Process for producing olefin compounds using an oxygen carrier material comprising strontium and manganese

Abstract

Olefin compounds can be produced by a process utilizing an oxygen carrier material. The oxygen carrier material can include 40 wt% to 100 wt% of a first composition and 0 wt% to 10 wt% of one or more promoters. At least 95 wt% of the first composition consists of 0.001 mole fraction to 1 mole fraction of strontium, 0 mole fraction to 0.999 mole fraction of calcium, 0.001 mole fraction to 1 mole fraction of manganese, 0 mole fraction to 0.999 mole fraction of a combination of one or more of titanium, zirconium, iron, or magnesium, and 0.001 mole fraction to 5 mole fraction of oxygen. The sum of the mole fraction of calcium and the mole fraction of strontium can equal 1. The sum of the mole fraction of manganese and the mole fraction of the combination of one or more of titanium, zirconium, iron, or magnesium can be 0.5 mole fraction to 2 mole fraction per mole. The one or more promoters can be selected from oxides of lithium, sodium, potassium, tungsten, molybdenum, silicon, sulfur, phosphorus, or combinations thereof.

Description

Cross-reference to related applications

[0001] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 601,968, filed November 22, 2023, the contents of which are incorporated herein by reference. Technical Field

[0002] The embodiments disclosed herein generally relate to chemical processing, and specifically to chemical processing for the production of olefin materials. Background Technology

[0003] Olefin compounds, such as light olefins (e.g., ethylene, butene, and propylene), can be used as base materials to produce a wide variety of materials, such as polyethylene, polypropylene, isopropanol, and acrylic acid, which can be used in, for example, packaging, construction, and textiles. As a result of this utility, there is a global demand for light olefins. Suitable processes for producing light olefins generally depend on the given chemical feedstock and include those utilizing fluidized bed catalysts. For example, light olefins can be formed by the catalytic dehydrogenation of alkanes in a fluidized bed reactor. However, there is a need to improve the methods for preparing light olefins. Summary of the Invention

[0004] There is a persistent need for methods to produce olefin compounds. This document describes a method for producing olefin compounds by means of a process that typically includes the dehydrogenation of hydrocarbons, such as alkanes, to form olefin compounds. In such embodiments, an oxygen carrier material can be utilized, which supplies oxygen to burn hydrogen formed by the dehydrogenation reaction. Burning hydrogen typically shifts the dehydrogenation equilibrium toward the products (hydrogen and olefin compounds). It has been found that certain oxygen carrier materials described herein exhibit relatively high selectivity for burning hydrogen compared to burning hydrocarbons, making them well-suited for this process. In particular, as described herein, oxygen carrier materials comprising at least strontium and manganese can possess this selectivity and are well-suited for the methods described herein.

[0005] According to one or more embodiments of this disclosure, olefin compounds can be produced by a method comprising: passing a feed stream into a reactor, wherein the feed stream contains one or more hydrocarbons; and passing an oxygen carrier material into the reactor. In the reactor, the one or more hydrocarbons can be dehydrogenated to form hydrogen and one or more olefin compounds, and at least a portion of the hydrogen can react with oxygen from the oxygen carrier material to produce water. The oxygen carrier material may comprise 40% to 100% by weight of a first composition and 0% to 10% by weight of one or more promoters. At least 95% by weight of the first composition consists of 0.001 to 1 mole of strontium, 0 to 0.999 mole of calcium, 0.001 to 1 mole of manganese, 0 to 0.999 mole of one or more of titanium, zirconium, iron, or magnesium, and 0.001 to 5 mole of oxygen. The sum of the molar amounts of calcium and strontium may be equal to 1. The sum of the molar amounts of manganese and the molar amounts of one or more of titanium, zirconium, iron, or magnesium can be from 0.5 to 2 molar amounts per mole. One or more accelerators can be selected from oxides of lithium, sodium, potassium, tungsten, molybdenum, silicon, sulfur, phosphorus, or combinations thereof.

[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 methods for producing olefin compounds are described in this disclosure. According to one or more embodiments of this disclosure, the methods for producing olefin compounds utilize oxygen-supported materials (sometimes simply referred to herein as "oxygen supports") described herein. For example, the process may utilize an oxygen-supported material comprising at least strontium, manganese, and oxygen.

[0013] As used herein, the term "olefin compound" refers to a hydrocarbon having one or more carbon-carbon double bonds, other than the formal double bonds found in aromatic compounds. For example, ethylene and styrene are olefin compounds, but ethylbenzene is not because the only double bond present in ethylbenzene is a formal double bond that exists as part of an aromatic structure.

[0014] 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 1 The 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 1The steps shown should not be construed as necessary steps, especially with respect to the method of the appended claims.

[0015] 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.

[0016] 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.

[0017] 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.

[0018] 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).

[0019] 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.

[0020] 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).

[0021] 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.

[0022] As described herein, the oxygen carrier material is transferred into reactor 110 and subsequently exits reactor 110. See again... Figure 1 In 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.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] In the embodiments disclosed herein, the oxygen carrier material may have a specific composition. As described herein, the oxygen carrier material may comprise a first composition and optionally one or more promoters and / or additional materials. In one or more embodiments, the first composition may comprise or consist of active materials that are generally conducive to oxygen carrying by the oxygen carrier material described herein. As described below, such active materials may also affect fuel combustion during regeneration. Generally, in the embodiments described herein, at least 95% by weight of the first composition may consist of strontium, manganese, oxygen, optionally manganese, and optionally one or more of titanium, zirconium, iron, or magnesium, the amount of which is defined by a specific ratio between these various components.

[0027] 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 additional materials, or may consist of a combination of the first composition, one or more accelerators, and one or more additional materials. For example, the oxygen carrier material may consist of a combination of the first composition, one or more accelerators, and one or more additional materials, wherein the one or more additional materials may act as a binder and fill the remainder of the oxygen carrier material that is not part of the first composition and the accelerator.

[0028] In one or more embodiments, the oxygen carrier material may comprise a first composition in an amount of 40% to 100% by weight. For example, the oxygen carrier material may comprise a first composition in amounts of 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 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. 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.

[0029] 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-carrying 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, the sum of the molar parts of calcium and strontium can be equal to 1 molar part, and oxygen can be present in amounts from 0.001 molar parts to 5 molar parts, meaning that all compositions satisfying this ratio 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 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 of titanium, zirconium, iron, or magnesium” is listed in amounts, that amount refers to the combination of all such elements together.

[0030] 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, optionally calcium, manganese, optionally titanium, zirconium, iron or magnesium, and oxygen in the proportions disclosed herein. For example, at least 96%, at least 97%, at least 98%, at least 99%, at least 99.5%, or at least 99.9% by weight of the first composition may consist of these elements. In some embodiments, the first composition may consist of these elements.

[0031] In one or more embodiments, strontium may be present in the first composition in a relative amount from 0.001 molar parts to 1 molar part. Unbound by theory, the incorporation of strontium can lead to increased selectivity for hydrogen combustion relative to hydrocarbon combustion. Additionally, in some embodiments, the incorporation of strontium can lead to improved stability of the perovskite phase relative to the irreversible phase transition observed in CaMnO3 perovskite after redox cycles.

[0032] As described herein, in embodiments, strontium may be present in the first composition in relative amounts 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 1.0 moles, or any combination of one or more of these ranges.

[0033] In some embodiments, strontium may be present in the first composition in a relative amount less than or equal to 1 mole and at least 0.05 moles, at least 0.10 moles, at least 0.15 moles, at least 0.20 moles, at least 0.25 moles, at least 0.30 moles, at least 0.35 moles, at least 0.40 moles, at least 0.45 moles, at least 0.50 moles, at least 0.55 moles, at least 0.60 moles, at least 0.65 moles, at least 0.70 moles, at least 0.75 moles, at least 0.80 moles, at least 0.85 moles, at least 0.90 moles, or at least 0.95 moles. In another embodiment, strontium may be present in the first composition in a relative amount of at least 0.001 moles and less than or equal to 0.95 moles, less than or equal to 0.90 moles, less than or equal to 0.85 moles, less than or equal to 0.80 moles, less than or equal to 0.75 moles, less than or equal to 0.70 moles, less than or equal to 0.65 moles, less than or equal to 0.60 moles, less than or equal to 0.55 moles, less than or equal to 0.50 moles, less than or equal to 0.45 moles, less than or equal to 0.40 moles, less than or equal to 0.35 moles, less than or equal to 0.30 moles, less than or equal to 0.25 moles, less than or equal to 0.20 moles, less than or equal to 0.15 moles, less than or equal to 0.10 moles, or less than or equal to 0.05 moles.

[0034] In one or more embodiments, the first composition may optionally comprise calcium, wherein the sum of the molar amounts of strontium and calcium equals 1 molar. That is, in some embodiments, calcium may be present in the first composition, and in other embodiments, calcium may not be present in the first composition. In one or more embodiments, calcium may be present in the first composition in a relative amount from 0 molar to 0.999 molar. In some embodiments, calcium may be present in the first composition in a relative amount from 0.001 molar to 0.999 molar.

[0035] In one or more embodiments, calcium may be present in the first composition 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.

[0036] In some embodiments, calcium may be present in the first composition in a relative amount of less than or equal to 0.999 moles and at least 0.05 moles, at least 0.10 moles, at least 0.15 moles, at least 0.20 moles, at least 0.25 moles, at least 0.30 moles, at least 0.35 moles, at least 0.40 moles, at least 0.45 moles, at least 0.50 moles, at least 0.55 moles, at least 0.60 moles, at least 0.65 moles, at least 0.70 moles, at least 0.75 moles, at least 0.80 moles, at least 0.85 moles, at least 0.90 moles, or at least 0.95 moles. In another embodiment, calcium may be present in the first composition in a relative amount of at least 0.001 moles and less than or equal to 0.95 moles, less than or equal to 0.90 moles, less than or equal to 0.85 moles, less than or equal to 0.80 moles, less than or equal to 0.75 moles, less than or equal to 0.70 moles, less than or equal to 0.65 moles, less than or equal to 0.60 moles, less than or equal to 0.55 moles, less than or equal to 0.50 moles, less than or equal to 0.45 moles, less than or equal to 0.40 moles, less than or equal to 0.35 moles, less than or equal to 0.30 moles, less than or equal to 0.25 moles, less than or equal to 0.20 moles, less than or equal to 0.15 moles, less than or equal to 0.10 moles, or less than or equal to 0.05 moles.

[0037] In one or more embodiments, manganese may be present in the first composition in a relative amount from 0.001 moles to 1 mole. Without being bound by any particular theory, manganese is believed to act as a major component that binds to and debindes with oxygen in redox reactions by altering its oxidation state.

[0038] In one or more embodiments, manganese may be present in the first composition in relative amounts 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 1.0 moles, or any combination of one or more of these ranges.

[0039] In some embodiments, manganese may be present in the first composition in a relative amount less than or equal to 1 mole and at least 0.05 moles, at least 0.10 moles, at least 0.15 moles, at least 0.20 moles, at least 0.25 moles, at least 0.30 moles, at least 0.35 moles, at least 0.40 moles, at least 0.45 moles, at least 0.50 moles, at least 0.55 moles, at least 0.60 moles, at least 0.65 moles, at least 0.70 moles, at least 0.75 moles, at least 0.80 moles, at least 0.85 moles, at least 0.90 moles, or at least 0.95 moles. In another embodiment, manganese may be present in the first composition in a relative amount of at least 0.001 moles and less than or equal to 0.95 moles, less than or equal to 0.90 moles, less than or equal to 0.85 moles, less than or equal to 0.80 moles, less than or equal to 0.75 moles, less than or equal to 0.70 moles, less than or equal to 0.65 moles, less than or equal to 0.60 moles, less than or equal to 0.55 moles, less than or equal to 0.50 moles, less than or equal to 0.45 moles, less than or equal to 0.40 moles, less than or equal to 0.35 moles, less than or equal to 0.30 moles, less than or equal to 0.25 moles, less than or equal to 0.20 moles, less than or equal to 0.15 moles, less than or equal to 0.10 moles, or less than or equal to 0.05 moles.

[0040] In one or more embodiments, the first composition may optionally comprise one or more of titanium, zirconium, iron, or magnesium. That is, in some embodiments, one or more of titanium, zirconium, iron, or magnesium may be present in the first composition, and in other embodiments, one or more of titanium, zirconium, iron, or magnesium may not be present in the first composition. In one or more embodiments, one or more of titanium, zirconium, iron, or magnesium may be present in the first composition in a relative amount from 0.001 molar parts to 0.999 molar parts. Without being bound by any particular theory, it is believed that titanium, zirconium, iron, and / or magnesium can act as components that bind and debind with oxygen in redox reactions by changing their oxidation state.

[0041] According to one or more embodiments, the sum of the molar parts of manganese and the combination of one or more of titanium, zirconium, iron, or magnesium can be from 0.5 molar parts to 2 molar parts per mole. For example, the sum of the molar parts of manganese and the combination of one or more of titanium, zirconium, iron, or magnesium can be from 0.5 molar parts to 0.75 molar parts, from 0.75 molar parts to 1 molar part, from 1 molar part to 1.25 molar parts, from 1.25 molar parts to 1.5 molar parts, from 1.5 molar parts to 1.75 molar parts, or from 1.75 molar parts to 2 molar parts. Generally speaking, this means that the sum of strontium and calcium in molar parts is relatively similar to the sum of manganese, titanium, zirconium, iron, and magnesium.

[0042] In some embodiments, titanium is present in the first composition, but iron, zirconium, and magnesium are absent. In other embodiments, iron is present in the first composition, but titanium, zirconium, and magnesium are absent. In other embodiments, magnesium is present in the first composition, but titanium, zirconium, and iron are absent. In other embodiments, zirconium is present in the first composition, but titanium, magnesium, and iron are absent.

[0043] In one or more embodiments, one or more of titanium, zirconium, iron, or magnesium may be present in the first composition in relative amounts of 0 to 0.1 moles, 0.1 to 0.2 moles, 0.2 to 0.3 moles, 0.3 to 0.4 moles, 0.4 to 0.5 moles, 0.5 to 0.6 moles, 0.6 to 0.7 moles, 0.7 to 0.8 moles, 0.8 to 0.9 moles, 0.9 to 0.999 moles, or any combination of one or more of these ranges. Each of titanium, zirconium, iron, or magnesium may be present individually in these amounts.

[0044] In another embodiment, one or more of titanium, zirconium, iron, or magnesium may be present in the first composition in relative amounts of less than or equal to 0.999 moles and at least 0.05 moles, at least 0.10 moles, at least 0.15 moles, at least 0.20 moles, at least 0.25 moles, at least 0.30 moles, at least 0.35 moles, at least 0.40 moles, at least 0.45 moles, at least 0.50 moles, at least 0.55 moles, at least 0.60 moles, at least 0.65 moles, at least 0.70 moles, at least 0.75 moles, at least 0.80 moles, at least 0.85 moles, at least 0.90 moles, or at least 0.95 moles. Each of titanium, zirconium, iron, or magnesium may be present individually in these amounts. In another embodiment, one or more of titanium, zirconium, iron, or magnesium may be present in the first composition in a relative amount of at least 0.001 moles and less than or equal to 0.95 moles, less than or equal to 0.90 moles, less than or equal to 0.85 moles, less than or equal to 0.80 moles, less than or equal to 0.75 moles, less than or equal to 0.70 moles, less than or equal to 0.65 moles, less than or equal to 0.60 moles, less than or equal to 0.55 moles, less than or equal to 0.50 moles, less than or equal to 0.45 moles, less than or equal to 0.40 moles, less than or equal to 0.35 moles, less than or equal to 0.30 moles, less than or equal to 0.25 moles, less than or equal to 0.20 moles, less than or equal to 0.15 moles, less than or equal to 0.10 moles, or less than or equal to 0.05 moles. Each of titanium, zirconium, iron, or magnesium can exist individually in these amounts.

[0045] In one or more embodiments, oxygen may be present in the first composition in a relative amount from 0.001 molar parts to 5 molar parts. 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.

[0046] In one or more embodiments, oxygen may be present in the first composition in a relative amount of 0.001 moles to 1.5 moles, 1.5 moles to 2 moles, 2 moles to 2.5 moles, 2.5 moles to 3 moles, 3 moles to 3.5 moles, 3.5 moles to 4 moles, 4 moles to 4.5 moles, 4.5 moles to 5 moles, or any combination of one or more of these ranges.

[0047] In some embodiments, oxygen may be present in the first composition in a relative amount of less than or equal to 5 moles and at least 0.5 moles, at least 1 mole, at least 1.5 moles, at least 2 moles, at least 2.5 moles, at least 3 moles, at least 3.5 moles, at least 4 moles, or at least 4.5 moles. In other embodiments, oxygen may be present in the first composition in a relative amount of at least 0.001 moles and less than or equal to 0.5 moles, less than or equal to 1 mole, less than or equal to 1.5 moles, less than or equal to 2 moles, less than or equal to 2.5 moles, less than or equal to 3 moles, less than or equal to 3.5 moles, less than or equal to 4 moles, or less than or equal to 4.5 moles.

[0048] According to one or more embodiments, and as described herein, the oxygen carrier material may optionally contain one or more promoters. Promoters may be selected from oxides of lithium, sodium, potassium, tungsten, molybdenum, silicon, sulfur, phosphorus, or combinations thereof. In embodiments, one or more promoters may be present in the oxygen carrier material in an amount from 0% to 10% by weight. That is, in some embodiments, the oxygen carrier material may contain one or more promoters, and in other embodiments, the oxygen carrier material may not contain one or more promoters. For example, in some embodiments where promoters are present, one or more promoters may be present in the oxygen carrier material in an amount from 0.1% to 10% by weight. Without being bound by theory, it is believed that the incorporation of promoters can promote selectivity for hydrogen combustion relative to hydrocarbon combustion.

[0049] As described herein, one or more accelerators may be selected from oxides of lithium, sodium, potassium, tungsten, molybdenum, silicon, sulfur, phosphorus, or combinations thereof. In some embodiments, a single accelerator may be present, which is an oxide of any one of lithium, sodium, potassium, tungsten, molybdenum, silicon, sulfur, and phosphorus. In other embodiments, any two, three, four, five, six, seven, or all eight of lithium, sodium, potassium, tungsten, molybdenum, silicon, sulfur, and phosphorus may be present in one or more accelerators.

[0050] In one or more embodiments, one or more promoters may be present in the oxygen carrier material in amounts of 0.001 wt% to 1 wt%, 1 wt% to 2 wt%, 2 wt% to 3 wt%, 3 wt% to 4 wt%, 4 wt% to 5 wt%, 5 wt% to 6 wt%, 6 wt% to 7 wt%, 7 wt% to 8 wt%, 8 wt% to 9 wt%, 9 wt% to 10 wt%, or any combination of one or more of these ranges.

[0051] In another embodiment, one or more accelerators may be present in the oxygen carrier material in an amount less than or equal to 10% by weight and greater than or equal to 1% by weight, greater than or equal to 2% by weight, greater than or equal to 3% by weight, greater than or equal to 4% by weight, greater than or equal to 5% by weight, greater than or equal to 6% by weight, greater than or equal to 7% by weight, greater than or equal to 8% by weight, or greater than or equal to 9% by weight. In another embodiment, one or more accelerators may be present in the oxygen carrier material in an amount greater than or equal to 0.001% by weight and less than or equal to 9% by weight, less than or equal to 8% by weight, less than or equal to 7% by weight, less than or equal to 6% by weight, less than or equal to 5% by weight, less than or equal to 4% by weight, less than or equal to 3% by weight, less than or equal to 2% by weight, or less than or equal to 1% by weight.

[0052] In embodiments, in addition to the first composition and optionally one or more promoters, the oxygen carrier material may also contain one or more additional materials. In embodiments, one or more additional materials may be used 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 aluminum, niobium, or combinations thereof. Generally, one or more additional materials may not contain elements other than oxygen present in the first composition or promoter. Mixtures of various oxides of the desired elements may be included in one or more additional materials. Non-limitingly, 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 additional materials that can act as a binder include, but are not limited to, alumina (α, θ, or γ phases).

[0053] According to the implementation scheme, the oxygen carrier material may contain 1% to 50% by weight of one or more other materials. For example, one or more other 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 contain 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 other 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.

[0054] 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.

[0055] 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 Technol, 7 (1973) 285-292, the entire contents of which are incorporated herein by reference.

[0056] 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 / coalescing bubbles, having a maximum bubble size and a large wake; a high level of solid mixing and gas backmixing, assuming U - umf is equal (U is the velocity of the carrier gas and Umf is the minimum fluidization velocity, usually 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 micrometers (μm); or with increasing pressure, temperature, viscosity, and density of the gas. 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 smooth fluidization occurs at low gas velocities; and may exhibit controlled bubbling with small bubbles at higher gas velocities.

[0057] 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 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 of 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.

[0058] 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.

[0059] 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 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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] This disclosure includes many aspects, including aspects 1 through 15 described herein.

[0064] Aspect 1. A method for producing an olefin compound, the method comprising: passing a feed stream into a reactor, wherein the feed stream comprises one or more hydrocarbons; passing an oxygen carrier material into the reactor, wherein in the reactor: dehydrogenating the one or more hydrocarbons to form hydrogen and one or more olefin compounds; and reacting at least a portion of the hydrogen with oxygen from the oxygen carrier material to produce water; wherein the oxygen carrier material comprises 40% to 100% by weight of a first composition and 0% to 10% by weight of one or more promoters, wherein at least 95% by weight of the first composition comprises the following Composition: 0.001 mol to 1 mol of strontium; 0 mol to 0.999 mol of calcium, wherein the sum of the molar amounts of calcium and strontium equals 1; 0.001 mol to 1 mol of manganese; 0 mol to 0.999 mol of one or more of titanium, zirconium, iron or magnesium, wherein the sum of the molar amounts of manganese and the molar amounts of one or more of titanium, zirconium, iron or magnesium is 0.5 mol to 2 mol per mole; and 0.001 mol to 5 mol of oxygen; and the one or more promoters are selected from oxides of lithium, sodium, potassium, tungsten, molybdenum, silicon, sulfur, phosphorus or combinations thereof.

[0065] Aspect 2. The method according to aspect 1, wherein the first composition comprises calcium.

[0066] Aspect 3. The method according to aspect 1, wherein the first composition does not contain calcium.

[0067] Aspect 4. The method according to aspect 1, 2 or 3, wherein the first composition comprises one or more of titanium, zirconium, iron or magnesium.

[0068] Aspect 5. The method according to aspect 1, 2 or 3, wherein the amount of one or more of the titanium, zirconium, iron or magnesium is from 0.001 moles to 0.2 moles.

[0069] Aspect 6. The method according to any one of Aspects 1 to 5, wherein the first composition does not contain titanium, zirconium, iron or magnesium.

[0070] Aspect 7. The method according to any one of Aspects 1 to 5, wherein the first composition comprises at least 0.1% by weight of the one or more promoters.

[0071] Aspect 8. The method according to any of the preceding aspects, wherein the first composition does not contain the one or more promoters.

[0072] Aspect 9. The method according to any of the preceding aspects, wherein: the one or more hydrocarbons include ethane, ethylbenzene, propane, butane or combinations thereof; and the one or more olefin compounds include ethylene, styrene, propylene, butene or combinations thereof.

[0073] Aspect 10. The method according to any of the preceding aspects, wherein the oxygen carrier material is circulated between the reactor and the regeneration unit, wherein the oxygen carrier material leaving the reactor is in an oxygen-deficient state, and the oxygen carrier material leaving the regeneration unit is in an oxygen-rich state.

[0074] Aspect 11. The method according to aspect 10, wherein fuel gas is burned in the regeneration unit to heat the oxygen carrier material.

[0075] Aspect 12. The method according to aspect 10, wherein the fuel gas comprises hydrogen, methane, ethane, propane, or combinations thereof.

[0076] Aspect 13. The method according to any of the preceding aspects, wherein the oxygen carrier material further comprises one or more additional materials selected from oxides of aluminum, niobium, or combinations thereof.

[0077] Aspect 14. The method according to aspect 13, wherein the one or more additional materials are used as adhesives.

[0078] Aspect 15. The method according to aspect 13, wherein the oxygen carrier comprises the first composition, the one or more promoters, and the one or more additional materials.

[0079] Example

[0080] 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.

[0081] Example 1 - Sample Preparation

[0082] Comparative Example X was prepared by first obtaining commercially available quartz sheets (Pyromatics). The quartz sheets were then sieved to 100-200 mesh before use.

[0083] Comparative Example A was prepared by first obtaining calcium carbonate (CaCO3, Sigma-Aldrich 99.0%) and manganese dioxide (MnO2, Sigma-Aldrich 99%) (both commercially available and used as is). Stoichiometric amounts of CaCO3 and MnO2 were weighed into a mortar. The dry powder was first ground with a pestle for 20 minutes (min). The powder was then shaken in a separate container for 1 minute and returned to the mortar. The grinding and shaking steps were repeated three times (a total of 60 minutes of grinding and 3 minutes of shaking). The powder was transferred to an alumina crucible and finally calcined in air at 1350°C for 5 hours.

[0084] Comparative Example B was prepared by first obtaining calcium nitrate tetrahydrate (Ca(NO3)2·4H2O, Sigma-Aldrich, 99%), manganese nitrate tetrahydrate (Mn(NO3)2·4H2O, Supelco, 98.5%), citric acid (CA, Alfa Aesar, 99%), and ethylene glycol (EG, Fisher Scientific, 99%) (all commercially available and used as is). Stoichiometric amounts of Ca(NO3)2·4H2O and Mn(NO3)2·4H2O were weighed and dissolved in 100 mL of deionized H2O in a 1 L beaker with vigorous stirring. Subsequently, citric acid and ethylene glycol were weighed and added to the solution in a molar ratio of (Ca+Mn):CA:EG = 1:1:1. The solution was heated to 80°C and stirred at a constant temperature until gelation occurred, which was identified by the presence of <10 mL of non-free-flowing residual liquid. The gel was transferred to an alumina crucible and dried in air at 120°C for at least 5 hours. The dried gel was calcined at 1000°C for 12 hours, and finally at 1200°C for 12 hours.

[0085] Comparative Example C was prepared by first weighing stoichiometric amounts of CaCO3 and MnO2 in a mortar. First, the dry powder was ground with a pestle for 5 minutes. Then, the powder was shaken in a separate container for 1 minute and returned to the mortar. The grinding and shaking steps were repeated twice (a total of 10 minutes of grinding and 2 minutes of shaking). Subsequently, after introducing 5 to 10 mL of deionized H2O, the powder was ground and gelatinized for 5 minutes. The paste was transferred to an alumina crucible and dried in air at 120°C for at least 5 hours. The dried mixture was calcined in air at 800°C for 2 hours and finally calcined at 1200°C for 24 hours.

[0086] Comparative Example D was prepared in the same manner as Comparative Example C, except that the calcination was carried out at 800°C for 2 hours and finally at 1350°C for 24 hours.

[0087] Comparative Example E was prepared in the same manner as Comparative Example C, except that the calcination was carried out at 800°C for 2 hours and finally at 1200°C for 48 hours.

[0088] Comparative Example F was prepared by first obtaining potassium tungstate solid (K2WO4, Thermo Scientific, 99.5%) (commercially available and used as is). An accelerator solution was first prepared by dissolving the desired amount of K2WO4 solid in deionized H2O. The sample of Comparative Example E was then impregnated with the accelerator solution. The impregnated material was dried below 200°C and then calcined in air at below 1000°C for 6 hours.

[0089] This was achieved by first obtaining potassium sulfate (K₂SO₄, Sigma-Aldrich, 99.0%) solid and sodium silicate solution (Na₂O(SiO₂)). x Comparative Examples G and H were prepared using K₂SO₄ solid dissolved in H₂O (commercial source and used as is). Comparative Examples G and H were prepared in the same manner as Comparative Example F, except that Na₂O (SiO₂) was diluted with H₂O by dissolving solid K₂SO₄ in H₂O (Comparative Example G). x The accelerator solution was prepared using a solution (Comparative Example H).

[0090] Sample 1 was prepared by first obtaining strontium carbonate (SrCO3, Sigma-Aldrich, 99.9%) (commercial source and used as is). Sample 1 was prepared in the same manner as Comparative Example E using stoichiometric amounts of CaCO3, SrCO3, and MnO2.

[0091] Samples 2-5 were prepared in the same manner as Comparative Example A using stoichiometric amounts of CaCO3, SrCO3, and MnO2, and were calcined in air at 1200°C for 48 hours.

[0092] Samples 6, 7 and 8 were prepared in the same manner as samples 2, 3 and 4, except that for all three samples, calcination was carried out in air at 1350°C for 48 hours.

[0093] Samples 9 and 10 were prepared in the same manner as samples 2 and 3, except that the calcination was carried out in air at 1450°C for 48 hours.

[0094] Samples 11-14 were prepared by first obtaining strontium nitrate (Sr(NO3)2, Sigma-Aldrich, 99.0%) (commercial source and used as is). Samples 11, 12, 13 and 14 were prepared in the same manner as Comparative Example B using stoichiometric amounts of Ca(NO3)2·4H2O, Sr(NO3)2, Mn(NO3)2·4H2O, CA and EG, wherein the molar ratio was modified to (Ca+Sr+Mn):CA:EG=1:1:1.

[0095] Sample 15 was prepared in the same manner as Comparative Example D using stoichiometric amounts of CaCO3, SrCO3, and MnO2.

[0096] Samples 16, 17, and 18 were prepared in the same manner as comparative samples F, G, and H, respectively, with sample 1 prepared using samples containing K2WO4, K2SO4, and Na2O (SiO2), respectively. x Impregnate with the corresponding accelerator solution.

[0097] Example 2 - Selective Hydrogen Combustion Performance

[0098] The selective hydrogen combustion performance of the sample was evaluated in a U-shaped fixed-bed reactor made of quartz. Typically, 125 mg of sample was prepared with a size of 100-200 mesh and diluted with 400 mg of quartz flakes (100-200 mesh) before being loaded into the reactor. The sample was heated to 750 °C under an air stream, purged with helium, and then subjected to three cycles at 750 °C at a total gas flow rate of 12 standard cubic centimeters (sccm). In each cycle, the sample was first exposed to 90% C₂H₆ / 10% N₂ for 1 minute, purged with helium, and finally regenerated in air for 15 minutes. After 23 seconds of ethane exposure, the composition of the outlet gas was analyzed by gas chromatography. The data presented in Table 1 below are the average values ​​from the three cycles.

[0099] The ethane conversion and carbon-based selectivity are calculated using the following equations, where [X] corresponds to the mole fraction and IS corresponds to the internal standard.

[0100]

[0101] Table 1. Selective hydrogen combustion performance of Sr-doped perovskite oxides prepared by solid-state synthesis

[0102]

[0103] As shown in Table 1, the samples containing strontium (i.e., samples 1-10) outperformed the samples without strontium (i.e., comparative examples X and A). For example, compared with comparative examples X containing strontium-containing oxygen carrier materials (such as sample 1 (0.34)), comparative examples X without oxygen carrier materials had a poorer H2 / C2H4 ratio (1.04). Furthermore, compared with the samples without strontium, the samples containing strontium showed significantly improved H2 / C2H4 ratios, C2H4 selectivity, and CO2 content. x Selectivity. For example, Comparative Example A, with a composition of CaMnO3, has an H2 / C2H4 ratio of 0.38, a C2H4 selectivity of 75.4%, and a CO selectivity of 17.8%. x Selectivity. Sample 1 has Ca 0.5 Sr 0.5 The composition of MnO3 is as follows, with an H2 / C2H4 ratio of 0.34, a C2H4 selectivity of 85.7%, and a CO content of 8.7%. x Selectivity. Therefore, the addition of strontium to oxygen carrier materials improves the performance of selective hydrogen combustion.

[0104] Table 2. Selective hydrogen combustion performance of Sr-doped perovskite oxides prepared by Pechini synthesis

[0105]

[0106] As shown in Table 2, the samples with strontium partially substituted for calcium (i.e., samples 11-13) showed better C2H4 selectivity and CO2 selectivity than the samples with only calcium (i.e., comparative example B). x Improvements in selectivity. For example, Comparative Example B exhibits 77.4% C2H4 selectivity and 17.2% CO selectivity. x Selectivity. Sample 11 exhibits 86.4% C2H4 selectivity and 7.9% CO selectivity. x Selectivity.

[0107] Furthermore, the sample with strontium fully substituted for calcium (i.e., sample 14) showed similar C2H4 selectivity and CO2 as the sample with strontium partially substituted for calcium. x Improved selectivity. Sample 14 exhibited 86.1% C2H4 selectivity and 8.1% CO selectivity. x Selectivity. Therefore, a strontium content greater than 0 to 1 mole significantly improves the selective hydrogen combustion performance of oxygen carrier materials.

[0108] Table 3. Selective hydrogen combustion performance of Sr-doped perovskite oxides prepared by solid-state synthesis .

[0109]

[0110] As shown in Table 3, samples containing strontium in the oxygen support material showed improved performance across all measured aspects, including the H2 / C2H4 ratio, C2H4 selectivity, and CO2 content. x Selectivity. For example, Comparative Example C, with a composition of CaMnO3, exhibits a C2H6 conversion of 33.5%, an H2 / C2H4 ratio of 0.39, a C2H4 selectivity of 75.7%, and a CO2 selectivity of 18.6%. x Selectivity. Having Ca 0.5 Sr 0.5 Sample 15, composed of MnO3, exhibited a C2H6 conversion of 35.3%, an H2 / C2H4 ratio of 0.34, a C2H4 selectivity of 82.7%, and a CO conversion of 10.3%. x Selectivity. Therefore, the presence of strontium improves the performance of oxygen-supported materials.

[0111] Table 4. Selective hydrogen combustion performance of Sr-doped perovskite oxides promoted by alkaline compounds

[0112]

[0113] As shown in Table 4, the samples with the added oxide accelerator and strontium (i.e., samples 16-18) showed better CO2 concentrations than the samples with only the added oxide accelerator and no strontium (i.e., Comparative Example FH) and the samples without the added oxide accelerator and only strontium (i.e., sample 1). x Significant improvement in selectivity. Although Sample 1 performed better than Comparative Example E without the oxide accelerator or strontium, the addition of the oxide accelerator with strontium greatly improved CO2 efficiency. x Selectivity. For example, Comparative Example E has 13.8% CO. x Selectivity: Sample 1 had 8.7% CO. x Selectivity, and sample 17 had 0.8% CO. x Selectivity.

[0114] Furthermore, samples containing both the oxide accelerator and strontium (i.e., samples 16-18) showed greater C2H4 selectivity and CO2 content than samples containing only the oxide accelerator without strontium (i.e., comparative example FH). x Overall improvement in selectivity. For example, sample 16 exhibited 91.2% C2H4 selectivity and 3.5% CO selectivity. x Selectivity. Comparative example F has 81.1% C2H4 selectivity and 13.6% CO selectivity. x Selectivity. Therefore, the selective hydrogen combustion performance of the oxygen carrier material was improved by adding strontium and optional oxide promoters.

[0115] 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.

[0116] 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.

[0117] 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.

[0118] 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.

[0119] 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.

[0120] 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".

[0121] 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.

[0122] 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. A method for producing an olefin compound, the method comprising: A feed stream is passed into the reactor, wherein the feed stream contains one or more hydrocarbons; The oxygen carrier material is transferred into the reactor, wherein in the reactor: To dehydrogenate one or more hydrocarbons to form hydrogen gas and one or more olefin compounds; as well as At least a portion of the hydrogen gas is reacted with oxygen from the oxygen carrier material to produce water; The oxygen carrier material comprises 40% to 100% by weight of a first composition and 0% to 10% by weight of one or more promoters, wherein; At least 95% by weight of the first composition comprises the following: 0.001 moles to 1 mole of strontium; 0 to 0.999 moles of calcium, wherein the sum of the moles of calcium and the moles of strontium equals 1; 0.001 moles to 1 mole of manganese; A combination of one or more of titanium, zirconium, iron, or magnesium, ranging from 0 to 0.999 moles, wherein the sum of the moles of manganese and the moles of one or more of titanium, zirconium, iron, or magnesium is 0.5 to 2 moles per mole; and 0.001 molar to 5 molar of oxygen; and The one or more accelerators are selected from oxides of lithium, sodium, potassium, tungsten, molybdenum, silicon, sulfur, phosphorus, or combinations thereof.

2. The method of claim 1, wherein the first composition comprises calcium.

3. The method of claim 1, wherein the first composition does not contain calcium.

4. The method according to claim 1, 2 or 3, wherein the first composition comprises one or more of titanium, zirconium, iron or magnesium.

5. The method according to claim 1, 2 or 3, wherein the amount of one or more of titanium, zirconium, iron or magnesium is from 0.001 moles to 0.2 moles.

6. The method according to any one of claims 1 to 5, wherein the first composition does not contain titanium, zirconium, iron or magnesium.

7. The method according to any one of claims 1 to 5, wherein the first composition comprises at least 0.1% by weight of the one or more promoters.

8. The method according to any of the preceding claims, wherein the first composition does not contain the one or more promoters.

9. The method according to any of the preceding claims, wherein: The one or more hydrocarbons include ethane, ethylbenzene, propane, butane, or combinations thereof; and The one or more olefin compounds include ethylene, styrene, propylene, butene, or combinations thereof.

10. The method according to any of the preceding claims, wherein the oxygen carrier material is circulated between the reactor and the regeneration unit, wherein the oxygen carrier material leaving the reactor is in an oxygen-deficient state, and the oxygen carrier material leaving the regeneration unit is in an oxygen-rich state.

11. The method of claim 10, wherein fuel gas is burned in the regeneration unit to heat the oxygen carrier material.

12. The method of claim 10, wherein the fuel gas comprises hydrogen, methane, ethane, propane, or combinations thereof.

13. The method according to any of the preceding claims, wherein the oxygen carrier material further comprises one or more other materials selected from oxides of aluminum, niobium, or combinations thereof.

14. The method of claim 13, wherein the one or more additional materials are used as an adhesive.

15. The method of claim 13, wherein the oxygen carrier comprises the first composition, the one or more promoters, and the one or more additional materials.

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