Methods for converting alkanes to alkenes and steam tolerant promoted dehydrogenation catalysts

Abstract

A method for converting alkanes to alkenes may include contacting a feed stream comprising alkanes with a promoted dehydrogenation catalyst in a reaction zone in the presence of steam, the promoted dehydrogenation catalyst comprising: zirconia and a metal, wherein the metal is selected from the group consisting of chromium, gallium, iron, and combinations thereof, and silicon. The method further includes converting at least a portion of the alkanes to alkenes, thereby yielding a product stream comprising alkanes, alkenes, and hydrogen, wherein the promoted dehydrogenation catalyst does not require a gaseous oxidant in the feed steam or as a co-feed to catalyze conversion of alkanes to alkenes.

Description

85056-WO-PCT / DOW 85056 WO 1 METHODS FOR CONVERTING ALKANES TO ALKENES AND STEAM TOLERANT PROMOTED DEHYDROGENATION CATALYSTS CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 511,263 filed June 30, 2023, the contents of which are incorporated in their entirety herein. TECHNICAL FIELD

[0002] The present disclosure relates to methods for efficiently converting various alkanes to alkenes. In particular, the present disclosure relates to the preparation of promoted dehydrogenation catalysts, and more particularly, silicon promoted dehydrogenation catalysts that tolerate steam, and methods of using the promoted dehydrogenation catalysts to achieve a high conversion of alkanes to alkenes in the presence of steam. BACKGROUND

[0003] Alkenes are used for a wide range of industrial applications, including producing plastics, fuels, and various downstream chemicals. Such alkenes include C2 to C4 materials, including ethene, propene, and butenes (also commonly referred to as ethylene, propylene, and butylenes, respectively). A variety of processes for producing these alkenes have been developed, including petroleum cracking and various synthetic processes.

[0004] One such process for producing alkenes is alkane dehydrogenation. Conventional alkane dehydrogenation is endothermic and equilibrium limited. Therefore, to reach economically feasible levels of alkane-to-alkene conversion, conventional alkane dehydrogenation necessitates the use of low pressures to shift the equilibrium toward producing products and high temperatures, often in excess of 800oC, to provide thermal energy. Additionally, conventional alkane dehydrogenation processes suffer from additional undesirable radical chemistry that may produce coke as a byproduct. The formation of coke may cause blockages, which may require periodic process shutdowns for decoking operations.85056-WO-PCT / DOW 85056 WO 2

[0005] Maintaining the low pressures and high temperatures necessary for economically feasible alkane-to-alkene conversion can be expensive. Accordingly, a need exists for methods and catalytic systems with high alkene selectivity that operate at higher pressures and lower temperatures while reaching economically feasible levels of alkane-to-alkene conversion. SUMMARY

[0006] Embodiments of the present disclosure address these and other needs by the methods of preparation of promoted dehydrogenation catalysts, and more particularly, silicon-promoted dehydrogenation catalysts that are capable of performing dehydrogenation chemistry in the presence of steam, and methods of using such promoted dehydrogenation catalysts. A promoted dehydrogenation catalyst, as described herein, comprises zirconia (ZrO2) and a metal selected from the group consisting of chromium (Cr), gallium (Ga), iron (Fe), and combinations thereof, and silicon (Si). This promoted dehydrogenation catalyst may then be used for converting alkanes to alkenes. The promoted dehydrogenation catalyst may be able to catalyze the conversion of alkanes to alkenes in the presence of steam.

[0007] According to one or more embodiments of the present disclosure, a method for converting alkanes to alkenes may comprise contacting a feed stream comprising alkanes with a promoted dehydrogenation catalyst in a reaction zone in the presence of steam, the promoted dehydrogenation catalyst comprising zirconia and a metal selected from the group consisting of chromium, gallium, iron, and combinations thereof, and silicon, converting at least a portion of the alkanes to alkenes, thereby yielding a product stream comprising alkanes, alkenes, and hydrogen.

[0008] According to one or more embodiments of the present disclosure, a method for forming a promoted dehydrogenation catalyst may comprise obtaining a zirconia support, adding a silicon- containing precursor to the zirconia support, adding a metal-containing precursor to the zirconia support, wherein the metal-containing precursor is selected from the group consisting of chromium, gallium, iron, and combinations thereof, to form a metal-containing zirconia, and calcining and drying the metal-containing zirconia to form a promoted dehydrogenation catalyst, wherein adding a silicon-containing precursor to the zirconia support and adding a metal- containing precursor to the zirconia support occur in any order.85056-WO-PCT / DOW 85056 WO 3

[0009] Additional features and advantages will be set forth in the detailed description that follows and, in part, will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments described herein, including the detailed description which follows in addition to the claims.

[0010] It is to be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter. DETAILED DESCRIPTION

[0011] Reference will now be made in detail to embodiments of methods for preparing promoted dehydrogenation catalysts, and more particularly, silicon promoted dehydrogenation catalysts that tolerate steam, and methods of using the promoted dehydrogenation catalysts to convert alkanes to alkenes in the presence of steam. As used herein, “steam conditions” refers to reaction conditions where at least some amount of steam is present. For example, a reaction might take place under 5 volume percent (v.%) steam conditions wherein 5% of the gas volume of the reaction section would be filled with steam. The steam that leads to steam conditions may come from any source. For example, the steam that leads to steam conditions may be generated by selective hydrogen combustion materials.

[0012] As used herein, “dehydrogenation” refers to a chemical process by which hydrogen is chemically removed from a chemical compound. For example, ethane may undergo dehydrogenation to be converted to ethylene. As used herein, “dehydrogenation catalyst(s)” refers to any substance that increases the rate of a dehydrogenation reaction without itself undergoing any permanent chemical change. As used herein, “promoted dehydrogenation catalyst(s)” refers to a catalyst that has had an amount of activator (also commonly referred to as catalytic promoter) added to the catalyst. The activator may increase the catalytic efficiency by improving catalytic selectivity, catalytic activity, or combinations thereof. When the activator improves both catalytic selectivity and catalytic activity, an improved product yield will result. For example, silicon might be added to a dehydrogenation catalyst to increase the dehydrogenation catalyst’s catalytic efficiency. As used herein, “background dehydrogenation activity” refers to the dehydrogenation activity that occurs in the presence of inert material, as measured under the same process85056-WO-PCT / DOW 85056 WO 4 conditions. For example, a dehydrogenation catalyst may have an activity equal to 1.1 times background dehydrogenation activity when the conversion rate using the dehydrogenation catalyst is 1.1 times the conversion rate when using quartz chips under the same process conditions.

[0013] As used herein, “alkane(s)” refers to any series of hydrocarbon molecules that consist of carbon single bonds where the carbon structure is saturated with hydrogen. Ethane, propane, and butane are examples of alkanes. As used herein, “alkene(s)” refers any series of hydrocarbon molecules, where at least two of the carbon atoms are not saturated with hydrogen and share a double bond. Ethylene, propylene, 1-butene, trans-2-butene, and cis-2-butene are examples of alkenes. Alkenes include dienes, which are series of hydrocarbons, where at least two sets of two of the carbon molecules, that may or may not be adjacent to each other, are not saturated with hydrogen and share a double bond.

[0014] As used herein, “metal-containing zirconia” refers to a zirconia where metal selected from the group consisting of chromium, gallium, iron, and combinations thereof is present on the surface of the zirconia, and / or metal selected from the group consisting of chromium, gallium, iron, and combinations thereof is present in the pores of the zirconia. The metal may be present in any form. For example, the metal may be in the form of a metal oxide.

[0015] As used herein, “silicon-containing zirconia” refers to a zirconia where silicon is present on the surface of the zirconia, and / or silicon is present on the pores of the zirconia, and / or silicon is present in the pores of the zirconia. The silicon may be present in any form. For example, the silicon may be in the form of silica. The use of dehydrogenation catalysts is known in the field of hydrocarbon products, such as plastics, fuels, and various downstream chemicals. For example, the Catofin propane dehydrogenation processes from Lummus Technology and the Oleflex propane dehydrogenation processes from Honeywell employ Cr / Al2O3and Pt-Sn-based dehydrogenation catalysts, respectively. Additionally, zirconia and metal catalysts and promoters are known for use in oxidative dehydrogenation of alkanes. In the oxidative dehydrogenation processes, alkanes are typically co-fed with a gaseous oxidant such as oxygen, air, carbon dioxide, or nitrogen oxides, thus shifting the equilibrium constraint of the dehydrogenation reaction towards product formation and alkane conversion.85056-WO-PCT / DOW 85056 WO 5

[0016] Oxidative dehydrogenation occurs at the surface of the catalyst by a reaction of alkane and oxidant and generates water. The presence of water and alkanes at high temperatures can lead to reduced alkene selectivity through oxidation and reforming reactions that yield methane and carbon oxide products such as carbon monoxide and carbon dioxide. Furthermore, many oxidative dehydrogenation catalysts, when used in the absence of a gaseous oxidant in the feed stream or as a co-feed, exhibit significantly reduced activity in the presence of steam. Thus, not every oxidative dehydrogenation catalyst is a steam tolerant alkane dehydrogenation catalyst. In contrast, the promoted dehydrogenation catalysts disclosed and described herein exhibit steam tolerance, even in the absence of a gaseous oxidant in the feed stream or as a co-feed. The preparation and composition of such promoted dehydrogenation catalysts used in embodiments are discussed below.

[0017] The promoted dehydrogenation catalyst may comprise zirconia (ZrO2). As used herein, the zirconia used in embodiments disclosed and described herein in the promoted dehydrogenation catalyst may be “phase pure zirconia”, which is defined herein as zirconia to which no other materials have intentionally been added during production. Thus, “phase pure zirconia” includes zirconia with small amounts of components other than zirconium (including oxides other than zirconia) that are unintentionally present in the zirconia as a natural part of the zirconia production process, such as, for example, hafnium (Hf). Accordingly, as used herein “zirconia” and “phase pure zirconia” are used interchangeably unless specifically indicated otherwise. In other embodiments, the zirconia can be non-phase pure zirconia, such as zirconia doped with calcium (Ca), yttria (Y2O3), lanthanum (La), cerium (Ce), or rare earth elements.

[0018] According to embodiments, the zirconia particles may include zirconia particles having a crystalline structure. The zirconia particles may include zirconia particles having monoclinic crystal form (also known as a baddeleyite structure), tetragonal crystal form, cubic crystal form, or combinations thereof.

[0019] The promoted dehydrogenation catalyst may comprise a metal selected from the group consisting of chromium (Cr), gallium (Ga), iron (Fe), and combinations thereof in any suitable oxidation state and silicon (Si) in any suitable oxidation state. According to embodiments, the chromium may have an oxidation state of +2, +3, +4, +5, +6, or combinations thereof. In85056-WO-PCT / DOW 85056 WO 6 embodiments, the dehydrogenation catalyst may comprise chromium having a single oxidation state or the dehydrogenation catalyst may comprise chromium having different oxidation states. According to embodiments, the gallium may have an oxidation state of +1, +3, or combinations thereof. In embodiments, the dehydrogenation catalyst may comprise gallium having a single oxidation state or the dehydrogenation catalyst may comprise gallium having different oxidation states. According to embodiments, the iron may have an oxidation state of +2, +3, +4, +6, or combinations thereof. In embodiments, the dehydrogenation catalyst may comprise iron having a single oxidation state or the dehydrogenation catalyst may comprise iron having different oxidation states. According to embodiments, the silicon may have an oxidation state of +2, +4, or combinations thereof. In embodiments, the dehydrogenation catalyst may comprise silicon having a single oxidation state or the dehydrogenation catalyst may comprise silicon having different oxidation states.

[0020] In one or more embodiments, the promoted dehydrogenation catalyst may comprise zirconia, where the zirconia acts as a metal oxide support. The term “metal oxide support” may refer to a support material that supports the other components of the promoted dehydrogenation catalyst, for example, chromium.

[0021] In one or more embodiments, a method for forming a promoted dehydrogenation catalyst may comprise obtaining a zirconia support, adding a metal-containing precursor to the zirconia support, wherein the metal-containing precursor is selected from the group consisting of chromium, gallium, iron, and combinations thereof to form a metal-containing zirconia, and calcining and drying the metal-containing zirconia. In embodiments, the metal-containing zirconia may be calcined and dried under air at a temperature of less than or equal to 1000 °C. In embodiments, the method may further comprise adding a silicon-containing precursor to the zirconia support. The metal-containing zirconia support may be calcined and dried. The method for forming a promoted dehydrogenation catalyst may further comprise preparing the zirconia support by precipitation reaction.

[0022] In one or more embodiments, adding a metal-containing precursor to the zirconia support, wherein the metal-containing precursor is selected from the group consisting of chromium, gallium, iron, and combinations thereof to form a metal-containing zirconia may85056-WO-PCT / DOW 85056 WO 7 comprise impregnating the zirconia support with a metal selected from the group consisting of chromium, gallium, iron, and combinations thereof to form a metal-impregnated-zirconia.

[0023] In one or more embodiments, a method for forming a promoted dehydrogenation catalyst may comprise obtaining a zirconia support, adding a silicon-containing precursor to the zirconia support, and calcining and drying the zirconia support. In embodiments, the zirconia support may be calcined and dried under air at a temperature of less than or equal to 1000 °C. In embodiments, the method may further comprise adding a metal-containing precursor to the zirconia support, wherein the metal-containing precursor is selected from the group consisting of chromium, gallium, iron, and combinations thereof, and may be calcined and dried. In one or more embodiments, a method for forming a promoted dehydrogenation catalyst may further comprise preparing the zirconia support by precipitation reaction.

[0024] In one or more embodiments, the promoted dehydrogenation catalyst may be prepared by precipitation. For example, the promoted dehydrogenation catalyst may be prepared by co- precipitating the zirconia support, a silicon-containing precursor, and a metal-containing precursor, wherein the metal is selected from the group consisting of chromium, gallium, iron, and combinations thereof. In embodiments, the promoted dehydrogenation catalyst may be prepared by a combination of impregnation and precipitation. For example, the zirconia support might first be prepared by precipitation, and then the zirconia support might be impregnated with a silicon-containing precursor to form a silicon-impregnated zirconia support. The silicon- impregnated-zirconia support might then be impregnated with a metal-containing precursor, wherein the metal is selected from the group consisting of chromium, gallium, iron, and combinations thereof by precipitation. As another example, the zirconia support might first be prepared by precipitation, and then the zirconia support might be impregnated with a metal- containing precursor, wherein the metal is selected from the group consisting of chromium, gallium, iron, and combinations thereof to form a metal-impregnated zirconia. The metal impregnated zirconia might then be impregnated with a silicon-containing precursor by precipitation.

[0025] In one or more embodiments, adding a silicon-containing precursor to the zirconia support any combination of contacting the zirconia support with a silicon-containing precursor,85056-WO-PCT / DOW 85056 WO 8 wherein the zirconia support is a fluidizable zirconia support, adding a silicon-containing precursor to the zirconia support by spray drying, or adding a silicon-containing precursor to the zirconia support by granulation.

[0026] In one or more embodiments, adding a metal-containing precursor to the zirconia support, wherein the metal-containing precursor is selected from the group consisting of chromium, gallium, iron, and combinations thereof to form a metal-containing zirconia support may comprise adding a metal-containing precursor to the zirconia support in a fluidized bed operation, wherein the zirconia support is a fluidizable zirconia support. In embodiments, adding a metal-containing precursor to the zirconia support to form a metal-containing zirconia support may comprise contacting the zirconia support with the metal by spray drying. In embodiments, adding a metal-containing precursor to the zirconia support may comprise contacting the zirconia support with the metal by granulation. In embodiments, adding a metal-containing precursor to the zirconia support may comprise any combination of adding a metal-containing precursor to the zirconia support wherein the zirconia support is a fluidizable zirconia support, adding a metal- containing precursor to the zirconia support by spray drying, or adding a metal-containing precursor to the zirconia support by granulation.

[0027] In one or more embodiments, adding a silicon-containing precursor to the zirconia support, wherein the zirconia support is a fluidizable zirconia support, may comprise placing the zirconia support in a fluidized bed reactor and adding a silicon-containing precursor to the zirconia support to form a silicon-containing zirconia. In embodiments, the silicon-containing precursor may be a dry powder or may be part of a solution or slurry. In embodiments, the silicon-containing zirconia support prepared using a fluidized bed operation may be spray dried. In embodiments, adding a silicon-containing precursor to the zirconia support by granulation may comprise combining powdered zirconia support with powdered silicon-containing precursor and combining the powdered zirconia support and powdered silicon-containing precursor to form silicon- containing zirconia.

[0028] In one or more embodiments, adding a metal-containing precursor to the zirconia support, wherein the metal-containing precursor is selected from the group consisting of chromium, gallium, iron, and combinations thereof, wherein the zirconia support is a fluidizable85056-WO-PCT / DOW 85056 WO 9 zirconia support may comprise placing the zirconia support in a fluidized bed reactor and adding a metal-containing precursor to the zirconia support. In embodiments, the metal may be a dry powder or may be part of a solution or slurry.

[0029] The promoted dehydrogenation catalyst may be prepared either by first adding a silicon-containing precursor to the zirconia support and adding a metal-containing precursor to the zirconia support, wherein the metal-containing precursor is selected from the group consisting of chromium, gallium, iron, and combinations thereof, or by first adding a metal-containing precursor to the zirconia support, wherein the metal-containing precursor is selected from the group consisting of chromium, gallium, iron, and combinations thereof and then adding a silicon- containing precursor to the zirconia support.

[0030] In embodiments, the surface area of the zirconia particles may be greater than or equal to 5 meters squared per gram (m2 / g). For example, the surface area of the zirconia particles may be at least 5 m2 / g, at least 10 m2 / g, at least 20 m2 / g, at least 50 m2 / g, at least 75 m2 / g, at least 100 m2 / g, at least 125 m2 / g, or at least 150 m2 / g. In embodiments, the surface area of the zirconia particle may be from 5 m2 / g to 200 m2 / g, from 10 m2 / g to 200 m2 / g, from 20 m2 / g to 200 m2 / g, such as from 30 m2 / g to 200 m2 / g, from 40 m2 / g to 200 m2 / g, from 50 m2 / g to 200 m2 / g, from 60 m2 / g to 200 m2 / g, from 70 m2 / g to 200 m2 / g, from 80 m2 / g to 200 m2 / g, from 90 m2 / g to 200 m2 / g, from 100 m2 / g to 200 m2 / g, from 110 m2 / g to 200 m2 / g, from 120 m2 / g to 200 m2 / g, from 130 m2 / g to 200 m2 / g, or from 140 m2 / g to 200 m2 / g. In embodiments, the surface area of the zirconia particles may be from 5 m2 / g to 180 m2 / g, from 5 m2 / g to 160 m2 / g, from 5 m2 / g to 140 m2 / g, from 5 m2 / g to 120 m2 / g, from 5 m2 / g to 100 m2 / g, from 5 m2 / g to 90 m2 / g, from 5 m2 / g to 80 m2 / g, from 5 m2 / g to 70 m2 / g, from 5 m2 / g to 60 m2 / g, from 5 m2 / g to 50 m2 / g, from 5 m2 / g to 40 m2 / g, from 5 m2 / g to 30 m2 / g, from 5 m2 / g to 20 m2 / g, or from 5 m2 / g to 10 m2 / g. In embodiments, the surface area of the zirconia particles may be from 10 m2 / g to 160 m2 / g, from 20 m2 / g to 130 m2 / g, from 30 m2 / g to 120 m2 / g, from 40 m2 / g to 110 m2 / g, from 50 m2 / g to 100 m2 / g, from 60 m2 / g to 90 m2 / g, or from 70 m2 / g to 80 m2 / g.

[0031] It should be understood that according to embodiments, the dehydrogenation catalyst may be made by other methods that eventually lead to intimate contact between the silicon, chromium, gallium, iron, and combinations thereof and zirconia. Some examples include vapor85056-WO-PCT / DOW 85056 WO phase deposition of precursors of chromium, gallium, iron, silicon, and combinations thereof (either organic or inorganic in nature), followed by their controlled decomposition.

[0032] In one or more embodiments, silicon may act as a promoter for the promoted dehydrogenation catalyst. Stated another way, in one or more embodiments, silicon contacted with a metal-containing zirconia support may increase the catalyst efficiency of the metal contacted with the zirconia support by increasing the catalytic efficiency of the metal-containing zirconia support when the metal of the metal-containing precursor is selected from the group consisting of chromium, gallium, iron, and combinations thereof.

[0033] In one or more embodiments, the silicon is at least partially derived from silica. For example, the silicon promoter of the promoted dehydrogenation catalyst may comprise silica (SiO2). In embodiments, the silicon may be at least partially derived from colloidal silica, silicon alkoxide, or combinations thereof.

[0034] In one or more embodiments, the promoted dehydrogenation catalyst comprises from 0.5 % to 20 % metal based on a total weight of the promoted dehydrogenation catalyst wherein the metal is selected from the group consisting of chromium, gallium, iron, and combinations thereof. In embodiments, the dehydrogenation catalyst may comprise from 0.5 % to 20 % metal, from 0.1 % to 49 %, 0.2 % to 49 %, 0.3 % to 49 %, 0.4 % to 49 %, 0.5 % to 49 %, 1 % to 49 %, 5 % to 49 %, 10 % to 49 %, 15 % to 49 %, 20 % to 49 %, 25 % to 49 %, 30 % to 49 %, 40 % to 49 %, 0.1 % to 40 %, 0.2 % to 40 %, 0.3 % to 40 %, 0.4 % to 40 %, 0.5 % to 40 %, 1 % to 40 %, 5 % to 40 %, 10 % to 40 %, 15 % to 40 %, 20 % to 40 %, 25 % to 40 %, 30 % to 40 %, 0.1 % to 30 %, 0.2 % to 30 %, 0.3 % to 30 %, 0.4 % to 30 %, 0.5 % to 30 %, 1 % to 30 %, 5 % to 30 %, 10 % to 30 %, 15 % to 30 %, 20 % to 30 %, 25 % to 30 %, 0.1 % to 20 %, 0.2 % to 20 %, 0.3 % to 20 %, 0.4 % to 20 %, 0.5 % to 20 %, 1 % to 20 %, 5 % to 20 %, 10 % to 20 %, 15 % to 20 % metal, or any combination thereof, based on a total weight of the promoted dehydrogenation catalyst, wherein the metal is selected from the group consisting of chromium, gallium, iron, and combinations thereof.

[0035] In one or more embodiments, the promoted dehydrogenation catalyst may comprise hafnium. In embodiments, the hafnium may be present in the zirconia as a natural part of the zirconia production process.85056-WO-PCT / DOW 85056 WO

[0036] In one or more embodiments, the dehydrogenation catalyst may comprise 1 wt.% to 5 wt.% metal, wherein the metal is selected from the group consisting of chromium, gallium, iron, and combinations thereof, 40 wt.% to 80 wt.% zirconium metal, and 0.1 wt.% to 15 wt.% silicon metal, wherein the weight percent is calculated based on a total weight of the promoted dehydrogenation catalyst (the total weight of the promoted dehydrogenation catalyst including the oxygen in the oxides).

[0037] In one or more embodiments, the promoted dehydrogenation catalyst is a promoted dehydrogenation catalyst comprising the formula M-Zr-Si-X-Q, wherein M is a metal selected from the group consisting of chromium, gallium, iron, and combinations thereof, X is selected from the group consisting of alkali metals, alkaline earth metals, and combinations thereof, and Q is selected from the group consisting of tin (Sn), platinum (Pt), boron (B), lanthanum (La), cerium (Ce), neodymium (Nd), samarium (Sm), gadolinium (Gd), dysprosium (Dy), praseodymium (Pr), europium (Eu) and combinations thereof and combinations thereof. In embodiments, X, Q, or combinations thereof of the formula M-Zr-Si-X-Q may be in any thermodynamically stable oxidation state. In embodiments, X, Q, or combinations thereof, of the formula M-Zr-Si-X-Q may be an oxide. In embodiments, Zr of the formula M-Zr-Si-X-Q may comprise zirconia (ZrO2).

[0038] In one or more embodiments, a method for converting alkanes to alkenes may comprise contacting a feed stream comprising alkanes with a promoted dehydrogenation catalyst in a reaction zone under steam conditions. In embodiments, the feed stream may comprise C2-C4 alkanes. In embodiments, the feed stream may comprise ethane, propane, butanes, or combinations thereof. In embodiments, the feed stream may be contacted with the promoted dehydrogenation catalyst for a controlled time of exposure. In embodiments, the controlled time of exposure may be selected based on the desired catalyst to feed stream mass to mass ratio. In embodiments, the controlled time of exposure may be from 5 seconds (sec) to 1 hour (h). In embodiments, the controlled time of exposure may be from 5 seconds (sec) to 1 h, from 10 sec to 30 minutes (min), from 15 sec to 15 min, from 20 sec to 10 min, from 25 sec to 5 min, from 25 sec to 30 sec, from 30 sec to 1 min, or any combination thereof.

[0039] In one or more embodiments, the reaction zone may be a zone inside a reactor adapted to allow the feed stream to be contacted with the promoted dehydrogenation catalyst. In one or85056-WO-PCT / DOW 85056 WO more embodiments, the reactor may be a fixed-bed reactor, including but not limited to a dual tube fixed-bed reactor. In embodiments, the reactor may be a circulating fluidized bed reactor. In embodiments, the reactor may be two or more reactors in series or parallel, and each reactor in series or parallel may be the same type of reactor as other reactors in the series, or may be a different type of reactor from other reactors in the series. In embodiments, the reaction zone may house a material that converts gaseous hydrogen to water.

[0040] In one or more embodiments, a method for converting alkanes to alkenes may comprise converting at least a portion of the alkanes to alkenes, thereby yielding a product stream comprising alkanes, alkenes, and hydrogen. In embodiments, the product stream may comprise ethylene, propylene, butylene, hydrogen, or combinations thereof. In embodiments, the product stream may comprise ethane, propane, butane, ethylene, propylene, butylene, hydrogen, or combinations thereof.

[0041] In one or more embodiments, at least a portion of the hydrogen in the product stream is combusted and yields water. In embodiments, the water may be in the form of steam. In embodiments, the steam may comprise gaseous water, liquid water, aerosolized water, or combinations thereof. Because of this hydrogen combustion, water—such as steam—will be present in the reaction zone during dehydrogenation of the alkanes in the feed stream. As mentioned above, many oxidative dehydrogenation catalysts lose conversion and selectivity when they are exposed to water and require a significant amount of oxidative gas to offset the loss of conversion and selectivity. However, the promoted dehydrogenation catalysts disclosed and described herein retain catalytic activity in the presence of water and retain all or some of their selectivity and conversion when the hydrogen is combusted and forms water. Therefore, the catalysts disclosed and described herein can operate in the presence of water without the addition of oxidative gas.

[0042] In one or more embodiments, the promoted dehydrogenation catalyst may have an alkene selectivity of greater than or equal to 40 carbon mole percent (Cmol%), greater than or equal to 45 Cmol%, greater than or equal to 50 Cmol%, greater than or equal to 55 Cmol%, greater than or equal to 65 Cmol%, greater than or equal to 75 Cmol%, greater than or equal to 85 Cmol%,85056-WO-PCT / DOW 85056 WO greater than or equal to 95 Cmol%, greater than or equal to 97 Cmol%, greater than or equal to 98 Cmol%, or greater than or equal to 99 Cmol%.

[0043] In one or more embodiments, the promoted dehydrogenation catalyst comprises a conversion rate of greater than or equal to 1.1 times background dehydrogenation activity. In embodiments, the promoted dehydrogenation catalyst comprises a conversion rate of greater than or equal to 1.1 times, 1.5 times, 2 times, 3 times, 4 times, 5 times, or 10 times background dehydrogenation activity.

[0044] In one or more embodiments, the promoted dehydrogenation catalyst retains at least some dehydrogenation activity above background dehydrogenation activity under greater than or equal to 5 v.% steam conditions based on a total volume of gaseous components in the reaction zone. In embodiments, the promoted dehydrogenation catalyst retains at least some dehydrogenation activity above background dehydrogenation activity under greater than or equal to 5 v.%, 10 v.%, 15 v.%, 20 v.%, 25 v.%, 30 v.%, 35 v.%, 40 v.%, 45 v.%, or 50 v.% steam conditions based on a total volume of gaseous components in the reaction zone.

[0045] In embodiments, the promoted dehydrogenation catalyst comprises a dehydrogenation activity of greater than or equal to 1.1 times, 1.5 times, 2 times, 3 times, 4 times, 5 times, or 10 times background dehydrogenation activity under greater than or equal to 5 v.%, 10 v.%, 15 v.%, 20 v.%, 25 v.%, 30 v.%, 35 v.%, 40 v.%, 45 v.%, or 50 v.% steam conditions based on a total volume of gaseous components in the reaction zone.

[0046] In one or more embodiments, the method for converting alkanes to alkenes may further comprise contacting the feed stream comprising alkanes with at least one other catalyst. In embodiments, the at least one other catalyst may comprise a selective hydrogen combustion material. For example, oxygen-carrier materials such as those disclosed in U.S. App. No. 62 / 725,504, entitled “METHODS OF PRODUCING HYDROGEN-SELECTIVE OXYGEN- CARRIER MATERIALS,” filed on, August 31, 2018, and U.S. App. No. 62 / 725,508, entitled “HYDROGEN-SELECTIVE OXYGEN-CARRIER MATERIALS AND METHODS OF USE,” filed on, August 31, 2018, are contemplated as suitable for the presently disclosed processes, and the teachings of these references are incorporated by reference herein. In one or more additional embodiments, the oxygen-carrier material may include those of U.S. Pat. No.5,430,209, U.S. Pat.85056-WO-PCT / DOW 85056 WO No. 7,122,495, and / or WO 2018 / 232133, each of which are incorporated by reference in their entireties.

[0047] In embodiments, the selective hydrogen combustion material may be a promoted selective hydrogen combustion material. In embodiments, the promoted dehydrogenation catalyst and the selective hydrogen combustion material are both present in the reaction zone. In embodiments, the promoted dehydrogenation catalyst and the selective hydrogen combustion material may be present in a mass to mass ratio of from 10:1 to 1:10. In embodiments, the promoted dehydrogenation catalyst and the selective hydrogen combustion material may be present in a mass to mass ratio of from 10:1 to 1:10, from 10:1 to 1:10, from 2:1 to 1:10, from 1:1 to 1:10, from 10:1 to 1:5, from 10:1 to 1:5, from 2:1 to 1:5, from 1:1 to 1:5, from 10:1 to 1:2, from 10:1 to 1:2, from 2:1 to 1:2, from 1:1 to 1:2, from 10:1 to 1:1, from 10:1 to 1:1, or from 2:1 to 1:1. In embodiments, the promoted dehydrogenation catalyst and the selective hydrogen combustion material may be in contact with each other. In embodiments, the promoted dehydrogenation catalyst and the selective hydrogen combustion material may have been mixed or otherwise combined prior to being placed in the reaction zone. In embodiments, the promoted dehydrogenation catalyst and the selective hydrogen combustion material may be mixed in the reaction zone. In embodiments, the promoted dehydrogenation catalyst and the selective hydrogen combustion material may be separate.

[0048] As mentioned above, many conventional alkane dehydrogenation processes, such as oxidative dehydrogenation processes, require the use of gaseous oxidants such as oxygen, air, carbon dioxide, or nitrogen oxides in the feed stream or as a co-feed. The term “gaseous oxidant(s)” may refer to a substance or substances other than water that may oxidize hydrogen. However, in one or more embodiments of the present disclosure, the promoted dehydrogenation catalyst maintains the conversion of alkanes to alkenes without the presence of a gaseous oxidant in the feed stream or as a co-feed. In some embodiments, the promoted dehydrogenation catalyst maintains the conversion of alkanes to alkenes with the presence of only a small amount of a gaseous oxidant in the feed stream or as a co-feed. In some embodiments, the dehydrogenation catalyst maintains the conversion of alkanes to alkenes with the presence of less than 5 v.%, less than 4 v.%, less than 3 v.%, less than 2 v.%, less than 1 v.%, less than 0.5 v.%, less than 0.25 v.%, or less than 0.1 v.% gaseous oxidant in the feed stream or as a co-feed.85056-WO-PCT / DOW 85056 WO

[0049] In one or more embodiments, the promoted dehydrogenation catalyst and the feed stream have a mass to mass ratio that is from 5:1 to 200:1. This mass ratio is defined as the ratio between the feed rate of catalyst to the reaction zone and the feed rate of alkane to the reaction zone. In embodiments, the promoted dehydrogenation catalyst and the feed stream have a mass to mass ratio that is from 5:1 to 200:1, from 10:1 to 200:1, from 25:1 to 200:1, from 50:1 to 200:1, from 75:1 to 200:1, from 100:1 to 200:1, from 150:1 to 200:1, from 5:1 to 150:1, from 10:1 to 150:1, from 25:1 to 150:1, from 50:1 to 150:1, from 75:1 to 150:1, from 100:1 to 150:1, from 5:1 to 100:1, from 10:1 to 100:1, from 25:1 to 100:1, from 50:1 to 100:1, from 75:1 to 100:1, from 5:1 to 75:1, from 10:1 to 75:1, from 25:1 to 75:1, from 50:1 to 75:1, from 5:1 to 50:1, from 10:1 to 50:1, from 25:1 to 50:1, from 5:1 to 25:1, from 10:1 to 25:1, or from 5:1 to 10:1.

[0050] In one or more embodiments, the promoted dehydrogenation catalyst and the feed stream may have a weight hourly space velocity (WHSV) of from 1 to 12 per hour (h-1), where WHSV is defined as the weight of the feed stream flow per weight of the promoted dehydrogenation catalyst present in the reaction zone per hour. In embodiments, the promoted dehydrogenation catalyst and the feed stream may have a WHSV of from 1 to 12 h-1, from 1 to 10 h-1, from 1 to 8 h-1, from 1 to 5 h-1, from 1 to 3 h-1, or from 1 to 2 h-1.

[0051] In one or more embodiments, the converting at least a portion of the alkanes to alkenes occurs at a temperature that is less than or equal to 750 °C. In embodiments, the converting at least a portion of the alkanes to alkenes occurs at a temperature that is less than or equal to 780 °C, less than or equal to 750 °C, less than or equal to 725 °C, less than or equal to 700 °C, less than or equal to 675 °C, or less than or equal to 650 °C.

[0052] In one or more embodiments, the converting at least a portion of the alkanes to alkenes occurs at a pressure that is equal to atmospheric pressure. In embodiments, the converting at least a portion of the alkanes to alkenes occurs at a pressure from 1-20 bar, when measured as an absolute pressure (bara). In embodiments, the converting at least a portion of the alkanes to alkenes occurs at a pressure from 1-20 bara, from 1-15 bara, from 1-10 bara, or from 1-5 bara.

[0053] In one or more embodiments, the method of converting alkanes to alkenes may further comprise removing spent promoted dehydrogenation catalyst from the reaction zone and introducing the spent promoted dehydrogenation catalyst into a regeneration zone. In85056-WO-PCT / DOW 85056 WO embodiments, the regeneration zone may be part of the reactor. In embodiments, the regeneration zone may the separate from the reactor.

[0054] The method of converting alkanes to alkenes may further comprise regenerating the spent promoted dehydrogenation catalyst, thereby forming regenerated promoted dehydrogenation catalyst. Regenerating the promoted dehydrogenation catalyst comprises contacting the promoted dehydrogenation catalyst with a regeneration stream comprising gaseous oxygen, air, or combinations thereof. The regeneration zone is purged with gaseous nitrogen prior to contacting the promoted dehydrogenation catalyst with the regeneration stream. The promoted dehydrogenation catalyst may be regenerated at a temperature of greater than or equal to 650 °C. The promoted dehydrogenation catalyst may be regenerated for a time of greater than or equal to 1 minute (min), greater than 5 min, greater than 10 min, or greater than 30 min. In embodiments, fuel may be combusted to increase the temperature of the promoted dehydrogenation catalyst prior to sending the promoted dehydrogenation catalyst back to the reaction zone.

[0055] In embodiments, the method of converting alkanes to alkenes may further comprise regenerating the spent selective hydrogen combustion material, thereby forming regenerated selective hydrogen combustion material. In embodiments, regenerating the selective hydrogen combustion material may comprise contacting the selective hydrogen combustion material with a regeneration stream comprising gaseous oxygen, air, or combinations thereof. In embodiments, the regeneration zone is purged with gaseous nitrogen prior to contacting the selective hydrogen combustion material with the regeneration stream. In embodiments, the selective hydrogen combustion material may be regenerated at a temperature of greater than or equal to 650 °C. In one or more embodiments, the selective hydrogen combustion material may be regenerated for a time of greater than or equal to 1 minute (min), greater than 5 min, greater than 10 min, or greater than 30 min. In embodiments, fuel may be combusted to increase the temperature of the selective hydrogen combustion material prior to sending the selective hydrogen combustion material back to the reaction zone to close heat balance. In embodiments, the selective hydrogen combustion material and the promoted dehydrogenation catalyst may be regenerated together.85056-WO-PCT / DOW 85056 WO

[0056] In one or more embodiments, the method of converting alkanes to alkenes may further comprise returning regenerated promoted dehydrogenation catalyst to the reaction zone where it is contacted with the feed stream. EXAMPLES

[0057] EXAMPLE 1

[0058] A promoted dehydrogenation catalyst was made by first preparing an impregnated Si- ZrO2support, and then by impregnating the Si-ZrO2support with chromium. First, a monoclinic ZrO2 support (NORPRO SZ311643 mm extrudates, BET = 100 m2 / g, pore volume determined by deionized (DI) water 0.4 mL / g) was crushed and sieved to 40-80 mesh size. Then, 5 grams (g) of ZrO2support was impregnated with 2 milliliters (mL) of impregnation solution, which had been prepared by mixing 1.4 mL of tetraethylorthosilicate (TEOS) and 0.6 mL of isopropanol, until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The Si-ZrO2support was then dried and calcined under air in the box oven using the following temperature program: room temperature to 177 °C at 5 degrees per minute (deg / min), dwell 2 hours (h), 177 to 750 °C at 5 deg / min, dwell 1 h, cool down to room temperature. The Si-ZrO2 support was sieved after calcination to remove fine particles smaller than 80 mesh.

[0059] Next, 2 g of the Si-ZrO2 support was impregnated with 0.8 mL of 1 M Cr (III) nitrate nonahydrate solution in DI water until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The chromium impregnated Si-ZrO2 support was dried and calcined under air in a box oven using the following temperature program: room temperature to 177 °C at 5 deg / min, dwell 2 h, 177 to 750 °C at 5 deg / min, dwell 1 h, cool down to room temperature. The catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.

[0060] EXAMPLE 2

[0061] A promoted dehydrogenation catalyst was made by first preparing an impregnated Si- ZrO2support, and then by impregnating the Si-ZrO2support with chromium. First, a monoclinic85056-WO-PCT / DOW 85056 WO ZrO2 support (NORPRO SZ311643 mm extrudates, BET = 100 m2 / g, pore volume determined by DI water 0.4 mL / g) was crushed and sieved to 40-80 mesh size. Then, 5 g of ZrO2 support was impregnated with 2 mL of tetraethylorthosilicate (TEOS) until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The material was dried and calcined under air in the box oven using the following temperature program: room temperature to 177 °C at 5 deg / min, dwell 2 h, 177 to 750 °C at 5 deg / min, dwell 1 h, cool down to room temperature. The support was sieved after calcination to remove fine particles smaller than 80 mesh.

[0062] Next, 2 g of Si-ZrO2 support was impregnated with 0.8 mL of 1 M Cr (III) nitrate nonahydrate solution in DI water until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The chromium impregnated Si-ZrO2 support was dried and calcined under air in a box oven using the following temperature program: room temperature to 177 °C at 5 deg / min, dwell 2 h, 177 to 750 °C at 5 deg / min, dwell 1 h, cool down to room temperature. The catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.

[0063] EXAMPLE3

[0064] A promoted dehydrogenation catalyst was made by first preparing an impregnated Si- ZrO2 support, and then by impregnating the Si-ZrO2 support with gallium. First, a Si-ZrO2 support was prepared using the Si-ZrO2 support preparation method of Example 1.

[0065] Next, 2 g of Si-ZrO2support was impregnated with 0.8 mL of 1 M Ga (III) nitrate solution in DI water until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The gallium impregnated Si-ZrO2support was dried and calcined under air in a box oven using the following temperature program: room temperature to 177 °C at 5 deg / min, dwell 2 h, 177 to 750 °C at 5 deg / min, dwell 1 h, cool down to room temperature. The catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.85056-WO-PCT / DOW 85056 WO

[0066] EXAMPLE 4

[0067] A promoted dehydrogenation catalyst was made by first preparing an impregnated Si- ZrO2support, and then by impregnating the Si-ZrO2support with gallium. First, a Si-ZrO2support was prepared using the Si-ZrO2 support preparation method of Example 2.

[0068] Next, 2 g of Si-ZrO2 support was impregnated with 0.8 mL of 1 M Ga (III) nitrate solution in DI water until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The gallium impregnated Si-ZrO2 support was dried and calcined under air in a box oven using the following temperature program: room temperature to 177 °C at 5 deg / min, dwell 2 h, 177 to 750 °C at 5 deg / min, dwell 1 h, cool down to room temperature. The catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.

[0069] EXAMPLE 5

[0070] A promoted dehydrogenation catalyst was made by first preparing an impregnated Cr / ZrO2 parent material, and then by impregnating the Cr / ZrO2 parent material with silicon. First, monoclinic ZrO2 support (NORPRO SZ311643 mm extrudates, BET = 100 m2 / g, pore volume determined by DI water 0.4 mL / g) was crushed and sieved to 40-80 mesh size. Then, 5 g of ZrO2support was impregnated with 2 mL of 1 M ammonium chromate in DI water until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The impregnated Cr / ZrO2 parent material was dried and calcined under air in the box oven using the following temperature program: room temperature to 177 °C at 5 deg / min, dwell 2 h, 177 to 750 °C at 5 deg / min, dwell 1 h, cool down to room temperature. The impregnated Cr / ZrO2 parent material was sieved after calcination to remove fine particles smaller than 80 mesh.

[0071] Next, 1.5 g of the impregnated Cr / ZrO2 parent material was impregnated with a solution comprising 0.3 mL tetraethylorthosilicate (TEOS) and 0.3 mL n-propanol until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The silicon impregnated Cr / ZrO2was dried and calcined under air in a box oven using the following temperature program: room temperature to85056-WO-PCT / DOW 85056 WO 177 °C at 5 deg / min, dwell 2 h, 177 to 750 °C at 5 deg / min, dwell 1 h, cool down to room temperature. The catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.

[0072] EXAMPLE 6

[0073] A promoted dehydrogenation catalyst was made by first preparing an impregnated Cr / ZrO2parent material, and then by impregnating the Cr / ZrO2parent material with silicon. First, a Cr / ZrO2parent material was prepared using the Cr / ZrO2parent material preparation method of Example 5.

[0074] Next, 1.5 g of the impregnated Cr / ZrO2 parent material was impregnated with 0.6 mL of tetraethylorthosilicate (TEOS) until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The silicon impregnated Cr / ZrO2 was dried and calcined under air in a box oven using the following temperature program: room temperature to 177 °C at 5 deg / min, dwell 2 h, 177 to 750 °C at 5 deg / min, dwell 1 h, cool down to room temperature. The catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.

[0075] EXAMPLE7

[0076] A promoted dehydrogenation catalyst was made by first preparing an impregnated Ga / ZrO2 parent material, and then by impregnating the Ga / ZrO2 parent material with silicon. First, monoclinic ZrO2 support (NORPRO SZ311643 mm extrudates, BET = 100 m2 / g, pore volume determined by DI water 0.4 mL / g) was crushed and sieved to 40-80 mesh size. Then, 6 g of ZrO2support was impregnated with 2 mL of 1 M solution of gallium (III) nitrate hydrate in DI water until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The material was dried and calcined under air in a box oven using the following temperature program: room temperature to 120 °C at 2 deg / min, dwell 2 h, 120 to 400 °C at 3 deg / min, dwell 4 h, cool down to room temperature. The Ga / ZrO2parent material was sieved after calcination to remove fine particles smaller than 80 mesh.85056-WO-PCT / DOW 85056 WO

[0077] Next, an impregnation solution was prepared by mixing 0.075 mL tetraethylorthosilicate (TEOS) with 1.525 mL of isopropanol. Then, 2 g of the Ga / ZrO2 parent material were impregnated with 0.8 mL of the impregnation solution until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The material was dried and calcined under air in the box oven using the following temperature program: room temperature to 177 °C at 5 deg / min, dwell 2 h, 177 to 750 °C at 5 deg / min, dwell 1 h, cool down to room temperature. The catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.

[0078] EXAMPLE8

[0079] A promoted dehydrogenation catalyst was made by first preparing an impregnated Ga / ZrO2 parent material, and then by impregnating the Ga / ZrO2 parent material with silicon. First, a Ga / ZrO2 parent material was prepared using the Ga / ZrO2 parent material preparation method of Example 7.

[0080] Next, an impregnation solution was prepared by mixing 0.15 mL tetraethylorthosilicate (TEOS) with 1.45 mL of iso-propanol. Then, 2 g of the Ga / ZrO2 parent material was impregnated with 0.8 mL of the impregnation solution until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The material was dried and calcined under air in the box oven using the following temperature program: room temperature to 177 °C at 5 deg / min, dwell 2 h, 177 to 750 °C at 5 deg / min, dwell 1 h, cool down to room temperature. The catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.

[0081] EXAMPLE 9

[0082] A promoted dehydrogenation catalyst was made by first preparing an impregnated Si- ZrO2 support, and then by impregnating the Si-ZrO2 support with chromium. First, a monoclinic ZrO2 support (NORPRO SZ311643 mm extrudates, BET = 100 m2 / g, pore volume determined by DI water 0.4 mL / g) was crushed and sieved to 40-80 mesh size. Then, 5 g of ZrO2support was impregnated with 2 mL of impregnation solution, prepared by mixing 0.43 mL of colloidal silica Ludox AS-30 (30 wt% SiO2) and 1.57 mL of DI water, until the impregnation solution was no85056-WO-PCT / DOW 85056 WO longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The material was dried and calcined under air in a box oven using the following temperature program: room temperature to 120 °C at 2 deg / min, dwell 2 h, 120 to 400 °C at 3 deg / min, dwell 4 h, cool down to room temperature. The support was sieved after calcination to remove fine particles smaller than 80 mesh.

[0083] Next, 1.5 g of Si-ZrO2support was impregnated with 0.6 mL of 1 M Cr (III) nitrate nonahydrate solution in DI water until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The material was dried and calcined under air in a box oven using the following temperature program: room temperature to 177 °C at 5 deg / min, dwell 2 h, 177 to 750 °C at 5 deg / min, dwell 1 h, cool down to room temperature. The catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.

[0084] EXAMPLE10

[0085] A promoted dehydrogenation catalyst was made by first preparing an impregnated Si- ZrO2 support, and then by impregnating the Si-ZrO2 support with chromium. First, a monoclinic ZrO2support (NORPRO SZ311643 mm extrudates, BET = 100 m2 / g, pore volume determined by DI water 0.4 mL / g) was crushed and sieved to 40-80 mesh size. Then, 5 g of ZrO2support was impregnated with 2 mL of impregnation solution, prepared by mixing 1.543 mL of colloidal silica Ludox AS-30 (30 wt% SiO2) and 0.457 mL of DI water, until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The material was dried and calcined under air in the box oven using the following temperature program: room temperature to 120 °C at 2 deg / min, dwell 2 h, 120 to 400 °C at 3 deg / min, dwell 4 h, cool down to room temperature. The support was sieved after calcination to remove fine particles smaller than 80 mesh.

[0086] Next, 1.5 g of Si-ZrO2 support was impregnated with 0.6 mL of 1 M Cr (III) nitrate nonahydrate solution in DI water until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The impregnated catalyst was dried and calcined under air in the box oven using the following temperature program: room temperature to 177 °C at 5 deg / min, dwell 2 h, 177 to 75085056-WO-PCT / DOW 85056 WO °C at 5 deg / min, dwell 1 h, cool down to room temperature. The catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.

[0087] EXAMPLE11

[0088] A promoted dehydrogenation catalyst was made by first preparing an impregnated Si- ZrO2 support, and then by impregnating the Si-ZrO2 support with gallium. First, a Si-ZrO2 support was prepared using the Si-ZrO2support preparation method of Example 9.

[0089] Next, 1.5 g of the Si-ZrO2support was impregnated with 0.6 mL of 1 M gallium (III) nitrate hydrate solution in DI water until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The impregnated catalyst was dried and calcined under air in the box oven using the following temperature program: room temperature to 177 °C at 5 deg / min, dwell 2 h, 177 to 750 °C at 5 deg / min, dwell 1 h, cool down to room temperature. The catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.

[0090] EXAMPLE 12

[0091] A promoted dehydrogenation catalyst was made by first preparing an impregnated Si- ZrO2support, and then by impregnating the Si-ZrO2support with gallium. First, a Si-ZrO2support was prepared using the Si-ZrO2support preparation method of Example 10.

[0092] Next, 1.5 g of the Si-ZrO2 support was impregnated with 0.6 mL of 1 M gallium (III) nitrate hydrate solution in DI water until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The impregnated catalyst was dried and calcined under air in the box oven using the following temperature program: room temperature to 177 °C at 5 deg / min, dwell 2 h, 177 to 750 °C at 5 deg / min, dwell 1 h, cool down to room temperature. The catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.

[0093] EXAMPLE 1385056-WO-PCT / DOW 85056 WO

[0094] A promoted dehydrogenation catalyst was made by first preparing an impregnated Si- ZrO2 support, and then by impregnating the Si-ZrO2 support with chromium. First, amorphous zirconium hydroxide from DKKK (Japan) was obtained (lot L30036, powder, pore volume determined by DI water 0.67 mL / g). Then, 10 g of the zirconium hydroxide was impregnated with 6.7 mL of impregnation solution, prepared by mixing 5.374 mL of colloidal silica Ludox AS-30 (30 wt% SiO2) and 1.326 mL of DI water, until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The material was dried and calcined under air in a box oven using the following temperature program: room temperature to 120 °C at 2 deg / min, dwell 2 h, 120 to 500 °C at 3 deg / min, dwell 4 h, cool down to room temperature. The support was sieved after calcination to remove fine particles smaller than 80 mesh.

[0095] Next, 1.5 g of Si-ZrO2 support was impregnated with 0.6 mL of 1 M Cr (III) nitrate nonahydrate solution in DI water until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The impregnated catalyst was dried and calcined under air in a box oven using the following temperature program: room temperature to 177 °C at 5 deg / min, dwell 2 h, 177 to 750 °C at 5 deg / min, dwell 1 h, cool down to room temperature. The catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.

[0096] EXAMPLE14

[0097] A promoted dehydrogenation catalyst was made by first preparing an impregnated Si- ZrO2 support, and then by impregnating the Si-ZrO2 support with chromium. First, amorphous zirconium hydroxide from DKKK (Japan) was obtained. (lot L30036, powder, pore volume determined by DI water 0.67 mL / g). Then, 10 g of the zirconium hydroxide were impregnated with support was impregnated with 6.7 mL of impregnation solution, prepared by mixing 0.891 mL of tetraethylorthosilicate (TEOS) and 5.809 mL isopropanol, until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The material was dried and calcined under air in the box oven using the following temperature program: room temperature to 120 °C at 2 deg / min,85056-WO-PCT / DOW 85056 WO dwell 2 h, 120 to 500 °C at 3 deg / min, dwell 4 h, cool down to room temperature. The support was sieved after calcination to remove fine particles smaller than 80 mesh.

[0098] Next, 1.5 g of the Si-ZrO2support was impregnated with 0.6 mL of 1 M Cr (III) nitrate nonahydrate solution in DI water until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The impregnated catalyst was dried and calcined under air in the box oven using the following temperature program: room temperature to 177 °C at 5 deg / min, dwell 2 h, 177 to 750 °C at 5 deg / min, dwell 1 h, cool down to room temperature. The catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.

[0099] EXAMPLE 15

[0100] A promoted dehydrogenation catalyst was made by first preparing an impregnated Si- ZrO2 support, and then by impregnating the Si-ZrO2 support with iron. First, a monoclinic ZrO2 support (NORPRO SZ311643 mm extrudates, BET = 100 m2 / g, pore volume determined by DI water 0.4 mL / g) was crushed and sieved to 40-80 mesh size. Then, 5 g of ZrO2 support was impregnated with 2 mL of tetraethylorthosilicate (TEOS) until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The material was dried and calcined under air in the box oven using the following temperature program: room temperature to 177 °C at 5 deg / min, dwell 2 h, 177 to 750 °C at 5 deg / min, dwell 1 h, cool down to room temperature. The support was sieved after calcination to remove fine particles smaller than 80 mesh.

[0101] Next, 1 g of the Si-ZrO2 support was impregnated with 0.4 mL of 1 M ammonium iron (III) citrate solution in DI water until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The impregnated catalyst was dried and calcined under air in the box oven using the following temperature program: room temperature to 177 °C at 5 deg / min, dwell 2 h, 177 °C to 750 °C at 5 deg / min, dwell 1 h, cool down to room temperature. The catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.

[0102] COMPARATIVE EXAMPLE 185056-WO-PCT / DOW 85056 WO

[0103] Commercially available quartz chips (Pyromatics part # 7359-05010) were used to determine background dehydrogenation activity.

[0104] COMPARATIVEEXAMPLE2

[0105] A dehydrogenation catalyst that is known to effectively perform the dehydrogenation of propylene to propane under the conditions described in US patent number 9834496, the entirety of which is hereby incorporated by reference, was used in the form of 70 micron particles.

[0106] COMPARATIVE EXAMPLE 3

[0107] A Ga / ZrO2 catalyst was prepared by incipient wetness method. First, monoclinic ZrO2 support (NORPRO SZ311643 mm extrudates, BET = 100 m2 / g, pore volume determined by DI water 0.4 mL / g) was crushed and sieved to 40-80 mesh size. Then, 3 g of the ZrO2support was impregnated with 1.2 mL of DI water until the water was no longer drawn into the pores of the support and the water was homogenously distributed over the support. The material was dried and calcined under air in a box oven using the following temperature program: room temperature to 120 °C at 2 deg / min, dwell 2 h, 120 to 400 °C at 3 deg / min, dwell 4 h, cool down to room temperature. The support was sieved after calcination to remove fine particles smaller than 80 mesh.

[0108] Next, 1 g of pre-treated ZrO2support was impregnated with 0.4 mL of 1 M gallium (III) nitrate hydrate solution in DI water until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The impregnated catalyst was dried and calcined under air in a box oven using the following temperature program: room temperature to 177 °C at 5 deg / min, dwell 2 h, 177 °C to 750 °C at 5 deg / min, dwell 1 h, cool down to room temperature. The catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.

[0109] COMPARATIVE EXAMPLE 4

[0110] A Cr / ZrO2 catalyst was prepared by incipient wetness method. First, a ZrO2 support was prepared using the ZrO2support preparation method of Comparative Example 3.85056-WO-PCT / DOW 85056 WO

[0111] Next, 1 g of the ZrO2 support was impregnated with 0.4 mL of 1 M Cr (III) nitrate nonahydrate solution in DI water until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The impregnated catalyst was dried and calcined under air in the box oven using the following temperature program: room temperature to 177 °C at 5 deg / min, dwell 2 h, 177 °C to 750 °C at 5 deg / min, dwell 1 h, cool down to room temperature. The catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.

[0112] COMPARATIVE EXAMPLE 5

[0113] A Cr / ZrO2 catalyst was prepared by incipient wetness method. First, 10 g of zirconium hydroxide Zr(OH)4(DKKK L30036, pore volume determined by DI water 0.67 mL / g) was impregnated with 6.7 mL of DI water until the water was no longer drawn into the pores of the support and the water was homogenously distributed over the support. The material was dried and calcined under air in the box oven using the following temperature program: room temperature to 120 °C at 3 deg / min, dwell 2 h, 120 to 500 °C at 3 deg / min, dwell 4 h, cool down to room temperature. The calcined support was compacted and sized to 40-80 mesh size.

[0114] Next, 1.5 g of ZrO2resulting support was impregnated with 0.6 mL of 1 M Cr (III) nitrate nonahydrate solution in DI water until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The impregnated catalyst was dried and calcined under air in the box oven using the following temperature program: room temperature to 177 °C at 5 deg / min, dwell 2 h, 177 to 750 °C at 5 deg / min, dwell 1 h, cool down to room temperature. The catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.

[0115] When analyzed using x-ray powder diffraction (XRD), the catalyst showed the presence of monoclinic and tetragonal zirconia.

[0116] COMPARATIVE EXAMPLE 6

[0117] A Si-ZrO2catalyst was prepared by incipient wetness method. First, a Si-ZrO2support was prepared using the Si-ZrO2support preparation method of Example 9.85056-WO-PCT / DOW 85056 WO

[0118] Next, 1 g of Si-ZrO2 support was impregnated with 0.4 mL of DI water until the water was no longer drawn into the pores of the support and the water was homogenously distributed over the support. The impregnated catalyst was dried and calcined under air in the box oven using the following temperature program: room temperature to 177 °C at 5 deg / min, dwell 2 h, 177 to 750 °C at 5 deg / min, dwell 1 h, cool down to room temperature. The catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.

[0119] COMPARATIVE EXAMPLE 7

[0120] A Cr / SiO2-Al2O3 catalyst was prepared by incipient wetness method. The SiO2-Al2O3 support was Siralox 1 from SASOL in the form of extrudates (1.7 / 250 M10596 spec Z600200, pore volume determined by DI water 0.5 mL / g). The support was crushed and sieved to 40-80 mesh size prior to use.

[0121] Then, 1.5 g of the SiO2-Al2O3 support was impregnated with 0.6 mL of 1 M Cr (III) nitrate nonahydrate solution in DI water until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The impregnated catalyst was dried and calcined under air in the box oven using the following temperature program: room temperature to 177 °C at 5 deg / min, dwell 2 h, 177 to 750 °C at 5 deg / min, dwell 1 h, cool down to room temperature. The catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.

[0122] COMPARATIVEEXAMPLE8

[0123] A Cr / SiO2catalyst was prepared by incipient wetness method. The SiO2support was SS61138 from NORPRO in the form of 3 mm extrudates (250 m2 / g, pore determined by DI water 1.0 mL / g). The support was crushed and sieved to 40-80 mesh size prior to use.

[0124] Then, 2 mL of impregnation solution was prepared by mixing 1.2 mL DI water with 0.8 mL of 1 M Cr (III) nitrate nonahydrate solution in DI water. Next, 2 g of SiO2 support was impregnated with the impregnation solution until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The impregnated catalyst was dried and calcined under air in the box oven using the85056-WO-PCT / DOW 85056 WO following temperature program: room temperature to 177 °C at 5 deg / min, dwell 2 h, 177 to 750 °C at 5 deg / min, dwell 1 h, cool down to room temperature. The catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.

[0125] COMPARATIVE EXAMPLE 9

[0126] A Fe / ZrO2 catalyst was prepared by incipient wetness method. Monoclinic ZrO2 support (NORPRO SZ311643 mm extrudates, BET = 100 m2 / g, pore volume determined by DI water 0.4 mL / g) was crushed and sieved to 40-80 mesh size. Then, 3 g of ZrO2support was impregnated with 0.6 mL of 1 M ammonium iron (III) citrate solution in DI water until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The impregnated catalyst was dried and calcined under air in the box oven using the following temperature program: room temperature to 177 °C at 5 deg / min, dwell 2 h, 177 to 750 °C at 5 deg / min, dwell 1 h, cool down to room temperature. The catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.

[0127] CATALYST CHARACTERIZATION

[0128] X-RAY FLUORESCENCE (XRF) MEASUREMENTS

[0129] Catalyst composition was determined by X-ray Fluorescence (XRF). XRF data were collected at room temperature (RT) with a PANalytical PW4400 spectrometer using an X-ray tube with a rhodium anode. The catalyst compositions are shown in Table 1. Elements that were below the detection limit or not present are represented as blank in the table. Oxygen represented the balance of the elemental composition. Table 1: Composition of Catalysts in Examples 1-8, & 14-15 and Comparative Examples 5 & 7-885056-WO-PCT / DOW 85056 WO

[0130] CATALYSTPERFORMANCETESTING

[0131] The performance of the catalysts of both in the examples and the comparative examples was assess under both wet and dry conditions. The reaction conditions of both the wet and dry conditions are shown in Table 2. Table 2: Reaction Conditions Used to Assess Catalyst Performance85056-WO-PCT / DOW 85056 WO

[0132] The catalysts of the examples and the comparative examples were tested for selectivity and activity in a dual tube fixed-bed reactor. The catalysts were sized to a 40-80 mesh size. The reactor bed comprised 300 milligrams (mg) of catalyst mixed with 1.5 grams (g) of 40-80 mesh size quartz chips. In Comparative Example 1, the catalyst was replaced with quartz chips. The catalysts were evaluated under the four sets of conditions summarized in Table 2.

[0133] First, the reactor was purged with nitrogen gas (N2) where the pressure was 1.08 bara (16 psia). The temperature was ramped to 400 °C under N2flow and then the N2flow was switched to 60% ethane – 20% H2O – 20% N2flow. Water inlet flow was controlled by a high pressure liquid chromatography (HPLC) pump. An evaporator was used to evaporate water to the gas phase. Feed analysis was performed by analyzing the feed gas composition using online gas chromatography (GC).

[0134] Then, the reactor was purged with N2 and the temperature was ramped to 650 °C followed by switching from the N2 to air. The catalyst was regenerated at 650 °C for 6 minutes (min) for Conditions 1 and 2, and 15 minutes for Conditions 3 and 4, followed by a N2purge step. Then, the feed composition was directed to the reactor at a controlled time of exposure (25-30 seconds (s) on stream corresponding to catalyst to ethane mass to mass ratio of 12-10). This completes a single cycle at a given temperature set point.

[0135] Regeneration of the catalyst after exposure to ethane-containing feed was performed at the same temperature as the corresponding reaction step. Every catalyst was evaluated under four sets of condition specified in Table 2. The wet tests were done first, followed by the dry test. For each condition and each temperature set point, 3 cycles (reaction-purge-regeneration) were completed. The average values were then calculated and reported in Table 3 and Table 4.

[0136] Alkane conversion and carbon based selectivities are calculated using the following equations:85056-WO-PCT / DOW 85056 WO Sj (Cmol%) = [αj · ηj, out / Σ αj · ηj, out] · 100 (Equation 1) Carbon Balance (%)· 100 (Equation 2) Ethane Conversion (%) = [(ηC2H6, in – ηC2H6, out) / ηC2H6, in] · 100 (Equation 3) Reforming Product sel. (Cmol%) = SCH4+ SCO+ SCO2(Equation 4) wherein η in is defined as the molar inlet flow of the component (mol / min), η, out is the molar outlet flow of the component (mol / min), Sj is defined as the carbon based selectivity to product j (%), and αj is the number of carbon atoms for product j. Table 3: Performance Data for the Examples85056-WO-PCT / DOW 85056 WO85056-WO-PCT / DOW 85056 WO85056-WO-PCT / DOW 85056 WOTable 4: Performance Data for the Comparative Examples85056-WO-PCT / DOW 85056 WO85056-WO-PCT / DOW 85056 WO

[0137] Examples 1-15 comprise catalysts containing zirconia and chromium, gallium, or iron promoted with a silicon promoter. As shown in Table 3, Examples 1-15 demonstrate substantial activity above the background dehydrogenation activity (as measured in Comparative Example 1 by using quartz chips in lieu of a catalyst). Additionally, the catalysts of Examples 1-15 also demonstrate steam tolerance when compared with Comparative Examples 2 and 6-9. Furthermore, the catalysts of Examples 1-15 show that silicon promoted dehydrogenation catalysts have a higher ethylene selectivity than dehydrogenation catalysts that lack silicon promoters, such as those of Comparative Examples 3-5.85056-WO-PCT / DOW 85056 WO

[0138] Examples 1-15 also demonstrate that a silicon promoter can be introduced to a promoted dehydrogenation catalyst from a variety of sources including surface modification sources such as TEOS and bulk modification sources such as Ludox. As such, the Examples demonstrate that a silicon promoter may be introduced from any surface modification source, including organosilicon sources. Additionally, the Examples demonstrate that a silicon promoter may be introduced from any bulk modification source, including colloidal silica sources.

[0139] The present disclosure includes one or more non-limiting aspects. A first aspect includes a method for converting alkanes to alkenes, the method including contacting a feed stream comprising alkanes with a promoted dehydrogenation catalyst in a reaction zone in the presence of steam, the promoted dehydrogenation catalyst including zirconia and a metal, wherein the metal is selected from the group consisting of chromium, gallium, iron, and combinations thereof, and silicon, and converting at least a portion of the alkanes to alkenes, thereby yielding a product stream comprising alkanes, alkenes, and hydrogen, wherein the promoted dehydrogenation catalyst does not require a gaseous oxidant in the feed steam or as a co-feed to catalyze conversion of alkanes to alkenes.

[0140] A second aspect of the present disclosure includes the first aspect, further including combusting at least a portion of the hydrogen to yield steam.

[0141] A third aspect of the present disclosure includes either the first aspect or the second aspect, wherein the dehydrogenation catalyst comprises an alkene selectivity greater than or equal to 40 Cmol%.

[0142] A fourth aspect of the present disclosure includes any of the first through third aspects, wherein the promoted dehydrogenation catalyst retains at least some dehydrogenation activity above background dehydrogenation activity under greater than or equal to 5 v.% steam conditions based on a total volume of gaseous components in the reaction zone.

[0143] A fifth aspect of the present disclosure includes any of the first through fourth aspects, further including contacting the feed stream comprising alkanes with a selective hydrogen combustion material, wherein the promoted dehydrogenation catalyst and the selective hydrogen combustion material are both present in the reaction zone.85056-WO-PCT / DOW 85056 WO

[0144] A sixth aspect of the present disclosure includes any of the first through fifth aspects, wherein the promoted dehydrogenation catalyst comprising zirconia and a metal, wherein the metal is selected from the group consisting of chromium, gallium, iron, and combinations thereof, and silicon, comprises zirconia impregnated with a metal, wherein the metal is selected from the group consisting of chromium, gallium, iron, and combinations thereof, and silicon.

[0145] A seventh aspect of the present disclosure includes any of the first through sixth aspects, wherein silicon acts as a promoter for the promoted dehydrogenation catalyst.

[0146] An eighth aspect of the present disclosure includes any of the first through seventh aspects, wherein the promoted dehydrogenation catalyst includes 0.5 wt.% to 20 wt.% of the metal selected from the group consisting of chromium, gallium, iron, and combinations thereof, 40 wt.% to 80 wt.% zirconium, and 0.1 wt.% to 15 wt.% silicon, wherein the weight percent is based on a total weight of the promoted dehydrogenation catalyst.

[0147] A ninth aspect of the present disclosure includes any of the first through eighth aspects, wherein the silicon is at least partially derived from colloidal silica, silicon alkoxide, or combinations thereof.

[0148] A tenth aspect of the present disclosure includes any of the first through ninth aspects, wherein the promoted dehydrogenation catalyst is a promoted dehydrogenation catalyst comprising the formula M-Zr-Si-X-Q, wherein M is a metal selected from the group consisting of chromium, gallium, iron, and combinations thereof, X is selected from the group consisting of alkali metals, alkaline earth metals, and combinations thereof, and Q is selected from the group consisting of tin, platinum, boron, lanthanum, cerium, neodymium, samarium, gadolinium, dysprosium, praseodymium, europium, and combinations thereof and combinations thereof.

[0149] An eleventh aspect of the present disclosure includes any of the first through tenth aspects, wherein the promoted dehydrogenation catalyst and the feed stream have a mass to mass ratio that is from 5:1 to 200:1.

[0150] A twelfth aspect of the present disclosure includes any of the first through eleventh aspects, wherein the converting at least a portion of the alkanes to alkenes occurs at a temperature85056-WO-PCT / DOW 85056 WO that is less than or equal to 750 °C, a pressure from 1 bara to 20 bara, and a WHSV of from 1 h-1to 12 h-1.

[0151] A thirteenth aspect of the present disclosure includes any of the first through twelfth aspects, wherein the method further includes removing spent promoted dehydrogenation catalyst from the reaction zone, introducing the spent promoted dehydrogenation catalyst into a regeneration zone, regenerating the spent promoted dehydrogenation catalyst, thereby forming regenerated promoted dehydrogenation catalyst, and returning the regenerated promoted dehydrogenation catalyst to the reaction zone where it is contacted with the feed stream.

[0152] A fourteenth aspect of the present disclosure includes any of the first through thirteenth aspects, wherein the promoted dehydrogenation catalyst comprises a conversion rate of greater than or equal to 1.1 times background dehydrogenation activity.

[0153] A fifteenth aspect of the present disclosure includes a method for forming a promoted dehydrogenation catalyst, the method including obtaining a zirconia support, adding a silicon- containing precursor to the zirconia support, adding a metal-containing precursor to the zirconia support, wherein the metal-containing precursor is selected from the group consisting of chromium, gallium, iron, and combinations thereof to form a metal-containing zirconia, and calcining and drying the metal-containing zirconia to form a promoted dehydrogenation catalyst, wherein adding the silicon-containing precursor to the zirconia support and adding the metal- containing precursor to the zirconia support occur in any order.

[0154] A sixteenth aspect of the present disclosure includes the fifteenth aspect, wherein adding the silicon-containing precursor to the zirconia support is a process selected from the group consisting of: adding the silicon-containing precursor to the zirconia support, wherein the zirconia support is a fluidizable zirconia support, adding the silicon-containing precursor to the zirconia support by spray drying, adding the silicon-containing precursor to the zirconia support, and combinations thereof, and contacting the zirconia support with the metal-containing precursor is a process selected from the group consisting of: adding the metal-containing precursor to the zirconia support, wherein the zirconia support is a fluidizable zirconia support, adding the metal- containing precursor to the zirconia support by spray drying, adding the metal-containing precursor to the zirconia support by granulation, and combinations thereof.85056-WO-PCT / DOW 85056 WO

[0155] The subject matter of the present disclosure has been described in detail and by reference to specific embodiments. It should be understood that any detailed description of a component or feature of an embodiment does not necessarily imply that the component or feature is essential to the particular embodiment or to any other embodiment. Further, it should be apparent to those skilled in the art that various modifications and variations can be made to the described embodiments without departing from the spirit and scope of the claimed subject matter.

[0156] It is noted that one or more of the following claims utilize the term “wherein” as a transitional phrase. For the purposes of defining the present technology, it is noted that this term is introduced in the claims as an open-ended transitional phrase that is used to introduce a recitation of a series of characteristics of the structure and should be interpreted in like manner as the more commonly used open-ended preamble term “comprising.”

[0157] It should be understood that where a first component is described as “comprising” a second component, it is contemplated that, in embodiments, the first component “consists” or “consists essentially of” that second component. It should further be understood that where a first component is described as “comprising” a second component, it is contemplated that, in embodiments, the first component comprises at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or even at least 99% that second component (where % can be weight % or molar %).

[0158] It is also noted that recitations herein of “at least one” component, element, etc., should not be used to create an inference that the alternative use of the articles “a” or “an” should be limited to a single component, element, etc.

Claims

85056-WO-PCT / DOW 85056 WO CLAIMS 1. A method for converting alkanes to alkenes, the method comprising: contacting a feed stream comprising alkanes with a promoted dehydrogenation catalyst in a reaction zone in the presence of steam, the promoted dehydrogenation catalyst comprising: zirconia and a metal, wherein the metal is selected from the group consisting of chromium, gallium, iron, and combinations thereof; and silicon; and converting at least a portion of the alkanes to alkenes, thereby yielding a product stream comprising alkanes, alkenes, and hydrogen; wherein the promoted dehydrogenation catalyst does not require a gaseous oxidant in the feed steam or as a co-feed to catalyze conversion of alkanes to alkenes.

2. The method of claim 1, further comprising combusting at least a portion of the hydrogen to yield steam.

3. The method of any of the preceding claims, wherein the dehydrogenation catalyst comprises an alkene selectivity greater than or equal to 40 Cmol%.

4. The method of any of the preceding claims, wherein the promoted dehydrogenation catalyst retains at least some dehydrogenation activity above background dehydrogenation activity under greater than or equal to 5 v.% steam conditions based on a total volume of gaseous components in the reaction zone.

5. The method of any of the preceding claims, further comprising contacting the feed stream comprising alkanes with a selective hydrogen combustion material, wherein the promoted dehydrogenation catalyst and the selective hydrogen combustion material are both present in the reaction zone.

6. The method of any of the preceding claims, wherein the promoted dehydrogenation catalyst comprising zirconia and a metal, wherein the metal is selected from the group consisting of chromium, gallium, iron, and combinations thereof, and silicon, comprises zirconia impregnated with a metal, wherein the metal is selected from the group consisting of chromium, gallium, iron, and combinations thereof, and silicon.85056-WO-PCT / DOW 85056 WO 7. The method of any of the preceding claims, wherein silicon acts as a promoter for the promoted dehydrogenation catalyst.

8. The method of any of the preceding claims, wherein the promoted dehydrogenation catalyst comprises: 0.5 wt.% to 20 wt.% of the metal selected from the group consisting of chromium, gallium, iron, and combinations thereof; 40 wt.% to 80 wt.% zirconium; and 0.1 wt.% to 15 wt.% silicon, wherein the weight percent is based on a total weight of the promoted dehydrogenation catalyst.

9. The method of any of the preceding claims, wherein the silicon is at least partially derived from colloidal silica, silicon alkoxide, or combinations thereof.

10. The method of any of the preceding claims, wherein the promoted dehydrogenation catalyst is a promoted dehydrogenation catalyst comprising the formula M-Zr-Si-X-Q, wherein M is a metal selected from the group consisting of chromium, gallium, iron, and combinations thereof, X is selected from the group consisting of alkali metals, alkaline earth metals, and combinations thereof, and Q is selected from the group consisting of tin, platinum, boron, lanthanum, cerium, neodymium, samarium, gadolinium, dysprosium, praseodymium, europium, and combinations thereof and combinations thereof.

11. The method of any of the preceding claims, wherein the promoted dehydrogenation catalyst and the feed stream have a mass to mass ratio that is from 5:1 to 200:

1.

12. The method of any of the preceding claims, wherein the converting at least a portion of the alkanes to alkenes occurs at a temperature that is less than or equal to 750 °C, a pressure from 1 bara to 20 bara, and a WHSV of from 1 h-1to 12 h-1.

13. The method of any of the preceding claims, wherein the method further comprises: removing spent promoted dehydrogenation catalyst from the reaction zone; introducing the spent promoted dehydrogenation catalyst into a regeneration zone;85056-WO-PCT / DOW 85056 WO regenerating the spent promoted dehydrogenation catalyst, thereby forming regenerated promoted dehydrogenation catalyst; and returning the regenerated promoted dehydrogenation catalyst to the reaction zone where it is contacted with the feed stream.

14. A method for forming a promoted dehydrogenation catalyst, the method comprising: obtaining a zirconia support; adding a silicon-containing precursor to the zirconia support; adding a metal-containing precursor to the zirconia support, wherein the metal- containing precursor is selected from the group consisting of chromium, gallium, iron, and combinations thereof to form a metal-containing zirconia; and calcining and drying the metal-containing zirconia to form a promoted dehydrogenation catalyst; wherein adding the silicon-containing precursor to the zirconia support and adding the metal-containing precursor to the zirconia support occur in any order.

15. The method of claim 14, wherein adding the silicon-containing precursor to the zirconia support is a process selected from the group consisting of: adding the silicon-containing precursor to the zirconia support, wherein the zirconia support is a fluidizable zirconia support; adding the silicon-containing precursor to the zirconia support by spray drying; adding the silicon-containing precursor to the zirconia support; and combinations thereof; and contacting the zirconia support with the metal-containing precursor is a process selected from the group consisting of: adding the metal-containing precursor to the zirconia support, wherein the zirconia support is a fluidizable zirconia support; adding the metal-containing precursor to the zirconia support by spray drying; adding the metal-containing precursor to the zirconia support by granulation; and combinations thereof.

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