Methods for making olefinic materials by dehydrogenation

Abstract

A method for making olefinic materials by dehydrogenation includes contacting a hydrocarbon-containing feed with a catalyst in a reactor to form an olefin-containing effluent, wherein the catalyst includes platinum, gallium, and one or more redox-active elemental additives, passing the catalyst to a combustor and heating the catalyst by combusting a supplemental fuel, passing the catalyst from the combustor to an oxygen treatment zone and exposing the catalyst to an oxygen-containing gas, passing the catalyst from the oxygen treatment zone to the reactor, such that at least a portion of the catalyst continuously cycles between the reactor, the combustor, and the oxygen treatment zone, and exposing the catalyst to an environment including at least 0.5 mol.% H2 downstream of the oxygen treatment zone and upstream of the reactor to remove a portion of oxygen present on the catalyst from the catalyst.

Description

86135-WO-PCT / DOW 86135 WO1METHODS FOR MAKING OLEFINIC MATERIALS BY DEHYDROGENATIONCROSS REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to U.S. Provisional Application Serial No. 63 / 696,903 filed September 20, 2024, the entire disclosure of which is hereby incorporated by reference.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 butenes, may be used as base materials to produce many different products, such as polyethylene, 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 given chemical feed and include those 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 may be dehydrogenated to form olefinic materials, such as forming propylene from propane by catalytic dehydrogenation. Redox-active elemental additives, such as iron, manganese, chromium, and cerium, may be used in platinum-gallium dehydrogenation catalysts to enhance supplemental fuel combustion. However, it has been observed that the redox-active nature of these elemental additives can lead to increased levels of COXand / or H2O during dehydrogenation, which can negatively affect catalyst performance and other downstream operations. It has presently been discovered that treating such catalysts with H2 prior to contact with the reactant may remove lattice oxygen from the redoxactive elemental additives, which can reduce the amount of COx, and / or H2O formed during dehydrogenation.86135-WO-PCT / DOW 86135 WO2

[0005] According to one or more embodiments of the present disclosure, a method for making olefinic materials by dehydrogenation may comprise contacting a hydrocarbon-containing feed with a catalyst in a reactor to form an olefin-containing effluent, wherein the catalyst comprises platinum, gallium, and one or more redox-active elemental additives. The method may further comprise passing the catalyst to a combustor and heating the catalyst by combusting a supplemental fuel, 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 at least a portion of the catalyst continuously cycles between the reactor, the combustor, and the oxygen treatment zone. The catalyst may be exposed to an environment comprising at least 0.5 mol.% H2 downstream of the oxygen treatment zone and upstream of the reactor to remove a portion of oxygen present on the catalyst from the catalyst.

[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 are86135-WO-PCT / DOW 86135 WO3 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.DETAILED DESCRIPTION

[0011] The present disclosure is directed to methods for making olefinic materials by dehydrogenation where particular catalyst compositions are utilized, as are described herein. 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), and an oxygen treatment zone. 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. Some embodiments of such suitable catalysts may include, for example, platinum, gallium, and one or more redox-active elemental additives. In order to improve the methane combustion activity, the one or more redox-active elemental additives, such as iron, manganese, and cerium, may be incorporated into the platinum-gallium catalyst. Even though these additives may enhance methane combustion activity, their redox-active activity may lead to increased levels of COXand H2O formation in the reactor, resulting in the loss of selectivity of the desired olefinic material products or inhibition of precious metal catalytic components, such as platinum. In particular, for processes that utilize fluidized beds, such impact may be more significant than for processes that do not utilize fluidized beds. In addition, COXspecies generated in the product stream may add to separation challenges downstream of the reactor.

[0012] As such, according to one or more embodiments and, as described herein, it has been discovered that the COXand H2O formation may be reduced by exposing dehydrogenation catalysts with an environment comprising H2 to remove a portion of oxygen present on the catalyst from the catalyst. Such oxygen may be lattice oxygen. As used herein, “lattice oxygen” may refer to the oxygen atoms that form the bulk phase of a crystal structure, and may be an active site in metal oxide catalysts, such as catalysts described herein. In particular, exposing catalysts that comprise platinum, gallium, and redox-active elemental additives with a hydrogen-containing environment may significantly reduce COXand H2O formation with minimal impact on dehydrogenation activity. For86135-WO-PCT / DOW 86135 WO4 example, the catalyst may be exposed to the hydrogen-containing environment downstream of an oxygen treatment zone, where lattice oxygen may build up on the catalyst, and upstream of the dehydrogenation reactor.

[0013] 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, butene, propylene, 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.

[0014] 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 product and 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 by86135-WO-PCT / DOW 86135 WO5 combustion, 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).

[0015] 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, it 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.

[0016] As is disclosed herein, in one or more embodiments, the supplemental fuel may comprise methane, ethane, propane, hydrogen, or combinations thereof. For example, the supplemental fuel may comprise an amount of methane, ethane, propane, hydrogen, or combinations thereof 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, ethane, propane, hydrogen, or combinations thereof in an amount no more than 10 mol.%. In some embodiments, the supplemental fuel may comprise methane, ethane, propane, hydrogen, or combinations thereof in an amount greater than 10 mol.%, such as greater than 20 mol.%, greater than 30 mol.%, greater than 40 mol.%, greater than86135-WO-PCT / DOW 86135 WO650 mol.%, greater than 60 mol.%, greater than 70 mol.%, greater than 80 mol.%, greater than 90 mol.%, or even 100 mol.%. In some 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 fuel combustion activity, such as those described herein, can better utilize methane, ethane, propane, hydrogen, or combinations thereof as a supplemental fuel to facilitate reheating 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.

[0017] 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 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.

[0018] In one or more embodiments, the catalyst may comprise, consist essentially of, or consist of platinum, gallium, and one or more redox-active elemental additives. In some86135-WO-PCT / DOW 86135 WO7 embodiments, the catalyst may comprise, consist essentially of, or consist of platinum, gallium, one or more redox-active elemental additives, and a support. 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, one or more redox-active elemental additives, a support, and one or both of alkali or alkaline earth metals. As is described herein, the catalyst may be solid particles suitable for fluidization.

[0019] In one or more embodiments, the catalyst may comprise gallium in an amount of from 0.1 wt.% to 10 wt.% based on the total mass of the catalyst. 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 2 wt.%, from 2 wt.% to 3 wt.%, from 3 wt.% to 4 wt.%, from 4 wt.% to 5 wt.%, from 5 wt.% to 6 wt.%, from 6 wt.% to 7 wt.%, from 7 wt.% to 8 wt.%, from 8 wt.% to 9 wt.%, from 9 wt.% to 10 wt.%, or any combination of these ranges. In some embodiments, the catalyst may comprise gallium in an amount from 0.1 wt.% to 9 wt.%, from 0.1 wt.% to 8 wt.%, from 0.1 wt.% to 7 wt.%, from 0.1 wt.% to 6 wt.%, or from 0.1 wt.% to 5 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 10 wt.% may negatively impact the catalyst’s cost and ability to catalyze the alkane dehydrogenation process, negatively impact the catalyst’s selectivity towards the intended product, or both.

[0020] In one or more embodiments, the catalyst may comprise platinum in an amount from 0.0005 wt.% to 0.1 wt.% based on the total mass of the catalyst. Such materials may catalyze the dehydrogenation of alkanes to alkenes, particularly when used in combination with gallium. Such materials may additionally catalyze the combustion of coke and supplemental fuels. For example, the catalyst may comprise platinum in an amount from 0.0005 wt.% to 0.005 wt.%, from 0.005 wt.% to 0.01 wt.%, from 0.01 wt.% to 0.02 wt.%, from 0.02 wt.% to 0.03 wt.%, from 0.03 wt.% to 0.04 wt.%, from 0.04 wt.% to 0.05 wt.%, from 0.05 wt.% to 0.06 wt.%, from 0.06 wt.% to 0.07 wt.%, from 0.07 wt.% to 0.08 wt.%, from 0.09 wt.% to 0.1 wt.%, or any combination of these ranges. In some86135-WO-PCT / DOW 86135 WO8 embodiments, the catalyst may comprise platinum in an amount from 0.0005 wt.% to 0.08 wt.%, from 0.0005 wt.% to 0.06 wt.%, from 0.0005 wt.% to 0.04 wt.%, from 0.0005 wt.% to 0.02 wt.%, from 0.0005 wt.% to 0.01 wt.%, from 0.001 wt.% to 0.005 wt.%, or any combinations of these ranges. Without being bound by any particular theory, it is believed that compositions having platinum in an amount less than 0.0005 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 platinum in an amount exceeding 0.1 wt.% may significantly increase the cost of the catalyst.

[0021] In one or more embodiments, the catalyst may comprise one or more redox-active elemental additives in an amount from 0.1 wt.% to 1 wt.% based on the total weight of the catalyst. As described herein, “redox-active elemental additives” refer to elemental additives 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). In some embodiments, the one or more redoxactive elemental additives may be chosen from iron, manganese, cerium, and chromium. 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 some embodiments.

[0022] In one or more embodiments, the catalyst may comprise the one or more redox-active elemental additives in an amount from 0.1 wt.% to 1 wt.% based on the total weight of the catalyst. For example, the catalyst may comprise one or more redox-active elemental additives in an amount from 0.15 wt.% to 1 wt.%, from 0.2 wt.% to 1 wt.%, from 0.25 wt.% to 1 wt.%, from 0.3 wt.% to 1 wt.%, from 0.35 wt.% to 1 wt.%, from 0.4 wt.% to 1 wt.%, from 0.45 wt.% to 1 wt.%, from 0.5 wt.% to 1 wt.%, from 0.55 wt.% to 1 wt.%, from 0.6 wt.% to 1 wt.%, from 0.65 wt.% to 1 wt.%, from 0.7 wt.% to 1 wt.%, from 0.75 wt.% to 1 wt.%, from 0.8 wt.% to 1 wt.%, from 0.9 wt.% to 1 wt.%, from0.95 wt.% to 1 wt.%, from 0.1 wt.% to 0.95 wt.%, from 0.1 wt.% to 0.9 wt.%, from 0.1 wt.% to 0.85 wt.%, from 0.1 wt.% to 0.8 wt.%, from 0.1 wt.% to 0.75 wt.%, from 0.1 wt.% to 0.7 wt.%, from 0.1 wt.% to 0.65 wt.%, from 0.1 wt.% to 0.6 wt.%, from 0.1 wt.% to 0.55 wt.%, from 0.1 wt.% to 0.5 wt.%, from 0.1 wt.% to 0.45 wt.%, from 0.1 wt.% to 0.4 wt.%, from 0.1 wt.% to 0.35 wt.%, from 0.1 wt.% to 0.3 wt.%, from 0.1 wt.% to 0.25 wt.%, from 0.1 wt.% to 0.2 wt.%, from 0.1 wt.% to 0.15 wt.%, from 0.2 wt.% to 0.9 wt.%, from 0.3 wt.% to 0.8 wt.%, from 0.4 wt.% to 0.6 wt.%, or any combinations of these ranges, based on the total weight of the catalyst. Without being bound by any86135-WO-PCT / DOW 86135 WO9 particular theory, it is believed that compositions having redox-active elemental additives in an amount less than 0.1 wt.% may not sufficiently improve the methane combustion performance of the catalyst. It is believed that compositions having redox-active elemental additives in an amount exceeding 5 wt.% may negatively impact the catalyst’s dehydrogenation performance by lowering the percentage of total alkane that is dehydrogenated and / or the percentage of dehydrogenated alkane that is the intended product. Further, the presence of these redox-active elemental additives in the catalyst may lead to increased levels of COXand H2O formation in the reactor, resulting in the loss of selectivity of the desired olefinic material products or inhibition of precious metal catalytic components (i.e., “poisoning”), such as platinum.

[0023] As is described herein, in one or more embodiments, the catalyst may comprise a support. In some embodiments, the support may comprise one or more of alumina, silica, titania, zirconia, or combinations thereof. For example, contemplated supports include alumina, silica- containing alumina, titania-containing alumina, and zirconia-containing alumina. The support may be present in an amount of at least 85 wt.% relative to the total weight of the catalyst, such as at least 85 wt.%, at least 86 wt.%, at least 87 wt.%, at least 88 wt.%, at least 89 wt.%, at least 90 wt.%, at least 91 wt.%, at least 92 wt.%, at least 93 wt.%, at least 94 wt.%, or at least 95 wt.%. In some embodiments, the support comprises less than or equal to 99.5 wt.% of the catalyst. Generally, the wt.% of the support may fdl the remainder of the total catalyst not specified by other materials described herein.

[0024] 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. However, it is believed that86135-WO-PCT / DOW 86135 WO10 compositions having alkali metals or alkaline earth metals in an amount exceeding 5 wt.% may reduce the catalyst’s dehydrogenation activity.

[0025] In one or more embodiments, the catalyst may comprise, consist essentially of, or consist of gallium, platinum, one or more redox-active elemental additives, and a support. For example, the catalyst may comprise, consist essentially of, or consist of from 0.0005 wt.% to 0.1 wt.% of platinum; from 0.1 wt.% to 10 wt.% of gallium; from 0.1 wt.% to 1 wt.% of one or more redoxactive elemental additives; and at least 85 wt.% of a support. In one or more embodiments, the catalyst may comprise, consist essentially of, or consist of gallium; platinum; and iron, manganese, cerium, chromium, or combinations thereof. For example, the catalyst may comprise, consist essentially of, or consist of from 0.0005 wt.% to 0.1 wt.% of platinum; from 0.1 wt.% to 10 wt.% of gallium; and from 0.1 wt.% to 1 wt.% of iron, manganese, cerium, chromium or combinations thereof. It should be understood that platinum and gallium are not redox-active elements.

[0026] In one or more embodiments, the catalyst may be formulated into 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.

[0027] 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 / recoalescing bubbles, 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 cfp; 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.86135-WO-PCT / DOW 86135 WO11

[0028] Geldart Group B is understood by those skilled in the art as representing a “sand-like” 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 < cfp < 500 pm when the density (pp) is 1.4 < pp < 4 g / cm3.

[0029] 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 precursors are 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, platinum, and one or more redox-active elemental additives; drying the support; and calcining the support, wherein the catalyst comprises from 0.0005 wt.% to 0.1 wt.% of platinum, from 0.1 wt.% to 10 wt.% of gallium, from 0.1 wt.% to 1 wt.% of one or more redox-active elemental additives, and at least 85 wt.% support.

[0030] 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. In one or more embodiments, the support is sequentially impregnated with gallium and platinum and then with the one or more redox-active elemental additives. For some embodiments, the method of making a catalyst may comprise impregnating the support with gallium and platinum, drying the support, calcining the support,86135-WO-PCT / DOW 86135 WO12 impregnating the support with one or more redox-active elemental additives following the drying and calcining, and drying and calcining the support following the impregnation with one or more redoxactive elemental additives, wherein the catalyst comprises from 0.0005 wt.% to 0.1 wt.% of platinum, from 0.1 wt.% to 10 wt.% of gallium, from 0.1 wt.% to 5 wt.% of one or more redox-active elemental additives, and at least 85 wt.% support. In additional embodiments, the method of making a catalyst may comprise impregnating the support with one or more redox-active elemental additives to create a redox-active elemental additive impregnated support, drying the redox-active elemental additive impregnated support, calcining the redox-active elemental additive impregnated support, impregnating the redox-active elemental additive impregnated support with gallium and platinum following the drying and calcining, and drying and calcining the redox-active elemental additive impregnated support following the impregnation with gallium and platinum, wherein the catalyst comprises from 0.0005 wt.% to 0.1 wt.% of platinum, from 0.1 wt.% to 10 wt.% of gallium, from 0.1 wt.% to 1 wt.% of one or more redox-active elemental additives, and at least 85 wt.% support.

[0031] 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 be 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.

[0032] Now referring again to FIG. 1, the hydrocarbon-containing feed may enter feed inlet 434 into the reactor 202, and the olefin-containing effluent may exit the reactor system 102 via 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 may contact the catalyst in the upstream reactor section 250, and each flow upwardly into and through the downstream reactor section 230 to produce an olefin-containing effluent. The reactor 202 may operate at relatively high temperatures, such as from 500 °C to 800 °C. For example, the reactor 202 may operate at a temperature of 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.

[0033] 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 reactor86135-WO-PCT / DOW 86135 WO13 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 crosssection of the upstream reactor section 250 to the size of the cross-section 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.

[0034] 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 somewhat deactivated, but may still, in some embodiments, be suitable for reaction in the upstream reactor section 250, particularly when used in combination with reactivated catalyst.

[0035] In one or more embodiments, the catalyst may have a residence time within the reactor portion 200 of less than or equal to 8 minutes. As the term is used herein, “residence time” refers to the average amount of time the catalyst or other specified material spends within a portion of the reactor system 102, such as 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 7.5 min., less than or equal to 7 min., less than or equal to 6.5 min., less than or equal to 6 min., less than or equal to 5.5 min., less than or equal to 5 min., less than or equal to 4.5 min., less than or equal to 4 min., less than or equal to 3.5 min., less than or equal to 3 min., less than or equal to 2.5 min., less86135-WO-PCT / DOW 86135 WO14 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 sufficient time for the catalyst to catalyze the dehydrogenation reaction.

[0036] 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.

[0037] 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 300.86135-WO-PCT / DOW 86135 WO15

[0038] 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.

[0039] Still referring to FIG. 1, the separated catalyst may be passed from the catalyst separation section 210 to the combustor 350. In some embodiments, the catalyst may be exposed to another oxygen-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.

[0040] 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 in86135-WO-PCT / DOW 86135 WO16 a catalytic reaction. Thus, the catalyst, in operation, may cycle between the reactor portion 200 and the catalyst processing portion 300. In general, the processed chemical streams, including the hydrocarbon-containing feed and olefin-containing effluent may be gaseous, and the catalyst may be fluidized particulate solid.

[0041] 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 oxygen-containing gas may comprise at least 10 mol.% oxygen. In some embodiments, the oxygen-containing gas may comprise at least 12 mol.% oxygen, at least 14 mol.% oxygen, at least 16 mol.% oxygen, at least 18 wt.% oxygen, 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 catalyst 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.

[0042] 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, and supplemental fuels such as a supplemental fuel, such as hydrogen, methane, ethane, propane, natural gas, or combinations thereof. Without being bound by any particular theory, when methane is utilized in the supplemental fuel, catalysts as described herein that include one or more redox-active elemental additives may better catalyze the combustion of methane to heat the catalyst.

[0043] 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 oxygen treatment zone 370. In general, the oxy gen-containing gas in the oxygen treatment zone 370 may comprise at86135-WO-PCT / DOW 86135 WO17 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.

[0044] In one or more embodiments, lattice oxygen may build up on the catalyst in the oxygen treatment zone 370. The redox-active elemental additives present in the catalyst, as described herein, may react with the oxygen in the oxygen treatment zone and lattice oxygen may form on the redoxactive elemental additives. The lattice oxygen may be carried on the catalyst to other portions of the reactor system 102 and may react with the hydrocarbon-containing feed and form COXand / or H2O in the reactor. Without being limited by any particular theory, COXmay be poisonous to the platinum present in the catalyst and H2O may inhibit active sites such as platinum and gallium present in the catalyst, which both can lead to a loss in dehydrogenation activity.

[0045] As is disclosed herein, in one or more embodiments, all or a portion of the catalyst may be exposed to an oxy gen-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 60 min., such as from 2 min. to 5 min., from 5 min. to 10 min., from 10 min. to 15 min., from 15 min. to 20 min., from 20 min. to 25 min., from 25 min. to 30 min., from 35 min. to 40 min., from 45 min. to 50 min., from 50 min. to 55 min., from 55 min. to 60 min. or any combination of these ranges. 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. In some embodiments, the catalyst may be exposed to an oxygen containing gas from 2 min. to 50 min., from 2 min. to 40 min., from 2 min. to 30 min., from 2 min. to 20 min., from 2 min. to 10 min., from 10 min. to 60 min., from 20 min. to 60 min., from 30 min. to 60 min., from 40 min. to 60 min., or from 50 min. to 60 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.86135-WO-PCT / DOW 86135 WO18

[0046] In one or more embodiments, the catalyst may be exposed to the oxygen-containing gas at a temperature of at least 650 °C. For example, the catalyst may be exposed to the oxy gencontaining gas at a temperature of at least 675 °C, least 700 °C, at least 725 °C, at least 750 °C, at least 775 °C, or 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 is loaded with one or more redox-active elemental additives, according to embodiments described herein.

[0047] As described herein, the presence of redox-active elemental additives in the dehydrogenation catalyst may lead to COXand / or H2O formation in the dehydrogenation reactor due to oxygen accumulation on the catalyst. In one or more embodiments, the catalyst may be exposed to an environment comprising at least 0.5 mol.% H2 downstream of the oxygen treatment zone 370 and upstream of the reactor portion 200 that may reduce the amount of lattice oxygen that accumulates on the redox-active elemental additives. In some embodiments, the amount of lattice oxygen removed from the regenerated catalyst may be less than or equal to 0.2 wt.%, such as less than or equal to 0.19 wt.%, less than or equal to 0.18 wt.%, less than or equal to 0.17 wt.%, less than or equal to 0.16 wt.%, less than or equal to 0.15 wt.%, less than or equal to 0.14 wt.%, less than or equal to 0.13 wt.%, less than or equal to 0.12 wt.%, less than or equal to 0.11 wt.%, less than or equal to 0.1 wt.%, less than or equal to 0.09 wt.%, less than or equal to 0.08 wt.%, less than or equal to 0.07 wt.%, less than or equal to 0.06 wt.%, or less than or equal to 0.05 wt.%.

[0048] According to one or more embodiments, the catalyst may be exposed to an environment comprising at least 0.5 mol.% H2. In some embodiments, catalyst may be exposed to an environment comprising at least 0.75 mol.% H2, at least 1 mol.% H2, at least 1.5 mol.% H2, at least 2 mol.% H2, at least 2.5 mol.% H2, at least 3 mol.% H2, at least 3.5 mol.% H2, at least 4 mol.% H2, at least 4.5 mol.% H2, at least 5 mol.% H2, at least 6 mol.% H2, at least 7 mol.% H2, at least 8 mol.% H2, at least 9 mol.% H2, at least 10 mol.% H2, at least 12 mol.% H2, at least 14 mol.% H2, at least 16 mol.% H2, at least 18 mol.% H2, at least 20 mol.% H2, at least 25 mol.% H2, or even at least 30 mol.% H2. The environment may be formed by injecting a hydrogen-containing stream into a particular area of the system 102, such that the catalyst is exposed to a hydrogen-containing environment. In some embodiments, the hydrogen-containing stream may comprise at least 2 mol.% H2, at least 2.5 mol.% H2, at least 3 mol.% H2, at least 3.5 mol.% H2, at least 4 mol.% H2, at least 4.5 mol.% H2, at least 5 mol.% H2, at least 6 mol.% H2, at least 7 mol.% H2, at least 8 mol.% H2, at least 9 mol.% H2, at least86135-WO-PCT / DOW 86135 WO1910 mol.% H2, at least 12 mol.% H2, at least 14 mol.% H2, at least 16 mol.% H2, at least 18 mol.% H2, at least 20 mol.% H2, at least 25 mol.% H2, or even at least 30 mol.% H2.

[0049] According to some embodiments, it is contemplated that the hydrogen-containing stream may be a wide variety of gas compositions as long as it includes at least 0.5 mol.% H2. According to some embodiments, the hydrogen-containing gas may be the same gas as is used for the supplemental fuel, as described herein. Such gas streams may be available as an off-gas from a demethanizer from a steam cracking system.

[0050] In some embodiments, the catalyst may be exposed to an environment comprising less than 0.1 mol.% O2, such as less than 0.09 mol.% O2, less than 0.08 mol.% O2, less than 0.07 mol.% O2, less than 0.06 mol.% O2, less than 0.05 mol.% O2, less than 0.04 mol.% O2, less than 0.03 mol.% O2, less than 0.02 mol.% O2, or less than 0.01 mol.% O2. In some embodiments, the environment may be free of O2. It is believed that exposing the catalyst to an environment comprising greater than 0.1 mol.% O2 will increase the risk of unsafe combustion when the environment comprises at least 0.5 mol.% H2.

[0051] According to one or more embodiments, the catalyst may be exposed to the hydrogencontaining environment between the oxygen treatment zone 370 and the reactor 200. In some embodiments, the catalyst may be exposed to the environment comprising H2 downstream of the oxygen treatment zone 370 and the reactor 200 relative to the motion of the catalyst. In some embodiments, the catalyst may be exposed to the environment comprising H2 in a particulate solids transfer line or catalyst mix pot between the oxygen treatment zone 370 and the reactor 200 relative to the direction of solid particulate motion. In additional embodiments, the environment comprising H2 is in a particulate solids transfer line or catalyst mix pot between the reactor and the combustor relative to solid particulate motion. In some embodiments, the hydrogen-containing stream may be passed or injected into a transfer line connecting the oxygen treatment zone 370 with the reactor 200. For example, the hydrogen-containing stream may be injected in the standpipe 424 or the transport riser 430 (catalyst mix-pots are not specifically illustrated but would be understood as incorporated in FIG. 1 by those skilled in the art).

[0052] As shown in FIG. 1, the hydrogen-containing stream may be injected into various portions of the reactor system 102. In one or more embodiments, the hydrogen-containing stream86135-WO-PCT / DOW 86135 WO20 may be injected into an injection port. Arrow 440 in FIG. 1 depicts where an injection port may be positioned on a transfer line between the oxygen treatment zone 370 and the reactor 200. Arrow 442 in FIG. 1 depicts another place where an injection port may be positioned on a transfer line between the oxygen treatment zone 370 and the reactor 200. Injection ports may be located on the standpipe 424 (as shown by arrow 440), the transport riser 430 (as shown by arrow 442), or other portions of the reactor system 102 downstream of the oxygen treatment zone 370 and upstream of the reactor 200. Multiple injection ports are contemplated in one or more embodiments. It should be understood that arrow 440 and arrow 442 are non-limiting examples where an injection port may be located. In one or more embodiments, injecting the hydrogen-containing stream into an injection port may form the hydrogen-containing environment within the reactor system 102. As a non-limiting example, injecting the hydrogen-containing stream into an injection port located at arrow 440 may form the hydrogen-containing environment in the standpipe 424. As the catalyst moves through the standpipe 424, the catalyst may be exposed to the hydrogen-containing environment such that a portion of oxygen present on the catalyst is removed from the catalyst.

[0053] In some embodiments, the catalyst may be exposed to the environment comprising H2 at a temperature of from 550 °C to 750 °C, such as from 550 °C to 725 °C, from 550 °C to 700 °C, from 550 °C to 675 °C, from 550 °C to 650 °C, from 550 °C to 625 °C, from 550 °C to 600 °C, from 575 °C to 750 °C, from 600 °C to 750 °C, from 625 °C to 750 °C, from 650 °C to 750 °C, from 675 °C to 750 °C, from 700 °C to 750 °C, or any combinations of these ranges.

[0054] In some embodiments, the catalyst may be exposed to the environment comprising H2 for less than or equal to 5 minutes. In other words, the catalyst may have a residence time in the environment comprising H2 of less than or equal to 5 minutes. As stated, “residence time” refers to the average amount of time the catalyst or other specified material spends within a portion of the reactor system 102, such as the environment comprising H2. As it is an average, the amount of time the catalyst may spend within the environment 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. For example, the catalyst may be exposed to the environment comprising H2 for less than or equal to 4.5 minutes, less than or equal to 4 minutes, less than or equal to 3.5 minutes, less than or equal to 3 minutes, less than or equal to 2.5 minutes, less than or equal to 2 minutes, less than or equal to 1.5 minutes, or even less than or equal to 1 minute. In some embodiments, the the catalyst may be exposed to the environment comprising H2 for from 0.5 minutes to 5 minutes, from 1 minute to 5 minutes, from 2 minutes to 586135-WO-PCT / DOW 86135 WO21 minutes, from 3 minutes to 5 minutes, from 4 minutes to 5 minutes, from 0.5 minutes to 4 minutes, from 0.5 minutes to 3 minutes, from 0.5 minutes to 2 minutes, or any combination of these ranges.

[0055] 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 butene. The term butene includes any isomers of butene, such as a-butylene, cis-|3-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

[0056] 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.

[0057] Example I - Sample Preparation

[0058] In Example I, samples of catalytically active particles (i.e., catalysts) were prepared by incipient wetness impregnation of mesoporous alumina support. The mesoporous alumina support had a surface area of 70 m2 / g and a pore volume of 0.24 ml / g. Stoichiometric quantities of metals were dissolved in the desired amount of deionized water to form a solution. The solution was then used to impregnate the support. The impregnated support was aged overnight in a sealed container followed by drying at 177 °C for 2 hours and calcination at 750 °C for 1 hour. The reagents used were tetramine platinum nitrate, gallium nitrate, potassium nitrate, iron nitrate, cerium nitrate, and manganese nitrate.86135-WO-PCT / DOW 86135 WO22

[0059] Example II: Catalyst Testing Method

[0060] Table 1 shows the results of the tests performed for propane dehydrogenation using catalysts with and without redox-active elemental additives and where the catalyst is either prereduced or not pre -reduced. Pre-reduction refers to contacting the catalyst with a hydrogencontaining stream. The testing was performed in fixed bed reactor. In samples with a pre-reduction step, 2% I b / l lc was introduced for 1 minute at 625 °C before introducing the propane feed (WHSV= 10 hr'1). Propane conversion, propylene selectivity, and COXselectivity are measured at 6 seconds into the dehydrogenation reaction pulse at cycle 20. Each cycle included 1 minute of dehydrogenation, 3 minutes of fuel combustion, and 2 minutes of air soak.Table 1: Dehydrogenation performance of catalysts

[0061] As shown in Table 1, the addition of a redox-active elemental additive (Fe) improved propane conversion. For example, Samples 1 and 2 with no redox-active elemental additive had a propane conversion of 52.23% and 47.28%, respectively, and Samples 3 and 4 with Fe had propane conversions of 56.16% and 53.52%, respectively. However, samples with the addition of a redoxactive elemental additive and no pre-reduction step saw an increase in COXselectivity from 0.03% (Sample 1) to 0.60% (Sample 3). Sample 4 shows that the addition of a pre-reduction step decreases COXselectivity. Thus, catalysts with a redox-active elemental additive may improve propane conversion and propylene selectivity and a pre -reduction step may decrease the formation of COXspecies during the reaction.

[0062] Table 2 shows the results of the tests performed for methane combustion performance of catalysts with and without redox-active additives and with and without a pre-reduction step. The testing was performed in fixed bed reactor at 730 °C.86135-WO-PCT / DOW 86135 WO23Table 2: Methane combustion performance of catalysts

[0063] As shown in Table 2, the addition of a redox-active elemental additive (Fe) in catalysts greatly improves methane combustion as compared to catalysts without a redox-active elemental additive. For example, Sample 5 has a CPU conversion of 91.39% and Sample 7, with Fe, has a CPU conversion of 98.75%. Thus, the redox-active elemental additive improves fuel combustion. The addition of the pre-reduction step does not significantly impact methane combustion for catalysts with or without the redox-active elemental additive.

[0064] Table 3 shows the results of the tests performed to measure the extent of CO formation during propane dehydrogenation for various catalysts with and without redox-active additives. All catalysts were tested under identical conditions in a pilot-scale fluidized bed reactor with a propane feed. The reactor and regenerator operated at a temperature between 620 °C to 630 °C and 720 °C to 730 °C, respectively. Circulation rates of the catalysts and propane feed rates were adjusted to operate the reactor under a catalyst / propane ratio of 45 g / g with corresponding weight hourly space velocity (WHSV) of 14 hr'1. A blend of H2 (75% by vol.) and CH4 (25% by vol.) was used as fuel in the regenerator, corresponding to a heat input of -440 kJ / mol. Product and flue gas streams exiting the reactor and regenerator, respectively, were analyzed at every ~6 minutes via separate gas chromatographs. The operating conditions for the reactor and regenerator were held constant for greater than 4 hours of steady state operation.Table 3: Extent of CO formation during the dehydrogenation step for catalysts86135-WO-PCT / DOW 86135 WO24

[0065] As shown in Table 3, the addition of a redox-active elemental additive increases the amount of CO in the product gas. Samples 10-12 utilize different redox-active elemental additives in different amounts, but all show an increase in CO in the product gas. Samples 10-12 also see an decrease in propane conversion and propylene selectivity. Thus, Table 2 shows that the presence of redox-active elemental additives increases CO concentration and decreases catalytic activity.

[0066] To study the impact of water on the performance of a dehydrogenation catalyst, a Pt- Ga based catalyst (Pt = 200 ppmw, Ga = 1.6 wt.%, K = 0.25 wt.%) was tested in a circulating fluidized bed reactor at 630 °C using a feed comprised of propane and water. The catalyst / oil ratio in the reactor was 16 and the propane-based WHSV was 6 hr'1. After each dehydrogenation step, the catalyst was transferred to a regenerator vessel where it was regenerated under air for a period of 35 minutes. Results of the tests are shown in Table 4.Table 4: Effect of H2O co-feed with propane on dehydrogenation activity for a Pt-Ga based catalyst

[0067] As shown in Table 4, the presence of water negatively impacts dehydrogenation activity of the catalyst. As the water concentration in the feed increased, the propane conversion and propylene selectivity decreased. Thus, when utilizing such catalysts described herein that comprise redox-active elemental additives, dehydrogenation activity would decrease due to the H2O or steam generated during the reaction.

[0068] Accordingly, T ables 3 and 4 indicate the need for the reduction of COXand H2O during dehydrogenation processes with catalysts comprising redox-active elemental additives. Tables 1 and 2 show that the addition of a pre-reduction step (i.e., contacting the catalyst with a hydrogencontaining stream) lowers the amount of COXand H2O formed during the reaction and therefore increases propane conversion and propylene selectivity.86135-WO-PCT / DOW 86135 WO25

[0069] The present disclosure includes numerous aspects, including aspects 1-15, described herein.

[0070] A first aspect of the present disclosure is directed to a method for making olefinic materials by dehydrogenation, the method comprising: contacting a hydrocarbon-containing feed with a catalyst in a reactor to form an olefin-containing effluent, wherein the catalyst comprises platinum, gallium, and one or more redox-active elemental additives; passing the catalyst to a combustor and heating the catalyst by combusting a supplemental fuel; passing the catalyst from the combustor to an oxygen treatment zone and exposing the catalyst to an oxygen-containing gas; passing the catalyst from the oxygen treatment zone to the reactor, such that at least a portion of the catalyst continuously cycles between the reactor, the combustor, and the oxygen treatment zone; and exposing the catalyst to an environment comprising at least 0.5 mol.% H2 downstream of the oxygen treatment zone and upstream of the reactor to remove a portion of oxygen present on the catalyst from the catalyst.

[0071] A second aspect of the present disclosure may include the first aspect, wherein a hydrogen-containing stream is injected into a transfer line connecting the oxygen treatment zone with the reactor.

[0072] A third aspect of the present disclosure may include the second aspect, wherein the hydrogen-containing stream comprises at least 2 mol.% H2.

[0073] A fourth aspect of the present disclosure may include the second aspect, wherein the transfer line is a standpipe connecting the oxygen treatment zone with the reactor.

[0074] A fifth aspect of the present disclosure may include the second aspect, wherein the transfer line is a transport riser connecting the oxygen treatment zone with the reactor.

[0075] A sixth aspect of the present disclosure may include any one of the second through fifth aspects, wherein the hydrogen-containing stream comprises the supplemental fuel.

[0076] A seventh aspect of the present disclosure may include any one of the first through sixth aspects, wherein the environment comprises at least 2 mol.% H2.86135-WO-PCT / DOW 86135 WO26

[0077] A eighth aspect of the present disclosure may include any one of the first through seventh aspects, wherein the environment comprises at least 0.5 mol.% H2 and less than 0.1 mol.% O2.

[0078] A ninth aspect of the present disclosure may include any one of the first through eighth aspects, wherein exposing the catalyst to the environment occurs at a temperature of from 550 °C to 750 °C.

[0079] A tenth aspect of the present disclosure may include any one of the first through ninth aspects, wherein contacting the catalyst with the hydrogen-containing stream occurs for less than or equal to 5 minutes.

[0080] An eleventh aspect of the present disclosure may include any one of the first through tenth aspects, wherein the one or more redox-active elemental additives comprises iron, manganese, cerium, chromium, or combinations thereof.

[0081] A twelfth aspect of the present disclosure may include any one of the first through eleventh aspects, wherein the catalyst comprises: from 0.0005 wt.% to 0.1 wt.% of platinum; from 0.1 wt.% to 10 wt.% of gallium; from 0.1 wt.% to 1 wt.% of one or more redox-active elemental additives; and at least 85 wt.% support.

[0082] A thirteenth aspect of the present disclosure may include any one of the first through twelfth aspects, wherein the catalyst has a residence time within the reactor of less than or equal to 8 minutes.

[0083] A fourteenth aspect of the present disclosure may include any one of the first through thirteenth aspects, wherein the catalyst is exposed to the oxygen-containing gas for from 2 minutes to 20 minutes in the oxygen treatment zone.

[0084] A fifteenth aspect of the present disclosure may include any one of the first through fourteenth aspects, wherein the supplemental fuel comprises methane in an amount of at least 1 mol.%.

[0085] 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 disclosed86135-WO-PCT / DOW 86135 WO 1 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.

[0086] 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.

[0087] 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 that may 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.

[0088] 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.

[0089] 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.

[0090] 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.”86135-WO-PCT / DOW 86135 WO28

[0091] 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

86135-WO-PCT / DOW 86135 WO29CLAIMS1. A method for making olefinic materials by dehydrogenation, the method comprising: contacting a hydrocarbon-containing feed with a catalyst in a reactor to form an olefin- containing effluent, wherein the catalyst comprises platinum, gallium, and one or more redox-active elemental additives; passing the catalyst to a combustor and heating the catalyst by combusting a supplemental fuel; passing the catalyst from the combustor to an oxygen treatment zone and exposing the catalyst to an oxygen-containing gas; passing the catalyst from the oxygen treatment zone to the reactor, such that at least a portion of the catalyst continuously cycles between the reactor, the combustor, and the oxygen treatment zone; and exposing the catalyst to an environment comprising at least 0.5 mol.% H2 downstream of the oxygen treatment zone and upstream of the reactor to remove a portion of oxygen present on the catalyst from the catalyst.2 The method of claim 1, wherein a hydrogen-containing stream is injected into a transfer line connecting the oxygen treatment zone with the reactor.3 The method of claim 2, wherein the hydrogen-containing stream comprises at least 2 mol.% H24 The method of claim 2, wherein the transfer line is a standpipe connecting the oxygen treatment zone with the reactor.5 The method of claim 2, wherein the transfer line is a transport riser connecting the oxygen treatment zone with the reactor.6 The method of any one of claims 2 to 5, wherein the hydrogen-containing stream comprises the supplemental fuel.86135-WO-PCT / DOW 86135 WO307. The method of any of the previous claims, wherein the environment comprises at least 2 mol.% H2.

8. The method of any of the previous claims, wherein the environment comprises at least 0.5 mol.% H2 and less than 0.1 mol.% O2.9 The method of any of the previous claims, wherein exposing the catalyst to the environment occurs at a temperature of from 550 °C to 750 °C.10 The method of any of the previous claims, wherein contacting the catalyst with the hydrogencontaining stream occurs for less than or equal to 5 minutes.11 The method of any of the previous claims, wherein the one or more redox-active elemental additives comprises iron, manganese, cerium, chromium, or combinations thereof.12 The method of any of the previous claims, wherein the catalyst comprises: from 0.0005 wt.% to 0.1 wt.% of platinum; from 0.1 wt.% to 10 wt.% of gallium; from 0.1 wt.% to 1 wt.% of one or more redox-active elemental additives; and at least 85 wt.% support.13 The method of any of the previous claims, wherein the catalyst has a residence time within the reactor of less than or equal to 8 minutes.14 The method of any of the previous claims, wherein the catalyst is exposed to the oxy gencontaining gas for from 2 minutes to 20 minutes in the oxygen treatment zone.15 The method of any of the previous claims, wherein the supplemental fuel comprises methane in an amount of at least 1 mol.%.

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