feed stream 104, and this circulation is continuous. Generally, the oxygen carrier material enters reactor 110 in an oxygen-enriched state, loses some or all of its oxygen atoms (to burn with hydrogen) in reactor 110, and leaves reactor 110 in an oxygen-deficient state via feed stream 103. The oxygen carrier material in the oxygen-deficient state can be transferred to regeneration unit 120, where it is exposed to oxygen and regenerated into its oxygen-enriched state. This oxygen-enriched oxygen carrier material can then be transferred back from regeneration unit 120 to reactor 110 via feed stream 104.

[0063] According to one or more embodiments, in regeneration unit 120, the oxygen carrier material may be exposed to oxygen, such as by exposure to air, oxygen-enriched air, or even pure oxygen. This exposure allows the oxygen carrier material to be replenished with oxygen. Additionally, in regeneration unit 120, fuel gas may be burned to heat the oxygen carrier material. This heat may be the primary heat source for maintaining the temperature in reactor 110, which uses heat for the dehydrogenation reaction. The fuel gas may include a variety of combustible compounds, such as hydrogen, methane, ethane, propane, etc. In some embodiments, methane may be the main component of the fuel gas. In embodiments, regeneration unit 120 may operate at elevated temperatures (such as 600°C to 900°C) or temperatures sufficient to heat the oxygen carrier material to such a temperature that it can be used to drive the dehydrogenation reaction in reactor 110.

[0064] As described herein, fuel gases (such as fuel gases containing methane) can be combusted in regeneration unit 120. According to some embodiments, it has been found that the composition of the oxygen carrier material can affect the combustion rate of the fuel gases. Therefore, it is undesirable to use oxygen carrier materials with compositions that would slow down hydrocarbon combustion. This is particularly problematic because oxygen carrier materials can be selected such that they promote hydrogen combustion in reactor 110 but not the combustion of alkanes and / or olefins. However, it has been observed that, according to one or more embodiments, the oxygen carrier materials of this disclosure can have an acceptable level of alkane combustion (such as methane combustion) promotion in regeneration unit 120, while exhibiting good hydrogen combustion selectivity relative to ethane combustion in reactor 110.

[0065] In some embodiments, the oxygen-enriched oxygen carrier material may be partially reduced before being delivered to reactor 110. This may include exposing the oxygen carrier material in stream 104 to a reducing gas, such as H2 and / or methane. Such treatment may allow some oxygen to be removed from the lattice of the oxygen carrier material. However, as disclosed herein, the amount of residual oxygen is still suitable for supplying oxygen to reactor 110 for hydrogen combustion.

[0066] This disclosure includes many aspects, including aspects 1 through 15 described herein.

[0067] Aspect 1. An oxygen carrier material comprising a first composition, wherein at least 95% by weight of the first composition comprises: 0.001 mol to 0.999 mol of iron; 0.001 mol to 0.999 mol of one or more of manganese, cerium, cobalt, copper, nickel or zinc, wherein the sum of the mol parts of iron and the mol parts of one or more of manganese, cerium, cobalt, copper, nickel or zinc equals 1 mol; 0.04 mol to 0.8 mol of one or more alkali metals; 0.02 mol to 0.4 mol of tungsten; 0 mol to 3 mol of titanium; and 1 mol to 10 mol of oxygen.

[0068] Aspect 2. The oxygen carrier material according to any of the preceding aspects, wherein the first composition comprises manganese.

[0069] Aspect 3. The oxygen carrier material according to any of the preceding aspects, wherein the first composition comprises cerium.

[0070] Aspect 4. The oxygen carrier material according to any of the preceding aspects, wherein the first composition comprises cobalt.

[0071] Aspect 5. The oxygen carrier material according to any of the preceding aspects, wherein the first composition comprises copper.

[0072] Aspect 6. The oxygen carrier material according to any of the preceding aspects, wherein the first composition comprises nickel.

[0073] Aspect 7. The oxygen carrier material according to any of the preceding aspects, wherein the first composition comprises zinc.

[0074] Aspect 8. The oxygen carrier material according to any of the preceding aspects, wherein the first composition comprises titanium.

[0075] Aspect 9. The oxygen carrier material according to any of the preceding aspects, wherein at least 99% by weight of the first composition comprises: 0.001 mol to 0.999 mol of iron; 0.001 mol to 0.999 mol of one or more of manganese, cerium, cobalt, copper, nickel or zinc, wherein the sum of the mol of iron and the mol of one or more of manganese, cerium, cobalt, copper, nickel or zinc is equal to 1 mol; 0.04 mol to 0.8 mol of one or more alkali metals; 0.02 mol to 0.4 mol of tungsten; 0 mol to 3 mol of titanium; and 1 mol to 10 mol of oxygen.

[0076] Aspect 10. The oxygen carrier material according to any of the preceding aspects, wherein the first composition comprises: 0.001 molar to 0.999 molar of iron; 0.001 molar to 0.999 molar of one or more of manganese, cerium, cobalt, copper, nickel or zinc, wherein the sum of the molar amounts of iron and the molar amounts of one or more of manganese, cerium, cobalt, copper, nickel or zinc is equal to 1 molar; 0.04 molar to 0.8 molar of one or more alkali metals; 0.02 molar to 0.4 molar of tungsten; 0 molar to 3 molar of titanium; and 1 molar to 10 molar of oxygen.

[0077] Aspect 11. The oxygen carrier material according to aspect 1, wherein the oxygen carrier material further comprises one or more additional materials selected from oxides of silicon, aluminum, calcium, magnesium, zirconium, niobium or combinations thereof.

[0078] Aspect 12, the oxygen carrier material according to aspect 11, wherein at least 99% by weight of the oxygen carrier material is the first composition and the one or more other materials.

[0079] Aspect 13. A method for manufacturing an oxygen carrier material according to any of the preceding aspects.

[0080] Aspect 14. The method according to aspect 13, wherein the method comprises wet or dry impregnation.

[0081] Aspect 15. The method according to aspect 13, wherein the method includes solid-state synthesis.

[0082] Example

[0083] Various embodiments of this disclosure will be further illustrated by the following examples. These examples are illustrative in nature and should not be construed as limiting the subject matter of this disclosure.

[0084] Example 1 - Sample Preparation

[0085] Comparative sample A was prepared as follows: First, stoichiometric amounts of Fe₂O₃, TiO₂ (Noah Technologies Corporation, anatase), and WO₃ (Sigma-Aldrich, < 25 μm) were weighed in a mortar. The dry powder was first ground with a pestle for 5 min. Then, the powder was shaken in a separate container for 1 min and returned to the mortar. The grinding and shaking were repeated twice (a total of 10 min of grinding and 2 min of shaking). Separately, a stoichiometric amount of K₂CO₃ powder was dissolved in approximately 10 mL of deionized H₂O. After introducing the alkaline solution, the mixed metal oxide powders were ground and gelatinized for 5 min. The paste was then transferred to an alumina crucible and dried in air at 120 °C for at least 2 hours. The dried mixture was calcined in air at 950 °C for 6 hours.

[0086] Comparative sample B was prepared as follows: First, stoichiometric amounts of Fe2O3 (Noah Technologies Corporation) and TiO2 (Sigma-Aldrich, 21 nm nanopowder) were weighed in a mortar and combined. The dry powder was ground with a pestle for 5 minutes. The powder was then shaken in a separate container for 1 minute and returned to the mortar. The grinding and shaking steps were repeated twice, for a total of 10 minutes of grinding and 2 minutes of shaking. Subsequently, 5 to 10 mL of deionized water was added to the mortar, and the mixture was ground into a paste for 5 minutes. The paste was transferred to an alumina crucible and dried in air at 120 °C for at least 2 hours. The dried mixture was then calcined in air at 950 °C for 24 hours.

[0087] Sample 1 was prepared as follows: First, stoichiometric amounts of Fe₂O₃, Mn₃O₄ (Elkem, MicroMax EU), TiO₂ (Noah Technologies Corporation, anatase), and WO₃ were weighed in a mortar. The dry powder was ground with a pestle for 5 min. Then, the powder was shaken in a separate container for 1 min and returned to the mortar. The grinding and shaking were repeated twice (a total of 10 min of grinding and 2 min of shaking). Separately, a stoichiometric amount of K₂CO₃ powder was dissolved in approximately 10 mL of deionized H₂O. After introducing the alkaline solution, the mixed metal oxide powders were ground and gelatinized for 5 min. The paste was then transferred to an alumina crucible and dried in air at 120 °C for at least 2 hours. The dried mixture was calcined in air at 950 °C for 6 hours.

[0088] Sample 2 was prepared in the same manner as Sample 1 using K2CO3, WO3, Fe2O3, CeO2 (Sigma-Aldrich, nanopowder, <50 nm) and TiO2 (Noah Technologies Corporation, anatase).

[0089] Sample 3 was prepared in the same manner as Sample 1 using K2CO3, WO3, Fe2O3, Co3O4 (Sigma-Aldrich, < 10 μm) and TiO2 (Noah Technologies Corporation, anatase).

[0090] Sample 4 was prepared in the same manner as Sample 1 using K2CO3, WO3, Fe2O3, CuO (Sigma-Aldrich, < 10 μm) and TiO2 (Noah Technologies Corporation, anatase).

[0091] Sample 5 was prepared in the same manner as Sample 1 using K2CO3, WO3, Fe2O3, ZnO (Sigma-Aldrich, nanopowder, <100nm) and TiO2 (Noah Technologies Corporation, anatase).

[0092] Samples 6 and 7 were prepared in the same manner as Sample 1 using K2CO3, WO3, Fe2O3, Mn3O4 and TiO2 (Noah Technologies Corporation, anatase) at different stoichiometry.

[0093] Sample 8 was prepared in the same manner as Sample 2 using K2CO3, WO3, Fe2O3, CeO2 and TiO2 (Noah Technologies Corporation, anatase) at different stoichiometry.

[0094] Sample 9 was prepared in the same manner as Sample 1 using K2CO3, WO3, Fe2O3, NiO (ThermoScientific) and TiO2 (Noah Technologies Corporation, anatase).

[0095] Example 2 - Selective Hydrogen Combustion and Methane Combustion Performance

[0096] Oxygen carrier testing was conducted in a fixed-bed laboratory reactor. A 0.5 g sample portion was loaded into a 0.5 inch outer diameter (OD) quartz sphere connected to a 0.25 inch outer diameter (OD) quartz tube. The sample bed was supported on a piece of quartz wool and a layer of 0.5 mm to 1.0 mm quartz sheet. The reactor was mounted in a flip-top furnace, and a nitrogen flow of 40 standard cubic centimeters (sccm) was introduced through the reactor tubes. The reactor was then heated from room temperature to 780°C under an air flow of 40 sccm. The oxygen carrier material was subjected to several cycles. Each cycle consisted of ethane dehydrogenation, a first regeneration in air, fuel (methane) combustion, and then a second regeneration in air, purged with inert nitrogen in the reaction tubes between reduction and oxidation pulses. The ethane dehydrogenation step was performed over 5.3 hours. -1 The reaction was carried out at a gravity hourly space velocity (WHSV). Specifically, a gas mixture containing 90 mol% ethane and 10 mol% helium was fed through the reactor at 40 sccm for 60 seconds while the reactor was maintained at 780°C. The composition of the product gas was analyzed midway through the 30-second pulse of the dehydrogenation reaction. The reactor was then heated from 780°C to 850°C under a nitrogen flow of 40 sccm. During the first regeneration step in air, air was fed through the reactor at 850°C for 2 minutes at 40 sccm. The fuel (methane) combustion step was carried out at 0.079 hr. -1 The process was performed using WHSV. Specifically, a gas mixture containing 2.5 mol% methane, 9 mol% oxygen, and the balance nitrogen was fed through the reactor at 40 sccm for 180 seconds while the reactor was maintained at 850°C. The composition of the product gas was analyzed during a 60-second fuel combustion pulse. Finally, a second air regeneration step was performed at 850°C by feeding 40 sccm of air through the reactor for 4 minutes, followed by cooling the reactor to 780°C under a 40 sccm nitrogen flow. The composition of the product gas was analyzed using a Siemens Maxim process gas chromatograph. Multiple parallel reduction-oxidation cycles were performed for each oxygen-carrying material. Ethane conversion, ethylene selectivity, and CO were reported at the 50th cycle. x Selectivity, hydrogen:ethylene ratio, and methane conversion rate.

[0097] Use the following formulas to calculate carbon-based ethane conversion and product selectivity, where [X] corresponds to the mole fraction.

[0098]

[0099] Table 1: Selective hydrogen combustion and methane combustion performance of the materials evaluated using the method of Example 2

[0100]

[0101] As shown in Table 1, all samples containing an additional transition metal (M) (i.e., samples 1 to 9) had higher CH4 conversion rates than samples without the additional metal (i.e., comparison samples A and B). For example, comparison sample A, which did not contain the additional metal, had a CH4 conversion rate of 77.6% and contained Cu. 0.1 Sample 4 showed a CH4 conversion rate of 95.7%, indicating that the presence of additional metals improved the methane combustion performance in the oxygen carrier material.

[0102] In addition, samples containing other metals showed improved CH4 conversion while maintaining or even improving C2H4 selectivity and CO conversion. x The selectivity and / or H2 / C2H4 ratio indicate that these oxygen-supporting materials are extremely effective for selective hydrogen combustion. For example, comparative sample A, without any additional metals, has a CH4 conversion of 77.6%, and in addition to the addition of Zn... 0.1 Sample 5, being identical to the previous sample, showed a CH4 conversion rate of 84.3%. Furthermore, compared to sample A, it exhibited a C2H4 selectivity of 94.4% and a CO conversion rate of 1.2%. x The selectivity and H2 / C2H4 ratio were 0.15, and sample 5 had 94.5% C2H4 selectivity and 0.7% CO2 selectivity. x The selectivity and H2 / C2H4 ratio of 0.09 indicate that the presence of additional metals generally maintains and / or improves the selective hydrogen combustion of oxygen carrier materials.

[0103] Therefore, Table 1 shows that, compared with oxygen carrier materials without additional metals, the presence of additional metals in the oxygen carrier materials as a partial substitution of iron leads to an improvement in CH4 conversion while maintaining the effectiveness of selective hydrogen combustion.

[0104] It will be apparent to those skilled in the art that various modifications and variations can be made to the technology disclosed herein without departing from the spirit and scope of this invention. Because modifications, combinations, sub-combinations, and variations of the disclosed embodiments can be made by those skilled in the art that incorporate the spirit and essence of the technology disclosed herein, this technology should be construed as including all things within the scope of the appended claims and their equivalents. Furthermore, although some aspects of this disclosure may be identified herein as preferred or particularly advantageous, this disclosure is not limited to these aspects upon consideration.

[0105] It should be noted that the various details described in this disclosure should not be construed as implying that such details relate to elements that are fundamental components of the various embodiments described in this disclosure, even where specific elements are shown in each of the accompanying drawings. Unless so expressly stated, none of the features disclosed and described herein should be interpreted as "essential." The embodiments considered in this art include those that include some or all of the features of the appended claims.

[0106] For the purposes of describing and defining this disclosure, it should be noted that the term "about" is used in this disclosure to indicate an inherent uncertainty attributable to any quantitative comparison, value, measurement, or other representation. The term "about" is also used in this disclosure to indicate the degree to which a quantitative representation may vary from a specified reference without causing a change in the essential function of the subject matter of interest.

[0107] In relevant contexts, where a composition is described as "comprising" one or more elements, embodiments of compositions "composed of" or "substantially composed of" those one or more elements are considered herein.

[0108] It should be understood that, in some embodiments, the composition range of a chemical component in a stream or reactor should be understood as a mixture containing isomers of that component. For example, specifying the composition range of butene may include a mixture of various isomers of butene. It should be understood that the embodiments provide composition ranges for various streams, and the total amount of isomers of a particular chemical composition may constitute a range.

[0109] It should be noted that one or more of the following claims and detailed descriptions utilize the term "where (or wherever)" as a transitional phrase. For the purpose of defining this technology, it should be noted that this term is introduced in the claims as an open transitional phrase used to introduce a description of a series of characteristics of the structure, and should be interpreted in a manner similar to the more commonly used open prepositional term "comprising".

[0110] It should be understood that any two quantitative values ​​assigned to a characteristic can constitute a range for that characteristic, and all combinations of ranges formed by all stated quantitative values ​​of a given characteristic are considered in this disclosure. Where multiple ranges of quantitative values ​​are provided, these ranges can be combined to form a wider range, as is considered in the embodiments described herein.

[0111] As understood in the context of the terminology used herein, the term "transfer" can include the direct transfer of matter between two parts of the disclosed system, and in some cases, it means the indirect transfer of matter between two parts of the disclosed system. For example, indirect transfer can include the step of said matter transfer via intermediate operating units, valves, sensors, etc.

Claims

1. An oxygen carrier material comprising a first composition, wherein at least 95% by weight of the first composition consists of: 0.001 molar to 0.999 molar of iron; From 0.001 molar parts to 0.999 molar parts of one or more of manganese, cerium, cobalt, copper, nickel or zinc, wherein the sum of the molar parts of iron and the molar parts of one or more of manganese, cerium, cobalt, copper, nickel or zinc equals 1 molar part. 0.04 molar to 0.8 molar of one or more alkali metals; 0.02 to 0.4 moles of tungsten; 0 to 3 moles of titanium; and 1 to 10 moles of oxygen.

2. The oxygen carrier material according to any of the preceding claims, wherein the first composition comprises manganese.

3. The oxygen carrier material according to any of the preceding claims, wherein the first composition comprises cerium.

4. The oxygen carrier material according to any of the preceding claims, wherein the first composition comprises cobalt.

5. The oxygen carrier material according to any of the preceding claims, wherein the first composition comprises copper.

6. The oxygen carrier material according to any of the preceding claims, wherein the first composition comprises nickel.

7. The oxygen carrier material according to any of the preceding claims, wherein the first composition comprises zinc.

8. The oxygen carrier material according to any of the preceding claims, wherein the first composition comprises titanium.

9. The oxygen carrier material according to any of the preceding claims, wherein at least 99% by weight of the first composition comprises: 0.001 molar to 0.999 molar of iron; From 0.001 molar parts to 0.999 molar parts of one or more of manganese, cerium, cobalt, copper, nickel or zinc, wherein the sum of the molar parts of iron and the molar parts of one or more of manganese, cerium, cobalt, copper, nickel or zinc equals 1 molar part. 0.04 molar to 0.8 molar of one or more alkali metals; 0.02 to 0.4 moles of tungsten; 0 to 3 moles of titanium; and 1 to 10 moles of oxygen.

10. The oxygen carrier material according to any of the preceding claims, wherein the first composition comprises: 0.001 molar to 0.999 molar of iron; From 0.001 molar parts to 0.999 molar parts of one or more of manganese, cerium, cobalt, copper, nickel or zinc, wherein the sum of the molar parts of iron and the molar parts of one or more of manganese, cerium, cobalt, copper, nickel or zinc equals 1 molar part. 0.04 molar to 0.8 molar of one or more alkali metals; 0.02 to 0.4 moles of tungsten; 0 to 3 moles of titanium; and 1 to 10 moles of oxygen.

11. The oxygen carrier material according to claim 1, wherein the oxygen carrier material further comprises one or more other materials selected from oxides of silicon, aluminum, calcium, magnesium, zirconium, niobium or combinations thereof.

12. The oxygen carrier material according to claim 11, wherein at least 99% by weight of the oxygen carrier material is the first composition and the one or more other materials.

13. A method for manufacturing an oxygen carrier material according to any of the preceding claims.

14. The method of claim 13, wherein the method comprises wet or dry impregnation.

15. The method of claim 13, wherein the method comprises solid-state synthesis.

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