Catalysts that include chromium and methods for making olefinic materials that utilize the same

Abstract

A method for making olefinic materials includes passing a hydrocarbon-containing feed and a catalyst into a reactor of an olefinic material production system, wherein the hydrocarbon-containing feed is reacted to form the olefinic material and the catalyst includes from 0.25 wt.% to 10 wt.% chromium and at least 85 wt.% of a support. The catalyst is passed to a combustor and heated by combusting a supplemental fuel or coke present on the catalyst. The catalyst is passed to an upstream reactor section, such that the catalyst is continuously cycled between the reactor and the combustor. A sulfur-containing compound is passed into the system and into contact with the catalyst. The catalyst may include from 0 wt.% to 0.1 wt.% of platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof, from 0 wt.% to 10 wt.% of gallium, indium, thallium, or combinations thereof, and the support may include silica-containing zirconia.

Description

86193-WO-PCT / DOW 86193 WO1CATALYSTS THAT INCLUDE CHROMIUM AND METHODS FOR MAKING OLEFINIC MATERIALS THAT UTILIZE THE SAMECROSS REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to U.S. Provisional Application Serial No. 63 / 713,294 filed October 29, 2024, the entire disclosure of which is hereby incorporated by reference.TECHNICAL FIELD

[0002] Embodiments of the present disclosure generally relate to chemical processing and, in particular, to methods and systems for making olefinic materials.BACKGROUND

[0003] Olefinic materials, such as ethylene, butene, styrene and propylene, may be used as base materials to produce many different products, such as polypropylene, polystyrene, polyethylene, 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 or alkyl aromatics in a fluidized bed reactor. There is a need for improvements in the methods and associated catalysts used to make olefinic materials.SUMMARY

[0004] Described herein, according to one or more embodiments, are methods for making olefins that comprise reacting hydrocarbon-containing feeds to form olefinic materials that utilize a catalyst that is circulated between a reactor and a combustor. The reaction may cause coking in the reactor and / or other portions of the system. Coking may be mitigated, as described in one or more embodiments herein, by utilizing a sulfur-containing compound. According to some embodiments, although the sulfur-containing compound may reduce the amount of coke formed in the system, it may negatively affect the catalytic activity of the catalyst. It is presently discovered that utilizing catalysts that comprise chromium may be more tolerant to exposure to sulfur, such that the catalytic activity is not greatly reduced by sulfur as compared to conventional catalysts.

[0005] According to one or more embodiments, a method for making olefinic materials may comprise passing a hydrocarbon-containing feed and a catalyst into a reactor of an olefinic material86193-WO-PCT / DOW 86193 WO2 production system, wherein a portion of the hydrocarbon-containing feed is reacted to form the olefinic material in the reactor and the catalyst comprises from 0.25 wt.% to 10 wt.% chromium and at least 85 wt.% of a support. The catalyst may be passed from the reactor to a combustor of the olefinic material production system and heated in the combustor by combusting one or both of a supplemental fuel or coke present on the catalyst in the combustor. The catalyst may be passed from the combustor to an upstream reactor section, such that all or a portion of the catalyst is continuously cycled between the reactor and the combustor, and a sulfur-containing compound may be passed into any portion of the olefinic material production system and into contact with the catalyst.

[0006] According to one or more additional embodiments, a catalyst suitable for dehydrogenation of hydrocarbons may comprise from 0.25 wt.% to 10 wt.% chromium, from 0 wt.% to 0.1 wt.% of platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof, from 0 wt.% to 10 wt.% of gallium, indium, thallium, or combinations thereof, and at least 85 wt.% support, wherein the support comprises silica-containing zirconia.

[0007] 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

[0008] The following detailed description may be better understood when read in conjunction with the following drawing, in which:

[0009] FIG. 1 schematically depicts an olefinic material production system, according to one or more embodiments of the present disclosure;86193-WO-PCT7DOW 86193 WO3

[0010] FIGS. 2A-2D depict graphs showing propane conversion (FIG. 2A), propylene selectivity (FIG. 2B), ethylene selectivity (FIG. 2C), and methane selectivity (FIG. 2D) for a conventional catalyst, according to one or more examples of the present disclosure;

[0011] FIGS. 3A-3D depict graphs showing propane conversion (FIG. 3A), propylene selectivity (FIG. 3B), ethylene selectivity (FIG. 3C), and methane selectivity (FIG. 3D) for catalysts according to one or more embodiments of the present disclosure;

[0012] FIGS. 4A-4D depict graphs showing propane conversion (FIG. 4A), propylene selectivity (FIG. 4B), ethylene selectivity (FIG. 4C), and methane selectivity (FIG. 4D) for conventional catalysts according to one or more examples of the present disclosure;

[0013] FIGS. 5A-5B depict graphs showing propane conversion (FIG. 5A) and propylene selectivity (FIG. 5B) for a conventional catalyst according to one or more examples of the present disclosure;

[0014] FIGS. 6A-6B depict graphs showing propane conversion (FIG. 6A) and propylene selectivity (FIG. 6B) for catalysts according to one or more embodiments of the present disclosure; and

[0015] FIGS. 7A-7D depict graphs showing propane conversion (FIG. 7A), propylene selectivity (FIG. 7B), ethylene selectivity (FIG. 7C), and methane selectivity (FIG. 7D) for catalysts according to one or more embodiments of the present disclosure.

[0016] When describing the simplified schematic illustration of FIG. 1, the numerous valves, temperature sensors, electronic controllers, and the like, which may be used and are well known to a person of ordinary skill in the art, are not included. Further, accompanying components that are often included in such reactor systems, such as air supplies, heat exchangers, surge tanks, and the like are also not included. However, it should be understood that these components are within the scope of the present disclosure.

[0017] Reference will now be made in greater detail to various embodiments, some of which are illustrated in the accompanying drawing.86193-WO-PCT / DOW 86193 WO4DETAILED DESCRIPTION

[0018] Described herein are methods for making olefinic materials. According to embodiments described herein, olefinic materials may be produced in olefinic material production systems that operate by circulating catalysts between reactors and combustors. The olefinic material production systems generally operate at elevated temperatures (e.g., at least 550 °C). Generally, metal surfaces that may be present in the olefinic material production systems may catalyze coking of hydrocarbons at such temperatures. Excessive coking can be mitigated by introducing a sulfur- containing compound into the system to form a passivation layer on the metal surfaces of the system. However, the sulfur may accumulate on the catalyst, which reduces the catalytic activity of the catalyst and cause a decrease in the production of the olefinic material. According to one or more embodiments, catalysts that comprise chromium may be sulfur tolerant such that the catalytic activity is not negatively affected by the sulfur present in the system.

[0019] Methods for making olefinic materials may utilize olefinic material production systems, and such methods are described in the context of such olefinic material production systems. As described herein, an olefinic material production system is any system that can produce olefinic materials. As described herein, olefinic materials refer to compounds that include at least one alkene moiety (i.e., a C=C double bond). In some embodiments, the olefinic materials may be “light olefins” such as ethylene, propylene, butene, or styrene. These olefinic materials can be produced via dehydrogenation from ethane, propane, butane, and ethylbenzene, respectively, which may be included as the feed into the reactor.

[0020] According to embodiments described herein, catalysts may be utilized in the process to form olefinic materials, whereby the catalysts continuously circulate between a reactor and a combustor during normal steady-state operation during olefinic material production. The olefinic materials are produced in the reactor, and the catalysts are heated in the combustor by combustion of a supplemental fuel, burning of coke, or both. Various reaction mechanisms, and associated reactants, may be utilized to form the olefinic materials. For example, dehydrogenation may be utilized to convert paraffins to olefins, such as ethane to ethylene, butane to butylene, and propane to propylene, or to convert ethylbenzene to styrene. A process of converting propane to propylene is described in U.S. Pat. No. 10,227,271, the entirety of which is incorporated by reference in this disclosure.

[0021] Embodiments of the methods presently disclosed are described in detail herein in the context of the olefinic material production system 100 of FIG. 1 operating as a fluidized86193-WO-PCT / DOW 86193 WO5 dehydrogenation reactor system to produce olefinic materials, such as propylene. It should be understood that not all portions of FIG. 1 should be construed as essential to the claimed subject matter.

[0022] Referring now to FIG. 1, an example olefinic material production system 100 that may be suitable for use with the methods and / or apparatuses described herein is schematically depicted. The olefinic material production system 100 generally comprises multiple system components that are included in a reactor portion 200 and a catalyst processing portion 300. As described herein, “system components” refer to portions of the olefinic material production system 100, 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 olefinic material production system 100 in which the major process reaction takes place (e.g., dehydrogenation) to form an olefinic material-containing effluent. A hydrocarbon-containing feed enters the reactor portion 200, is contacted with a catalyst, converted to an olefinic material-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 olefinic material-containing effluent formed in the reactor 202. Also, as used herein the catalyst processing portion 300 generally refers to the portion of the olefinic material production system 100 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).

[0023] Generally, as is described herein, in embodiments illustrated in FIG. 1, catalyst is circulated 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 olefinic material production system 100. The catalyst that exits the reactor portion 200 may be deactivated catalyst.86193-WO-PCT / DOW 86193 WO6As 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 hydrogen, 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. 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.

[0024] To mitigate coke formation in the system 100 during the process described herein, a sulfur-containing compound may be passed to any portion of the olefinic production system 100. The sulfur-containing compound may be, but is not limited to hydrogen sulfide. It has been found that sulfur may accumulate on the catalyst, causing a decrease in catalytic activity. However, catalysts as described herein that comprise chromium may be tolerant to sulfur such that the catalytic activity of the catalyst is not as negatively affected by the presence of sulfur in the system 100 as compared to catalysts that do not comprise chromium.

[0025] In one or more embodiments, the catalyst may comprise, consist essentially of, or consist of chromium and a support. In additional embodiments, the catalyst may comprise, consist essentially of, or consist of chromium, 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). In additional embodiments, the catalyst may comprise, consist essentially of, or consist of chromium, one or more of gallium, indium, or thallium; one or more of platinum, palladium, rhodium, iridium, ruthenium, or osmium; 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.86193-WO-PCT / DOW 86193 WO7

[0026] In one or more embodiments, the catalyst may comprise chromium in an amount of from 0.25 wt.% to 10 wt.% based on the total mass of the catalyst. In some embodiments, the catalyst may comprise chromium in an amount of from 0.25 wt.% to 3 wt.% based on the total mass of the catalyst. The presence of chromium in the catalyst in such amounts may allow the catalyst to be sulfur-tolerant, such that the catalytic activity is not as negatively affected by sulfur as conventional dehydrogenation catalyst without chromium. For example, the catalyst may comprise chromium in an amount 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 chromium in an amount from 0.25 wt.% to 9 wt.%, from 0.25 wt.% to 8 wt.%, from 0.25 wt.% to 7 wt.%, from 0.25 wt.% to 6 wt.%, or from 0.25 wt.% to 5 wt.%. Without being bound by any particular theory, it is believed that compositions having chromium in an amount less than 0.25 wt.% may not be tolerant to sulfur and catalytic activity may not be improved in the presence of sulfur as compared to conventional catalysts. It is also believed that compositions having chromium in an amount of greater than 10 wt.% may cause potential safety concerns and increased costs.

[0027] In one or more embodiments, the catalyst may comprise a support. In some embodiments, the support may comprise alumina, silica, zirconia, or combinations thereof. The alumina, silica, zirconia, or combinations thereof may act as a metal oxide support. The term “metal oxide support” may refer to a support material that supports the other components of the catalyst, for example, chromium. Contemplated supports include pure phase alumina, pure phase zirconia, silica- containing alumina, zirconia-containing alumina, and silica-containing zirconia. As used herein, “phase pure” zirconia or alumina may refer to zirconia or alumina to which no other materials have intentionally been added during formation. Thus, “phase pure zirconia” includes zirconia with small amounts of components other than zirconium (including oxides other than zirconia) that are unintentionally present in the zirconia as a natural part of the zirconia formation process and “pure phase alumina” includes alumina with small amounts of components other than aluminum (including oxides other than alumina) that are unintentionally present in the alumina as a natural part of the alumina formation process. In other embodiments, the zirconia or alumina can be non-phase pure zirconia or alumina, such as silica-containing alumina, zirconia-containing alumina, and silica- containing zirconia.86193-WO-PCT / DOW 86193 WO8

[0028] In embodiments comprising silica-containing alumina, the support may comprise less than or equal to 5 wt.% silica, less than or equal to 4 wt.% silica, less than or equal to 3 wt.% silica, less than or equal to 2 wt.% silica, or less than or equal to 1 wt.% silica.

[0029] In some embodiments, the support may comprise, consist essential of, or consist of silica-containing zirconia. In such embodiments, the support may comprise less than or equal to 10 wt.% silica, such as less than or equal to 9 wt.% silica, less than or equal to 8 wt.% silica, less than or equal to 7 wt.% silica, less than or equal to 6 wt.% silica, less than or equal to 5 wt.% silica, less than or equal to 4 wt.% silica, less than or equal to 3 wt.% silica, less than or equal to 2 wt.% silica, or less than or equal to 1 wt.% silica.

[0030] 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.%, at least 95 wt.%, at least 96 wt.%, at least 97 wt.%, at least 98 wt.%, or at least 99 wt.%. In some embodiments, the support comprises less than or equal to 99.5 wt.% or less than or equal to 99.75 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.

[0031] In one or more embodiments, the catalyst may optionally comprise gallium in an amount of from 0 wt.% to 10 wt.% based on the total mass of the catalyst. In one or more embodiments, the catalyst may comprise gallium in an amount of from 0.05 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 wt.% to 0.25 wt.%, from 0.05 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 0.05 wt.% to 9 wt.%, from 0.05 wt.% to 8 wt.%, from 0.05 wt.% to 7 wt.%, from 0.05 wt.% to 6 wt.%, or from 0.05 wt.% to 5 wt.%.

[0032] In one or more embodiments, the catalyst may optionally comprise platinum in an amount from 0 wt.% to 0.1 wt.% based on the total mass of the catalyst. In one or more embodiments, the catalyst may comprise platinum in an amount from 0.0005 wt.% to 0.1 wt.% based on the total86193-WO-PCT7DOW 86193 WO9 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 wt.% to 0.005 wt.%, 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 some 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 exceeding 0.1 wt.% may significantly increase the cost of the catalyst.

[0033] 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 that compositions having alkali metals or alkaline earth metals in an amount exceeding 5 wt.% may reduce the catalyst’s dehydrogenation activity.

[0034] In one or more embodiments, the catalyst may comprise, consist essentially of, or consist of chromium and a support. In one or more embodiments, the catalyst may comprise, consist essentially of, or consist of from 0.25 wt.% to 10 wt.% chromium and at least 85 wt.% of a support. In one or more embodiments, the catalyst may comprise, consist essentially of, or consist of chromium, gallium, platinum, 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 0.05 wt.% to 10 wt.%86193-WO-PCT / DOW 86193 WO10 of gallium; and at least 85 wt.% of a support. In one or more embodiments, the catalyst may comprise, consist essentially of, or consist of from 0.25 wt.% to 10 wt.% chromium; gallium; platinum; and at least 85 wt.% of a support. In one or more embodiments, the catalyst may comprise, consist essentially of, or consist of from 0.25 wt.% to 10 wt.% chromium and at least 85 wt.% of silica- containing zirconia.

[0035] In one or more embodiments, the catalyst may comprise a binder. The binder may increase mechanical strength, density, or other physical properties of the catalyst. In some embodiments, the catalyst may comprise less than or equal to 50 wt.%, less than or equal to 45 wt.%, less than or equal to 40 wt.%, less than or equal to 35 wt.%, less than or equal to 30 wt.%, less than or equal to 25 wt.%, less than or equal to 20 wt.%, less than or equal to 15 wt.%, or less than or equal to 10 wt.% binder. In some embodiments, the binder may comprise alumina, titania, silica, zirconia, or combinations thereof. In embodiments where the binder comprises alumina, silica, and / or zirconia, the amount of binder present in the catalyst may be separate from the amount of support present in the catalyst.

[0036] In one or more embodiments, the catalyst may include solid particulates that are capable of fluidization. In some embodiments, the catalyst may exhibit properties known in the industry as “Geldart A” or “Geldart B” properties. Catalyst type may be classified as “Group A” or “Group B” according to D. Geldart, Gas Fluidization Technology, John Wiley & Sons (New York, 1986), 34-37; and D. Geldart, “Types of Gas Fluidization,” Powder Technol. 7 (1973) 285-292, the disclosures of which are incorporated herein by reference in their entireties.

[0037] 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 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 density86193-WO-PCT / DOW 86193 WO11(< 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.

[0038] 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 < dp < 500 pm when the density (pp) is 1.4 < pp < 4 g / cm3.

[0039] Still referring to FIG. 1, as described herein the olefinic material production system 100 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, butane, and 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 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 ethylbenzene. 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, i-butane, or combinations thereof.

[0040] The hydrocarbon-containing feed may enter feed inlet 434 into the reactor 202, and the olefinic material-containing effluent may exit the olefinic material production system 100 via pipe 420. According to one or more embodiments, the olefinic material production system 100 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. The reactor 202 may operate at relatively high86193-WO-PCT / DOW 86193 WO12 temperatures, such as from 500 °C to 800 °C (e.g., from 500 °C to 550 °C, from 550 °C to 600 °C, from 600 °C to 650 °C, from 650 °C to 700 °C, from 700 °C to 750 °C, from 750 °C to 800 °C, or any combination of one or more of these ranges).

[0041] Now referring to FIG. 1 in detail, the reactor portion 200 may comprise an upstream reactor section 250, a transition section 258, and a downstream reactor section 230, such as a riser. The transition section 258 may connect the upstream reactor section 250 with the downstream reactor section 230. As depicted in FIG. 1, the upstream reactor section 250 may be positioned below the downstream reactor section 230. Such a configuration may be referred to as an upflow configuration in the reactor 202. The upstream reactor section 250 may include a vessel, drum, barrel, vat, or other container suitable for a given chemical reaction. As depicted in FIG. 1, the upstream reactor section 250 may be connected to the downstream reactor section 230 via the transition section 258. The upstream reactor section 250 may generally comprise a greater cross-sectional area than the downstream reactor section 230. The transition section 258 may be tapered from the size of the 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.

[0042] 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 atransport 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.

[0043] In one or more embodiments, the catalyst may have a residence time within the reactor portion 200 of less than or equal to 5 minutes. As the term is used herein, “residence time” refers to the average amount of time the catalyst or other specified material spends within the reactor portion86193-WO-PCT / DOW 86193 WO13200 in contact with the feed (e.g., time from first contact with feed to time of separation from product). 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 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., less than or equal to 2 min., less than or equal to 1.5 min., less than or equal to 1 min., less than or equal to 0.5, or less than or equal to 0.1 min. Without being bound by 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.

[0044] 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.

[0045] According to embodiments, the olefinic material-containing effluent and the catalyst may be passed out of the downstream reactor section 230 to a separation device 220 in the catalyst86193-WO-PCT / DOW 86193 WO14 separation section 210, where the catalyst is at least partially separated from the olefm-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.

[0046] 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.

[0047] Still referring to FIG. 1, the separated catalyst is passed from the catalyst separation section 210 to the combustor 350. In some embodiments, the catalyst may be exposed to another 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.

[0048] In the combustor 350, the catalyst may be processed by, for example, combustion of coke with oxygen (if coke is present) and with combustion of supplemental fuel. 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 in86193-WO-PCT / DOW 86193 WO15 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 olefinic material-containing effluent may be gaseous, and the catalyst may be fluidized particulate solid.

[0049] 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. Oxy gen-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, such as at least 12 mol.% oxygen, at least 14 mol.% oxygen, at least 16 mol.% oxygen, at least 18 mol.% oxygen, at least 20 mol.% oxygen, at least 25 mol.% oxygen, or at least 30 mol.% oxygen.

[0050] 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.

[0051] In some embodiments, 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.86193-WO-PCT7DOW 86193 WO16

[0052] As described herein, according to one or more embodiments, the sulfur-containing compound may be passed into any portion of the olefinic material production system 100. In some embodiments, the sulfur-containing compound may be passed into the combustor 350 in a variety of ways. According to some embodiments, the sulfur-containing compound may be passed directly into the combustor 350 via a port on the combustor 350, represented by arrow 602 in FIG. 1. In additional embodiments, the sulfur-containing compound may be passed into the combustor 350 with the oxygen-containing gas, such as through pipe 428, represented by arrow 604 in FIG. 1. In additional embodiments, the sulfur-containing compound may be passed into the combustor 350 with the supplemental fuel, such as through fuel inlet 354, represented by arrow 606 in FIG. 1. In additional embodiments, the sulfur-containing compound may be passed into the combustor 350 with the catalyst, such as through standpipe 426, represented by arrow 608 in FIG. 1. In additional embodiments not depicted, the sulfur-containing compound may be passed into the combustor 350 with the catalyst that is recycled from the catalyst separation section 310. In additional embodiments not depicted, the sulfur-containing compound may be passed into the reactor 202.

[0053] In additional embodiments, the sulfur-containing compound may be passed downstream of the combustor 350 and upstream of the reactor 202, relative to the motion of the catalyst through the olefinic material production system 100 to prevent the catalyst from encountering the sulfur-containing compound in the reactor 202. According to some embodiments, the sulfur- containing compound may be passed directly into the riser 330 via a port on the riser 330, represented by arrow 610 in FIG. 1. In additional embodiments, the sulfur-containing compound may be passed into the oxygen treatment zone 370, represented by arrow 612 in FIG. 1. In additional embodiments, the sulfur-containing compound may be passed into the oxygen treatment zone 370 via the oxy gencontaining gas inlet 372 along with the oxygen-containing gas. Such an injection point is represented by arrow 614 in FIG. 1.

[0054] According to embodiments, the sulfur-containing compound may be passed into the olefinic material production system 100 in amounts suitable to properly passivate the metal surfaces in the reactor 202. In such embodiments, the sulfur-containing compound may act as a passivation agent. A “passivation agent” may refer to a chemical compound that can form a passivation layer over a surface, which reduces propensity for coking. Without being bound by any particular theory, in general, passivation refers to coating a material so that it becomes "passive", or less readily affected by the environment, as is understood by those skilled in the art. In one or more embodiments, the sulfur-containing compound may be passed in amount of from 1 ppmv to 10000 ppmv relative to the86193-WO-PCT / DOW 86193 WO17 stream into which the sulfur-containing compound is passed. For example, the sulfur-containing compound may be passed in an amount of from 1 ppmv to 25 ppmv, from 1 ppmv to 50 ppmv, from 1 ppmv to 100 ppmv, from 1 ppmv to 250 ppmv, from 1 ppmv to 500 ppmv, from 1 ppmv to 750 ppmv, from 1 ppmv to 1000 ppmv, from 1 ppmv to 2000 ppmv, from 1 ppmv to 3000 ppmv, from 1 ppmv to 4000 ppmv, from 1 ppmv to 5000 ppmv, from 1 ppmv to 6000 ppmv, from 1 ppmv to 7000 ppmv, from 1 ppmv to 8000 ppmv, from 1 ppmv to 9000 ppmv, from 50 ppmv to 500 ppmv, from 100 ppmv to 500 ppmv, from 50 ppmv to 10000 ppmv, from 250 ppmv to 10000 ppmv, from 500 ppmv to 10000 ppmv, from 1000 ppmv to 10000 ppmv, from 2000 ppmv to 10000 ppmv, from 3000 ppmv to 10000 ppmv, from 4000 ppmv to 10000 ppmv, from 5000 ppmv to 10000 ppmv, from 6000 ppmv to 10000 ppmv, from 7000 ppmv to 10000 ppmv, from 8000 ppmv to 10000 ppmv, from 9000 ppmv to 10000 ppmv, or any combinations of these ranges.

[0055] According to one or more embodiments, the sulfur-containing compound may be any chemical compound that includes at least one sulfur atom. According to embodiments, without limitation, sulfur-containing compounds may be chosen from compounds that include FPS or those that can decompose to H?S. For example, the sulfur-containing compound may be chosen from hydrogen sulfide, carbon sulfide (CS2), methyl mercaptan, dimethylsulfide (DMS), dimethyl disulfide (DMDS), dipropyldisulphides, dibutyldisulphides, ditertbutyldisulphide (DTBDS), diphenyldisulphide (DPDS), carbon disulphide, benzothiophenes, bibenzyl sulphide, phosphorothioate, methanedithione, methyldisulfanyl, methaylsulfanyl, and dimethyl sulfoxides. In some embodiments, the sulfur-containing compound is hydrogen sulfide. The hydrogen sulfide may be present in the reactor 202, particularly in the upstream reactor section 250, but also in the transition section 258, and the downstream reactor section 230. As described herein, the sulfur may form a passivation layer onto metal in the reactor 202, including sidewalls, internals, pipes, etc., where exposed metal is present. Catalysts described herein that comprise chromium may be tolerant to the sulfur present in the olefinic material production system 100 and may not lose as much catalytic activity as compared to conventional dehydrogenation catalysts.

[0056] Referring still to FIG. 1, 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 oxy gen-containing gas, such as air, is conducted in the oxygen treatment zone 370. In general, as described herein, the oxygen-containing gas in the oxygen treatment zone 370 may comprise at least 10 mol.% oxygen, and is substantially void of combustible gaseous hydrocarbons that are present in the combustor 350. In some86193-WO-PCT / DOW 86193 WO18 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.

[0057] 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 be exposed to an oxygen-containing gas for from 2 min. to 20 min., such as from 2 min. to 4 min., from 4 min. to 6 min., from 6 min. to 8 min., from 8 min. to 10 min., from 10 min. to 12 min., from 12 min. to 14 min., from 14 min. to 16 min., from 16 min. to 18 min., from 18 min. to 20 min., or any combination of these ranges. 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 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. In one or more embodiments, the catalyst may be exposed to the oxygencontaining gas at a temperature of at least 650 °C, such as from 650 °C to 800 °C.

[0058] In one or more embodiments, an optional reductant may be passed into the olefin material production system 100. The reductant may be any material that reduces the chromium present in the catalyst. In some embodiments, the reductant may be passed, such as injected, into the olefinic material production system 100 in any location after the oxygen treatment zone 370 and before the reactor 202.

[0059] In one or more embodiments, the olefinic material may be present in a “product stream” sometimes called an “olefin product-containing effluent” and include light olefins. Such a stream exits the olefinic material production system 100 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 u-butylene, cis-[3-butylene, trans-[3- butylene, and isobutylene. In some embodiments, the olefm-containing effluent includes at least 2586193-WO-PCT / DOW 86193 WO19 wt.% olefinic materials based on the total weight of the olefm-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

[0060] 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.

[0061] Sample Preparation

[0062] Comparative Samples A and B were 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. Comparative Sample A was retrieved from a reactor-regenerator system comprising of dehydrogenation, fuel combustion, and regeneration, after 9 months’ time-on-stream, while Comparative Sample B was used as-is. Comparative Example C was the same dehydrogenation catalyst of Comparative Example B with the addition of 1000 ppmw (0.1 wt.%) of chromium.

[0063] Comparative Example D, Examples 1-5, and 7-9 were prepared by incipient wetness impregnation. First, the support was modified. Monoclinic ZrCft support (NORPRO SZ31164 3 mm extrudates, BET = 100 meters squared per gram (m2 / g), pore volume determined by deionized water 0.4 milliliters per gram (mL / g)) was crushed and sieved to 40-80 mesh size. A ZrCft support (5 g) was impregnated with a solution prepared by mixing 0.56 mL of tetraethylortho silicate (TEOS) and 0.24 mL of isopropanol. The impregnated material was dried and calcined under air in the box oven using the following temperature program: room temperature to 120 degrees Celsius (°C) at 3 degrees per minute (deg / min), dwell 2 hours (h); 120 to 400 °C at 3 deg / min, dwell 4 h; cool down to room temperature. The support was sieved after calcination to remove fine particles smaller than 80 mesh. The catalysts were then prepared by conventional incipient wetness impregnation, which includes loading the designated metal and promoter to the Si-modified ZrCh support using nitrate or amine86193-WO-PCT / DOW 86193 WO20 nitrate precursors, followed by drying at temperature less than 200 °C, and calcination at temperature less than 800 °C.

[0064] Example 6 was prepared by loading 2 wt.% of chromium to a Siralox support using conventional incipient wetness impregnation which includes loading the designated metal and promoter to the Siralox support using nitrate or amine nitrate precursors.

[0065] Catalyst Testing Method

[0066] Table 1 shows the formulations of the catalyst samples prepared and the sulfur tolerance of each sample. FIGS. 2A-2D, 3A-3D, 4A-4D, 5A-5B, 6A-6B and 7A-7D depict graphs of the testing results.

[0067] The catalysts were tested in a fixed bed reactor for 60 cycles with a propane feed. Each cycle included 8 minutes of dehydrogenation and 5 minutes of air soak. The catalyst first underwent 20 cycles with only the propane feed, as indicated in the Figures as (a). Then, 20 ppmv of hydrogen sulfide (EES) was introduced into the reactor at cycle 20 for another 20 cycles, as indicated in the Figures as (b). Finally, the hydrogen sulfide stream was stopped at cycle 40 and the catalyst underwent 20 cycles with only the propane feed, as indicated in the Figures as (c). Propane conversion, propylene selectivity, ethylene selectivity, and methane selectivity were measured throughout the cycles and are shown in the FIGS. 2A-2D, 3A-3D, 4A-4D, 5A-5B, 6A-6B and 7A- 7D.Table 1: Catalyst compositions86193-WO-PCT / DOW 86193 WO21

[0068] FIGS. 2A-2D depicts the propane conversion (FIG. 2A), propylene selectivity (FIG. 2B), ethylene selectivity (FIG. 2C), and methane selectivity (FIG. 2D) for Comparative Example A. Comparative Example A was a conventional dehydrogenation catalyst with no addition of chromium. As shown, the propane conversion and propylene selectivity decreased with the addition of H2S from cycle 20 to 40 (b). The ethylene selectivity and methane selectivity also increased dramatically during (b), which is not desired.

[0069] FIGS. 3A-3D depicts the propane conversion (FIG. 3A), propylene selectivity (FIG. 3B), ethylene selectivity (FIG. 3C), and methane selectivity (FIG. 3D) for Examples 1-5, which have different amounts of chromium on a silica-modified zirconia support. As shown, the propane conversion and propylene selectivity stay generally even when the hydrogen sulfide stream is introduced into the reactor. The ethylene selectivity and methane selectivity also stay generally the same throughout the testing cycles. As such, as shown in (b) in FIGS. 3A-3D, the presence of chromium improves catalytic activity of a dehydrogenation catalyst when sulfur is present as compared to Comparative Example A in FIGS. 2A-2D, which has no chromium.

[0070] FIGS. 4A-4D depicts the propane conversion (FIG. 4A), propylene selectivity (FIG. 4B), ethylene selectivity (FIG. 4C), and methane selectivity (FIG. 4D) for Comparative Examples B and C. Comparative Example B is a dehydrogenation catalyst with no addition of chromium. Comparative Example C is the same dehydrogenation catalyst of Comparative Example B with the addition of 1000 ppmw (0.1 wt.%) of chromium. As shown in FIGS. 4A-4D, the presence of chromium in the low amount of 1000 ppmw still loses catalytic activity when sulfur is present, as shown in (b). Thus, it is believed that amounts greater than 0.1 wt.% of chromium is needed for the catalyst to be tolerant of sulfur.

[0071] FIGS. 5A-5B depicts the propane conversion (FIG. 5A) and propylene selectivity (FIG. 5B) of Comparative Example D, which has no chromium and uses a silica-modified zirconia support. The catalytic activity of Comparative Example D does not show any improvement of catalytic activity when sulfur is present with the use of a silica-modified zirconia support. Thus, it is believed that chromium is the compound that allows the catalyst to be sulfur tolerant.

[0072] FIGS. 6A-6B depicts the propane conversion (FIG. 6A) and propylene selectivity (FIG. 6B) of Examples 1, 4, and 6, which have 2 wt.% of chromium. Example 1 utilizes a silica- modified zirconia support, Example 4 has the addition of potassium and uses a Siralox support, and86193-WO-PCT / DOW 86193 WO22Example 7 has the addition of gallium and has a silica-modified zirconia support. The catalytic activity of these examples stay generally even throughout the testing cycles. FIGS. 6A-6B show that the addition of gallium or an alkali metal, such as potassium may affect initial propane conversion and propylene selectivity of the catalyst, but will not negatively affect the catalytic activity when hydrogen sulfide is introduced to the system.

[0073] FIGS. 7A-7D depicts the propane conversion (FIG. 7 A), propylene selectivity (FIG. 7B), ethylene selectivity (FIG. 7C), and methane selectivity (FIG. 7D) for Examples 1 and 8-10, which have 2 wt.% of chromium and use different promoters, such as cerium and calcium. These promoters may improve propylene selectivity, as shown in FIG. 7B. However, as described, it is believed that chromium is the compound that allows the catalyst to be sulfur tolerant.

[0074] A first aspect of the present disclosure is directed to a method for making olefinic materials, the method comprising: passing a hydrocarbon-containing feed and a catalyst into a reactor of an olefinic material production system, wherein: a portion of the hydrocarbon-containing feed is reacted to form the olefinic material in the reactor; the catalyst comprises from 0.25 wt.% to 10 wt.% chromium and at least 85 wt.% of a support; passing the catalyst from the reactor to a combustor of the olefinic material production system and heating the catalyst in the combustor by combusting one or both of a supplemental fuel or coke present on the catalyst in the combustor; passing the catalyst from the combustor to an upstream reactor section, such that all or a portion of the catalyst is continuously cycled between the reactor and the combustor; and passing a sulfur-containing compound into any portion of the olefinic material production system and into contact with the catalyst.

[0075] A second aspect of the present disclosure may include the first aspect, wherein the catalyst comprises: from 0 wt.% to 0.1 wt.% of platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof; from 0 wt.% to 10 wt.% of gallium, indium, thallium, or combinations thereof.

[0076] A third aspect of the present disclosure may include any one of the first or second aspects, wherein the support comprises alumina, silica, zirconia, or combinations thereof.

[0077] A fourth aspect of the present disclosure may include any one of the first through third aspects, wherein the catalyst comprises from 0.25 wt.% to 3 wt.% chromium.86193-WO-PCT7DOW 86193 WO23

[0078] A fifth aspect of the present disclosure may include any one of the first through fourth aspects, wherein the sulfur-containing compound is passed into the combustor or any portion of the olefinic material production system downstream of the combustor and upstream of the reactor, relative to the motion of the catalyst through the olefinic material production system.

[0079] A sixth aspect of the present disclosure may include any one of the first through fifth aspects, wherein from 1 ppmv to 10000 ppmv of the sulfur-containing compound is passed into any portion of the olefinic material production system.

[0080] A seventh aspect of the present disclosure may include any one of the first through sixth aspects, wherein from 1 ppmv to 500 ppmv of the sulfur-containing compound is passed into any portion of the olefinic material production system.

[0081] An eighth aspect of the present disclosure may include any one of the first through seventh aspects, wherein the sulfur-containing compound is chosen from hydrogen sulfide, carbon sulfide (CS2), methyl mercaptan, dimethylsulfide (DMS), dimethyl disulfide (DMDS), dipropyldisulphides, dibutyldisulphides, ditertbutyldisulphide (DTBDS), diphenyldisulphide (DPDS), carbon disulphide, benzothiophenes, bibenzyl sulphide, phosphorothioate, methanedithione, methyldisulfanyl, methaylsulfanyl, and dimethyl sulfoxides.

[0082] A ninth aspect of the present disclosure may include any one of the first through eighth aspects, wherein the passing the catalyst from the combustor to the upstream reactor section comprises: passing the catalyst from the combustor to an oxygen treatment zone and exposing the catalyst to an oxygen-containing gas; and passing the catalyst from the oxygen treatment zone to the reactor, such that all or a portion of the catalyst continuously cycles between the reactor, the combustor, and the oxygen treatment zone.

[0083] A tenth aspect of the present disclosure is directed to a catalyst suitable for dehydrogenation of hydrocarbons, the catalyst comprising: from 0.25 wt.% to 10 wt.% chromium; from 0 wt.% to 0.1 wt.% of platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof; from 0 wt.% to 10 wt.% of gallium, indium, thallium, or combinations thereof; and at least 85 wt.% support, wherein the support comprises silica-containing zirconia.86193-WO-PCT / DOW 86193 WO24

[0084] An eleventh aspect of the present disclosure may include the tenth aspect, wherein the catalyst comprises from 0.0005 wt.% to 0.1 wt% of platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof.

[0085] A twelfth aspect of the present disclosure may include any one of the tenth or eleventh aspects, wherein the catalyst comprises from 0.05 wt.% to 10 wt.% of gallium, indium, thallium, or combinations thereof.

[0086] A thirteenth aspect of the present disclosure may include any one of the tenth through twelfth aspects, wherein the catalyst comprises from 0.01 wt.% to 5 wt.% of one or more alkali or alkaline earth metals.

[0087] A fourteenth aspect of the present disclosure may include the tenth aspect, wherein the catalyst consists of from 0.25 wt.% to 3 wt.% chromium and at least 97 wt.% silica-containing zirconia.

[0088] A fifteenth aspect of the present disclosure may include the tenth aspect, wherein the catalyst consists of: from 0.25 wt.% to 3 wt.% chromium; from 0.05 wt.% to 1 wt.% gallium; and at least 96 wt.% silica-containing zirconia.

[0089] 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. Additionally, the term “consisting essentially of’ is used in this disclosure to refer to quantitative values that do not materially affect the basic and novel characteristic(s) of the disclosure. For example, a chemical stream “consisting essentially” of a particular chemical constituent or group of chemical constituents should be understood to mean that the stream includes at least about 99.5% of a that particular chemical constituent or group of chemical constituents.

[0090] 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 the86193-WO-PCT7DOW 86193 WO25 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.

[0091] It is noted that one or more of the following claims utilize the term “wherein” as a transitional phrase. For the purposes of defining the present technology, it is noted that this term is introduced in the claims as an open-ended transitional phrase that is used to introduce a recitation of a series of characteristics of the structure and should be interpreted in like manner as the more commonly used open-ended preamble term “comprising.”

[0092] 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. 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.

[0093] Having described the subject matter of the present disclosure in detail and by reference to specific embodiments, 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. Rather, the claims appended hereto should be taken as the sole representation of the breadth of the present disclosure and the corresponding scope of the various embodiments described in this disclosure. Further, it will be apparent that modifications and variations are possible without departing from the scope of the appended claims.

Claims

86193-WO-PCT / DOW 86193 WO26CLAIMS1. A method for making olefinic materials, the method comprising: passing a hydrocarbon-containing feed and a catalyst into a reactor of an olefinic material production system, wherein: a portion of the hydrocarbon-containing feed is reacted to form the olefinic material in the reactor; the catalyst comprises from 0.25 wt.% to 10 wt.% chromium and at least 85 wt.% of a support; passing the catalyst from the reactor to a combustor of the olefinic material production system and heating the catalyst in the combustor by combusting one or both of a supplemental fuel or coke present on the catalyst in the combustor; passing the catalyst from the combustor to an upstream reactor section, such that all or a portion of the catalyst is continuously cycled between the reactor and the combustor; and passing a sulfur-containing compound into any portion of the olefinic material production system and into contact with the catalyst.2 The method of claim 1, wherein the catalyst comprises: from 0 wt.% to 0.1 wt.% of platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof; from 0 wt.% to 10 wt.% of gallium, indium, thallium, or combinations thereof.3 The method of any one of the previous claims, wherein the support comprises alumina, silica, zirconia, or combinations thereof.4 The method of any one of the previous claims, wherein the catalyst comprises from 0.25 wt.% to 3 wt.% chromium.5 The method of any one of the previous claims, wherein the sulfur-containing compound is passed into the combustor or any portion of the olefinic material production system downstream of the combustor and upstream of the reactor, relative to the motion of the catalyst through the olefinic material production system.86193-WO-PCT / DOW 86193 WO276. The method of any of one the previous claims, wherein from 1 ppmv to 10000 ppmv of the sulfur-containing compound is passed into any portion of the olefinic material production system.

7. The method of any one of the previous claims, wherein from 1 ppmv to 500 ppmv of the sulfur-containing compound is passed into any portion of the olefinic material production system.8 The method of any one of the previous claims, wherein the sulfur-containing compound is chosen from hydrogen sulfide, carbon sulfide (CS2), methyl mercaptan, dimethylsulfide (DMS), dimethyl disulfide (DMDS), dipropyldisulphides, dibutyldisulphides, ditertbutyldisulphide (DTBDS), diphenyldisulphide (DPDS), carbon disulphide, benzothiophenes, bibenzyl sulphide, phosphorothioate, methanedithione, methyldisulfanyl, methaylsulfanyl, and dimethyl sulfoxides.9 The method of any one of the previous claims, wherein the passing the catalyst from the combustor to the upstream reactor section comprises: passing the catalyst from the combustor to an oxygen treatment zone and exposing the catalyst to an oxygen-containing gas; and passing the catalyst from the oxygen treatment zone to the reactor, such that all or a portion of the catalyst continuously cycles between the reactor, the combustor, and the oxygen treatment zone.10 A catalyst suitable for dehydrogenation of hydrocarbons, the catalyst comprising: from 0.25 wt.% to 10 wt.% chromium; from 0 wt.% to 0.1 wt.% of platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof; from 0 wt.% to 10 wt.% of gallium, indium, thallium, or combinations thereof; and at least 85 wt.% support, wherein the support comprises silica-containing zirconia.11 The catalyst of claim 10, wherein the catalyst comprises from 0.0005 wt.% to 0.1 wt% of platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof.12 The method of any one of claims 10 or 11, wherein the catalyst comprises from 0.05 wt.% to 10 wt.% of gallium, indium, thallium, or combinations thereof.86193-WO-PCT / DOW 86193 WO2813. The catalyst of any one of claims 10 to 12, wherein the catalyst comprises from 0.01 wt.% to 5 wt.% of one or more alkali or alkaline earth metals.

14. The catalyst of claim 10, wherein the catalyst consists of from 0.25 wt.% to 3 wt.% chromium and at least 97 wt.% silica-containing zirconia.

15. The catalyst of claim 10, wherein the catalyst consists of: from 0.25 wt.% to 3 wt.% chromium; from 0.05 wt.% to 1 wt.% gallium; and at least 96 wt.% silica-containing zirconia.

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