Methods of making olefinic materials by dehydrogenation

Abstract

A method for making olefinic materials by dehydrogenation includes operating a dehydrogenation system that utilizes a fluidized process catalyst. The process catalyst includes from 0.1 wt.% to 10 wt.% of one or more metals chosen from gallium, indium, thallium, or combinations thereof, from 1 ppmw to 1000 ppmw of one or more metals chosen from platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof, and at least 85 wt.% support. The method further includes withdrawing the process catalyst from the system. The withdrawn process catalyst includes less than 500 ppmw coke and has, on average, been continuously present in the system for at least 1 month. The method further includes exposing the withdrawn process catalyst to a gaseous environment at a temperature of from 600 °C to 950 °C for a time period of greater than or equal to 0.5 hours and passing the catalyst back to the system.

Description

86136-WO-PCT / DOW 86136 WO1METHODS OF MAKING OLEFINIC MATERIALS BY DEHYDROGENATIONCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 697,673 filed September 23, 2024, the contents of which are incorporated by reference in its entirety herein.TECHNICAL FIELD

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

[0003] Olefinic materials, such as ethylene, propylene, and butene, 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] Some methods and associated systems used to make olefinic materials may utilize a catalyst which 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 have catalytic activity not only for the dehydrogenation of alkanes, but also for the combustion of supplemental fuels. Some embodiments of such suitable catalysts include, for example, gallium and platinum on a support. In some embodiments, conventional catalysts used for dehydrogenation may, over a period of use, suffer from lowered catalytic activity, as compared to86136-WO-PCT / DOW 86136 WO2 a fresh catalyst that has not yet been used in a dehydrogenation system. Such used catalysts may no longer sufficiently catalyze dehydrogenation of alkanes. The catalyst may be deactivated as it ages through continuous use in the dehydrogenation system. As is described herein, it has been discovered that the deactivated catalysts may be regenerated by exposing the catalyst to a gaseous environment at from 600 °C to 950 °C for greater than or equal to 0.5 hours, which may restore catalytic activity for the dehydrogenation of alkanes as compared with conventional catalysts that, for example, have not been treated in this manner.

[0005] According to one or more embodiments of the present disclosure, a method for making olefinic materials by dehydrogenation may comprise operating a dehydrogenation system whereby a hydrocarbon-containing feed is converted to olefinic materials. The dehydrogenation system may utilize a fluidized process catalyst that circulates between a reactor, a combustor, and an oxygen treatment zone. The process catalyst may comprise from 0.1 wt.% to 10 wt.% of one or more metals chosen from gallium, indium, thallium, or combinations thereof, from 1 ppmw to 1000 ppmw of one or more metals chosen from platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof, and at least 85 wt.% support. The portion or all of the process catalyst may be withdrawn from the dehydrogenation system, wherein the portion or all of the process catalyst withdrawn from the dehydrogenation system comprises less than 500 ppmw coke, and wherein the portion or all of the process catalyst withdrawn from the dehydrogenation system has, on average, been continuously present in the dehydrogenation system for at least 1 month. The portion or all of the withdrawn process catalyst may be exposed to a gaseous environment at a temperature of from 600 °C to 950 °C for a time period of greater than or equal to 0.5 hours to form a regenerated catalyst and the regenerated catalyst may be passed back to the dehydrogenation system.

[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 embodiments86136-WO-PCT / DOW 86136 WO3 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 depicts a flow chart that includes steps for making olefinic materials, according to one or more embodiments of the present disclosure; and

[0009] FIG. 2 schematically depicts a reactor system, according to one or more embodiments of the present disclosure.

[0010] When describing the simplified schematic illustration of FIG. 2, 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.

[0011] Reference will now be made in greater detail to various embodiments, some of which are illustrated in the accompanying drawing.DETAILED DESCRIPTION

[0012] The present disclosure is directed to methods for making olefinic materials by dehydrogenation, which may include steps such as operating a dehydrogenation system, withdrawing a portion or all of a process catalyst from the dehydrogenation system, wherein the portion or all of the process catalyst withdrawn from the dehydrogenation system comprises less than 500 ppmw coke and wherein the portion or all of the process catalyst has, on average, been continuously present in the dehydrogenation system for at least 1 month, exposing the portion or all of the process catalyst to a gaseous environment at a temperature of from 600 °C to 950 °C for a time period of greater than or equal to 0.5 hours to form regenerated catalyst, and passing the86136-WO-PCT / DOW 86136 WO4 regenerated catalyst back to the dehydrogenation system. The process catalyst may comprise from 0.1 wt.% to 10 wt.% of one or more metals chosen from gallium, indium, thallium, or combinations thereof, from 1 to 1000 ppmw of one or more metals chosen from platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof, and at least 85 wt.% support. Unexpectedly, in one or more embodiments, such regenerated catalysts provide improved catalytic functionality for dehydrogenation of alkanes. Such modified catalysts may be particularly well suited for fluidized dehydrogenation of light alkanes to light olefins.

[0013] As is described herein, exposing the portion of the process catalyst to a gaseous environment at from 600 °C to 950 °C for greater than or equal to 0.5 hours may allow for reusing / recycling and continued use of the process catalyst, which may contain valuable materials such as platinum and gallium. Treating the process catalyst in this manner may increase the propane conversion of the process catalyst, once regenerated, as compared to the process catalyst when it is withdrawn from the dehydrogenation system. Such a regeneration procedure may be distinct from the normal operating conditions within a dehydrogenation system.

[0014] As used in the present disclosure, the term “process catalyst” refers to a catalyst that is used in a dehydrogenation system. A process catalyst may have a composition that is generally similar to that of a fresh catalyst that has not yet been introduced to a dehydrogenation system. The regenerated catalyst is a process catalyst that has undergone treatment outside of the dehydrogenation system as described herein, and is generally re-inserted into a dehydrogenation system thereafter.

[0015] Referring to FIG. 1, the steps of a method for making olefinic materials 100 is shown, according to one or more embodiments described herein. FIG. 1 depicts, in sequential order, step 110 of operating a dehydrogenation system, step 120 of withdrawing a portion or all of the process catalyst, step 130 of exposing the portion or all of the process catalyst to a gaseous environment to form a regenerated catalyst, and step 140 of passing the regenerated catalyst back into the dehydrogenation system.

[0016] Step 110 generally includes operating a dehydrogenation system. In the operating of the dehydrogenation system in step 110, a hydrocarbon-containing feed is converted to olefinic materials, which may include light olefins, in an olefin-containing effluent. The dehydrogenation86136-WO-PCT / DOW 86136 WO5 system of step 110 may be performed using a reactor system as schematically depicted in FIG. 2. The steps of FIG. 1 are sometimes described in the context of the reactor system of FIG. 2, as described herein. It should be understood that when describing the systems and associated methods of FIG. 2, the described “catalyst” may refer to the process catalyst or the regenerated catalyst, unless specified. Generally, the movement and fluidization of the process catalyst and the regenerated catalyst through the system of FIG. 2 is identical.

[0017] Embodiments of the methods presently disclosed will now be described in detail herein in the context of the reactor system of FIG. 2 operating as a fluidized dehydrogenation reactor system to produce olefinic materials, such as propylene. 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. 2 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. 2, such recited method steps should be understood as adaptable to other systems, as would be understood by those skilled in the art.

[0018] Now referring to FIG. 2, 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. 2, 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. 2, the reactor portion 200 may additionally include a catalyst separation section 210, which serves to separate the catalyst from86136-WO-PCT / DOW 86136 WO6 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 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).

[0019] Generally, as is described herein, in embodiments illustrated in FIG. 2, 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 temporarily reduced catalytic activity or is cooler as compared to catalyst entering the reactor portion 200. However, deactivated catalyst may maintain some catalytic activity. In typical FCC processes, the reduced catalytic activity may result from contamination with a substance such as coke. Coke may form on conventional FCC catalysts in amounts greater than 500 ppmw. In contrast, catalysts as described herein, which may comprise platinum and gallium, may have reduced catalytic activity that does not primarily result from coke formation. In one or more embodiments described herein, the process catalyst exiting the reactor portion 200 may comprise less than 500 ppmw coke, such as less than 475 ppmw coke, less than 450 ppmw coke, less than 425 ppmw coke, less than 400 ppmw coke, less than 375 ppmw, coke, less than 350 ppmw coke, less than 325 ppmw coke, less than 300 ppmw coke, less than 275 ppmw coke, less than 250 ppmw coke, less than 225 ppmw coke, less than 200 ppmw coke, less than 175 ppmw coke, less than 150 ppmw coke, less than 125 ppmw coke, less than 100 ppmw coke, less than 75 ppmw coke, less than 50 ppmw coke, or even less than 25 ppmw coke.86136-WO-PCT / DOW 86136 WO7

[0020] Reactivation in the dehydrogenation system may remove the contaminant such as coke, raise the temperature of the catalyst, or both. In some embodiments, deactivated catalyst may be reactivated by catalyst reactivation in the catalyst processing portion 300. The deactivated catalyst may be reactivated in the dehydrogenation system 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, or combinations thereof. The reactivated catalyst from the catalyst processing portion 300 is then passed back to the reactor portion 200.

[0021] 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, and i- butane. 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.

[0022] In one or more embodiments, the process catalyst may comprise, consist essentially of, or consist of one or more of gallium, indium, or thallium, one or more of platinum, palladium, rhodium, iridium, ruthenium, or osmium, 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). As is described herein, the catalyst may be solid particles suitable for fluidization.86136-WO-PCT / DOW 86136 WO

[0023] In one or more embodiments, the process catalyst may comprise one or more of gallium, indium, or thallium in an amount of from 0.1 wt.% to 10 wt.% based on the total mass of the process catalyst. Such materials may catalyze the dehydrogenation of alkanes to alkenes, particularly when used in combination with one or more of platinum, palladium, rhodium, iridium, ruthenium, or osmium. For example, the process catalyst may comprise one or more of gallium, indium, or thallium 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 one or more of gallium, indium, or thallium 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.%. In some embodiments, the process catalyst comprises only gallium but not indium or thallium, only indium but not gallium or thallium, or only thallium but not gallium or indium. It should be understood that the compositional ranges describing the amount of gallium, indium, and thallium represent ranges for any one of these materials, or for the combination of these materials. Without being bound by theory, it is believed that compositions having one or more of gallium, indium, or thallium in an amount less than 0.1 wt.% negatively impacts the process 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 one or more of gallium, indium, or thallium in an amount exceeding 10 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.

[0024] In one or more embodiments, the process catalyst may comprise one or more of platinum, palladium, rhodium, iridium, ruthenium, or osmium in an amount from 1 ppmw to 1000 ppmw based on the total mass of the process catalyst. Such materials may catalyze the dehydrogenation of alkanes to alkenes, particularly when used in combination with one or more of gallium, indium, or thallium. For example, the process catalyst may comprise one or more of platinum, palladium, rhodium, iridium, ruthenium, or osmium in an amount from 1 ppmw to 50 ppmw, from 5 ppmw to 50 ppmw, from 50 ppmw to 100 ppmw, from 100 ppmw to 200 ppmw, from 200 ppmw to 300 ppmw, from 300 ppmw to 400 ppmw, from 400 ppmw to 500 ppmw, from86136-WO-PCT / DOW 86136 WO9500 ppmw to 600 ppmw, from 600 ppmw to 700 ppmw, from 700 ppmw to 800 ppmw, from 800 ppmw to 900 ppmw, from 900 ppmw to 1000 ppmw, or any combination of these ranges. In some embodiments, the process catalyst may comprise one or more of platinum, palladium, rhodium, iridium, ruthenium, or osmium in an amount from 1 ppmw to 900 ppmw, from 1 ppmw to 800 ppmw, from 1 ppmw to 700 ppmw, from 1 ppmw to 600 ppmw, from 1 ppmw to 500 ppmw, or from 10 ppmw to 400 ppmw. In some embodiments, the process catalyst comprises only platinum but not palladium, rhodium, iridium, ruthenium, or osmium, only palladium but not platinum, rhodium, iridium, ruthenium, or osmium, only rhodium, but not platinum palladium, iridium, ruthenium, or osmium, only iridium, but not platinum palladium, rhodium, ruthenium, or osmium, only ruthenium but not platinum, palladium, rhodium, iridium, or osmium, or only osmium but not platinum, palladium, rhodium, iridium, or ruthenium. It should be understood that the compositional ranges describing the amount of platinum, palladium, rhodium, iridium, ruthenium, and osmium represent ranges for any one of these materials, or for the combination of these materials. Without being bound by theory, it is believed that compositions having one or more of platinum, palladium, rhodium, iridium, ruthenium, or osmium in an amount less than 1 ppmw negatively impacts the process 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 one or more of platinum, palladium, rhodium, iridium, ruthenium, or osmium in an amount exceeding 1000 ppmw 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.

[0025] As is described herein, in one or more embodiments, the catalyst may comprise a support. The support may comprise one or more of alumina, silica, or combinations thereof. For example, in some embodiments the support may comprise one or more of alumina, silica- containing alumina, zirconia-containing alumina, titania-containing alumina, and lanthanum- 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 90 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 fill the remainder of the total catalyst not specified by other materials.86136-WO-PCT / DOW 86136 WO10

[0026] In one or more embodiments, the process 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 0.5 wt.% based on the total mass of the catalyst. For example, the process 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.%, form 0.05 wt.% to 0.1 wt.%, from 0.1 wt.% to 0.15 wt.%, from 0.15 wt.% to 0.2 wt.%, from 0.2 wt.% to 0.25 wt.%, from 0.25 wt.% to 0.3 wt.%, from 0.3 wt.% to 0.35 wt.%, from 0.35 wt.% to 0.4 wt.%, from 0.4 wt.% to 0.45 wt.%, from 0.45 wt.% to 0.5 wt.%, or any combination of these ranges. In some embodiments, the process 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. Without being bound by theory, it is believed that compositions having alkali metals or alkaline earth metals in an amount less than 0.01 wt.% may cause the production of undesired products during the dehydrogenation reaction. However, it is believed that compositions having alkali metals or alkaline earth metals in an amount exceeding 0.5 wt.% may reduce the catalyst’s dehydrogenation activity.

[0027] In one or more embodiments, the process catalyst may include solid particulates that are capable of fluidization. In some embodiments, the process 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.

[0028] 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, assuming86136-WO-PCT / DOW 86136 WO11 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.

[0029] 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.

[0030] Still referring again to FIG. 2, 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 contacts 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.

[0031] Now referring to FIG. 2 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. 2, 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 tapered86136-WO-PCT / DOW 86136 WO12 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.

[0032] 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. 2). 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.

[0033] 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” may refer 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 have a distribution and 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 min., or less than or equal to 0.1 min. Without being bound by 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.86136-WO-PCT / DOW 86136 WO13

[0034] Still referring to FIG. 2, 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. 2 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.

[0035] According to 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.

[0036] 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. In86136-WO-PCT / DOW 86136 WO14 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.

[0037] Still referring to FIG. 2, the separated catalyst is passed from the catalyst separation section 210 to the combustor 350. 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 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.86136-WO-PCT / DOW 86136 WO15

[0038] Referring now to the catalyst processing portion 300, as depicted in FIG. 2, 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. 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 reactivation. 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.

[0039] 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 theory, when methane is utilized in the supplemental fuel, catalysts as described herein that have been treated may better catalyze the combustion of methane to heat the catalyst. Catalysts that have not been treated, when methane is utilized in the supplemental fuel, may be deficient by not promoting heating of the catalyst to a temperature needed for dehydrogenation.

[0040] 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 is conducted in the oxygen treatment zone 370. 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 9,815,040.86136-WO-PCT / DOW 86136 WO16The 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.

[0041] As is disclosed herein, in one or more embodiments the catalyst may be exposed to an oxygen-containing gas in oxygen treatment zone 370. For example, the catalyst may have a residence time in the oxygen treatment zone 370, such that the catalyst may be exposed to an oxygen-containing gas in the oxygen treatment zone 370, for from 2 minutes (min) to 20 min. As the term is used herein, “residence time” may refer to the average amount of time the catalyst or other specified material spends within a specific portion of the system 102, such as the oxygen treatment zone 370. As it is an average, the amount of time the catalyst may spend within the oxygen treatment zone 370 during any given cycle may have a distribution and 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 have a residence time in the oxygen treatment zone 370 of 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. 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 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 reactivation efficiency. However, it is believed that oxygen-containing gas exposure for less than 2 minutes may lead to less efficient reactivation of the catalyst, which may reduce the catalyst’s dehydrogenation activity. This oxygen treatment may be utilized to remove excess coke from the catalyst; however, as described herein, process catalysts that may comprise platinum and gallium may be treated to further regenerate the catalytic activity of the process catalyst.

[0042] In one or more embodiments, the olefinic materials may be present in a “product stream” sometimes called an “olefin-containing effluent” and include light olefins. Such a stream exits the reactor system 102 of FIG. 2 and may be subsequently processed. As used in the present disclosure, the term “light olefins” refers to one or more of ethylene, propylene, and butene. The86136-WO-PCT / DOW 86136 WO17 term butene includes any isomers of butene, such as a-butylene, cis-P-butylene, trans-P-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.

[0043] Now referring again to FIG. 1, step 120 generally includes withdrawing a portion or all of the process catalyst from the dehydrogenation system. Over time, the process catalyst may degrade or age while in use within the dehydrogenation system. This degradation may include the loss of catalytically active components, such as platinum from the process catalyst or the deactivation of the catalytic components of the process catalyst. Without being bound by any particular theory, the mechanisms for deactivation may involve sintering of active sites, enhanced interaction of active sites with underlying support, or a change in oxidation state of active sites. Under conventional procedures, this loss of catalytic materials may eventually necessitate the process catalyst to be replaced with fresh catalyst. The replacement of the process catalyst with fresh catalyst may be wasteful, as many of the components of the process catalyst, such as the catalytic materials and the support remain functional. As will be described herein, removing the catalyst from the system and treating the process catalyst as described herein may allow for the reuse of functional catalyst materials, such as platinum and gallium, which may reduce waste production.

[0044] In one or more embodiments, the process catalyst withdrawn from the dehydrogenation system has a lesser rate of propane to propylene conversion than the regenerated catalyst in the dehydrogenation system. For example, the process catalyst withdrawn from the dehydrogenation system may have a rate of propane to propylene conversion that is less than 5%, less than 6%, less than 7%, less than 8%, less than 9%, less than 10%, less than 12%, less than 14%, less than 16%, less than 18%, less than 20%, less than 25%, less than 30%, less than 35%, less than 40%, less than 45%, or even less than 50% than the rate of propane to propylene86136-WO-PCT / DOW 86136 WO18 conversion than the regenerated catalyst. It is believed that the rate of propane to propylene conversion of the catalyst may increase after exposure to the gaseous environment.

[0045] In one or more embodiments, the withdrawing of the process catalyst may be done in bulk, such that the dehydrogenation system is stopped and a significant portion of the process catalyst present in the dehydrogenation system is removed. For example, the amount of catalyst withdrawn may be at least 5% of the total catalyst present, at least 10%, at least 20%, at least 30 %, at least 40 %, at least 50 %, at least 60%, at least 70%, at least 80%, at least 90%, or even 100% of the total catalyst present may be withdrawn. The process catalyst may be withdrawn in bulk and shipped offsite for treatment.

[0046] In one or more embodiments, the process catalyst is continuously withdrawn. As used in the present disclosure, the term “continuously withdrawn” means the withdrawal of the process catalyst occurs such that some of the process catalyst is being withdrawn from the dehydrogenation system consistently so as to not require the dehydrogenation system to stop in order to withdraw the process catalyst. For example, continuous withdrawal may be accomplished by installation of catalyst withdrawal systems, such as the Johnson Matthey INTERCAT™ continuous Catalyst Withdrawal System. In some embodiments, the amount of process catalyst continuously withdrawn and the amount of catalyst added back to the dehydrogenation system is determined by measuring the catalyst loss from unit through mechanical attrition and the rate of performance of the process catalyst as it ages, so the process catalyst may be continuously withdrawn to maintain performance. In some embodiments, when the process catalyst is continuously withdrawn at least 0.05% of the process catalyst may be withdrawn from the dehydrogenation system. For example, at least 0.1% of the process catalyst may be withdrawn from the dehydrogenation system, at least 0.25% of the process catalyst, at least 0.5% of the process catalyst, at least 1.0% of the process catalyst, at least 1.5% of the process catalyst, at least 2.0% of the process catalyst, at least 2.5% of the process catalyst, at least 3.0% of the process catalyst, at least 3.5% of the process catalyst, at least 4.0% of the process catalyst, at least 4.5% of the process catalyst, or even up to 5.0% of the process catalyst may be continuously withdrawn.

[0047] In one or more embodiments, the process catalyst may be withdrawn when there is a decrease in dehydrogenation or combustion activity such that the targeted productivity (e.g. olefin production rate) or combustion activity can no longer be achieved by adding fresh catalyst to86136-WO-PCT / DOW 86136 WO19 compensate for the mechanical loss of catalyst from the unit or by applying high severity operation conditions, such as higher reaction temperature, higher reactivation temperature, or changing the catalyst to oil ratio. For example, the process catalyst may be withdrawn when combustion activity is not sufficient to reach at least 5% lower flammability limit (LFL), at least 10% LFL, at least 20% LFL, or at least 40% LFL, or the process catalyst may be withdrawn in bulk when productivity drops to 95% of the nameplate productivity, 90% of the nameplate productivity, 85% of the nameplate productivity, or 80% of the nameplate productivity. As used in the present disclosure, the term “lower flammability limit” refers to the lower end of the concentration range over which a flammable mixture of gas or vapor in air can be ignited at a given temperature and pressure. The LFL of the combustion gases may be determined by reactive chemistry testing or as described by Michael G. Zabetakis, Flammability Characteristics of Combustible Gases and Vapors, 627 Bureau of Mines 1 (1965), with pressure adjustments according to Coward et al., Limits of Flammability of Gases and Vapors, 503 Bureau of Mines 1 (1952). In some embodiments, when mechanical loss of catalyst is low and as such does not provide enough replacement space to allow addition of catalyst to compensate for the loss in dehydrogenation and combustion activity, catalyst may be intentionally withdrawn from the unit on a routine basis to provide replacement space to allow for the addition of catalyst. In some embodiments, the portion or all of the process catalyst that is withdrawn from the dehydrogenation system may have at least a 50% decrease in combustion activity as compared to when it was fresh catalyst. For example, the decrease in combustion activity may be at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, or at least 95%.

[0048] In one or more embodiments, the portion or all of the process catalyst may be withdrawn after being used in the dehydrogenation system for a given amount of time. For example, the portion or all of the process catalyst withdrawn from the dehydrogenation system may have, on average, been continuously present in the dehydrogenation system for at least 1 month. The portion or all of the process catalyst withdrawn may have an average time in the dehydrogenation system 102 of at least 1 month. As it is an average, the amount of time the catalyst may spend within the system 102 may have a distribution of catalyst particles that have spent at least 1 month in the dehydrogenation system 102. The catalyst particles may include fresh catalyst, process catalyst, and / or regenerated catalyst, as described herein. In some embodiments, the portion or all of the process catalyst withdrawn from the dehydrogenation system may have,86136-WO-PCT / DOW 86136 WO20 on average, been continuously present in the dehydrogenation system for at least 2 months, at least 3 months, at least 4 months, at least 5 months, at least 6 months, at least 7 months, at least 8 months, at least 9 months, at least 10 months, at least 11 months, or at least 1 year.

[0049] Now referring again to FIG. 1, step 130 generally includes exposing the process catalyst to a gaseous environment to form a regenerated catalyst. As used in the present disclosure the term “regenerated catalyst” refers to a process catalyst that has been exposed to a gaseous environment and has increased catalytic activity as compared to process catalyst that has not yet been exposed to a gaseous environment as described herein. In one or more embodiments, the process catalyst may be exposed to a gaseous environment at from 600 °C to 950 °C for greater than or equal to 0.5 hours to form a regenerated catalyst. The process catalyst may be withdrawn and placed in a separate vessel, such as, but not limited to, a batch kiln, rotary kiln, tunnel kiln, or elevator kiln, including a high-temperature batch furnace or a continuous operating rotary calciner. Such vessels may be electrically heated with no use of hydrocarbon-based fuels.

[0050] Without being bound by any particular theory, regeneration of the process catalyst by exposing the catalyst to a gaseous environment at from 600 °C to 950 °C for greater than or equal to 0.5 hours may affect the platinum and / or gallium present in catalysts described herein such that the dehydrogenation activity of the catalyst improves. For example, treating the aged catalysts as described herein may disperse or redistribute the platinum and / or gallium, increase the platinum-gallium interaction, partially or completely reoxidize the platinum and / or gallium present in the catalyst, or combinations thereof, which may increase the dehydrogenation activity of the catalyst. It should be understood that the treatment described herein of exposing the process catalyst to a gaseous environment to regenerate catalytic activity occurs outside of the system 102 described herein.

[0051] In some embodiments, the gaseous environment may comprise greater than or equal to 0.5 mol.% oxygen, greater than or equal to 1 mol.% oxygen, greater than or equal to 1.5 mol.% oxygen, greater than or equal to 2 mol.% oxygen, greater than or equal to 2.5 mol.% oxygen, greater than or equal to 3 mol.% oxygen, greater than or equal to 3.5 mol.% oxygen, greater than or equal to 4 mol.% oxygen, greater than or equal to 4.5 mol.% oxygen, greater than or equal to 5 mol.% oxygen, greater than or equal to 5.5 mol.% oxygen, greater than or equal to 6 mol.% oxygen, greater than or equal to 6.5 mol.% oxygen, greater than or equal to 7 mol.%86136-WO-PCT / DOW 86136 WO21 oxygen, greater than or equal to 7.5 mol.% oxygen, greater than or equal to 8 mol.% oxygen, greater than or equal to 8.5 mol.% oxygen, greater than or equal to 9 mol.% oxygen, greater than or equal to 9.5 mol.% oxygen, or greater than or equal to 10 mol.% oxygen. In some embodiments, the gaseous environment does not comprise oxygen and may comprise one or more inert gases. For example, the one or more inert gases may be selected from the group consisting of helium, argon, and nitrogen. In one or more embodiments, the inert gas is helium.

[0052] In one or more embodiments, the process catalyst may be exposed to the gaseous environment at a temperature of from 600 °C to 950 °C. For example, the process catalyst may be exposed to the gaseous environment at a temperature of from 625 °C to 950 °C, from 650 °C to 950 °C, from 675 °C to 950 °C, from 700 °C to 950 °C, from 725 °C to 950 °C, from 750 °C to950 °C, from 775 °C to 950 °C, from 800 °C to 950 °C, from 825 °C to 950 °C, from 850 °C to950 °C, from 875 °C to 950 °C, from 900 °C to 950 °C, from 600 °C to 925 °C, from 600 °C to900 °C, from 600 °C to 875 °C, from 600 °C to 850 °C, from 600 °C to 825 °C, from 600 °C to800 °C, from 600 °C to 775 °C, from 600 °C to 750 °C, from 600 °C to 725 °C, from 600 °C to700 °C, from 600 °C to 675 °C, from 600 °C to 650 °C, or any combinations of these ranges.

[0053] In one or more embodiments, the process catalyst may be exposed to the gaseous environment for greater than or equal to 0.5 hours. For example, the process catalyst may be exposed to the gaseous environment for greater than or equal to 1 hour, greater than or equal to 1.5 hours, greater than or equal to 2 hours, greater than or equal to 2.5 hours, greater than or equal to 3 hours, greater than or equal to 3.5 hours, greater than or equal to 4 hours, greater than or equal to 4.5 hours, greater than or equal to 5 hours, greater than or equal to 10 hours, greater than or equal to 12 hours, greater than or equal to 15 hours, greater than or equal to 20 hours, greater than or equal to 1 day, greater than or equal to 1.5 days, greater than or equal to 2 days, greater than or equal to 2.5 days, greater than or equal to 3 days, greater than or equal to 3.5 days, greater than or equal to 4 days, or even greater than or equal to 4.5 days. The process catalyst may be exposed to the gaseous environment for from 0.5 hours to 5 days. It is believed that a period of less than 0.5 hours in the gaseous environment would not sufficiently regenerate the process catalyst and a period of greater than 5 days in the gaseous environment would further improve the dehydrogenation activity of the process catalyst.86136-WO-PCT / DOW 86136 WO22

[0054] In one or more embodiments, the process catalyst may comprise less than 0.001 wt.% of manganese, vanadium, iron, chromium, or combinations thereof. In some embodiments, the process catalyst may be free of manganese, vanadium, iron, chromium, or combinations thereof. It should be understood that the regenerated catalyst (i.e., the catalyst that has been exposed to the gaseous environment) has generally the same composition as the process catalyst. The catalyst may not change in composition when exposed to the gaseous environment.

[0055] Referring again to FIG. 1, step 140 generally includes passing the regenerated catalyst back to the dehydrogenation system. The regenerated catalyst may be passed back to the system 102 in various portions of the system 102, such as, but not limited to, standpipe 422, standpipe 424, and transport riser 430. The regenerated catalyst may then cycle through the steps of the method of making olefinic materials 100 by being utilized in step 110 as a process catalyst, withdrawn in step 120, treated in step 130 to become a regenerated catalyst, and added back to the dehydrogenation system in step 140.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: Preparation of Catalyst Samples

[0058] Comparative Sample A was prepared by impregnating fluidizable mesoporous alumina with solution containing Pt, Ga, and K, then drying the impregnated catalyst at less than 200 °C and calcining the dried catalyst in air at less than 800 °C.

[0059] Comparative Sample B was generated by running the Comparative Sample A in a circulating fluidized bed reactor-regenerator comprising of dehydrogenation, methane fuel combustion, and air-based regeneration for a period of more than two months. The amount of coke on the catalyst was 60 ppmw.

[0060] Sample 1 was prepared by treating Comparative Sample B at 625 °C in air for a period of 1 hour.86136-WO-PCT / DOW 86136 WO23

[0061] Sample 2 was prepared by treating Comparative Sample B at 730 °C in helium for a period of 1 hour.

[0062] Sample 3 was prepared by treating Comparative Sample B at 730 °C in a 5% O2 / N2 mixture for a period of 1 hour.

[0063] Sample 4 was prepared by treating Comparative Sample B at 730 °C in air for a period of 1 minute.

[0064] Sample 5 was prepared by treating Comparative Sample B at 730 °C in air for a period of 15 minutes.

[0065] Sample 6 was prepared by treating Comparative Sample B at 730 °C in air for a period of 1 hour.

[0066] Sample 7 was prepared by treating Comparative Sample B at 730 °C in air for a period of 12 hours.

[0067] Sample 8 was prepared by treating Comparative Sample B at 800 °C in helium for a period of 1 hour.

[0068] Sample 9 was prepared by treating Comparative Sample B at 800 °C in helium for a period of 12 hours.

[0069] Sample 10 was prepared by treating Comparative Sample B at 800 °C in air for a period of 1 hour.

[0070] Sample 11 was prepared by treating Comparative Sample B at 800 °C in air for a period of 12 hours.

[0071] Sample 12 was prepared by treating Comparative Sample B at 800 °C in air for a period of 5 days.

[0072] Sample 13 was prepared by treating Comparative Sample B at 900 °C in air for a period of 1 hour.

[0073] Example II: Catalyst Testing86136-WO-PCT / DOW 86136 WO24

[0074] In Example II, different samples of catalytically active particles were prepared and tested. Performance testing for all samples was conducted in a lab-scale fixed bed reactor using simulated reaction-combustion-reactivation cycles in a fixed-bed rig. The samples were tested at ambient pressure under conditions of 0.5 grams (g) of the samples was mixed with 1.0 g of inert silicon carbide and loaded into a quartz reactor. The standard reaction combustion reactivation cycle was performed in three steps. First, dehydrogenation was performed at 625 °C with a feed composition of 90% propane / 10% nitrogen and weight hourly space velocity “WHSV” of propane of 10 hr1for 60 seconds. Second, combustion was performed at 730 °C under 2.5 mol% Methane / balance air with a total flow of 50 standard cubic centimeters per minute (seem) and a WHSV of methane of 0.1 hr1for 3 minutes. Finally, the reactivation step was performed at 730 °C under 100% air with a flow rate of 50 seem for 2 minutes (for the 1stcycle data) and 15 minutes for the remaining cycles. The dehydrogenation performance data was collected at 30 seconds time on stream and the combustion data was collected at 60 seconds time on stream. Dehydrogenation and combustion performances after Cycle 1 and Cycle 8 are reported in Table 1.Table 1: Propane dehydrogenation performance data86136-WO-PCT / DOW 86136 WO25

[0075] Table 1 indicates that, Comparative Sample B, the deactivated catalyst, has reduced propane conversion and propene selectivity when compared to Comparative Sample A, which has not been aged. Samples 1-13, which have been treated under specific temperatures and durations in various gaseous environments, have improved propane conversion and propene selectivity than Comparative Sample B. Additionally, longer durations of time in the gaseous environment show an improvement in propane conversion. For example, Sample 6 was treated at the same temperature and gaseous environment (e.g., air) but a shorter time period of 1 hour than Sample 7, which was treated for 12 hours. Sample 7 had a 43.2% propane conversion and Sample 6 has 25.1% propane conversion. Table 1 also indicates that increased temperatures may improve dehydrogenation activity of the catalyst, as shown in Samples 10-13. Table 1 indicates that exposing aged catalyst to a gaseous environment, as described herein, may improve catalytic activity of the catalyst.

[0076] The present disclosure includes numerous aspects, including aspects 1-15 described herein.

[0077] A first aspect of the present disclosure is directed to a method for making olefinic materials by dehydrogenation, the method comprising: operating a dehydrogenation system whereby a hydrocarbon-containing feed is converted to olefinic materials, wherein the dehydrogenation system utilizes a fluidized process catalyst that circulates between a reactor, a combustor, and an oxygen treatment zone, wherein the process catalyst comprises: from 0.1 wt.% to 10 wt.% of one or more metals chosen from gallium, indium, thallium, or combinations thereof; from 1 ppmw to 1000 ppmw of one or more metals chosen from platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof; and at least 85 wt.% support; withdrawing a portion or all of the process catalyst from the dehydrogenation system, wherein the portion or all of the process catalyst withdrawn from the dehydrogenation system comprises less than 500 ppmw coke, and wherein the portion or all of the process catalyst withdrawn from the dehydrogenation system has, on average, been continuously present in the dehydrogenation system for at least 1 month; exposing the portion or all of the withdrawn process catalyst to a gaseous environment at a temperature of from 600 °C to 950 °C for a time period of greater than86136-WO-PCT / DOW 86136 WO26 or equal to 0.5 hours to form a regenerated catalyst; and passing the regenerated catalyst back to the dehydrogenation system.

[0078] A second aspect of the present disclosure may include the first aspect, wherein the process catalyst withdrawn from the dehydrogenation system has a lesser rate of propane to propylene conversion than the regenerated catalyst in the dehydrogenation system.

[0079] A third aspect of the present disclosure may include either one of the first or second aspects, wherein the process catalyst has a residence time in the oxygen treatment zone of from 2 minutes to 20 minutes.

[0080] A fourth aspect of the present disclosure may include any one of the first through third aspects, wherein the portion or all of the process catalyst that is withdrawn from the dehydrogenation system has at least a 50% decrease in combustion activity as compared to when it was fresh catalyst.

[0081] A fifth aspect of the present disclosure may include any one of the first through fourth aspects, wherein the gaseous environment does not comprises oxygen, and wherein the gaseous environment comprises one or more inert gases selected from the group consisting of helium, argon, and nitrogen.

[0082] A sixth aspect of the present disclosure may include any one of the first through fifth aspects, wherein the gaseous environment comprises greater than or equal to 0.5 mol.% oxygen.

[0083] A seventh aspect of the present disclosure may include any one of the first through sixth aspects, wherein the gaseous environment comprise greater than or equal to 1 mol.% oxygen.

[0084] An eighth aspect of the present disclosure may include any one of the first through seventh aspects, wherein the regenerated catalyst comprises less than or equal to 100 ppmw coke.

[0085] A ninth aspect of the present disclosure may include any one of the first through eighth aspects, wherein the exposing of the portion or all of the withdrawn process catalyst to the gaseous environment is for greater than or equal to 1 hour.86136-WO-PCT / DOW 86136 WO27

[0086] A tenth aspect of the present disclosure may include any one of the first through ninth aspects, wherein the portion or all of the process catalyst is exposed to the gaseous environment at a temperature of from 700 °C to 950 °C.

[0087] An eleventh aspect of the present disclosure may include any one of the first through tenth aspects, wherein the process catalyst comprises less than 0.001 wt.% of manganese, vanadium, iron, chromium, or combinations thereof.

[0088] A twelfth aspect of the present disclosure may include any one of the first through eleventh aspects, wherein the portion or all of the process catalyst withdrawn from the dehydrogenation system has, on average, been continuously present in the dehydrogenation system for at least 3 months.

[0089] A thirteenth aspect of the present disclosure may include any one of the first through twelfth aspects, wherein the process catalyst comprises: from 0.1 wt.% to 10 wt.% of gallium; from 1 ppmw to 1000 ppmw of platinum; and at least 85 wt.% support.

[0090] A fourteenth aspect of the present disclosure may include any one of the first through thirteenth aspects, wherein the process catalyst comprises from 0.01 wt.% to 0.5 wt.% of one or more alkali metals, one or more alkaline earth metals, or both.

[0091] A fifteenth aspect of the present disclosure may include any one of the first through fourteenth aspects, wherein the support comprises of alumina, silica, or combinations thereof.

[0092] 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 preferred or particularly advantageous, it is contemplated that the present disclosure is not limited to these aspects.86136-WO-PCT / DOW 86136 WO28

[0093] 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.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] 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.”86136-WO-PCT / DOW 86136 WO29

[0098] 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

86136-WO-PCT / DOW 86136 WO30CLAIMS1. A method for making olefinic materials by dehydrogenation, the method comprising: operating a dehydrogenation system whereby a hydrocarbon-containing feed is converted to olefinic materials, wherein the dehydrogenation system utilizes a fluidized process catalyst that circulates between a reactor, a combustor, and an oxygen treatment zone, wherein the process catalyst comprises: from 0.1 wt.% to 10 wt.% of one or more metals chosen from gallium, indium, thallium, or combinations thereof; from 1 ppmw to 1000 ppmw of one or more metals chosen from platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof; at least 85 wt.% support; withdrawing a portion or all of the process catalyst from the dehydrogenation system, wherein the portion or all of the process catalyst withdrawn from the dehydrogenation system comprises less than 500 ppmw coke, and wherein the portion or all of the process catalyst withdrawn from the dehydrogenation system has, on average, been continuously present in the dehydrogenation system for at least 1 month; exposing the portion or all of the withdrawn process catalyst to a gaseous environment at a temperature of from 600 °C to 950 °C for a time period of greater than or equal to 0.5 hours to form a regenerated catalyst; and passing the regenerated catalyst back to the dehydrogenation system.

2. The method of claim 1, wherein the process catalyst withdrawn from the dehydrogenation system has a lesser rate of propane to propylene conversion than the regenerated catalyst in the dehydrogenation system.

3. The method of any of the previous claims, wherein the process catalyst has a residence time in the oxygen treatment zone of from 2 minutes to 20 minutes.

4. The method of any of the previous claims, wherein the portion or all of the process catalyst that is withdrawn from the dehydrogenation system has at least a 50% decrease in combustion activity as compared to when it was fresh catalyst.86136-WO-PCT / DOW 86136 WO315. The method of any of the previous claims, wherein the gaseous environment does not comprises oxygen, and wherein the gaseous environment comprises one or more inert gases selected from the group consisting of helium, argon, and nitrogen.

6. The method of any of the previous claims, wherein the gaseous environment comprises greater than or equal to 0.5 mol.% oxygen.

7. The method of any of the previous claims, wherein the gaseous environment comprise greater than or equal to 1 mol.% oxygen.

8. The method of any of the previous claims, wherein the regenerated catalyst comprises less than or equal to 100 ppmw coke.

9. The method of any of the previous claims, wherein the exposing of the portion or all of the withdrawn process catalyst to the gaseous environment is for greater than or equal to 1 hour.

10. The method of any of the previous claims, wherein the portion or all of the process catalyst is exposed to the gaseous environment at a temperature of from 700 °C to 950 °C.

11. The method of any of the previous claims, wherein the process catalyst comprises less than 0.001 wt.% of manganese, vanadium, iron, chromium, or combinations thereof.

12. The method of any of the previous claims, wherein the portion or all of the process catalyst withdrawn from the dehydrogenation system has, on average, been continuously present in the dehydrogenation system for at least 3 months.

13. The method of any of the previous claims, wherein the process catalyst comprises: from 0.1 wt.% to 10 wt.% of gallium; from 1 ppmw to 1000 ppmw of platinum; and at least 85 wt.% support.86136-WO-PCT / DOW 86136 WO3214. The method of any of the previous claims, wherein the process catalyst comprises from 0.01 wt.% to 0.5 wt.% of one or more alkali metals, one or more alkaline earth metals, or both.

15. The method of any of the previous claims, wherein the support comprises of alumina, silica, or combinations thereof.

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