Methods for making olefinic materials utilizing catalysts that include silica-zirconia supports

Abstract

A method for making olefinic materials includes contacting a hydrocarbon-containing feed with a catalyst in a reactor to form an olefinic-containing effluent, passing the catalyst from the reactor to a combustor and heating the catalyst in the combustor by combusting a supplemental fuel, and passing the catalyst from the combustor to an upstream reactor section, such that all or a portion of the catalyst is continuously cycled between the reactor and the combustor. The catalyst includes gallium and platinum supported on a silica-zirconia support, and the catalyst includes from 0.1 wt.% to 4 wt.% gallium, from 5 ppmw to 1000 ppmw platinum, and at least 90 wt.% zirconia, and from 0.1 wt.% to 2 wt.% silica.

Description

86421 -WO-PCT / DOW 86421 WO1METHODS FOR MAKING OLEFINIC MATERIALS UTILIZING CATALYSTS THAT INCLUDE SILICA-ZIRCONIA SUPPORTSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application Serial No.63 / 738,852 filed December 26, 2024, the contents of which are incorporated in their entirety herein.TECHNICAL FIELD

[0002] Embodiments described herein generally relate to chemical processing and, more specifically, to methods and systems for the production of olefinic materials.BACKGROUND

[0003] Olefinic materials, such as ethylene, propylene, and butylene may be used as building blocks to produce many different products, such as polypropylene, isopropanol, and acrylic acid, which may be used in, for example, packaging, construction, and textiles. As a result of this utility, there is a worldwide demand for olefinic materials. Suitable processes for producing olefinic materials generally depend on the feedstock and include processes that utilize fluidized catalysts. For example, olefinic materials may be formed by the catalytic dehydrogenation of alkanes in a fluidized bed reactor. There is a need for improvements in the methods and associated catalysts used to make olefinic materials.SUMMARY

[0004] As described herein, according to one or more embodiments, hydrocarbons, such as paraffins for example, may be dehydrogenated to form olefinic materials, such as forming propylene from propane by catalytic dehydrogenation. Surprisingly, it has been presently discovered that utilizing catalysts that include platinum, gallium, and a silica-zirconia support may provide for enhanced catalytic activity as compared with catalysts that do not include these components.

[0005] According to embodiments of the present disclosure, a method for making olefinic materials includes contacting a hydrocarbon-containing feed with a catalyst in a reactor to form an olefinic-containing effluent, passing the catalyst from the reactor to a combustor and heating86421 -WO-PCT / DOW 86421 WO2the catalyst in the combustor by combusting a supplemental fuel, and passing the catalyst from the combustor to an upstream reactor section, such that all or a portion of the catalyst is continuously cycled between the reactor and the combustor. The catalyst includes gallium and platinum supported on a silica-zirconia support, and the catalyst includes from 0.1 wt.% to 4 wt.% gallium, from 5 ppmw to 1000 ppmw platinum, at least 90 wt.% zirconia, and from 0.1 wt.% to 2 wt.% silica.

[0006] It is to be understood that both the preceding 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. Additional features and advantages of the embodiments will be set forth in the detailed description and, in part, will be readily apparent to persons of ordinary skill in the art from that description, which includes the accompanying drawing and claims, or recognized by practicing the described embodiments. The drawing is included to provide a further understanding of the embodiments and, together with the detailed description, serves to explain the principles and operations of the claimed subject matter. However, the embodiment depicted in the drawing is illustrative and exemplary in nature, and not intended to limit the claimed subject matter.BRIEF DESCRIPTION OF THE DRAWINGS

[0007] The following detailed description may be better understood when read in conjunction with the following drawing, in which:

[0008] FIG. 1 schematically depicts a reactor system, according to one or more embodiments of the present disclosure.

[0009] When describing the simplified schematic illustration of FIG. 1, the numerous valves, temperature sensors, electronic controllers, and the like, which may be used and are well known to a person of ordinary skill in the art, are not included. Further, accompanying components that are often included in such reactor systems, such as air supplies, heat exchangers, surge tanks, and the like are also not included. However, it should be understood that these components are within the scope of the present disclosure.

[0010] Reference will now be made in greater detail to various embodiments, some of which are illustrated in the accompanying drawing.86421 -WO-PCT / DOW 86421 WO3DETAILED DESCRIPTION

[0011] The present disclosure is directed to methods for making olefinic materials by dehydrogenation where particular catalyst compositions are utilized, as described herein. For example, catalysts useful for dehydrogenation may include a catalyst comprising gallium and platinum supported on a silica-zirconia support, and the catalyst comprises from 0.1 wt.% to 4 wt.% of gallium; from 5 ppmw to 1000 ppmw of platinum; at least 90 wt.% zirconia; and from 0.1 wt.% to 2 wt.% silica. In one or more embodiments, such catalysts provide dual catalytic functionality for dehydrogenation of alkanes as well as combustion of supplemental fuels. Such catalysts including platinum, gallium, and a silica-zirconia support may be particularly well suited for fluidized dehydrogenation of alkanes to olefinic materials, such as propane to propylene, where a fuel, such as methane, is utilized as a supplemental fuel to heat the catalyst.

[0012] Some methods and associated systems used to make olefinic materials may utilize supplemental fuels that are combusted to heat the catalyst during the production process. For example, the catalyst may be cycled between a reactor, where olefinic materials are produced in an endothermic reaction, and a combustor, where the catalyst is heated by exothermic combustion of at least a supplemental fuel (sometimes along with combustion of coke). Such catalysts may desirably have catalytic activity not only for the dehydrogenation of alkanes to form olefins, but also for the combustion of supplemental fuels. Embodiments of such suitable catalysts include, for example, gallium and platinum on a zirconia-containing support. In some embodiments, methane may be used in the supplemental fuel. In such embodiments, conventional catalysts used for dehydrogenation may suffer from relatively low methane combustion activity, meaning that using methane as a supplemental fuel may not provide heat sufficient to raise the temperature of the catalyst to the desired temperatures utilized in the dehydrogenation reaction. Further, using conventional catalysts that may suffer from low methane combustion activity may negatively impact the safety of the dehydrogenation process, as un-combusted methane may exceed the low flammability level required to safely operate the regenerator. Catalytic activity in the combustion step of dehydrogenation is important as it may dictate the flowrate of fuel entering the vessel and the residual un-combusted fuel exiting the combustion zone.

[0013] To enhance fuel combustion, zirconia (ZrCh) may be used as a support. However, although the use of zirconia alone in the support may increase combustion activity, dehydrogenation activity and selectivity of the catalyst may be reduced due to increased rates of undesired side reactions. The reduction in dehydrogenation activity may, without being bound to86421 -WO-PCT / DOW 86421 WO4any particular theory, be attributed to the loss of surface area of the catalyst, which leads to a lower dispersion of catalytically active elements. Accordingly, there is a need for catalysts that have improved fuel combustion activity along with acceptable dehydrogenation activity and selectivity.

[0014] As is described herein, it has been discovered that adding silica (SiCh) to the zirconia-containing support in specific amounts may result in high fuel combustion activity while maintaining desired dehydrogenation activity and selectivity for platinum-gallium catalysts, as compared with conventional catalysts that, for example, do not include a silica-zirconia support,. The catalysts described herein may also be tolerant to steam, such that catalytic activity does not significantly decrease with the presence of steam.

[0015] Embodiments of the methods presently disclosed are described in detail herein in the context of the reactor system of FIG. 1 operating as a fluidized dehydrogenation reactor system to produce olefinic materials. As described herein, “olefinic materials” may refer to a class of chemicals made up of hydrogen and carbon with one or more pairs of carbon atoms linked by a double bond. In some embodiments, olefinic materials may include light olefins, such as ethylene, propylene, butylene, and styrene. However, it should be understood that the principles disclosed and taught herein may be applicable to other systems which utilize different system components oriented in different ways. For example, the concepts described herein may be equally applied to other systems with alternate reactor units and regeneration units, such as those that operate under non- fluidized conditions or include downers rather than risers. It should be further understood that not all portions of FIG. 1 should be construed as essential to the claimed subject matter. Moreover, while the recited method steps in the appended claims are described herein in the context of FIG.1, such recited method steps should be understood as adaptable to other systems, as would be understood by those skilled in the art.

[0016] Now referring to FIG. 1, an example reactor system 102 that may be suitable for use with the methods and / or apparatuses described herein is schematically depicted. The reactor system 102 generally comprises multiple system components, such as a reactor portion 200 and a catalyst processing portion 300. As described herein, “system components” refer to portions of the reactor system 102, such as reactors, separators, transfer lines, combinations thereof, and the like. As used herein in the context of FIG. 1, the reactor portion 200 generally refers to the portion of the reactor system 102 in which the major process reaction takes place (e.g, dehydrogenation) to form the olefin-containing effluent. A hydrocarbon-containing feed enters the reactor portion 200, is contacted with a catalyst, converted to an olefin-containing effluent (containing product86421 -WO-PCT / DOW 86421 WO5and unreacted feed), and exits the reactor portion 200. The reactor portion 200 comprises a reactor 202 which may include an upstream reactor section 250 and a downstream reactor section 230. According to one or more embodiments, as depicted in FIG. 1, the reactor portion 200 may additionally include a catalyst separation section 210, which serves to separate the catalyst from the olefin-containing effluent formed in the reactor 202. Also, as used herein, the catalyst processing portion 300 generally refers to the portion of the reactor system 102 where the catalyst is in some way processed, such as by a combustion reaction, to, e.g., improve catalytic activity by decoking and / or heating the catalyst. The catalyst processing portion 300 may comprise a combustor 350 and a riser 330, and may additionally comprise a catalyst separation section 310. In one or more embodiments, the catalyst separation section 210 may be in fluid communication with the combustor 350 (e.g., via standpipe 426) and the catalyst separation section 310 may be in fluid communication with the upstream reactor section 250 (e.g, via standpipe 424 and transport riser 430).

[0017] Generally, as is described herein, in embodiments illustrated in FIG. 1, catalyst is cycled between the reactor portion 200 and the catalyst processing portion 300. It should be understood that when “catalysts” are referred to herein, they may refer to solid materials that are catalytically active for a desired reaction. The terms “catalytic activity” and “catalyst activity” refer to the degree to which the catalyst is able to catalyze the reactions conducted in the reactor system 102. The catalyst that exits the reactor portion 200 may be deactivated catalyst. As used herein, “deactivated” may refer to a catalyst that has reduced catalytic activity or is cooler as compared to catalyst entering the reactor portion 200. However, deactivated catalyst may maintain some catalytic activity. Reduced catalytic activity may result from contamination with a substance such as coke. Coke may form on the catalyst within the reactor portion 200. Reactivation (sometimes called “regeneration” herein) may remove the contaminant such as coke, raise the temperature of the catalyst, or both. In embodiments, deactivated catalyst may be reactivated by catalyst reactivation in the catalyst processing portion 300. The deactivated catalyst may be reactivated by, but not limited to, removing coke by combustion, oxidizing the catalyst, other reactivation process, or combinations thereof. In some embodiments, the catalyst may be heated during reactivation by combustion of a supplemental fuel, such as methane, ethane, propane, natural gas, hydrogen, or combinations thereof. The reactivated catalyst from the catalyst processing portion 300 is then passed back to the reactor portion 200.86421 -WO-PCT / DOW 86421 WO6

[0018] As is disclosed herein, in one or more embodiments the supplemental fuel may comprise methane. For example the supplemental fuel may comprise an amount of methane greater than or equal to 1 mol.%, such as greater than or equal to 2 mol.%, greater than or equal to 3 mol.%, greater than or equal to 4 mol.%, or even greater than or equal to 5 mol.%. In some embodiments the supplemental fuel comprises methane in an amount no more than 10 mol.%. In some embodiments, the supplemental fuel may comprise methane in an amount greater than 10 mol.%, such as greater than 20 mol.%, greater than 30 mol.%, greater than 40 mol.%, greater than 50 mol.%, greater than 60 mol.%, greater than 70 mol.%, greater than 80 mol.%, greater than 90 mol.%, or even 100 mol.%. Catalysts with improved methane combustion activity, such as those described herein that include one or more non-redox-active elemental additives, can better utilize methane as a supplemental fuel to facilitate re-heating of the catalyst. The catalyst is heated during regeneration to aid with regeneration and also because heated catalyst serves as a heat carrier to carry heat from the combustor 350 to the reactor portion 200 to facilitate the dehydrogenation reaction.

[0019] In non-limiting examples, the reactor system 102 described herein may be utilized to produce olefinic materials from a hydrocarbon-containing feed. According to one or more embodiments, the reaction may be a dehydrogenation reaction. According to such embodiments, the hydrocarbon-containing feed may comprise C2-C4 paraffins. According to such embodiments, the hydrocarbon-containing feed may comprise one or more of ethane, propane, n-butane, i-butane, or ethylbenzene. In one or more embodiments, the hydrocarbon-containing feed 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 ethane. In additional embodiments, the hydrocarbon-containing feed 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 additional embodiments, the hydrocarbon-containing feed 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 n-butane. In additional embodiments, the hydrocarbon-containing feed 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 i-butane. In additional embodiments, the hydrocarbon-containing feed 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 the sum of ethane, propane, n-butane, and i-butane.86421 -WO-PCT / DOW 86421 WO7

[0020] The catalyst may comprise, consist essentially of, or consist of gallium, platinum, and a support comprising silica and zirconia. As described herein, “consisting essentially of’ refers to materials with less than 1 wt.% of the non-recited materials (i.e., consisting essentially of A and B means A and B combined are at least 99 wt.% of the composition). In additional embodiments, the catalyst may comprise, consist essentially of, or consist of gallium, platinum, a support comprising silica and zirconia, and one or both of alkali or alkaline earth metals. As is described herein, the catalyst may be solid particles suitable for fluidization.

[0021] The catalyst may comprise gallium in an amount from 0.1 wt.% to 4 wt.% based on the total weight of the catalyst. As used herein, “total weight of the catalyst” includes the mass of the support and the mass of any materials present on or impregnated into the support, such as any active materials and / or promoters. Such materials may catalyze the dehydrogenation of alkanes to alkenes, particularly when used in combination with platinum. Such materials may additionally catalyze the combustion of coke and supplemental fuels. For example, the catalyst may comprise gallium in an amount from 0.1 wt.% to 0.25 wt.%, from 0.25 wt.% to 0.5 wt.%, from 0.5 wt.% to 0.75 wt.%, from 0.75 wt.% to 1 wt.%, from 1 wt.% to 1.25 wt.%, from 1.25 wt.% to 1.5 wt.%, from 1.5 wt.% to 1.75 wt.%, from 1.75 wt.% to 2 wt.%, from 2 wt.% to 2.25 wt.%, from 2.25 wt.% to 2.5 wt.%, from 2.5 wt.% to 2.75 wt.%, from 2.75 wt.% to 3 wt.%, from 3 wt.% to 3.25 wt.%, from 3.25 wt.% to 3.5 wt.%, from 3.5 wt.% to 3.75 wt.%, from 3.75 wt.% to 4 wt.%, or any combination of these ranges and endpoints. In embodiments, the catalyst may comprise gallium in an amount from 0.1 wt.% to 3.75 wt.%, from 0.1 wt.% to 3.5 wt.%, from 0.1 wt.% to 3.25 wt.%, from 0.1 wt.% to 3 wt.%, from 0.1 wt.% to 2.75 wt.%, from 0.1 wt.% to 2.5 wt.%, from 0.1 wt.% to 2.25 wt.%, from 0.1 wt.% to 2 wt.%, or from 0.1 wt.% to 1.75 wt.%. Without being bound by any particular theory, it is believed that compositions having gallium in an amount less than 0.1 wt.% negatively impacts the catalyst’s ability to catalyze the alkane dehydrogenation process by lowering both the percentage of total alkane dehydrogenated and the percentage of dehydrogenated alkane that is the intended product. However, it is believed that compositions having gallium in an amount exceeding 4 wt.% may negatively impact the catalyst’s ability to catalyze the alkane dehydrogenation process, negatively impact the catalyst’s selectivity towards the intended product, or both.

[0022] The catalyst may comprise platinum in an amount from 5 ppmw to 1000 ppmw based on the total weight of the catalyst. Such materials may catalyze the dehydrogenation of alkanes to alkenes, particularly when used in combination with gallium. Such materials may additionally86421 -WO-PCT / DOW 86421 WO8catalyze the combustion of coke and supplemental fuels. The catalyst may comprise platinum in an amount from 5 ppmw to 50 ppmw, from 50 ppmw to 100 ppmw, from 100 ppmw to 150 ppmw, from 150 ppmw to 200 ppmw, from 200 ppmw to 250 ppmw, from 250 ppmw to 300 ppmw, from 300 ppmw to 350 ppmw, from 350 ppmw to 400 ppmw, from 400 ppmw to 450 ppmw, from 450 ppmw to 500 ppmw, from 500 ppmw to 550 ppmw, from 550 ppmw to 600 ppmw, from 600 ppmw to 650 ppmw, from 650 ppmw to 700 ppmw, from 700 ppmw to 750 ppmw, from 750 ppmw to 800 ppmw, from 800 ppmw to 850 ppmw, from 850 ppmw to 900 ppmw, from 900 ppmw to 950 ppmw, from 950 ppmw to 1000 ppmw or any combination of these ranges and endpoints. In some embodiments, the catalyst may comprise platinum in an amount from 5 ppmw to 900 ppmw, from 5 ppmw to 800 ppmw, from 5 ppmw to 700 ppmw, from 5 ppmw to 600 ppmw, from 5 ppmw to 500 ppmw, from 5 ppmw to 400 ppmw, from 5 ppmw to 300 ppmw, from 5 ppmw to 200 ppmw, from 15 ppmw to 500 ppmw, from 15 ppmw to 400 ppmw, from 15 ppmw to 350 ppmw, or any combinations of these ranges and endpoints. Without being bound by any particular theory, it is believed that compositions having platinum in an amount exceeding 1000 ppmw may significantly increase the cost of the catalyst.

[0023] The catalyst may comprise a support comprising silica (SiCh) and zirconia (ZrCh). The catalyst may comprise at least 90 wt.% zirconia based on the total weight of the catalyst, where the zirconia is present in the catalyst as a component of the silica-zirconia support. The zirconia may be in the form of various polymorphs, such as monoclinic, tetragonal, cubic, or combinations thereof. Generally, the wt.% of the zirconia may fill the remainder of the total catalyst not specified by other materials described herein. The catalyst may comprise at least 91 wt.%, at least 92 wt.%, at least 93 wt.%, at least 94 wt.%, at least 95 wt.%, at least 96 wt.%, at least 97 wt.%, at least 98 wt.%, at least 99 wt.%, or at least 99.5 wt.% zirconia based on the total mass of the catalyst. Without being bound by any particular theory, it is believed that the higher particle density of zirconia may allow for a larger number of active sites of the catalyst for a given volumetric flow of solids compared to conventional catalysts that may, for example include an alumina-based support. This is particularly useful in applications of the catalyst in circulating fluidized beds, such as in embodiments described herein. Additionally, as stated, it is believed that zirconia may improve fuel combustion efficiency of the catalyst. However, using zirconia alone may lead to a compromise in the reduction of dehydrogenation activity due to a loss in surface area and a lower dispersion of active elements. It has presently been discovered that doping a zirconia support with silica may preserve the surface area of the zirconia to maintain the86421 -WO-PCT / DOW 86421 WO9dehydrogenation activity while also improving fuel combustion, particularly in temperatures less than or equal to 800 °C.

[0024] The catalyst may comprise from 0.1 wt.% to 2 wt.% silica based on the total weight of the catalyst, where the silica is present in the catalyst as part of the zirconia-silica support. Silica may maintain dehydrogenation activity in zirconia-based catalysts. The catalyst may comprise silica in an amount from 0.1 wt.% to 0.2 wt.%, from 0.2 wt.% to 0.3 wt.%, from 0.3 wt.% to 0.4 wt.%, from 0.4 wt.% to 0.5 wt.%, from 0.5 wt.% to 0.6 wt.%, from 0.6 wt.% to 0.7 wt.%, from 0.7 wt.% to 0.8 wt.%, from 0.8 wt.% to 0.9 wt.%, from 1 wt.% to 1.1 wt.%, from 1.1 wt.% to 1.2 wt.%, from 1.2 wt.% to 1.3 wt.%, from 1.3 wt.% to 1.4 wt.%, from 1.4 wt.% to 1.5 wt.%, from 1.5 wt.% to 1.6 wt.%, from 1.6 wt.% to 1.7 wt.%, from 1.7 wt.% to 1.8 wt.%, from 1.8 wt.% to 1.9 wt.%, from 1.9 wt.% to 2 wt.% silica based on the total weight of the catalyst. In some embodiments, the catalyst may comprise silica in an amount from 0.1 wt.% to 1.5 wt.%, from 0.1 wt.% to 1 wt.%, from 0.1 wt.% to 0.5 wt.%, from 0.2 wt.% to 1.5 wt.%, from 0.2 wt.% to 1 wt.%, from 0.2 wt.% to 0.5 wt.%, or any combinations of these ranges and endpoints, based on the total weight of the catalyst. Without being bound by any particular theory, it is believed that catalysts that include silica in amounts less than 0.1 wt.% may not have improved dehydrogenation activity compared to other zirconia-based catalysts. It is also believed that catalysts that include silica in amounts greater than 2 wt.% may lead to loss of alkane conversion and fuel combustion.

[0025] In one or more embodiments, the catalyst may optionally comprise one or more alkali metals, one or more alkaline earth metals, or both, in an amount from 0.01 wt.% to 5 wt.% based on the total weight of the catalyst. For example, the catalyst may comprise one or more alkali metals, one or more alkaline earth metals, or both in an amount from 0.01 wt.% to 0.05 wt.%, from 0.05 wt.% to 0.1 wt.%, from 0.1 wt.% to 0.2 wt.%, from 0.2 wt.% to 0.3 wt.%, from 0.3 wt.% to 0.4 wt.%, from 0.4 wt.% to 0.5 wt.%, from 0.5 wt.% to 0.6 wt.%, from 0.6 wt.% to 0.7 wt.%, from 0.7 wt.% to 0.8 wt.%, from 0.8 wt.% to 0.9 wt.%, from 0.9 wt.% to 1 wt.%, from 1 wt.% to 2 wt.%, from 2 wt.% to 3 wt.%, from 3 wt.% to 4 wt.%, from 4 wt.% to 5 wt.%, or any combination of these ranges. In some embodiments, the catalyst may comprise one or more alkali metals, one or more alkaline earth metals, or both from 0.01 wt.% to 1 wt.%, from 0.02 wt.% to 0.75 wt.%, from 0.03 wt.% to 0.5 wt.%, from 0.04 wt.% to 0.4 wt.%, or from 0.05 wt.% to 0.3 wt.%. In some embodiments, the one or more alkali metals or one or more alkaline earth metals may be potassium (K). Without being bound by any particular theory, it is believed that86421 -WO-PCT / DOW 86421 WO10compositions having alkali metals or alkaline earth metals in an amount exceeding 5 wt.% may reduce the catalyst’s dehydrogenation activity.

[0026] In one or more embodiments, the catalyst may comprise additional components. For example, phase and sintering stabilizers may be added to the catalyst, such as lanthanum (La) and / or yttrium (Y). Phase stabilizers may be any substance that prevents the catalyst particles from agglomerating, changing size, or phase separating. Sintering stabilizers may prevent the growth of active metal particles on the catalysts, which can reduce the catalyst surface area and activity. The catalyst may also comprise one or more redox-active elemental additives, such as iron, manganese, cerium, chromium, or combinations thereof. A “redox-active elemental additive” refers to an elemental additive capable of undergoing reduction in the presence of a reducing agent (e.g., hydrogen) and oxidation in the presence of an oxidizing agent (e.g., oxygen or air). The incorporation of one or more redox-active elemental additives may promote combustion of supplemental fuels such as methane, particularly when incorporated with platinum-gallium catalysts, according to embodiments herein. As a non-limiting example, the catalyst may comprise gallium, platinum, potassium, and cerium.

[0027] In embodiments, the catalyst may comprise, consist essentially of, or consist of gallium, platinum, and a silica-zirconia support. For example, the catalyst may comprise, consist essentially of, or consist of gallium and platinum supported on a silica-zirconia support, and the catalyst comprises, consists essentially of, or consists of from 0.1 wt.% to 4 wt.% of gallium, from 5 ppmw to 1000 ppmw of platinum, at least 90 wt.% zirconia, and from 0.1 wt.% to 2 wt.% silica based on the total weight of the catalyst. In one exemplary embodiment, the catalyst may comprise, consist essentially of, or consist of from 0.1 wt.% to 2 wt.% of gallium; from 5 ppmw to 350 ppmw of platinum; at least 90 wt.% zirconia, and from 0.2 wt.% to 1 wt.% silica.

[0028] In one or more embodiments, the catalyst may include solid particulates that are capable of fluidization. In some embodiments, the catalyst may exhibit properties known in the industry as “Geldart A” or “Geldart B” properties. Catalyst type may be classified as “Group A” or “Group B” according to D. Geldart, Gas Fluidization Technology, John Wiley & Sons (New York, 1986), 34-37; and D. Geldart, “Types of Gas Fluidization,” Powder Technol. 7 (1973) 285-292, the disclosures of which are incorporated herein by reference in their entireties.

[0029] Geldart Group A is understood by those skilled in the art as representing an aeratable powder, having a bubble- free range of fluidization; a high bed expansion; a slow and linear deaeration rate; bubble properties that may include a predominance of splitting / recoalescing86421 -WO-PCT / DOW 86421 WO11bubbles, with a maximum bubble size and large wake; high levels of solids mixing and gas backmixing, assuming equal U-Umf (U is the velocity of the carrier gas, and Umf is the minimum fluidization velocity, typically though not necessarily measured in meters per second, m / s, i.e., there is excess gas velocity); axisymmetric slug properties; and no spouting, except in very shallow beds. The properties listed tend to improve as the mean particle size decreases, assuming equal dp; or as the < 45 micrometers (pm) proportion is increased; or as pressure, temperature, viscosity, and density of the gas increase. In general, the particles may exhibit a small mean particle size and / or low particle density (< 1.4 grams per cubic centimeter, g / cm3), fluidize easily, with smooth fluidization at low gas velocities, and may exhibit controlled bubbling with small bubbles at higher gas velocities.

[0030] Geldart Group B is understood by those skilled in the art as representing a “sandlike” powder that starts bubbling at Umf; that exhibits moderate bed expansion; a fast deaeration; no limits on bubble size; moderate levels of solids mixing and gas backmixing, assuming equal U-Umf; both axisymmetric and asymmetric slugs; and spouting in only shallow beds. These properties tend to improve as mean particle size decreases, but particle size distribution and, with some uncertainty, pressure, temperature, viscosity, or density of gas seem to do little to improve them. In general, most of the particles having a particle size (dp) of 40 pm < dp < 500 pm when the density (pp) is 1.4 < pp < 4 g / cm3.

[0031] As described hereinabove, the catalyst comprises gallium and platinum supported on a silica-zirconia support. As used here “supported” includes embodiments where one or both of gallium and platinum are present on the surface of a silica-zirconia support and / or where one or both of gallium and platinum are present in the pores of a silica-zirconia support. The catalyst may further comprise one or more alkali or alkaline earth metals supported on a silica-zirconia catalyst. The one or more alkali or alkaline earth metals may be present on the surface of a silica-zirconia support and / or present in the pores of a silica-zirconia catalyst.

[0032] In one or more embodiments, the catalyst may be prepared via incipient wetness impregnation also known as dry impregnation or capillary impregnation. For example, such a process is described in Marceau et al., Impregnation and Drying, Synthesis of Solid Catalysts 59 (2008), which is incorporated herein by reference in its entirety. For example, the support may be impregnated using metal precursors, then dried at temperatures less than 200 °C, and then calcined at temperatures less than 800 °C to produce the catalyst. For example, suitable metal precursors may include nitrate or amine nitrate metal precursors. Additionally, other suitable metal precursors86421 -WO-PCT / DOW 86421 WO12are contemplated herein, as would be known by those skilled in the art. In some embodiments, the method of making the catalyst may comprise impregnating the support with gallium and platinum; drying the support; and calcining the support, wherein the catalyst comprises from 0.1 wt.% to 4 wt.% of gallium, from 5 ppmw to 1000 ppmw of platinum, at least 90 wt.% zirconia, and from 0.1 wt.% to 2 wt.% silica.

[0033] In one or more embodiments, the catalyst may be prepared by incipient wetness sequential impregnation, where materials are impregnated in a specific order, either before or after drying and calcining. In incipient wetness sequential impregnation, the catalyst is first impregnated with one or more metal precursors, dried at temperatures less than 200 °C, and then calcined at temperatures less than 800 °C. The catalyst then undergoes a least one additional cycle of impregnation, drying, and calcining with an additional metal precursor to create a finished catalyst. In incipient wetness sequential impregnation, the metals added to the catalyst can be added in sequential order in successive impregnation cycles. For some embodiments, the method of making a catalyst may comprise impregnating the support with gallium, drying the support, calcining the support, impregnating the support with platinum following the drying and calcining, and drying and calcining the support following the impregnation with platinum, wherein the catalyst comprises from 0.1 wt.% to 4 wt.% of gallium, from 5 ppmw to 1000 ppmw of platinum, at least 90 wt.% zirconia, and from 0.1 wt.% to 2 wt.% silica. In additional embodiments, the method of making a catalyst may comprise impregnating the support with silica to create a silica-impregnated support, drying the silica-impregnated support, calcining the silica- impregnated support, impregnating the silica-impregnated support with gallium and platinum following the drying and calcining, and drying and calcining the silica-impregnated support following the impregnation with gallium and platinum, wherein the catalyst comprises from 0.1 wt.% to 4 wt.% of gallium, from 5 ppmw to 1000 ppmw of platinum, at least 90 wt.% zirconia, and from 0.1 wt.% to 2 wt.% silica.

[0034] Incipient wetness sequential impregnation allows the support to be impregnated with metals in a sequential order where some metals may be impregnated onto the support before others. The order of impregnation can therefore be altered as desired. Additionally, other suitable methods for making the catalysts described herein are contemplated, as would be known by those skilled in the art.

[0035] Now referring again to FIG. 1, the hydrocarbon-containing feed may enter feed inlet 434 into the reactor 202, and the olefm-containing effluent may exit the reactor system 10286421 -WO-PCT / DOW 86421 WO13via pipe 420. According to one or more embodiments, the reactor system 102 may be operated by feeding a hydrocarbon-containing feed (e.g., in a feed stream) and a fluidized catalyst into the upstream reactor section 250. The hydrocarbon-containing feed contacts the catalyst in the upstream reactor section 250, and each flow upwardly into and through the downstream reactor section 230 to produce an olefm-containing effluent. The reactor 202 may operate at relatively high temperatures, such as from 500 °C to 800 °C (e.g., from 500 °C to 550 °C, from 550 °C to 600 °C, from 600 °C to 650 °C, from 650 °C to 700 °C, from 700 °C to 750 °C, from 750 °C to 800 °C, or any combination of one or more of these ranges.

[0036] Now referring to FIG. 1 in detail, the reactor portion 200 may comprise an upstream reactor section 250, a transition section 258, and a downstream reactor section 230, such as a riser. The transition section 258 may connect the upstream reactor section 250 with the downstream reactor section 230. As depicted in FIG. 1, the upstream reactor section 250 may be positioned below the downstream reactor section 230. Such a configuration may be referred to as an upflow configuration in the reactor 202. The upstream reactor section 250 may include a vessel, drum, barrel, vat, or other container suitable for a given chemical reaction. As depicted in FIG. 1 , the upstream reactor section 250 may be connected to the downstream reactor section 230 via the transition section 258. The upstream reactor section 250 may generally comprise a greater cross-sectional area than the downstream reactor section 230. The transition section 258 may be tapered from the size of the cross-section of the upstream reactor section 250 to the size of the crosssection of the downstream reactor section 230 such that the transition section 258 projects inwardly from the upstream reactor section 250 to the downstream reactor section 230. For example, the transition section 258 may be a frustum.

[0037] The upstream reactor section 250 may be connected to a transport riser 430, which, in operation may provide reactivated catalyst in a feed stream to the reactor portion 200. The reactivated catalyst and / or reactant chemicals may be mixed with a distributor 260 housed in the upstream reactor section 250. The catalyst entering the upstream reactor section 250 via transport riser 430 may be passed through standpipe 424 to a transport riser 430, thus arriving from the catalyst processing portion 300. In some embodiments, catalyst may come directly from the catalyst separation section 210 via standpipe 422 and into a transport riser 430, where it enters the upstream reactor section 250, where in such embodiments some of the catalyst is not passed through the catalyst processing portion 300. The catalyst can also be fed via standpipe 422 directly to the upstream reactor section 250 (not depicted in FIG. 1). This catalyst may be somewhat86421 -WO-PCT / DOW 86421 WO14deactivated, but may still, in some embodiments, be suitable for reaction in the upstream reactor section 250, particularly when used in combination with reactivated catalyst.

[0038] In one or more embodiments, the catalyst may have a residence time within the reactor portion 200 of less than or equal to 3 minutes. As the term is used herein, “residence time” refers to the average amount of time the catalyst or other specified material spends within the reactor portion 200. As it is an average, the amount of time the catalyst may spend within the reactor portion 200 during any given cycle may not be equal to the average, but over time will average out to be equal to about the residence time. In some embodiments, the catalyst may have a residence time within the reactor portion 200 of less than or equal to 2.5 min., less than or equal to 2 min., less than or equal to 1.5 min., less than or equal to 1 min., less than or equal to 0.5, or less than or equal to 0.1 min. Without being bound by any particular theory, it is believed that catalyst residence time greater than 3 minutes may increase equipment costs without a matching increase in catalyst dehydrogenation performance. However, it is believed that catalyst residence time less than 0.1 minutes may not allow the catalyst to sufficiently catalyze the dehydrogenation reaction.

[0039] As mentioned above, contacting the hydrocarbon-containing feed with the catalyst in the reactor portion 200 may occur in the presence of steam. The catalysts described herein may be tolerant to the presence of steam, such that catalytic activity is not significantly impacted by 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 in-situ by selective hydrogen combustion materials.

[0040] In one or more embodiments, hydrogen may be formed from the dehydrogenation reaction and may be present in the olefin-containing effluent. At least a portion of the hydrogen in the product stream may be combusted and yield 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 reactor portion 200 during dehydrogenation of the alkanes in the feed stream. Many 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.86421 -WO-PCT / DOW 86421 WO15However, the dehydrogenation catalysts disclosed and described herein may retain catalytic activity in the presence of water and retain all or some of their conversion or selectivity when the hydrogen is combusted and forms water.

[0041] Still referring to FIG. 1 , in one or more embodiments, based on the shape, size, and other processing conditions (such as temperature and pressure) in the upstream reactor section 250 and the downstream reactor section 230, the upstream reactor section 250 may operate as a fluidized bed, such as in a fast fluidized, turbulent, or bubbling bed upflow reactor, while the downstream reactor section 230 may operate in more of a plug flow manner, such as in a riser reactor. For example, the reactor 202 of FIG. 1 may comprise an upstream reactor section 250 operating as a fast fluidized, turbulent, or bubbling bed reactor and a downstream reactor section 230 operating as a dilute phase riser reactor, with the result that the average catalyst and gas flow moves concurrently upward. As the term is used herein, “average flow” refers to the net flow, i.e., the total upward flow minus the retrograde or reverse flow, as is typical of the behavior of fluidized particles in general. As described herein, a “fast fluidized” reactor may refer to a reactor utilizing a fluidization regime wherein the superficial velocity of the gas phase is greater than the choking velocity and may be semi-dense in operation. As described herein, a “turbulent” reactor may refer to a fluidization regime where the superficial velocity of less than the choking velocity and is more dense than the fast fluidized regime. As described herein, a “bubbling bed” reactor may refer to a fluidization regime wherein well defined bubbles in a highly dense bed are present in two distinct phases. The “choking velocity” refers to the minimum velocity required to maintain solids in the dilute-phase mode in a vertical conveying line. As described herein, a “dilute phase riser” may refer to a riser reactor operating at above choking velocity.

[0042] According to one or more embodiments, the olefin-containing effluent and the catalyst may be passed out of the downstream reactor section 230 to a separation device 220 in the catalyst separation section 210, where the catalyst is at least partially separated from the olefin-containing effluent, which is transported out of the catalyst separation section 210. According to one or more embodiments, following separation from vapors in the separation device 220, the catalyst may generally move through the stripper 224 to the catalyst outlet port 222 where the catalyst is transferred out of the reactor portion 200 via standpipe 426 and into the catalyst processing portion 300.86421 -WO-PCT / DOW 86421 WO16

[0043] According to one or more embodiments, the separation device 220 may be a cyclonic separation system, which may include two or more stages of cyclonic separation. In embodiments where the separation device 220 comprises more than one cyclonic separation stages, the first separation device into which the fluidized stream enters is referred to a primary cyclonic separation device. The fluidized effluent from the primary cyclonic separation device may enter into a secondary cyclonic separation device for further separation. Primary cyclonic separation devices may include, for example, primary cyclones, and systems commercially available under the names VSS (commercially available from UOP), LD2 (commercially available from Stone and Webster), and RS2 (commercially available from Stone and Webster). Primary cyclones are described, for example, in U.S. Patent Nos. 4,579,716; 5,190,650; and 5,275,641, which are each incorporated by reference in their entirety herein. In some separation systems utilizing primary cyclones as the primary cyclonic separation device, one or more set of additional cyclones, e.g. secondary cyclones and tertiary cyclones, are employed for further separation of the catalyst from the product gas. It should be understood that any primary cyclonic separation device may be used in embodiments of the present disclosure.

[0044] Still referring to FIG. 1 , the separated catalyst is passed from the catalyst separation section 210 to the combustor 350. In some embodiments, the catalyst may be exposed to another oxy gen-containing gas, such as air, downstream of the reactor 202 and upstream of the combustor 350, such as in a standpipe leading to the combustor 350. Such oxygen exposure may serve to oxidize the catalyst prior to combustion, which may improve combustion catalytic functionality.

[0045] In the combustor 350, the catalyst may be processed by, for example, combustion of coke with oxygen. For example, and without limitation, the catalyst may be de-coked and / or supplemental fuel may be combusted to heat the catalyst. The catalyst is then passed out of the combustor 350 and through the riser 330 to a riser termination separator 378, where the gas and solid components from the riser 330 are at least partially separated. The vapor and remaining solids are transported to a secondary separation device 320 in the catalyst separation section 310 where the remaining catalyst is separated from the gases from the catalyst processing (e.g., gases emitted by combustion of spent catalyst or supplemental fuel, referred to herein as flue gas). The flue gas may pass out of the catalyst processing portion 300 via outlet pipe 432. The separated catalyst is then passed through the oxygen treatment zone 370 within the catalyst separation section 310 to the upstream reactor section 250 via standpipe 424 and transport riser 430, where it is further utilized in a catalytic reaction. Thus, the catalyst, in operation, may cycle between the86421 -WO-PCT / DOW 86421 WO17reactor portion 200 and the catalyst processing portion 300. In general, the processed chemical streams, including the hydrocarbon-containing feed and olefm-containing effluent may be gaseous, and the catalyst may be fluidized particulate solid.

[0046] Referring now to the catalyst processing portion 300, as depicted in FIG. 1, the combustor 350 of the catalyst processing portion 300 may include one or more lower reactor portion inlet ports 352 and may be in fluid communication with the riser 330. Oxygen-containing gas, such as air, may be passed through pipe 428 into the combustor 350. In general, the oxygencontaining gas may comprise at least 10 mol.% oxygen. In some embodiments, the oxygencontaining gas may comprise at least 12 mol.%, at least 14 mol.%, at least 16 mol.%, at least 18 wt.%, or even at least 20 wt.% oxygen. The combustor 350 may be in fluid communication with the catalyst separation section 210 via standpipe 426, which may supply spent catalyst from the reactor portion 200 to the catalyst processing portion 300 for regeneration. The combustor 350 and riser 330, collectively referred to as the combustion reactor 302, may operate with similar or identical fluidization regimes as to what was disclosed with respect to the upstream reactor section 250 and downstream reactor section 230 of the reactor portion 200. That is, the combustor 350 may operate as a fluidized bed, such as in a fast fluidized, turbulent, or bubbling bed upflow reactor, while the riser 330 may operate in more of a plug flow manner, such as in a riser reactor. Geometries as described with respect to the upstream reactor section 250 and downstream reactor section 230 may equally apply to the combustor 350 and riser 330. Additionally, the combustor 350 may also include a fuel inlet 354, which may supply a fuel, such as a hydrocarbon stream, to the combustor 350.

[0047] As described herein, the catalyst may be heated in the catalyst processing portion 300 by combustion of supplemental fuels. Supplemental fuels may combust with oxygen to heat the catalyst. Supplemental fuels may comprise hydrogen, methane, ethane, propane, natural gas, or combinations thereof. Without being bound by any particular theory, when methane is utilized as the supplemental fuel, catalysts as described herein that include platinum, gallium, and a silica-zirconia support may better catalyze the combustion of methane to heat the catalyst. Catalysts that do not contain these components, when methane is utilized in the supplemental fuel, may be deficient by not promoting heating of the catalyst to a temperature needed for dehydrogenation.

[0048] As described in one or more embodiments, following separation of flue gas from catalyst in the riser termination separator 378 and secondary separation device 320, treatment of the processed catalyst with an oxygen-containing gas, such as air, is conducted in the oxygen86421 -WO-PCT / DOW 86421 WO18treatment zone 370. In general, the oxygen-containing gas in the oxygen treatment zone 370 may comprise at least 10 mol. % oxygen, and is substantially void of combustible gaseous hydrocarbons that are present in the combustor 350. In some embodiments, the oxygen treatment zone 370 includes a fluid solids contacting device. The fluid solids contacting device may include baffles or grid structures to facilitate contact of the processed catalyst with the oxygen-containing gas. Examples of fluid solid contacting devices are described in further detail in U.S. Patent Nos.9,827,543 and 9,815,040. The fluidization regime within the oxygen treatment zone may be bubbling bed type fluidization. The oxygen treatment zone 370 may include an oxygen-containing gas inlet 372, which may supply an oxygen-containing gas to the oxygen treatment zone 370 for oxygen treatment of the catalyst.

[0049] As is disclosed herein, in one or more embodiments, all or a portion of the catalyst may be exposed to an oxygen-containing gas in oxygen treatment zone 370. For example, all or a portion of the catalyst may be exposed to an oxy gen-containing gas for 2 min. to 20 min., such as from 2 min. to 4 min., from 4 min. to 6 min., from 6 min. to 8 min., from 8 min. to 10 min., from 10 min. to 12 min., from 12 min. to 14 min., from 14 min. to 16 min., from 16 min. to 18 min., from 18 min. to 20 min., or any combination of these ranges and endpoints. In some embodiments, the catalyst may be exposed to an oxygen containing gas from 4 min. to 18 min., from 6 min. to 17 min., from 8 min. to 16 min., or from 10 min. to 15 min. Without being bound by any particular theory, it is believed that exposure of the catalyst to an oxygen-containing gas for more than 20 minutes may increase equipment costs without a matching increase in catalyst regeneration efficiency. However, it is believed that oxygen-containing gas exposure for less than 2 minutes may lead to less efficient regeneration of the catalyst, which may reduce the catalyst’s dehydrogenation activity.

[0050] In one or more embodiments, the catalyst may be exposed to the oxygen-containing gas at a temperature of at least 650 °C, such as from 650 °C to 800 °C. Without being bound by any particular theory, it is believed that the regeneration may be most effective at temperatures of at least 650 °C when the catalyst has the compositions according to embodiments described herein.

[0051] In one or more embodiments, the olefinic materials may be present in a “product stream” sometimes called an “olefin-containing effluent” and include olefinic materials, which may include light olefins. Such a stream exits the reactor system of FIG. 1 and may be subsequently processed. As used herein, “light olefins” may refer to one or more of ethylene, propylene, and butylene. The term butylene includes any isomers of butylene, such as u-butylene,86421 -WO-PCT / DOW 86421 WO19cis-P-butylene, trans-[3-butylene, and isobutylene. In some embodiments, the olefin-containing effluent includes at least 25 wt.% olefinic materials based on the total weight of the olefin-containing effluent. For example, the olefin-containing effluent may include at least 35 wt.% olefinic materials, at least 45 wt.% olefinic materials, at least 55 wt.% olefinic materials, at least 65 wt.% olefinic materials, or at least 75 wt.% olefinic materials based on the total weight of the olefin-containing effluent. The olefin-containing effluent may further comprise unreacted components of the hydrocarbon-containing effluent, as well as other reaction products that are not considered olefinic materials. The olefinic materials may be separated from unreacted components in subsequent separation steps.EXAMPLES

[0052] The various embodiments of the present disclosure will be further clarified by the following examples. The examples are illustrative in nature and should not be understood to limit the subject matter of the present disclosure.

[0053] Catalyst samples were prepared with the compositions shown in Table 1. Comparative Example X was a conventional dehydrogenation catalyst prepared according to U.S. Patent No. 9,834,496. Comparative Example X included an AhCh-SiCh support obtained from Sasol (Siralox). Comparative Examples A- J and Examples 1-4 included ZrCh supports obtained fromNorpro (SZ31164, SZ61152) and DKKK (Z3186), as indicated in Table 1.Table 1: Catalyst sample compositions86421 -WO-PCT / DOW 86421 WO20

[0054] Catalyst Testing Method

[0055] The samples were tested by adding 100 mg of the catalyst samples of Table 1 into a quartz reactor. Three conditions were tested on various samples and the resulting data is shown in Tables 2 and 3. More than five tests were conducted for each sample. Tables 2 and 3 show mean values with a standard deviation less than 1%.

[0056] Condition 1: The samples were tested in a cycle with three steps: reaction / dehydrogenation, combustion, and reactivation. The reaction / dehydrogenation step was performed for 1 minute at a temperature of 625 °C with a weight hourly space velocity (WHSV) of propane of 50 hr'1. The feed composition was 90 mol.% propane / 10 mol.% helium and the feed had a flow rate of 50 cubic centimeters per minute (NTP, seem). The reported propane conversion and propylene selectivity correspond to values measured at a time-on-stream (TOS) of 25 s. The combustion step was performed at a temperature of 730 °C under 2.5 mol.% methane with balance of air with a total flow of 50 seem (NTP) for 3 minutes. The reported fuel conversion corresponds to values measured at a TOS of 60 s. The reactivation step was performed by heating the samples at 730 °C under 100% dry air with a flow rate of 50 seem (NTP) for 2.5 minutes.

[0057] Condition 2: The samples were tested in a cycle with two steps: reaction / dehydrogenation and regeneration. The reaction / dehydrogenation step was performed for 1 minute at a temperature of 625 °C with a WHSV of propane of 50 hr'1and 2.5% steam. The feed composition was 90 mol.% propane / 10 mol.% helium with a flow rate of 50 seem. The reactivation step was performed by heating the samples at 730 °C under 100% dry air with a flow rate of 50 seem for 15 minutes. The reported propane conversion and propylene selectivity correspond to values measured at a time-on-stream (TOS) of 25 s.

[0058] Condition 3: The samples were tested in a cycle with three steps: reaction / dehydrogenation, combustion, and reactivation. The steps were the same as in Condition 1, except the reactivation step occurred for a duration of 15 minutes.86421 -WO-PCT / DOW 86421 WO21Table 2: Catalytic performance under Conditions 1 and 2

[0059] As shown in Table 2, the presence of zirconia in catalyst samples improves fuel combustion compared to samples without zirconia. For example, Comparative Example X with no zirconia had a methane conversion of 45.9% under Condition 1. All comparative examples and inventive examples 1-4 showed an increase in methane conversion, with Examples 1-4 having methane conversions of 100%.

[0060] Samples with silica show improved propane conversion under Condition 1. Examples 1 and 2 contain 0.4 wt.% silica and have propane conversions of 28.7% and 29.9%, respectively. Comparative Example A and B, which contain no silica, have propane conversions of 10.8% and 11.8%, respectively. Thus, it has been found that silica added to platinum-gallium catalysts improves propane conversion.

[0061] Further, samples with relatively high amounts of gallium do not show improvement compared to conventional dehydrogenation catalysts. For example, Comparative Examples G, H,86421 -WO-PCT / DOW 86421 WO22and J, which have 12% gallium, have lower propane conversion and propylene selectivity values in Condition 1 than Comparative Example X, with 1.6 wt.% gallium. Additionally, Comparative Examples G, H, and J have much lower propane conversion and methane combustion than Examples 1-4. Thus, catalysts with relative high amounts of gallium do not show improvement in catalytic activity compared to catalysts as described herein.

[0062] Samples were tested under Condition 2 to evaluate steam tolerance. As shown in Table 2, Comparative Examples C and D have lower propane conversion and propylene selectivity than Examples 3 and 4. It is believed that catalysts described herein containing silica are steam tolerant such that propane conversion and / or propylene selectivity are maintained or even increase in the presence of steam.Table 3: Catalytic performance under Condition 3

[0063] As shown in Table 3, the addition of silica in amounts greater than 2 wt.% does not improve methane conversion compared to conventional dehydrogenation catalysts. Comparative Examples E and F show a much lower methane conversion (29.2% and 26.3%, respectively) than Comparative Example X (41.3%). The methane conversion of Comparative Examples E and F are also much lower than Inventive Examples 1-4, shown in Table 2. Thus, it is believed that catalyst with greater than 2 wt.% silica may not have improved methane conversion compared to conventional catalysts.

[0064] Additionally, the samples in Table 3 were tested at the same conditions as Condition 1, except the reactivation step occurred for 15 minutes. A longer reactivation time is expected to allow for a greater propane conversion. However, it was found that a reactivation time of 15 minutes does not increase propane conversion compared to a conventional dehydrogenation catalyst, Comparative Example X.86421 -WO-PCT / DOW 86421 WO23

[0065] The present disclosure includes numerous aspects, including aspects 1-15 described herein.

[0066] Aspect 1. A method for making olefinic materials, the method comprising: contacting a hydrocarbon-containing feed with a catalyst in a reactor to form an olefmic-containing effluent; passing the catalyst from the reactor to a combustor and heating the catalyst in the combustor by combusting a supplemental fuel; and passing the catalyst from the combustor to an upstream reactor section, such that all or a portion of the catalyst is continuously cycled between the reactor and the combustor, wherein the catalyst comprises gallium and platinum supported on a silica-zirconia support, and the catalyst comprises: from 0.1 wt.% to 4 wt.% gallium; from 5 ppmw to 1000 ppmw platinum; and at least 90 wt.% zirconia; and from 0.1 wt.% to 2 wt.% silica.

[0067] Aspect 2. The method of aspect 1, wherein passing the catalyst from the combustor to the upstream reactor section comprises: passing the catalyst from the combustor to an oxygen treatment zone and exposing the catalyst to an oxygen-containing gas; and passing the catalyst from the oxygen treatment zone to the reactor, such that all or a portion of the catalyst continuously cycles between the reactor, the combustor, and the oxygen treatment zone.

[0068] Aspect 3. The method of aspect 2, wherein the catalyst is exposed to an oxygen-containing gas for from 2 minutes to 20 minutes in the oxygen treatment zone.

[0069] Aspect 4. The method of any one of the previous aspects, wherein the catalyst has a residence time within the reactor of less than or equal to 3 minutes.

[0070] Aspect 5. The method of any one of the previous aspects, wherein contacting the hydrocarbon-containing feed with the catalyst occurs at a temperature from 500 °C to 700 °C.

[0071] Aspect 6. The method of any one of the previous aspects, wherein the supplemental fuel comprises methane, ethane, propane, hydrogen, or combinations thereof.

[0072] Aspect 7. The method of any one of the previous aspects, wherein contacting the hydrocarbon-containing feed with the catalyst in the reactor occurs in the presence of steam.

[0073] Aspect 8. The method of any one of the previous aspects, wherein the hydrocarbon-containing feed comprises propane and the olefm-containing effluent comprises propylene.

[0074] Aspect 9. The method of any one of the previous aspects, wherein the catalyst comprises from 0.01 wt.% to 5 wt.% of one or more alkali or alkaline earth metals.86421 -WO-PCT / DOW 86421 WO24

[0075] Aspect 10. The method of any one of the previous aspects, wherein the catalyst comprises: from 0.1 to 2 wt.% gallium; from 5 ppmw to 350 ppmw platinum; at least 90 wt.% zirconia; and from 0.2 wt.% to 1 wt.% silica.

[0076] Aspect 11. A catalyst suitable for dehydrogenation of hydrocarbons, the catalyst comprising gallium and platinum supported on a silica-zirconia support, and the catalyst comprises: from 0.1 wt.% to 4 wt.% gallium; from 5 ppmw to 1000 ppmw platinum; at least 90 wt.% zirconia; and from 0.1 wt.% to 2 wt.% silica.

[0077] Aspect 12. The catalyst of aspect 11, wherein the catalyst comprises from 5 ppmw to 350 ppmw of platinum.

[0078] Aspect 13. The method of any one of aspects 11 or 12, wherein the catalyst comprises from 0.1 wt.% to 2 wt.% of gallium.

[0079] Aspect 14. The method of any one of aspects 11 to 13, wherein the catalyst comprises from 0.01 wt.% to 5 wt.% of one or more alkali or alkaline earth metals.

[0080] Aspect 15. The catalyst of any one of aspects 11 to 14, wherein the catalyst comprises from 0.2 wt.% to 1 wt.% silica.

[0081] It will be apparent to those skilled in the art that various modifications and variations can be made to the presently disclosed technology without departing from the spirit and scope of the technology. Since modifications combinations, sub-combinations and variations of the disclosed embodiments incorporating the spirit and substance of the presently disclosed technology may occur to persons skilled in the art, the technology should be construed to include everything within the scope of the appended claims and their equivalents. Additionally, although some aspects of the present disclosure may be identified herein as favored or particularly advantageous, it is contemplated that the present disclosure is not limited to these aspects.

[0082] It is noted that the various details described in this disclosure should not be taken to imply that these details relate to elements that are essential components of the various embodiments described in this disclosure, even in cases where a particular element is illustrated in each of the drawings that accompany the present description. Unless specifically identified as such, no feature disclosed and described herein should be construed as “essential”. Contemplated embodiments of the present technology include those that include some or all of the features of the appended claims.

[0083] For the purposes of describing and defining the present disclosure it is noted that the term “about” are utilized in this disclosure to represent the inherent degree of uncertainty that86421 -WO-PCT / DOW 86421 WO25may be attributed to any quantitative comparison, value, measurement, or other representation. The term “about” are also utilized in this disclosure to represent the degree by which a quantitative representation may vary from a stated reference without resulting in a change in the basic function of the subject matter at issue.

[0084] In relevant cases, where a composition is described as “comprising” one or more elements, embodiments of that composition “consisting of’ or “consisting essentially of’ those one or more elements is contemplated herein.

[0085] It should be appreciated that compositional ranges of a chemical constituent in a stream or in a reactor should be appreciated as containing, in some embodiments, a mixture of isomers of that constituent. For example, a compositional range specifying butene may include a mixture of various isomers of butene. It should be appreciated that the examples supply compositional ranges for various streams, and that the total amount of isomers of a particular chemical composition can constitute a range.

[0086] It is noted that one or more of the following claims and the detailed description utilize the terms “where” or “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.”

[0087] It should be understood that any two quantitative values assigned to a property may constitute a range of that property, and all combinations of ranges formed from all stated quantitative values of a given property are contemplated in this disclosure. Where multiple ranges for a quantitative value are provided, these ranges may be combined to form a broader range, which is contemplated in the embodiments described herein.

Claims

86421 -WO-PCT / DOW 86421 WO26CLAIMS1. A method for making olefinic materials, the method comprising:contacting a hydrocarbon-containing feed with a catalyst in a reactor to form an olefmic-containing effluent;passing the catalyst from the reactor to a combustor and heating the catalyst in the combustor by combusting a supplemental fuel; andpassing the catalyst from the combustor to an upstream reactor section, such that all or a portion of the catalyst is continuously cycled between the reactor and the combustor, wherein the catalyst comprises gallium and platinum supported on a silica-zirconia support, and the catalyst comprises:from 0.1 wt.% to 4 wt.% gallium;from 5 ppmw to 1000 ppmw platinum; andat least 90 wt.% zirconia; andfrom 0.1 wt.% to 2 wt.% silica.

2. The method of claim 1, wherein passing the catalyst from the combustor to the upstream reactor section comprises:passing the catalyst from the combustor to an oxygen treatment zone and exposing the catalyst to an oxygen-containing gas; andpassing the catalyst from the oxygen treatment zone to the reactor, such that all or a portion of the catalyst continuously cycles between the reactor, the combustor, and the oxygen treatment zone.

3. The method of claim 2, wherein the catalyst is exposed to an oxygen-containing gas for from 2 minutes to 20 minutes in the oxygen treatment zone.

4. The method of any one of the previous claims, wherein the catalyst has a residence time within the reactor of less than or equal to 3 minutes.

5. The method of any one of the previous claims, wherein contacting the hydrocarbon-containing feed with the catalyst occurs at a temperature from 500 °C to 700 °C.86421 -WO-PCT / DOW 86421 WO276. The method of any one of the previous claims, wherein the supplemental fuel comprises methane, ethane, propane, hydrogen, or combinations thereof.

7. The method of any one of the previous claims, wherein contacting the hydrocarbon-containing feed with the catalyst in the reactor occurs in the presence of steam.

8. The method of any one of the previous claims, wherein the hydrocarbon-containing feed comprises propane and the olefm-containing effluent comprises propylene.

9. The method of any one of the previous claims, wherein the catalyst comprises from 0.01 wt.% to 5 wt.% of one or more alkali or alkaline earth metals.

10. The method of any one of the previous claims, wherein the catalyst comprises:from 0.1 to 2 wt.% gallium;from 5 ppmw to 350 ppmw platinum;at least 90 wt.% zirconia; andfrom 0.2 wt.% to 1 wt.% silica.

11. A catalyst suitable for dehydrogenation of hydrocarbons, the catalyst comprising gallium and platinum supported on a silica-zirconia support, and the catalyst comprises:from 0.1 wt.% to 4 wt.% gallium;from 5 ppmw to 1000 ppmw platinum;at least 90 wt.% zirconia; andfrom 0.1 wt.% to 2 wt.% silica.

12. The catalyst of claim 11, wherein the catalyst comprises from 5 ppmw to 350 ppmw of platinum.

13. The method of any one of claims 11 or 12, wherein the catalyst comprises from 0.1 wt.% to 2 wt.% of gallium.86421 -WO-PCT / DOW 86421 WO2814. The method of any one of claims 11 to 13, wherein the catalyst comprises from 0.01 wt.% to 5 wt.% of one or more alkali or alkaline earth metals.

15. The catalyst of any one of claims 11 to 14, wherein the catalyst comprises from 0.2 wt.% to 1 wt.% silica.

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