Method for producing light olefins by dehydrogenation using an iron-containing catalyst

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 is passed through a combustor and heated by burning an auxiliary fuel. The auxiliary fuel contains methane in an amount of 1 mol% or more. The catalyst is passed from the combustor to the reactor such that at least a portion of the catalyst continuously circulates between the reactor and the combustor. The catalyst contains one or more metals selected from gallium, indium, thallium, or combinations thereof in an amount of 0.1 wt% to 10 wt%, one or more metals selected from platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof in an amount of 5 ppmw to 1000 ppmw, iron in an amount of 100 ppmw to 30000 ppmw, 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 Patent Application No. 63 / 352,015, filed Jun. 14, 2022, which is hereby incorporated by reference in its entirety.

[0002] The 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, which 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 are needed in the systems and related catalysts used to make light olefins.

Summary of the Invention

[0004] Some methods and related systems used to produce light olefins may utilize auxiliary fuel that is burned to heat the catalyst during the manufacturing process. For example, the catalyst may be circulated between a reactor in which light olefins are produced by an endothermic reaction and a combustor in which the catalyst is heated by at least the exothermic combustion of the auxiliary fuel (sometimes together with the combustion of coke). Such a catalyst may have catalytic activity not only for the dehydrogenation of alkanes but also for the combustion of the auxiliary fuel. Some embodiments of such suitable catalysts include, for example, gallium and platinum on a support. In some embodiments, methane may be used in the auxiliary fuel. In such embodiments, conventional catalysts used for dehydrogenation may suffer from low methane combustion activity, which means that using methane as the auxiliary fuel may not provide enough heat to raise the temperature of the catalyst to the desired temperature utilized in the dehydrogenation reaction. Further, using conventional catalysts that may suffer from low methane combustion activity can negatively impact the safety of the dehydrogenation process because unburned methane can exceed the low flammability levels required in the regenerator. As described herein, it has been discovered that catalysts further containing iron can enhance the combustion of methane, for example, compared to conventional catalysts that do not contain iron.

[0005] According to one or more embodiments of the present disclosure, 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 passed through a combustor in which the catalyst can be heated by burning an auxiliary fuel. The auxiliary fuel may include methane in an amount exceeding 1 mol%. The catalyst may be passed from the combustor to the reactor such that at least a portion of the catalyst can continuously circulate between the reactor and the combustor. The catalyst may include one or more metals selected from gallium, indium, thallium, or combinations thereof in an amount of 0.1 wt% to 10 wt%, one or more metals selected from platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof in an amount of 5 ppmw to 1000 ppmw, iron in an amount of 100 ppmw to 30000 ppmw, 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 describe 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 will be readily apparent to those skilled in the art from that description, including the accompanying drawings and the claims, or 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 exemplary and illustrative 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 describing the simplified schematic diagram of FIG. 1, many valves, temperature sensors, electronic controllers, etc. that can be used and are well known to those skilled in the art are not included. Further, accompanying 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.

DETAILED DESCRIPTION OF THE INVENTION

[0010] The present disclosure is directed to a method for producing light olefins by dehydrogenation in which a specific catalyst composition is utilized, as described herein. For example, a catalyst useful for dehydrogenation comprises one or more metals selected from 0.1 wt% to 10 wt% of gallium, indium, thallium, or combinations thereof, one or more metals selected from 5 ppmw to 1000 ppmw of platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof, 100 ppmw to 30000 ppmw of iron, and at least 85 wt% of a support. In one or more embodiments, such a catalyst provides a dual catalyst function for the dehydrogenation of alkanes and the combustion of auxiliary fuel. Such a catalyst containing iron may be particularly well suited for the fluidized dehydrogenation of light alkanes such as propane to light olefins such as propylene, where methane is utilized as the auxiliary fuel for heating the catalyst.

[0011] Embodiments of the methods disclosed herein are described in detail herein in the context of the reactor system of FIG. 1 that 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 downcomer rather than a riser. Further, it should be understood that not all parts of FIG. 1 should be construed as essential to the claimed subject matter. Further, the method steps recited in the appended claims are described herein in the context of FIG. 1, but 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.

[0012] 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 component" refers to a part of reactor system 102 such as a reactor, a separator, a transfer line, a combination thereof, etc. In the context of FIG. 1 as used herein, reactor section 200 generally refers to the part 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 functions 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 part of reactor system 102 that treats the catalyst in some way, such as by combustion, 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).

[0013] Generally, as described herein, in the embodiment shown 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 can 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" can 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 still maintain some catalytic activity. The decrease in catalytic activity can be due to contamination by substances such as coke. Coke can form on the catalyst within the reactor section 200. By reactivation (also sometimes referred to herein as "regeneration"), it is possible to remove contaminants such as coke, raise the temperature of the catalyst, or both. 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.

[0014] 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 to facilitate reheating of the catalyst. The catalyst is heated during regeneration to assist in regeneration, as the heated catalyst serves as a heat carrier that transports heat from the combustor 350 to the reactor section 200 to promote dehydrogenation reactions.

[0015] 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% 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% 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% 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% 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.

[0016] In one or more embodiments, the catalyst may comprise, consist essentially of, or consist of one or more of gallium, indium, or thallium; one or more of platinum, palladium, rhodium, iridium, ruthenium, or osmium; iron; and a support. As described herein, "consisting essentially of" refers to a material that contains less than 1 wt% of unlisted materials (i.e., consisting essentially of A and B means that A and B together are at least 99 wt% of the composition). As described herein, the catalyst can be solid particles suitable for fluidization.

[0017] In one or more embodiments, the catalyst may contain one or more of gallium, indium, or thallium 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, iridium, ruthenium, or osmium. Such materials can further catalyze the combustion of coke and auxiliary fuels. For example, the catalyst may contain one or more of gallium, indium, or thallium 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 any combination of these ranges. In some embodiments, the catalyst may contain one or more of gallium, indium, or thallium 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 does not contain indium or thallium, or contains only indium and does not contain gallium or thallium, or contains only thallium and does not contain gallium or indium. It should be understood that the compositional ranges described for the amounts of gallium, indium, and thallium represent the ranges for any one of these materials or a combination of these materials. Without being bound by theory, compositions having less than 0.1 wt% of one or more of gallium, indium, or thallium are thought to adversely affect the ability of the catalyst to catalyze the alkane dehydrogenation process by decreasing both the percentage of total dehydrogenated alkanes and the percentage of dehydrogenated alkanes that are the intended product. However, compositions having more than 10 wt% of one or more of gallium, indium, or thallium can be thought to adversely affect the ability of the catalyst to catalyze the alkane dehydrogenation process, the selectivity of the catalyst for the intended product, or both.

[0018] In one or more embodiments, the catalyst may contain one or more of platinum, palladium, rhodium, iridium, ruthenium, or osmium in an amount of 5 ppmw to 1000 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, indium, or thallium. 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, iridium, ruthenium, or osmium 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, 500 ppmw to 600 ppmw, 600 ppmw to 700 ppmw, 700 ppmw to 800 ppmw, 800 ppmw to 900 ppmw, 900 ppmw to 1000 ppmw, or a combination of these ranges. In some embodiments, the catalyst may contain one or more of platinum, palladium, rhodium, iridium, ruthenium, or osmium in an amount of 5 ppmw to 900 ppmw, 5 ppmw to 800 ppmw, 5 ppmw to 600 ppmw, 5 ppmw to 500 ppmw, or 10 ppmw to 400 ppmw. In some embodiments, the catalyst contains only platinum and not palladium, rhodium, iridium, ruthenium, or osmium; only palladium and not platinum, rhodium, iridium, ruthenium, or osmium; only rhodium and not platinum, palladium, iridium, ruthenium, or osmium; only iridium and not platinum, palladium, rhodium, ruthenium, or osmium; only ruthenium and not platinum, palladium, rhodium, iridium, or osmium; only osmium and not platinum, palladium, rhodium, iridium, or ruthenium; or only osmium and not platinum, palladium, rhodium, iridium, or ruthenium. It should be understood that the compositional ranges describing the amounts of platinum, palladium, rhodium, iridium, ruthenium, and osmium represent the ranges of any one of these materials or combinations of these materials.Although not bound by theory, a composition having one or more of platinum, palladium, rhodium, iridium, ruthenium, or osmium in an amount less than 5 ppmw is thought to adversely affect the ability of a catalyst to catalyze an alkane dehydrogenation process by reducing both the percentage of dehydrogenated total alkanes and the percentage of dehydrogenated alkane that is the intended product. However, a composition having one or more of platinum, palladium, rhodium, iridium, ruthenium, or osmium in an amount exceeding 1000 ppmw is thought to potentially adversely affect the ability of a catalyst to catalyze an alkane dehydrogenation process, the selectivity of the catalyst for the intended product, or both.

[0019] In one or more embodiments, the catalyst may contain iron in an amount of 100 ppmw to 30,000 ppmw, based on the total weight of the catalyst. The incorporation of iron can promote the combustion of methane while having little effect on the dehydrogenation of alkanes. For example, the catalyst may contain iron in an amount of 100 ppmw to 500 ppmw, 500 ppmw to 1000 ppmw, 1000 ppmw to 2500 ppmw, 2500 ppmw to 5000 ppmw, 5000 ppmw to 7500 ppmw, 7500 ppmw to 10,000 ppmw, 10,000 ppmw to 15,000 ppmw, 15,000 ppmw to 20,000 ppmw, 20,000 ppmw to 25,000 ppmw, 25,000 ppmw to 30,000 ppmw, or combinations of amounts within these ranges. In some embodiments, the catalyst may contain iron in an amount of 100 ppmw to 25,000 ppmw, 150 ppmw to 20,000 ppmw, 200 ppmw to 15,000 ppmw, 300 ppmw to 12,500 ppmw, 400 ppmw to 10,000 ppmw, or 500 ppmw to 8000 ppmw. Without being bound by theory, it is believed that compositions having an amount of iron less than 100 ppmw may not sufficiently improve the methane combustion performance of the catalyst. However, compositions having an amount of iron greater than 30,000 ppmw may be considered to adversely affect the dehydrogenation performance of the catalyst by reducing both the percentage of all alkanes dehydrogenated and the percentage of dehydrogenated alkanes that are the intended product. Without being bound by theory, iron may also help reduce the rate at which the methane combustion activity of the catalyst decreases over time during the operation of the dehydrogenation process.

[0020] In one or more embodiments, the catalyst may contain iron in a total amount of 100 ppmw to 30,000 ppmw in combination with one or more of chromium, manganese, or vanadium based on the total weight of the catalyst. For example, the catalyst may contain iron in combination with one or more of iron, chromium, manganese, or vanadium in a total amount of 100 ppmw to 500 ppmw, 500 ppmw to 1000 ppmw, 1000 ppmw to 2500 ppmw, 2500 ppmw to 5000 ppmw, 5000 ppmw to 7500 ppmw, 7500 ppmw to 10,000 ppmw, 10,000 ppmw to 15,000 ppmw, 15,000 ppmw to 20,000 ppmw, 20,000 ppmw to 25,000 ppmw, 25,000 ppmw to 30,000 ppmw, or combinations of these ranges. In some embodiments, the catalyst contains iron and chromium but does not contain manganese or vanadium, contains iron and manganese but does not contain chromium or vanadium, contains iron and vanadium but does not contain chromium or manganese, contains iron, chromium, and manganese but does not contain vanadium, contains iron, chromium, and vanadium but does not contain manganese, or contains iron, manganese, and vanadium but does not contain chromium.

[0021] 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 combinations 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 comprises 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.

[0022] In one or more embodiments, the catalyst may optionally contain one or more alkali metals, one or more alkaline earth metals, or both, in an amount of 0.01 wt% to 2.5 wt% based on the total weight of the catalyst. For example, the catalyst may contain 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 0.2 wt%, 0.2 wt% to 0.3 wt%, 0.3 wt% to 0.4 wt%, 0.4 wt% to 0.5 wt%, 0.5 wt% to 0.6 wt%, 0.6 wt% to 0.7 wt%, 0.7 wt% to 0.8 wt%, 0.8 wt% to 0.9 wt%, 0.9 wt% to 1 wt%, 1 wt% to 1.25 wt%, 1.25 wt% to 1.5 wt%, 1.5 wt% to 1.75 wt%, 1.75 wt% to 2 wt%, 2 wt% to 2.25 wt%, 2.25 wt% to 2.5 wt%, or any combination of these ranges. In some embodiments, the catalyst may contain one or more alkali metals, one or more alkaline earth metals, or both, in an amount of 0.01 wt% to 1 wt%, 0.02 wt% to 0.75 wt%, 0.03 wt% to 0.5 wt%, 0.04 wt% to 0.4 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 compositions 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 compositions having an amount of alkali metal or alkaline earth metal exceeding 2.5 wt% may reduce the dehydrogenation activity of the catalyst.

[0023] In one or more embodiments, the catalyst may comprise, consist essentially of, or consist of gallium, platinum, iron, 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 1000 ppmw platinum, 100 ppmw to 30000 ppmw iron, 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, 500 ppmw to 8000 ppmw iron, and at least 85 wt% carrier.

[0024] 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.

[0025] Group A of Geldart is understood by those skilled in the art to represent aeratable powders having the following: fluidization in a range without bubbles, high bed expansion, slow and linear de - aeration rate, the possibility of dominant breakup / recombination bubbles, bubble characteristics with a 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 slug characteristics, and no jetting except for very shallow beds.

[0026]

Number

[0027] 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 degassing, no limitation on bubble size, and 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 to some extent with 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, most of the particles

[0028]

Number

[0029] 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 iron, drying the support, and calcining the support, and the catalyst comprises 0.1 wt% to 10 wt% gallium, 5 ppmw to 1000 ppmw platinum, 100 ppmw to 30000 ppmw iron, and at least 85 wt% support.

[0030] 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 using 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 iron. 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 iron after drying and calcination, and drying and calcining the support after iron impregnation, and the catalyst comprises 0.1 wt% to 10 wt% gallium, 5 ppmw to 1000 ppmw platinum, 100 ppmw to 30000 ppmw iron, and at least 85 wt% support. In additional embodiments, the method of making the catalyst may include impregnating the support with iron to create an iron-impregnated support, drying the iron-impregnated support, calcining the iron-impregnated support, impregnating the iron-impregnated support with gallium and platinum after drying and calcination, and drying and calcining the iron-impregnated support after gallium and platinum impregnation, and the catalyst comprises 0.1 wt% to 10 wt% gallium, 5 ppmw to 1000 ppmw platinum, 100 ppmw to 30000 ppmw iron, and at least 85 wt% support.

[0031] 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.

[0032] 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 feeding 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.

[0033] 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.

[0034] The upstream reactor section 250 can be connected to a transfer riser 430 that can provide the reactivated catalyst in the feed stream to the reactor section 200 during operation. The reactivated catalyst and / or reaction chemicals can be mixed in 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 directly into the transfer riser 430 from the catalyst separation section 210 via a vertical pipe 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 vertical pipe 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.

[0035] In one or more embodiments, the catalyst can have a residence time within the reactor section 200 of three 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 the catalyst can spend within the reactor section 200 during any given cycle may not be equal to the average but will average out to approximately the residence time over 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, it is believed that a catalyst residence time exceeding three minutes can increase the equipment cost without increasing the matching in catalyst dehydrogenation performance. However, a catalyst residence time of less than 0.1 minutes is believed to potentially prevent the catalyst from adequately catalyzing the dehydrogenation reaction.

[0036] 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 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 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 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 can 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 the density is higher than that of the fast fluidization regime. As described herein, a "bubble bed" reactor may be able to 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 the solid 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 blockage velocity.

[0037] 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 riser tube 426 and is transferred to the catalyst treatment section 300.

[0038] 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.

[0039] 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 and is sent through the riser 330 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 a 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 standpipe 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.

[0040] 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, turbulent bed, or 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.

[0041] As described herein, the catalyst may be heated within the catalyst treatment unit 300 by the combustion of auxiliary fuel. The auxiliary fuel may burn with oxygen to heat the catalyst, and the auxiliary fuel is such as auxiliary fuel such as hydrogen, methane, ethane, propane, natural gas, or combinations thereof. Without being bound by any theory, when methane is utilized as the auxiliary fuel, the catalyst described herein containing iron may better catalyze the combustion of methane to heat the catalyst. A catalyst that does not contain iron 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.

[0042] As described in one or more embodiments, following the separation of flue gas from the catalyst in the riser termination separator 378 and the secondary separation device 320, treatment of the treated catalyst with an oxygen-containing gas is performed 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 to the oxygen treatment zone 370 for the oxygen treatment of the catalyst.

[0043] 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 2 to 20 minutes, such as 2 to 4 minutes, 4 to 6 minutes, 6 to 8 minutes, 8 to 10 minutes, 10 to 12 minutes, 12 to 14 minutes, 14 to 16 minutes, 16 to 18 minutes, 18 to 20 minutes, or any combination of these ranges. In some embodiments, the catalyst may be exposed to the oxygen-containing gas for 4 to 18 minutes, 6 to 17 minutes, 8 to 16 minutes, or 10 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 catalyst regeneration efficiency that can reduce the dehydrogenation activity of the catalyst.

[0044] In one or more embodiments, light olefins may be present in a “product stream,” sometimes referred to as an “olefin-containing effluent,” and may include light olefins. Such a stream exits the reactor system of FIG. 1 and may subsequently be processed. As used in this disclosure, the term “light olefins” refers to one or more of ethylene, propylene, and butenes. The term butenes includes any isomers of butenes such as α-butylene, cis-β-butylene, trans-β-butylene, and isobutylene. In some embodiments, the olefin-containing effluent comprises at least 25 wt % light olefins, based on the total weight of the olefin-containing effluent. For example, the olefin-containing effluent can comprise 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 may further comprise 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.

Examples

[0045] The various embodiments of the present 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.

[0046] Example 1 - Effect of Iron Loading In Example 1, twelve different samples of catalytically active particles (i.e., catalysts) were prepared and the effect of iron loading on the catalytically active particles was observed. For the purposes of Example 1, first, a microspherical alumina support was prepared by spray drying a mixture of hydrated alumina and Ludox® silica, and then the resulting spray-dried particles were sized in the range of 5 μm to 300 μm, had a pore volume of 0.20 ± 0.10 mL / g, and a surface area of 70 ± 20 m 2Samples were prepared by heating to a temperature of at least 1000 °C sufficient to achieve particles having a surface area of / g and a silica content of 2.5 ± 2.5 wt%. The catalyst material was prepared by loading the specified metal(s) onto the support using the incipient wetness impregnation method with 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 composition of the samples is provided in Table 1.

[0047] Samples were tested at ambient pressure under the condition that 0.5 grams (g) of the sample was mixed with 1.0 g of inactive silicon carbide and loaded into a quartz reactor. A reaction combustion reactivation cycle was performed with 10 rest cycles, followed by dehydrogenation and regeneration test cycles. The interruptions in the cycles were carried out by performing two steps: 10 hours -1 of propane hourly weight hourly space velocity “WHSV” and a feed composition of 90% propane / 10% nitrogen to perform a dehydrogenation process at 625 °C for 60 seconds; and a reactivation step of heating the catalyst to 730 °C for 5 minutes under 100% air at a flow rate of 50 standard cubic centimeters per minute (sccm). After the catalyst was run through 10 interruption cycles, it was tested in dehydrogenation and regeneration test cycles. The dehydrogenation and regeneration test cycles were carried out by performing the following three steps: a dehydrogenation step using the same conditions as the dehydrogenation step of the interruption in the cycle where dehydrogenation performance data was collected over a 30 - second on - stream time, a combustion step where combustion was carried out at 730 °C for 3 minutes under 2.5 mol% methane / balance air having a WHSV of methane of 0.1 hours -1 and combustion performance data was collected over a 60 - second on - stream time, and a reactivation step where the sample was heated to 730 °C for 2 minutes under 100% air having a flow rate of 50 sccm. The dehydrogenation and combustion performance of the samples after 25 cycles was reported in Table 1.

[0048]

Table 1

[0049] As shown in Table 1, all samples containing iron (i.e., Samples 1 - 6) showed an improvement in methane conversion. Some samples containing iron showed an improvement in methane conversion, propane conversion, and propylene selectivity. For example, Comparative Example A (without iron) had worse propane conversion, propylene selectivity, and methane conversion than Samples 1 - 4 which were identical to Comparative Example A except for the absence of iron. Table 1 also shows that while an increase in the iron composition in the samples continued to improve the methane conversion up to 100%, samples with a high iron loading (i.e., Sample 6) showed a decrease in propane conversion and propylene selectivity when compared to samples with a lower iron loading (i.e., Samples 1 - 4). Samples with a higher iron loading still resulted in acceptable propane conversion and propylene selectivity. Further, Table 1 shows that samples containing neither platinum nor gallium (i.e., Comparative Examples B - F) had lower propane conversion and propylene selectivity than samples containing both platinum and gallium (i.e., Samples 1 - 6). That is, Table 1 shows that the overall catalyst composition of platinum, gallium, and iron is important for improving methane conversion while maintaining acceptable propane conversion and propylene selectivity.

[0050] Example 2 - Effect of Multiple Metal Promoters In Example 2, two samples of catalytically active particles (i.e., catalysts) were prepared and the effect of multiple metal promoters on catalytic performance was observed. Using the catalyst preparation procedure of Example 1, the samples were prepared and tested. The composition of the samples and their dehydrogenation and combustion performance are reported in Table 2.

[0051] [Table 2]

[0052] As shown by Tables 1 and 2, Sample 7, which has both iron and chromium as promoters, showed an improvement in methane conversion rate, propane conversion rate, and propylene conversion rate when compared with the base catalyst of Comparative Example A. Tables 1 and 2 further show that Sample 8, which has both iron and manganese as promoters, showed an improvement in methane conversion rate and propane conversion rate with the same propylene selectivity when compared with Comparative Example A.

[0053] Example 3 - Effect of Sequential Impregnation In Example 3, samples of catalytically active particles (i.e., catalysts) were prepared, and the effect of sequential impregnation on the dehydrogenation and combustion performance of the catalytically active particles was investigated. The samples of Example 3 were prepared by using the base catalyst (i.e., Comparative Example A) prepared using the catalyst preparation procedure of Example 1. The pre-prepared catalyst was then impregnated with an iron(III) nitrate solution in DI water, subsequently dried at a temperature below 200 °C, and then promoted by calcination at a temperature below 800 °C. The composition of the samples and their dehydrogenation and combustion performance are reported in Table 3.

[0054]

Table 3

[0055] As shown by Tables 1 and 3, the sample prepared by sequential impregnation (i.e., Sample 9) did not lose significant dehydrogenation or combustion activity when compared with the sample prepared by co-impregnation (i.e., Sample 3). That is, the catalyst can be prepared using either sequential impregnation or co-impregnation.

[0056] Example 4 - Effect of the Order of Sequential Impregnation In Example 4, two different samples of catalytically active particles (i.e., catalysts) were prepared, and the effect of sequential impregnation on the dehydrogenation and combustion performance of the catalytically active particles was observed. The samples of Example 4 were prepared by loading the metal using sequential impregnation, subsequently drying at a temperature below 200 °C, and then calcining at a temperature below 800 °C after each impregnation step. The composition of the samples, the order of their impregnation, and their dehydrogenation and combustion performance are reported in Table 4.

[0057]

Table 4

[0058] As shown in Table 4, the samples prepared by sequential impregnation (i.e., Samples 10 and 11) did not lose much dehydrogenation or combustion activity when compared with the samples prepared by co-impregnation (i.e., Sample 6). That is, the catalyst can be prepared using either sequential impregnation or co-impregnation.

[0059] Example 5 - Effect of Gallium and Platinum Compositions on Catalyst Performance In Example 5, three different samples of catalytically active particles (i.e., the catalyst) were prepared and the effects of various compositions on dehydrogenation and combustion activity were observed. The samples of Example 6 were prepared using the catalyst preparation procedure of Example 1. The compositions of the samples and their dehydrogenation and combustion performance are reported in Table 5.

[0060]

Table 5

[0061] As shown in Table 5, the samples containing iron showed an improvement in methane conversion with acceptable propane conversion and propylene selectivity over a range of platinum and gallium compositions. For example, Sample 13 had less platinum and more gallium than Comparative Example A, but showed improved methane conversion, propane conversion, and propylene selectivity when compared with Comparative Example A. All samples in Table 5 (i.e., Samples 12 - 14) showed improved methane conversion compared with Comparative Example A.

[0062] Example 6 - Effect of Fuel Used during Combustion In Example 6, three different samples of catalytically active particles (i.e., catalysts) were prepared, and the effect of the fuel composition on dehydrogenation and combustion activity was observed. In Example 6, the catalytically active particles were prepared using the catalyst preparation procedure from Example 1. Then, the dehydrogenation and regeneration test cycles were performed as described in Example 1, but the combustion step was changed to combustion at 730 °C for 3 minutes under 2.5 mol% H2 / balance air (100% H2 - fuel) with a flow rate of 50 sccm. Combustion data was still collected with 60 seconds of on-stream time, as in the previous examples. The composition of the samples and their dehydrogenation and combustion performance are reported in Table 6.

[0063]

Table 6

[0064] As shown in Table 6, the iron-containing samples (i.e., Samples 3 and 4) showed improved propane conversion and propylene selectivity even when the process was run without using methane as an auxiliary fuel, compared to the iron-free sample (i.e., Comparative Example A). The iron-containing samples (i.e., Samples 3 and 4) showed the most significant improvement in fuel conversion and propane conversion when compared to iron-free Comparative Example A in the presence of methane fuel, but some improvement in propane conversion was also seen when compared to Comparative Example A where methane was not used as a fuel.

[0065] In a first aspect of the present disclosure, light olefins can be produced by dehydrogenation by a method that includes contacting a hydrocarbon-containing feedstock 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 is heated by passing it through a combustor and burning an auxiliary fuel. The auxiliary fuel contains methane in an amount of 1 mol% or more. The catalyst is passed from the combustor to the reactor such that at least a portion of the catalyst continuously circulates between the reactor and the combustor. The catalyst contains 0.1 wt% to 10 wt% of one or more metals selected from gallium, indium, thallium, or combinations thereof, 5 ppmw to 1000 ppmw of one or more metals selected from platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof, 100 ppmw to 30000 ppmw of iron, and at least 85 wt% of a carrier.

[0066] A second aspect of the present disclosure may include the first aspect, wherein the method further includes passing the catalyst from the combustor through an oxygen treatment zone, 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.

[0067] A third aspect of the present disclosure may include the second aspect, wherein the catalyst is exposed to the oxygen-containing gas in the oxygen treatment zone for 8 to 20 minutes.

[0068] A fourth aspect of the present disclosure may include any of the preceding aspects, wherein the auxiliary fuel contains at least 3 mol% of methane.

[0069] A fifth aspect of the present disclosure may include any of the preceding aspects, wherein the catalyst has a residence time of 3 minutes or less in the reactor.

[0070] A sixth aspect of the present disclosure may include any of the preceding aspects, wherein the catalyst has a residence time of 1 minute or less in the reactor.

[0071] A seventh aspect of the present disclosure may include any of the preceding aspects, wherein the catalyst contains 0.1 wt% to 10 wt% of gallium and 5 ppmw to 1000 ppmw of platinum.

[0072] An eighth aspect of the present disclosure may include any of the foregoing aspects, wherein the catalyst contains 0.1 wt% to 5 wt% of gallium and 10 ppmw to 400 ppmw of platinum.

[0073] A ninth aspect of the present disclosure may include any of the foregoing aspects, wherein the catalyst contains 500 ppmw to 10000 ppmw of iron.

[0074] A tenth aspect of the present disclosure may include any of the foregoing aspects, wherein the catalyst further contains 0.01 wt% to 2.5 wt% of one or more alkali metals or alkaline earth metals.

[0075] An eleventh aspect of the present disclosure may include the first aspect, wherein the catalyst further contains 0.01 wt% to 2.5 wt% of potassium.

[0076] A twelfth aspect of the present disclosure may include any of the foregoing aspects, wherein the catalyst contains 0.1 wt% to 5 wt% of gallium, 10 ppmw to 400 ppmw of platinum, and 500 ppmw to 8000 ppmw of iron.

[0077] A thirteenth aspect of the present disclosure may include any of the foregoing aspects, wherein the carrier contains one or more of alumina, silica, or a combination thereof.

[0078] A fourteenth aspect of the present disclosure may include any of the foregoing aspects, wherein the catalyst has the characteristics of Geldart group A or Geldart group B.

[0079] A fifteenth aspect of the present disclosure may include any of the foregoing aspects, wherein the hydrocarbon-containing feed contains propane and the olefin-containing effluent contains propylene.

[0080] 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 that incorporate 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.

[0081] Note 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. Unless specifically so specified, the features disclosed and described in this specification 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.

[0082] For the purposes of describing and defining the present disclosure, note that the term "about" is used in the present disclosure to represent the degree of inherent uncertainty that can 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 can vary from the reference of the description without causing a change in the basic function of the subject matter in question.

[0083] Where 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.

[0084] It should be understood that in some embodiments, the flow or the composition range of chemical components in the reactor contains a mixture of isomers of the components. For example, the composition range specifying butene may include a mixture of various isomers of butene. It should be understood that the examples supply various composition ranges of the flow, and that the total amount of isomers of a particular chemical composition may constitute the range.

[0085] 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 present 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".

[0086] 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 the recited quantitative values of a given property are contemplated in the present disclosure. If 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 process involves passing the catalyst through a combustor and heating the catalyst by burning an auxiliary fuel, wherein the auxiliary fuel contains methane in an amount of 1 mol% or more. This includes passing the catalyst from the combustor to the reactor so that at least a portion of the catalyst circulates continuously between the reactor and the combustor, The catalyst, 0.1% to 10% by weight of one or more metals selected from gallium, indium, thallium, or combinations thereof. One or more metals selected from platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof, with a power of 5 ppmW to 1000 ppmW. Iron with a power output of 100 ppmW to 30,000 ppmW, and a method comprising at least 85% by weight of a carrier.

2. 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. The method according to claim 1, further comprising passing the catalyst from the oxygen treatment zone to the reactor.

3. The method according to claim 2, wherein the catalyst is exposed to the oxygen-containing gas in the oxygen treatment zone for 8 to 20 minutes.

4. The method according to claim 1, wherein the auxiliary fuel contains at least 3 mol% of methane.

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

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

7. The catalyst, 0.1% to 10% by weight of gallium, and The method according to claim 1, comprising platinum in a strength of 5 ppmW to 1000 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 500 ppm W to 10,000 ppm W of iron.

10. The method according to claim 1, wherein the catalyst further comprises 0.01% to 2.5% 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 2.5% 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 iron in a strength of 500 ppmW to 8000 ppmW.

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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