Method for producing light olefins by dehydrogenation using a catalyst containing manganese

Abstract

The method may include contacting a hydrocarbon-containing feed with a catalyst in a reactor to form an olefin-containing effluent, and then at least partially separating the olefin-containing effluent from the catalyst. The catalyst may be sent to a combustor where the catalyst can be heated. The catalyst may be passed from the combustor to an oxygen treatment zone and exposed to an oxygen-containing gas for 2 to 20 minutes. The catalyst may be passed from the oxygen treatment zone to the reactor such that at least a portion of the catalyst can continuously circulate between the reactor, the combustor, and the oxygen treatment zone. The catalyst may include one or more metals selected from 0.1 wt% to 10 wt% of gallium, indium, or a combination thereof, one or more metals selected from 1 ppmw to 500 ppmw of platinum, palladium, rhodium, iridium, or a combination thereof, 0.01 wt% to 1 wt% of manganese, and at least 85 wt% of a support.

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims priority to U.S. Provisional Application No. 63 / 352,022, filed on June 14, 2022, which is hereby incorporated by reference in its entirety.

[0002] Embodiments described herein generally relate to chemical processing, and more specifically, to methods and systems for producing light olefins.

Background Art

[0003] Light olefins such as propylene can be used as base materials for producing many different materials such as polypropylene, isopropanol, and acrylic acid, and these materials can be used, for example, in packaging, construction, and fabrics. As a result of this utility, there is a worldwide demand for light olefins. Suitable processes for producing light olefins generally depend on a given chemical feedstock and include those that utilize fluid catalysts. For example, light olefins can be formed by catalytic dehydrogenation of alkanes in a fluidized bed reactor. However, improvements in the systems and related catalysts used to make light olefins are needed.

Summary of the Invention

[0004] Some of the methods and related systems used to produce light olefins may utilize a reactivation step. For example, a catalyst may be circulated between a reactor in which light olefins are produced by an endothermic reaction, a combustor in which the catalyst can be heated, for example, by exothermic combustion of at least auxiliary fuel (sometimes with combustion of coke), and an oxygen treatment zone in which the catalyst is reactivated by exposure to an oxygen-containing gas. Since the heating and heating environment caused by exothermic combustion can partially deactivate the catalyst, some catalysts used in the production of light olefins can be improved by reactivation by exposure to oxygen. Catalysts containing (a) gallium or indium and (b) platinum, palladium, rhodium, or iridium may be useful in such dehydrogenation reactions. As described herein, it has been discovered that catalysts further containing manganese can improve catalyst performance, for example, compared to conventional catalysts that do not contain manganese.

[0005] According to one or more embodiments of the present disclosure, the method may include contacting a hydrocarbon-containing feed in a reactor with a catalyst in the reactor to form an olefin-containing effluent, and then at least partially separating the olefin-containing effluent from the catalyst. The catalyst may be sent to a combustor where the catalyst can be heated. The catalyst may be passed from the combustor to an oxygen treatment zone and exposed to an oxygen-containing gas for 2 to 20 minutes. The catalyst may be passed from the oxygen treatment zone to the reactor so that at least a portion of the catalyst can continuously circulate between the reactor, the combustor, and the oxygen treatment zone. The catalyst may include 0.1 wt% to 10 wt% of one or more metals selected from gallium, indium, thallium, or combinations thereof, 5 ppmw to 500 ppmw of one or more metals selected from platinum, palladium, rhodium, iridium, or combinations thereof, 0.01 wt% to 1 wt% of manganese, and at least 85 wt% of a support.

[0006] It should be understood that both the foregoing general description and the following detailed description are intended to present various embodiments and provide an overview or framework for understanding the nature and characteristics of the claimed subject matter. Additional features and advantages of the embodiments will be described in the detailed description, and some of them will be readily apparent to those skilled in the art from that description, including the accompanying drawings and the claims, or will be recognized by practicing the described embodiments. The drawings are included to provide a further understanding of the embodiments and, together with the detailed description, serve to explain the principles and operations of the claimed subject matter. However, the embodiments shown in the drawings are illustrative and exemplary in nature and are not intended to limit the claimed subject matter.

Brief Description of the Drawings

[0007] The following detailed description can be better understood when read in conjunction with the following drawings.

Figure 1

[0008] When explaining the simplified schematic diagram of FIG. 1, numerous valves, temperature sensors, electronic controllers, etc. that can be used and are well known to those skilled in the art are not included. Further, associated components that are often included within such a reactor system, such as air suppliers, heat exchangers, surge tanks, etc. are also not included. However, it should be understood that these components are within the scope of the present disclosure.

[0009] Here, various embodiments are referred to in more detail, some of which are illustrated in the accompanying drawings.

Modes for Carrying Out the Invention

[0010] The present disclosure is directed to a method for making light olefins by dehydrogenation in which certain catalyst compositions are utilized, as described herein. For example, a catalyst useful for dehydrogenation can include a catalyst comprising from 0.1 wt% to 10 wt% of one or more metals selected from gallium, indium, or combinations thereof, from 5 ppmw to 500 ppmw of one or more metals selected from platinum, palladium, rhodium, iridium, or combinations thereof, from 0.01 wt% to 1 wt% of manganese, and at least 85 wt% of a support. Such a catalyst can result in enhanced catalyst reactivation. Such a catalyst containing manganese may be particularly well-suited for the fluidized dehydrogenation of light alkanes to light olefins, e.g., propane to propylene, in which the catalyst undergoes reactivation.

[0011] Surprisingly, the addition of manganese to one or more of the embodiments described herein enables an acceptable conversion and selectivity of alkanes to olefins while, in many cases, enhancing the combustion of auxiliary fuel (e.g., combustion of methane). Further, such a catalyst may be operable in reactions with relatively short catalyst residence times (e.g., 3 minutes or less) and relatively short oxygen reactivation residence times (e.g., less than 20 minutes). In some embodiments, the presence of manganese can reduce the oxygen exposure time required as compared to a catalyst that does not contain manganese.

[0012] Embodiments of the methods disclosed herein are described in detail herein in the context of the reactor system of FIG. 1, which operates as a fluidized dehydrogenation reactor system for producing light olefins, such as propylene. However, it should be understood that the principles disclosed and taught herein may be applicable to other systems that utilize different system components oriented in different manners. For example, the concepts described herein may be equally applicable to other systems with alternative reactor units and regeneration units that operate in a non-fluidized state or that include a downer instead of a riser. Further, it should be understood that not all parts of FIG. 1 should be construed as essential to the claimed subject matter. Additionally, while the method steps recited in the appended claims are described herein in the context of FIG. 1, such recited method steps should be understood to be adaptable to other systems, as would be understood by one of ordinary skill in the art.

[0013] Next, referring to FIG. 1, an exemplary reactor system 102 that may be suitable for use with the methods and / or apparatuses described herein is schematically shown. Reactor system 102 generally includes a plurality of system components such as a reactor section 200 and a catalyst treatment section 300. As used herein when describing, "system components" refers to portions of reactor system 102 such as reactors, separators, transfer lines, combinations thereof, and the like. In the context of FIG. 1 as used herein, reactor section 200 generally refers to the portion of reactor system 102 where a main process reaction (e.g., dehydrogenation) takes place to form an olefin-containing effluent. A hydrocarbon-containing feed enters reactor section 200, contacts a catalyst, is converted to an olefin-containing effluent (containing product and unreacted feed), and exits reactor section 200. Reactor section 200 includes a reactor 202 that may comprise an upstream reactor section 250 and a downstream reactor section 230. According to one or more embodiments, as shown in FIG. 1, reactor section 200 may further comprise a catalyst separation section 210 that serves to separate the catalyst from the olefin-containing effluent formed within reactor 202. Also, as used herein, catalyst treatment section 300 generally refers to the portion of reactor system 102 that treats the catalyst in some manner such as by combustion, etc. to improve the catalyst activity, e.g., by decoking and / or heating the catalyst. Catalyst treatment section 300 may comprise a combustor 350 and a riser 330, and may further comprise a catalyst separation section 310. In one or more embodiments, catalyst separation section 210 can be in fluid communication with combustor 350 (e.g., via a water distribution tower 426), and catalyst separation section 310 can be in fluid communication with upstream reactor section 250 (e.g., via a water distribution tower 424 and a transfer riser 430).

[0014] Generally, as described herein, in the embodiment illustrated in FIG. 1, the catalyst is circulated between the reactor section 200 and the catalyst treatment section 300. When "catalysts" are referred to herein, it should be understood that they may refer to solid materials that are catalytically active for the desired reaction. The terms "catalytic activity" and "catalyst activity" refer to the extent to which a catalyst can catalyze the reactions taking place within the reactor system 102. The catalyst exiting the reactor section 200 may be a deactivated catalyst. As used herein, "deactivated" may refer to a catalyst that has a lower catalytic activity or is at a lower temperature compared to the catalyst entering the reactor section 200. However, a deactivated catalyst may maintain some catalytic activity. The decrease in catalytic activity may be due to contamination by substances such as coke. Coke may form on the catalyst within the reactor section 200. By reactivation (also sometimes referred to herein as "regeneration"), contaminants such as coke can be removed, the temperature of the catalyst can be increased, or both can be done. In an embodiment, the deactivated catalyst can be reactivated by catalyst reactivation in the catalyst treatment section 300. The deactivated catalyst can be reactivated by, but is not limited to, removing coke by combustion, oxidizing the catalyst, other reactivation processes, or combinations thereof. In some embodiments, the catalyst may be heated during reactivation by the combustion of an auxiliary fuel such as methane, ethane, propane, natural gas, or combinations thereof. The reactivated catalyst from the catalyst treatment section 300 is then returned to the reactor section 200.

[0015] As disclosed herein, in one or more embodiments, the auxiliary fuel may include methane. For example, the auxiliary fuel may include methane in an amount of 1 mol% or more, such as 2 mol% or more, 3 mol% or more, 4 mol% or more, or even 5 mol% or more. In some embodiments, the auxiliary fuel includes methane in an amount of 10 mol% or less. In some embodiments, the auxiliary fuel may include methane in an amount of more than 10 mol%, such as more than 20 mol%, more than 30 mol%, more than 40 mol%, more than 50 mol%, more than 60 mol%, more than 70 mol%, more than 80 mol%, more than 90 mol%, or even 100 mol%. A catalyst having improved methane combustion activity, such as the catalysts described herein that include manganese, can better utilize methane as an auxiliary fuel and facilitate reheating of the catalyst. The catalyst is heated during regeneration to assist in regeneration, because the heated catalyst serves as a heat carrier that transfers heat from the combustor 350 to the reactor section 200 to promote the dehydrogenation reaction.

[0016] In a non-limiting example, the reactor system 102 described herein can be utilized to produce light olefins from a hydrocarbon-containing feed. According to one or more embodiments, the reaction can be a dehydrogenation reaction. According to such embodiments, the hydrocarbon-containing feed may include one or more of ethane, propane, n-butane, and i-butane. In one or more embodiments, the hydrocarbon-containing feed may include 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 include 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 include 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 include 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 include 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 total of ethane, propane, n-butane, and i-butane.

[0017] In one or more embodiments, the catalyst may comprise, consist essentially of, or consist of one or more of gallium or indium, one or more of platinum, palladium, rhodium, or iridium, manganese, and a carrier. As described herein, "consisting essentially of" refers to a material that contains materials not listed that are less than 1 wt% (i.e., consisting essentially of A and B means that the combination of A and B is at least 99 wt% of the composition). As described herein, the catalyst can be solid particles suitable for fluidization.

[0018] In one or more embodiments, the catalyst may contain one or more of gallium or indium in an amount of 0.1 wt% to 10 wt% based on the total mass of the catalyst. Such materials can catalyze the dehydrogenation of alkanes to alkenes, particularly when used in combination with one or more of platinum, palladium, rhodium, or iridium. Such materials can further catalyze the combustion of coke and auxiliary fuel. For example, the catalyst may contain one or more of gallium or indium in an amount of 0.1 wt% to 0.25 wt%, 0.25 wt% to 0.5 wt%, 0.5 wt% to 0.75 wt%, 0.75 wt% to 1 wt%, 1 wt% to 2 wt%, 2 wt% to 3 wt%, 3 wt% to 4 wt%, 4 wt% to 5 wt%, 5 wt% to 6 wt%, 6 wt% to 7 wt%, 7 wt% to 8 wt%, 8 wt% to 9 wt%, 9 wt% to 10 wt%, or in any combination of amounts within these ranges. In some embodiments, the catalyst may contain one or more of gallium or indium in an amount of 0.1 wt% to 9 wt%, 0.1 wt% to 8 wt%, 0.1 wt% to 7 wt%, 0.1 wt% to 6 wt%, or 0.1 wt% to 5 wt%. In some embodiments, the catalyst contains only gallium and no indium, or only indium and no gallium. It should be understood that the compositional ranges described for the amounts of gallium and indium represent the range of either one of these materials or a combination of these materials. Without being bound by theory, a composition having one or more of gallium or indium in an amount less than 0.1 wt% is thought to adversely affect the ability of the catalyst to catalyze the alkane dehydrogenation process by reducing both the percentage of total dehydrogenated alkanes and the percentage of dehydrogenated alkanes that are the intended product. However, a composition having one or more of gallium or indium in an amount greater than 10 wt% may adversely affect the ability of the catalyst to catalyze the alkane dehydrogenation process, the selectivity of the catalyst for the intended product, or both.

[0019] In one or more embodiments, the catalyst may contain one or more of platinum, palladium, rhodium, or iridium in an amount of 5 ppmw to 500 ppmw based on the total mass of the catalyst. Such materials can catalyze the dehydrogenation of alkanes to alkenes, particularly when used in combination with one or more of gallium or indium. Such materials can further catalyze the combustion of coke and auxiliary fuel. For example, the catalyst may contain one or more of platinum, palladium, rhodium, or iridium in an amount of 5 ppmw to 50 ppmw, 50 ppmw to 100 ppmw, 100 ppmw to 200 ppmw, 200 ppmw to 300 ppmw, 300 ppmw to 400 ppmw, 400 ppmw to 500 ppmw, or any combination of these ranges. In some embodiments, the catalyst may contain one or more of platinum, palladium, rhodium, or iridium in an amount of 5 ppmw to 475 ppmw, 5 ppmw to 450 ppmw, or 10 ppmw to 400 ppmw. In some embodiments, the catalyst contains only platinum and does not contain palladium, rhodium, or iridium, or contains only palladium and does not contain platinum, rhodium, or iridium, or contains only rhodium and does not contain platinum, palladium, or iridium, or contains only iridium and does not contain platinum, palladium, or rhodium. It should be understood that the compositional ranges describing the amounts of platinum, palladium, rhodium, or iridium represent the ranges of any one of these materials or combinations of these materials. Without being bound by theory, a composition having an amount of one or more of platinum, palladium, rhodium, or iridium less than 5 ppmw is thought to adversely affect the ability of the catalyst to catalyze the alkane dehydrogenation process by reducing both the percentage of total dehydrogenated alkanes and the percentage of dehydrogenated alkanes that are the intended product. However, a composition having an amount of one or more of platinum, palladium, rhodium, or iridium greater than 500 ppmw may adversely affect the ability of the catalyst to catalyze the alkane dehydrogenation process, may adversely affect the selectivity of the catalyst for the intended product, or both.

[0020] In one or more embodiments, the catalyst may contain manganese in an amount of 0.01 wt% to 1 wt% based on the total weight of the catalyst. Incorporation of manganese can promote the combustion of methane and the reactivation of the catalyst while having relatively little impact on the dehydrogenation of alkanes. For example, the catalyst may contain manganese in an amount of 0.01 wt% to 0.05 wt%, 0.05 wt% to 0.1 wt%, 0.1 wt% to 0.2 wt%, 0.2 wt% to 0.3 wt%, 0.3 wt% to 0.4 wt%, 0.5 wt% to 0.6 wt%, 0.7 wt% to 0.8 wt%, 0.8 wt% to 0.9 wt%, 0.9 wt% to 1 wt%, or any combination of these ranges. In some embodiments, the catalyst may contain manganese in an amount of 0.02 wt% to 0.9 wt%, 0.03 wt% to 0.8 wt%, 0.04 wt% to 0.7 wt%, or 0.05 wt% to 0.6 wt%. Without being bound by theory, it is believed that compositions having an amount of manganese less than 0.01 wt% may not sufficiently improve the reactivation performance of the catalyst. However, compositions having an amount of manganese greater than 1 wt% may negatively affect the dehydrogenation performance of the catalyst by reducing the percentage of total alkane dehydrogenated. Without being bound by theory, it is believed that manganese can improve the reactivation of the catalyst by reducing the amount of time required to achieve sufficient catalyst reactivation.

[0021] In one or more embodiments, the catalyst may contain manganese in combination with one or more of chromium, iron, or vanadium. In some embodiments, the catalyst contains manganese and chromium but does not contain iron or vanadium, contains iron and manganese but does not contain chromium or vanadium, contains manganese and vanadium but does not contain chromium or iron, contains iron, chromium, and manganese but does not contain vanadium, contains manganese, chromium, and vanadium but does not contain iron, or contains iron, manganese, and vanadium but does not contain chromium.

[0022] As described herein, in one or more embodiments, the catalyst may include a carrier. The carrier may include one or more of alumina, silica, or a combination thereof. For example, in some embodiments, the carrier may include one or more of alumina, silica-containing alumina, zirconia-containing alumina, titania-containing alumina, and lanthanum-containing alumina. The carrier may be present in an amount of at least 85 wt%, such as at least 85 wt%, at least 90 wt%, or at least 95 wt% based on the total weight of the catalyst. In some embodiments, the carrier includes 99.5 wt% or less of the catalyst. Generally, the wt% of the carrier may satisfy the remainder of the total catalyst not specified by other materials.

[0023] In one or more embodiments, the catalyst may optionally include one or more alkali metals, one or more alkaline earth metals, or both, in an amount of 0.01 wt% to 5 wt% based on the total weight of the catalyst. For example, the catalyst may include one or more alkali metals, one or more alkaline earth metals, or both, in an amount of 0.01 wt% to 0.05 wt%, 0.05 wt% to 0.1 wt%, 0.1 wt% to 0.5 wt%, 0.5 wt% to 1 wt%, 1 wt% to 2 wt%, 2 wt% to 3 wt%, 3 wt% to 4 wt%, 4 wt% to 5 wt%, or any combination of these ranges. In some embodiments, the catalyst may include one or more alkali metals, one or more alkaline earth metals, or both, in an amount of 0.01 wt% to 3 wt%, 0.02 wt% to 2 wt%, 0.03 wt% to 1 wt%, 0.04 wt% to 0.5 wt%, or 0.05 wt% to 0.3 wt%. In some embodiments, one or more alkali metals or one or more alkaline earth metals may be potassium. Without being bound by theory, it is believed that a composition having an amount of alkali metal or alkaline earth metal less than 0.01 wt% may cause the formation of undesirable products during the dehydrogenation reaction. However, it is believed that a composition having an amount of alkali metal or alkaline earth metal exceeding 5 wt% may reduce the dehydrogenation activity of the catalyst.

[0024] In one or more embodiments, the catalyst may comprise, consist essentially of, or consist of gallium, platinum, manganese, and a carrier. For example, the catalyst may comprise, consist essentially of, or consist of 0.1 wt% to 10 wt% gallium, 5 ppmw to 500 ppmw platinum, 0.01 wt% to 1 wt% manganese, and at least 85 wt% carrier. In an exemplary embodiment, the catalyst may comprise, consist essentially of, or consist of 0.1 wt% to 5 wt% gallium, 10 ppmw to 400 ppmw platinum, 0.05 wt% to 0.6 wt% manganese, and at least 85 wt% carrier.

[0025] In one or more embodiments, the catalyst may include solid particles capable of fluidization. In some embodiments, the catalyst may exhibit properties known in the industry as "Geldart A" or "Geldart B" properties. The particle 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 hereby incorporated by reference in their entirety.

[0026] Group A of Geldart is understood by those skilled in the art to represent a fluidizable powder having the following: fluidization in the bubble - free regime, high bed expansion, slow and linear defluidization rate, possible predominance of splitting / recombining bubbles, bubble characteristics with maximum bubble size and large wake, high levels of solid mixing and gas back - mixing assuming equal U - Umf (where U is the velocity of the carrier gas and Umf is the minimum fluidization velocity, typically not necessarily measured in meters per second, m / s, i.e., there is an excess gas velocity), axisymmetric slugging characteristics, and no jetting except for very shallow beds.

[0027]

Number

[0028] Geldart group B is understood by those skilled in the art to represent powders that start to foam at Umf, exhibit moderate bed expansion, rapid deaeration, no limitation on bubble size, assuming U-Umf is equal, have a moderate level of solid mixing and gas backmixing, both axisymmetric slugs and asymmetric slugs; and "sand-like" powders that jet only in shallow beds. These properties tend to improve as the average particle size decreases, but the particle size distribution and, with some uncertainty, the gas pressure, temperature, viscosity, or density do not appear to contribute much to the improvement of the above properties. Generally, when the density (ρp) is 1.4 < ρp < 4 g / cm 3 3, the average particle size

[0029]

Number

[0030]

Number

[0031] In one or more embodiments, the catalyst may be prepared by incipient wetness impregnation, also known as dry impregnation or capillary impregnation. For example, such a process is described in Marceau et al., Impregnation and Drying, Synthesis of Solid Catalysts 59 (2008), which is hereby incorporated by reference in its entirety. For example, the support may be impregnated with a metal precursor and then dried at a temperature below 200 °C and then calcined at a temperature below 800 °C to produce the catalyst. For example, suitable metal precursors may include nitrates or amine nitrate metal precursors. Further, as known to those skilled in the art, other suitable metal precursors are contemplated herein. In some embodiments, the method of making the catalyst includes impregnating a support with gallium, platinum, and manganese, drying the support, and calcining the support, and the catalyst includes 0.1 wt% to 10 wt% gallium, 5 ppmw to 500 ppmw platinum, 0.01 wt% to 1 wt% ppmw manganese, and at least 85 wt% support.

[0032] In one or more embodiments, the catalyst may be prepared by incipient wetness sequential impregnation, and the materials are impregnated in a specific order either before or after drying and calcination. In incipient wetness sequential impregnation, the catalyst is first impregnated with one or more metal precursors, dried at a temperature below 200 °C, and then calcined at a temperature below 800 °C. The catalyst then undergoes at least one additional cycle of impregnation, drying, and calcination with additional metal precursors to yield the finished catalyst. In incipient wetness sequential impregnation, the metals added to the catalyst can be added sequentially in successive impregnation cycles. In one or more embodiments, the support is sequentially impregnated with gallium and platinum, and then manganese. In some embodiments, the method of making the catalyst may include impregnating the support with gallium and platinum, drying the support, calcining the support, impregnating the support with manganese after drying and calcination, and drying and calcining the support after impregnation with manganese, and the catalyst comprises 0.1 wt% to 10 wt% gallium, 5 ppmw to 500 ppmw platinum, 0.01 wt% to 1 wt% manganese, and at least 85 wt% support. In additional embodiments, the method of making the catalyst may include impregnating the support with manganese to create a manganese-impregnated support, drying the manganese-impregnated support, calcining the manganese-impregnated support, impregnating the manganese-impregnated support with gallium and platinum after drying and calcination, and drying and calcining the manganese-impregnated support after impregnation with gallium and platinum, and the catalyst comprises 0.1 wt% to 10 wt% gallium, 5 ppmw to 500 ppmw platinum, 0.01 wt% to 1 wt% manganese, and at least 85 wt% support.

[0033] Incipient wetness sequential impregnation allows the support to be impregnated with metals in a sequential order in which some metals can be impregnated onto the support before others. Thus, the order of impregnation can be changed as desired. Further, as will be known to those skilled in the art, other suitable methods for making the catalysts described herein are contemplated.

[0034] Referring again to FIG. 1, the hydrocarbon-containing feed may enter the reactor 202 from the feed inlet 434, and the olefin-containing effluent may exit the reactor system 102 via the pipe 420. According to one or more embodiments, the reactor system 102 may be operated by supplying a hydrocarbon-containing feed (e.g., in the feed stream) and a fluid catalyst to the upstream reactor section 250. The hydrocarbon-containing feed contacts the catalyst within the upstream reactor section 250, and each flows upward into the downstream reactor section 230 and through the downstream reactor section 230 to produce an olefin-containing effluent.

[0035] Referring now in detail to FIG. 1, the reactor section 200 may comprise an upstream reactor section 250, a transfer section 258, and a downstream reactor section 230 such as a riser. The transfer section 258 can connect the upstream reactor section 250 to the downstream reactor section 230. As shown in FIG. 1, the upstream reactor section 250 may be disposed below the downstream reactor section 230. Such a configuration can be referred to as an upflow configuration in the reactor 202. The upstream reactor section 250 may include a tank, drum, barrel, vat, or other container suitable for a given chemical reaction. As shown in FIG. 1, the upstream reactor section 250 can be connected to the downstream reactor section 230 via the transfer section 258. The upstream reactor section 250 can generally have a larger cross-sectional area than the downstream reactor section 230. The transfer section 258 may be tapered from the cross-sectional size of the upstream reactor section 250 toward the cross-sectional size of the downstream reactor section 230 such that the transfer section 258 projects inwardly from the upstream reactor section 250 toward the downstream reactor section 230. For example, the transfer section 258 may be a frustum of a cone.

[0036] The upstream reactor section 250 can be connected to a transfer riser 430 that can provide reactivated catalyst in the feed stream to the reactor section 200 during operation. The reactivated catalyst and / or reaction chemicals can be mixed at a distributor 260 housed within the upstream reactor section 250. The catalyst entering the upstream reactor section 250 via the transfer riser 430 can be sent to the transfer riser 430 through a water distribution tower 424 and thus arrives from the catalyst treatment section 300. In some embodiments, the catalyst may enter the transfer riser 430 directly from the catalyst separation section 210 via a water distribution tower 422, in which case the catalyst enters the upstream reactor section 250, and in such embodiments, a portion of the catalyst does not pass through the catalyst treatment section 300. The catalyst can also be directly supplied to the upstream reactor section 250 via the water distribution tower 422 (not shown in FIG. 1). This catalyst may be somewhat deactivated but may still be suitable for reactions within the upstream reactor section 250 in some embodiments, particularly when used in combination with the reactivated catalyst.

[0037] In one or more embodiments, the catalyst can have a residence time within the reactor section 200 of 3 minutes or less. As used herein, the term "residence time" refers to the average amount of time that a catalyst or other specific material spends within the reactor section 200. Since it is an average, the amount of time that a catalyst can spend within the reactor section 200 during any given cycle may not be equal to the average but will, on average over time, be approximately equal to the residence time. In some embodiments, the catalyst may have a residence time within the reactor section 200 of 2.5 minutes or less, 2 minutes or less, 1.5 minutes or less, 1 minute or less, 0.5 minutes or less, or 0.1 minutes or less. Without being bound by theory, a catalyst residence time exceeding 3 minutes is thought to increase the equipment cost without increasing the matching in the dehydrogenation performance of the catalyst. However, a catalyst residence time of less than 0.1 minutes is thought to possibly prevent the catalyst from adequately catalyzing the dehydrogenation reaction.

[0038] Referring further to FIG. 1, in one or more embodiments, based on the shape, size, and other processing conditions (such as temperature and pressure) of the upstream reactor section 250 and the downstream reactor section 230, the upstream reactor section 250 can operate as a fluidized bed such as a fast fluidized bed, a turbulent fluidized bed, or a bubble bed riser reactor, while the downstream reactor section 230 can operate in a plug flow mode such as a riser reactor. For example, the reactor 202 of FIG. 1 may include an upstream reactor section 250 that operates as a fast fluidized bed, a turbulent fluidized bed, or a bubble bed reactor, and a downstream reactor section 230 that operates as a dilute phase riser reactor, such that the average catalyst and gas flow move upward simultaneously. As used herein, the term "average flow" generally refers to the net flow, i.e., the flow obtained by subtracting the reverse flow or countercurrent flow from the total upward flow, as is typical of the behavior of fluidized particles. As described herein, a "fast fluidized" reactor may refer to a reactor that utilizes a fluidization regime in which the superficial gas velocity is faster than the choking velocity and may be semi-dense during operation. As described herein, a "turbulent" reactor may refer to a fluidization regime in which the superficial velocity is slower than the choking velocity and has a higher density than the fast fluidization regime. As described herein, a "bubble bed" reactor may refer to a fluidization regime in which distinct bubbles in a high-density bed exist in two separate phases. The "choking velocity" refers to the minimum velocity required to maintain solids in a dilute phase mode in a vertical transport line. As described herein, a "dilute phase riser" may refer to a riser reactor that operates at a velocity above the flooding velocity.

[0039] According to an embodiment, the olefin-containing effluent and the catalyst may be discharged from the downstream reactor section 230 and sent to the separator 220 within the catalyst separation section 210, where the catalyst is at least partially separated from the olefin-containing effluent and the olefin-containing effluent is transported from the catalyst separation section 210. According to one or more embodiments, following separation from the vapor in the separator 220, the catalyst may generally move through the stripper 224 to the catalyst outlet port 222, where the catalyst exits the reactor section 200 via the water distribution tower 426 and is transferred to the catalyst treatment section 300.

[0040] According to one or more embodiments, the separator 220 may be a cyclone separation system that can include two or more stages of cyclone separation. In embodiments where the separator 220 includes more than one cyclone separation stage, the first separator into which the fluidized stream enters is referred to as the primary cyclone separator. The fluid effluent from the primary cyclone separator can enter a secondary cyclone separator for further separation. Examples of primary cyclone separators can include primary cyclones, as well as 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, each of which is hereby incorporated by reference in its entirety. In some separation systems that utilize a primary cyclone as the primary cyclone separator, one or more additional cyclones, such as secondary and tertiary cyclones, are used to further separate the catalyst from the product gas. It should be understood that any primary cyclone separator may be used in the embodiments of the present disclosure.

[0041] Referring further to FIG. 1, the separated catalyst moves from the catalyst separation section 210 to the combustor 350. In the combustor 350, the catalyst can be treated, for example, by combustion of coke with oxygen. For example, but not limited to, the catalyst can remove coke and / or burn auxiliary fuel to heat the catalyst. Next, the catalyst exits the combustor 350, passes through the riser 330 and is sent to the riser end separator 378, where the gas and solid components from the riser 330 are at least partially separated. The vapor and remaining solids are transferred to the secondary separator 320 within the catalyst separation section 310, where the remaining catalyst is separated from the gas from the catalyst treatment (e.g., the gas released by combustion of the spent catalyst or auxiliary fuel, referred to herein as flue gas). The flue gas can exit the catalyst treatment unit 300 via the outlet pipe 432. Next, the separated catalyst moves through the oxygen treatment zone 370 within the catalyst separation section 310 via the water distribution tower 424 and the transfer riser 430 to the upstream reactor section 250, where it is further utilized for the catalytic reaction. Thus, the catalyst can circulate between the reactor section 200 and the catalyst treatment section 300 during operation. Generally, the treated chemical stream containing the hydrocarbon-containing feed and the olefin-containing effluent may be gaseous, and the catalyst may be a fluid particulate solid.

[0042] Referring now to the catalyst treatment unit 300, as shown in FIG. 1, the combustor 350 of the catalyst treatment unit 300 may include one or more lower reactor section inlet ports 352 and may be in fluid communication with the riser 330. An oxygen-containing gas such as air can move through the pipe 428 to the combustor 350. The combustor 350 can be in fluid communication with the catalyst separation section 210 via the water distribution tower 426, and the water distribution tower 426 can supply the spent catalyst from the reactor section 200 to the catalyst treatment unit 300 for regeneration. The combustor 350 and the riser 330, collectively referred to as the catalytic combustion reactor 302, can operate in a fluidization regime similar to or the same as that disclosed for the upstream reactor section 250 and the downstream reactor section 230 of the reactor section 200. That is, the combustor 350 can operate as a fluidized bed in a high-speed fluidized bed, a turbulent fluidized bed, or a bubble bed riser reactor, etc., while the riser 330 can operate in a plug flow mode such as a riser reactor. The geometric shapes described for the upstream reactor section 250 and the downstream reactor section 230 can be equally applied to the combustor 350 and the riser 330. Further, the combustor 350 may also include a fuel inlet 354 through which a fuel such as a hydrocarbon stream can be supplied to the combustor 350.

[0043] As described herein, the catalyst may be heated within the catalyst treatment unit 300 by the combustion of an auxiliary fuel. The auxiliary fuel may burn with oxygen to heat the catalyst, and auxiliary fuels such as hydrogen, methane, ethane, propane, natural gas, or combinations thereof may be utilized. Without being bound by any theory, when methane is utilized as the auxiliary fuel, the catalysts described herein containing manganese may better catalyze the combustion of methane to heat the catalyst. Catalysts that do not contain manganese may be insufficient by not promoting the heating of the catalyst to the temperature required for dehydrogenation when methane is used as the auxiliary fuel.

[0044] As described in one or more embodiments, following the separation of the flue gas from the catalyst in the riser termination separator 378 and the secondary separation device 320, the treated catalyst is treated with an oxygen-containing gas in the oxygen treatment zone 370. In some embodiments, the oxygen treatment zone 370 includes a fluid-solid contact device. The fluid-solid contact device can include a baffle or grid structure to facilitate contact of the treated catalyst with the oxygen-containing gas. Examples of fluid-solid contact devices are described in more detail in U.S. Patent Nos. 9,827,543 and 9,815,040. The fluidization regime within the oxygen treatment zone may be a bubbling bed type fluidization. The oxygen treatment zone 370 can include an oxygen-containing gas inlet 372 that can feed an oxygen-containing gas into the oxygen treatment zone 370 for treatment of the catalyst with the oxygen-containing gas.

[0045] As disclosed herein, in one or more embodiments, the catalyst may be exposed to an oxygen-containing gas in the oxygen treatment zone 370. For example, the catalyst can be exposed to the oxygen-containing gas for from 2 minutes to 20 minutes, such as from 2 minutes to 4 minutes, 4 minutes to 6 minutes, 6 minutes to 8 minutes, 8 minutes to 10 minutes, 10 minutes to 12 minutes, 12 minutes to 14 minutes, 14 minutes to 16 minutes, 16 minutes to 18 minutes, 18 minutes to 20 minutes, or any combination of these ranges. In some embodiments, the catalyst may be exposed to the oxygen-containing gas for from 4 minutes to 18 minutes, 6 minutes to 17 minutes, 8 minutes to 16 minutes, or 10 minutes to 15 minutes. Without being bound by theory, it is believed that exposure of the catalyst to the oxygen-containing gas for more than 20 minutes can increase the equipment cost without increasing the matching in catalyst regeneration efficiency. However, exposure of the catalyst to the oxygen-containing gas for less than 2 minutes can result in a decrease in the regeneration efficiency of the catalyst that can reduce the dehydrogenation activity of the catalyst.

[0046] Without being bound by theory, it is believed that the catalysts described herein that contain manganese can enhance the reactivation of the catalyst within the oxygen treatment zone 370. This enhanced reactivation can reduce the amount of time required to reactivate the catalyst and thus reduce the amount of time that must be spent in the oxygen treatment zone 370 for the catalyst to be fully reactivated.

[0047] In one or more embodiments, the light olefins can be present in a “product stream,” sometimes referred to as an “olefin-containing effluent,” and can include light olefins. Such streams can exit the reactor system of FIG. 1 and subsequently be processed. As used in this disclosure, the term “light olefins” refers to one or more of ethylene, propylene, and butene. The term butene includes any isomers of butene such as α-butylene, cis-β-butylene, trans-β-butylene, and isobutylene. In some embodiments, the olefin-containing effluent includes at least 25 wt % light olefins, based on the total weight of the olefin-containing effluent. For example, the olefin-containing effluent can include at least 35 wt % light olefins, at least 45 wt % light olefins, at least 55 wt % light olefins, at least 65 wt % light olefins, or at least 75 wt % light olefins, based on the total weight of the olefin-containing effluent. The olefin-containing effluent can further include unreacted components of the hydrocarbon-containing effluent and other reaction products not considered light olefins. The light olefins can be separated from the unreacted components in a subsequent separation step.

[0048] Test Methods The various test methods of this disclosure are further discussed and referenced in the following examples.

[0049] Catalyst Productivity Catalyst productivity is calculated using Equation 1 (Equation 1):

[0050]

Number

Examples

[0051] The various embodiments of this disclosure are further clarified by the following examples. These examples are illustrative in nature and should not be understood as limiting the subject matter of this application.

[0052] Example 1 - Sample Compositions and Aging Protocols In Example 1, eight different samples of catalytically active particles (i.e., catalysts and / or combustion additives) were prepared. For the purposes of Example 1, a microspherical alumina support was prepared by spray drying a mixture of hydrated alumina and Ludox® silica, and then heating the resulting spray-dried particles at a temperature of at least 1000 °C sufficient to achieve particles having a particle size in the range of 5 μm to 300 μm, a pore volume of 0.20 ± 0.10 mL / g, a surface area of 70 ± 20 m 2 / g, and a silica content of 2.5 ± 2.5 wt%. The catalyst materials were prepared by the incipient wetness impregnation method of loading the specified metals onto the support using nitrate or amine nitrate metal precursors, followed by drying at a temperature below 200 °C and then calcining at a temperature below 800 °C. The exact compositions of the samples are provided in Table 1.

[0053] An accelerated laboratory aging protocol was applied to the catalysts to degrade the catalysts in order to simulate the aging of the catalysts after some use in a reactor. In Aging Protocol A, samples CE1 and E1 - E5 were subjected to six high temperature treatment - jet treatment cycles. Each cycle included a 24-hour treatment in air at 800 °C, followed by a 6-hour treatment under a nitrogen jet having a jet velocity of 150 ft / sec. The jet treatment was performed in a pilot jet cup attrition facility as described in Cocco et al., Jet Cup Attrition Testing, 200 Powder Technology 224 (2010), which is incorporated by reference in its entirety. In Aging Protocol B, samples CE1 and E3 were aged in air at 800 °C in a furnace for 5 days using a catalyst treatment.

[0054] [Table 1]

[0055] Example 2 - Effect of Manganese Loading In Example 2, the sample prepared in Example 1 was tested for dehydrogenation activity and combustion activity under a dehydrogenation-combustion-reactivation cycle that was simulated in a laboratory in a fixed-bed rig hereinafter referred to as a DH (short time)-combustion-reactivation cycle. For comparison, Comparative Example CE1-aged A and samples E1-aged A and E3-aged A were also run under a simulated DH (long time)-combustion-reactivation cycle. In the DH (short time)-combustion-reactivation cycle, at ambient pressure, 0.5 g of the sample was mixed with 1.0 g of inactive silicon carbide and loaded into a quartz reactor. The simulated DH (short time)-combustion-reactivation cycle was carried out in three steps. First, dehydrogenation was carried out at 625 °C for 60 seconds using a feed composition of 90% propane / 10% nitrogen and a weight hourly space velocity “WHSV” of propane of 10 hours -1 Second, combustion was carried out at 730 °C for 3 minutes with a total flow rate of 50 standard cubic centimeters per minute (sccm) and a WHSV of methane of 0.1 hour -1 under 2.5 mol% methane / remaining air. Finally, the reactivation step was carried out at 730 °C for 10 minutes with a flow rate of 40 sccm under 100% air. Dehydrogenation performance data were collected at the 30-second point during operation, and combustion data were collected at the 60-second point during operation. The results of subjecting samples CE1 and E1-E5 to the DH (short time)-combustion-reactivation cycle after 15 cycles are reported in Table 3.

[0056] The simulated DH (long time)-combustion-reactivation cycle was carried out at ambient pressure by loading 1 g of the sample into a quartz reactor. Then, dehydrogenation was carried out at 625 °C for 15 minutes with a feed composition of 50% propane / 50% inert gas (37.5% He and 12.5% N2) and a WHSV of propane of 2.2 hours -1 Next, under 2.5 mol% methane / remaining air, with a total flow rate of 50 sccm and a WHSV of 0.1 hour -1Combustion was carried out at 730 °C for 3 minutes with a WHSV of methane of . Subsequently, regeneration was carried out at 730 °C for 20 minutes under 100% air with a flow rate of 40 sccm. Dehydrogenation performance data was collected at the 10-minute point during operation, and combustion performance data was collected at the 60-second point during operation. Dehydrogenation and combustion data collected from reaction-regeneration cycle 15 are reported in Table 2.

[0057]

Table 2

[0058]

Table 3

[0059] Table 2 shows that a catalyst composition containing manganese, such as sample E3-aged A, does not have significantly improved performance compared to comparative example CE1-aged A without manganese when tested in a DH (long time)-combustion-reactivation cycle simulating both catalysts. However, Table 3 shows that samples containing manganese, such as sample E3-aged A, have improved methane conversion rate, propane conversion rate, and propylene selectivity compared to comparative example CE1-aged A when tested in a DH (short time) combustion-reactivation cycle. Both Table 2 and Table 3 show that the significant improvement in catalyst performance due to the presence of manganese depends on the dehydrogenation process conditions. Table 3 further shows that comparative examples having only manganese and no platinum or gallium (i.e., comparative examples CE2 and CE3) decreased the propane conversion rate and propylene selectivity even when compared to aged samples CE1 to E5-aged A having platinum, gallium, and manganese. That is, Table 3 shows that the overall catalyst composition of platinum, gallium, and manganese is important for improving the methane conversion rate while maintaining an acceptable propane conversion rate and propylene selectivity.

[0060] Table 3 further shows that the addition of manganese hardly improves the propane conversion rate for non-aged catalysts (i.e., Comparative Example CE1 and Sample E2). For example, the presence of manganese only increased the propane conversion rate by 1.7% in the non-aged catalyst. Surprisingly, after aging, the presence of manganese increased the propane conversion rate up to 7.4% in the aged catalyst. This indicates that manganese improves both the methane conversion rate and dehydrogenation performance after aging.

[0061] Example 3 - Effect of Manganese Addition on Different Fuel Gas Compositions In Example 3, the DH (short time)-combustion-reactivation cycle was changed by changing the fuel used in the combustion step of the cycle from 2.5 mol% methane / the remaining air to 2.5 mol% hydrogen / the remaining air at a total flow rate of 50 sccm for 3 minutes. The results of this change in the fuel gas are recorded in Tables 4, 5, and 6 after 15, 30, and 50 cycles, respectively.

[0062] [Table 4]

[0063] [Table 5]

[0064] [Table 6]

[0065] As shown in Tables 5 - 7, the sample containing manganese (i.e., Sample E2 - aged A) has an improved propane conversion rate, propylene selectivity, and methane conversion rate in the presence of methane fuel compared to Comparative Example CE1 - aged A without manganese. Tables 5 - 7 further show that Sample E2 - aged A also has improved propane conversion rate and propylene selectivity even without using methane fuel when compared to Comparative Example CE1 - aged A. Comparative Examples CE2 and CE3 in Table 3 show that manganese itself does not sufficiently promote dehydrogenation. Therefore, the presence of manganese in the catalyst must improve the catalyst re - activation that explains the improved propane conversion rate when compared to a manganese - free catalyst, even without using methane as an auxiliary fuel. Briefly speaking, the data in Tables 5 - 7 show that the improvement in catalyst performance observed from the presence of manganese is due not only to the result of the improvement in methane combustion activity but also to the result of manganese improving the catalyst re - activation.

[0066] Example 4 - Effect of Changing the Re - activation Time In Example 4, the effect of changing the re - activation time of the DH (short - time) - combustion - re - activation cycle was investigated. The DH (short - time) - combustion - re - activation cycle was changed by varying the length of the 10 - minute re - activation cycle to 20, 15, 5, 2, or 0.5 minutes. The performance results obtained from Cycle 15 from this change in re - activation time are recorded in Tables 8 - 12.

[0067] [Table 7]

[0068] [Table 8]

[0069] [Table 9]

[0070]

Table 10

[0071]

Table 11

[0072] Tables 8 - 12 show that, under all the tested reactivation cycle times, a manganese loading of less than 1.0 wt% such as in E1 - aged A has improved propane conversion, propylene selectivity, and methane conversion when compared to manganese - free Comparative Example CE1 - aged A. A sample having a manganese loading equal to 1.0 wt%, for example E5 - aged A, has an improved methane conversion when compared to Comparative Example CE1 - aged A. Further, manganese - containing samples tested at shorter reactivation times, such as those in Table 10, have a greater improvement in propane conversion than samples tested at longer reactivation times as in Table 8 when compared to Comparative Example CE1 - aged A. This indicates that manganese - containing samples undergo sufficient reactivation faster than manganese - free Comparative Example CE1 - aged A. Tables 8 - 12 also show that reactivation times of 2 - 20 minutes recover performance significantly better than shorter reactivation times such as 0.5 minutes.

[0073] Example 5 - Effect of Changing the Catalyst Composition In Example 5, four samples were prepared using the sample preparation procedure and aging protocol B from Example 1. The DH (short - time) - combustion - reactivation cycle was used to test the effect of various changes to the catalyst composition on the catalyst performance. The composition of each sample is reported in Table 13. The performance results from Cycle 12 are also reported in Table 13.

[0074]

Table 12

[0075] Table 13 shows that samples having manganese as part of those compositions have sufficient propane conversion, propylene selectivity, and methane conversion over a wide range of possible catalyst compositions including dual noble metal-containing catalysts such as sample E8-aged B, dual group 13 element-containing catalysts such as sample E9-aged B, and catalysts having a high gallium content such as sample E7-aged B. Put simply, Table 13 shows that manganese can be part of a wide range of catalyst compositions having sufficient methane conversion, propane conversion, and propylene selectivity.

[0076] In a first aspect of the present disclosure, light olefins can be produced by dehydrogenation by a method comprising contacting a hydrocarbon-containing feed with a catalyst in a reactor to form an olefin-containing effluent, at least partially separating the olefin-containing effluent from the catalyst, passing the catalyst through a combustor to heat the catalyst, passing the catalyst from the combustor to an oxygen treatment zone and exposing the catalyst to an oxygen-containing gas for 2 to 20 minutes, and passing the catalyst from the oxygen treatment zone to the reactor such that at least a portion of the catalyst continuously circulates between the reactor, the combustor, and the oxygen treatment zone. Here, the catalyst comprises one or more metals selected from 0.1 wt% to 10 wt% of gallium, indium, or a combination thereof, one or more metals selected from 5 ppmw to 500 ppmw of platinum, palladium, rhodium, iridium, or a combination thereof, 0.01 wt% to 1 wt% of manganese, and at least 85 wt% of a carrier.

[0077] A second aspect of the present disclosure may include the first aspect, where the catalyst has a residence time of 3 minutes or less in the reactor.

[0078] A third aspect of the present disclosure may include any of the foregoing aspects, where the catalyst has a residence time of 1 minute or less in the reactor.

[0079] A fourth aspect of the present disclosure may include any of the foregoing aspects, where the catalyst is exposed to the oxygen-containing gas for 8 to 20 minutes in the oxygen treatment zone.

[0080] The fifth aspect of the present disclosure may include any of the above aspects, wherein the method further includes heating the catalyst by burning an auxiliary fuel.

[0081] The sixth aspect of the present disclosure may include the fifth aspect, wherein the auxiliary fuel includes at least 1 mol% methane.

[0082] The seventh aspect of the present disclosure may include any of the above aspects, wherein the catalyst includes 0.1 wt% to 10 wt% gallium and 1 ppmw to 500 ppmw platinum.

[0083] The eighth aspect of the present disclosure may include any of the above aspects, wherein the catalyst includes 0.1 wt% to 5 wt% gallium and 10 ppmw to 400 ppmw platinum.

[0084] The ninth aspect of the present disclosure may include any of the above aspects, wherein the catalyst includes 0.05 wt% to 0.6 wt% manganese.

[0085] The tenth aspect of the present disclosure may include any of the above aspects, wherein the catalyst further includes 0.01 wt% to 5 wt% of one or more alkali metals or alkaline earth metals.

[0086] The eleventh aspect of the present disclosure may include the first aspect, wherein the catalyst further includes 0.01 wt% to 5 wt% potassium.

[0087] The twelfth aspect of the present disclosure may include the first aspect, wherein the catalyst includes 0.1 wt% to 5 wt% gallium, 10 ppmw to 400 ppmw platinum, and 0.05 wt% to 0.6 wt% manganese.

[0088] The thirteenth aspect of the present disclosure may include any of the above aspects, wherein the carrier includes one or more of alumina, silica, or a combination thereof.

[0089] A fourteenth aspect of the present disclosure may include any of the above aspects, where the catalyst has the characteristics of Geldart group A or Geldart group B.

[0090] A fifteenth aspect of the present disclosure may include any of the above aspects, where the hydrocarbon-containing feed includes propane and the olefin-containing effluent includes propylene.

[0091] It will be apparent to those skilled in the art that various modifications and changes can be made to the technology of the present disclosure without departing from the spirit and scope of the technology. Combinations, sub-combinations, and variations of modifications of the disclosed embodiments incorporating the spirit and substance of the technology of the present disclosure can be conceived by those skilled in the art, and thus the technology should be construed to include all within the scope of the appended claims and their equivalents. Further, 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.

[0092] It should be noted that the various details described in the present disclosure should not be construed as implying that these details are related to elements that are essential components of the various embodiments described in the present disclosure, even if a particular element is illustrated in each of the accompanying drawings herein. Unless specifically so specified, the features disclosed and described herein should not be construed as "essential." The contemplated embodiments of the technology include those that include some or all of the features of the appended claims.

[0093] Note that for the purpose of describing and defining the present disclosure, the term "about" is used in the present disclosure to represent the degree of inherent uncertainty that may result from any quantitative comparison, value, measurement, or other representation. The term "about" is also used in the present disclosure to represent the degree to which a quantitative expression may vary from the reference of the description without causing a change in the basic function of the subject matter in question.

[0094] When relevant, when a composition is described as "comprising" one or more elements, embodiments of the composition "consisting of" or "consisting essentially of" those one or more elements are contemplated herein.

[0095] It should be understood that in some embodiments, the composition range of the stream or chemical components in the reactor is to be understood to contain a mixture of isomers of that component. For example, a composition range specifying butene may include a mixture of various isomers of butene. It should be understood that the examples supply composition ranges for various streams and that the total amount of isomers of a particular chemical composition may constitute the range.

[0096] It should be noted that one or more of the following claims utilize the terms "where" or "wherein" as transitional phrases. For the purpose of defining the technology, this term is introduced into the claims as a non-limiting transitional phrase used to introduce a recitation of a series of features of a structure and should be construed in the same manner as the more commonly used non-limiting preamble term "comprising".

[0097] It should be understood that any two quantitative values assigned to a property can constitute a range of that property and that all combinations of ranges formed from all the recited quantitative values of a given property are contemplated in the present disclosure. When multiple ranges are given for a quantitative value, these ranges may be combined to form a broader range, which is contemplated in the embodiments described herein.

Claims

1. A method for producing light olefins by dehydrogenation, In the reactor, a hydrocarbon-containing feed is brought into contact with a catalyst to form an olefin-containing effluent, To separate the olefin-containing effluent from the catalyst at least partially, The catalyst is passed through a combustor and the catalyst is heated, The catalyst is passed from the combustor to the oxygen treatment zone, and the catalyst is exposed to an oxygen-containing gas for 2 to 20 minutes. This includes passing the catalyst from the oxygen treatment zone to the reactor so that at least a portion of the catalyst circulates continuously between the reactor, the combustor, and the oxygen treatment zone. The catalyst, 0.1% to 10% by weight of one or more metals selected from gallium, indium, or combinations thereof. One or more metals selected from platinum, palladium, rhodium, iridium, or combinations thereof, with a power of 5 ppmW to 500 ppmW. 0.01% to 1% by weight of manganese, A method comprising at least 85% by weight of a carrier.

2. The method according to claim 1, wherein the catalyst has a residence time of 3 minutes or less in the reactor.

3. The method according to claim 1, wherein the catalyst has a residence time of 1 minute or less in the reactor.

4. The method according to claim 1, wherein the catalyst is exposed to the oxygen-containing gas in the oxygen treatment zone for 8 to 20 minutes.

5. The method according to claim 1, further comprising heating the catalyst by burning an auxiliary fuel.

6. The method according to claim 5, wherein the auxiliary fuel contains at least 1 mol% methane.

7. The catalyst, 0.1% to 10% by weight of gallium, and The method according to any one of the claims, comprising platinum in an amount of 1 ppmW to 500 ppmW.

8. The catalyst, 0.1% to 5% by weight of gallium, and The method according to claim 1, comprising platinum in an amount of 10 ppmW to 400 ppmW.

9. The method according to claim 1, wherein the catalyst contains 0.05% to 0.6% by weight of manganese.

10. The method according to claim 1, wherein the catalyst further comprises 0.01% to 5% by weight of one or more alkali metals or alkaline earth metals.

11. The method according to claim 1, wherein the catalyst further comprises 0.01% to 5% by weight of potassium.

12. The catalyst, 0.1% to 5% by weight of gallium, Platinum with a power of 10 ppmW to 400 ppmW, and The method according to claim 1, comprising 0.05% to 0.6% by weight of manganese.

13. The method according to claim 1, wherein the carrier comprises one or more of alumina, silica, or a combination thereof.

14. The method according to claim 1, wherein the catalyst has the properties of Geldart group A or Geldart group B.

15. The method according to any one of claims 1 to 14, wherein the hydrocarbon-containing feed contains propane and the olefin-containing effluent contains propylene.

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