Process for preparation of light olefins including catalyst modification

Abstract

A method may include operating a dehydrogenation process, whereby a hydrocarbon-containing feed is converted to light olefins, where the dehydrogenation process utilizes a fluidized process catalyst circulated between a reactor and a combustor. The method may include withdrawing the process catalyst from the dehydrogenation process, modifying the process catalyst to form a modified catalyst, and adding the modified catalyst back to the dehydrogenation process. The process catalyst may include 0.1 wt.% to 10 wt.% of one or more metals selected from gallium, indium, thallium, or a combination thereof, 1 ppmw to 1000 ppmw of one or more metals selected from platinum, palladium, rhodium, iridium, ruthenium, osmium, or a combination thereof, and at least 85 wt.% of a support. Modifying the process catalyst may include adding one or more of manganese, iron, chromium, or vanadium.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Application Serial No. 63 / 352,020, filed on June 14, 2022, which is hereby incorporated by reference in its entirety. Technical Field

[0003]

[0013] Various embodiments described herein relate generally to chemical processing and, more particularly, to methods and systems for producing light olefins. Background Art

[0004] Light olefins such as propylene can be used as substrate materials to produce many different materials, such as polypropylene, isopropanol and acrylic acid, which can be used for example for packaging, construction and textiles. As a result of this utility, there is a demand for light olefins worldwide. Suitable processes for producing light olefins generally depend on given chemical feeds and include those processes utilizing fluidized catalysts. For example, light olefins can be formed by the catalytic dehydrogenation of alkanes in a fluidized bed reactor. However, it is necessary to improve the system and related catalysts for the preparation of light olefins. Summary of the invention

[0005] Some methods and related systems for preparing light olefins can utilize a catalyst that can be circulated between a reactor and a burner, in which the light olefins are produced in an endothermic reaction, and in the burner, the catalyst is heated by the exothermic combustion of at least one supplementary fuel (sometimes accompanied by the combustion of coke). Such catalysts are not only catalytically active for the dehydrogenation of alkanes, but also catalytically active for the combustion of the supplementary fuel. Some embodiments of such suitable catalysts include, for example, gallium and platinum on a carrier. In some embodiments, compared with conventional catalysts that have not been used in dehydrogenation processes, conventional catalysts for dehydrogenation may experience a reduction in catalytic activity after use for a period of time. Such used catalysts may no longer fully catalyze the dehydrogenation of alkanes, the combustion of supplementary fuel, or both. As described herein, it has been found that, compared with conventional catalysts that are not modified by adding metals such as manganese, iron, chromium, or vanadium, a method for modifying a partially deactivated catalyst by adding metals such as manganese, iron, chromium, or vanadium can restore the catalytic activity, combustion activity, or both of the dehydrogenation of alkanes.

[0006] According to one or more embodiments of the present disclosure, a method may include operating a dehydrogenation process, thereby converting a hydrocarbon-containing feed into light olefins, wherein the dehydrogenation process utilizes a fluidized process catalyst that circulates between a reactor and a combustor. The method may also include extracting a process catalyst from the dehydrogenation process, modifying the process catalyst to form a modified catalyst, and adding the modified catalyst back into the dehydrogenation process. Wherein the process catalyst comprises 0.1wt.% to 10wt.% of one or more metals selected from gallium, indium, thallium or a combination thereof, 1ppmw to 1000ppmw of one or more metals selected from platinum, palladium, rhodium, iridium, ruthenium, osmium or a combination thereof, and at least 85wt.% of a carrier. Modification of the process catalyst may include adding one or more of manganese, iron, chromium, vanadium or aluminum.

[0007] It should be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to 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 set forth in the specific embodiments, and in part, will be readily apparent to those of ordinary skill in the art from the description, including the drawings and claims, or may be recognized by practicing the described embodiments. The drawings are included to provide a further understanding of the embodiments, and together with the specific embodiments, to explain the principles and operation of the claimed subject matter. However, the embodiments depicted in the drawings are illustrative and exemplary in nature, and are not intended to limit the claimed subject matter. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0009] Figure 1 depicts a flow chart including steps for preparing light olefins according to one or more embodiments of the present disclosure; and

[0010] Figure 2 A reactor system according to one or more embodiments of the present disclosure is schematically depicted.

[0011] When describing Figure 2 While the simplified schematic depiction of FIG. 1 does not include the many valves, temperature sensors, electronic controllers, etc. that may be used and are well known to those of ordinary skill in the art, are not included. Also, the accompanying components that are typically included in such reactor systems, such as air supply, heat exchangers, buffer tanks, etc., are not included. However, it should be understood that these components are within the scope of the present disclosure.

[0012] Reference will now be made in greater detail to various embodiments, some of which are illustrated in the accompanying drawings. DETAILED DESCRIPTION

[0013] The present disclosure relates to a method for preparing light olefins by dehydrogenation, which may include the following steps: such as operating a dehydrogenation process, extracting a process catalyst from the dehydrogenation process, modifying the process catalyst to form a modified catalyst, and adding the modified catalyst back into the dehydrogenation process. The process catalyst may contain 0.1wt.% to 10wt.% of one or more metals selected from gallium, indium, thallium or a combination thereof, 1ppmw to 1000ppmw of one or more metals selected from platinum, palladium, rhodium, iridium, ruthenium, osmium or a combination thereof, and at least 85wt.% of a carrier. As described herein, the modification of the process catalyst may include adding one or more of manganese, iron, chromium or vanadium. In one or more embodiments, such modified catalysts provide improved dual catalytic functions for the dehydrogenation of alkanes and the combustion of supplementary fuels. Such modified catalysts may be particularly suitable for fluidizing and dehydrogenating light alkanes into light olefins.

[0014] As described herein, modification of the process catalyst to a modified catalyst and its subsequent use in a dehydrogenation process can allow for continued use of the process catalyst that may still contain valuable materials such as platinum and gallium, etc. However, according to one or more embodiments, the addition of manganese, iron, chromium, or vanadium can enhance dehydrogenation activity, combustion activity, or both.

[0015] As used in this disclosure, the term "process catalyst" refers to a catalyst that has been used in a dehydrogenation process. A process catalyst may have a different composition than a fresh catalyst that has not been introduced into a dehydrogenation process. A modified catalyst is a process catalyst that has undergone modification as described herein and is typically reinserted into a dehydrogenation process.

[0016] refer to Figure 1 , showing steps of a method 100 for producing light olefins according to one or more embodiments described herein. Figure 1 Depicted in sequence are the steps of operating a dehydrogenation process 110, extracting a process catalyst 120, modifying the process catalyst to form a modified catalyst 130, and loading the modified catalyst back into the dehydrogenation process 140.

[0017] Step 110 generally comprises operating a dehydrogenation process. In the operation of the dehydrogenation process in step 110, the hydrocarbon-containing feed is converted into light olefins in the olefin-containing effluent. The dehydrogenation process in step 110 may be performed using, for example, Figure 2 As described herein, Figure 1 The steps are sometimes Figure 2 It should be understood that when describing Figure 2 When describing systems and related methods, the term "catalyst" may refer to either a process catalyst or a modified catalyst unless otherwise specified. Typically, process catalysts and modified catalysts are referred to as Figure 2 The movement and fluidization of the system are the same.

[0018] This article will now focus on a process for operating a fluidized dehydrogenation reactor system to produce light olefins such as propylene. Figure 2 Embodiments of the disclosed methods are described in detail in the context of a reactor system for a reactor system. However, it should be understood that the principles disclosed and taught herein can be applied to other systems utilizing different system components oriented in different ways. For example, the concepts described herein can be equally applied to other systems having alternative reactor units and regeneration units, such as those operating under non-fluidized conditions, or those systems containing downcomers instead of risers. It should also be understood that not all systems are designed to be fluidized. Figure 2 All parts of the claims should be interpreted as being essential to the claimed subject matter. In addition, although the method steps listed in the appended claims are herein Figure 2 Although described in the context of the present invention, such enumerated method steps should be understood to be applicable to other systems, as understood by those skilled in the art.

[0019] Reference now Figure 2 , schematically depicts an exemplary reactor system 102 that may be suitable for use with the methods and / or apparatus described herein. The 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, a "system component" refers to a portion of the reactor system 102, such as a reactor, a separator, a transfer line, a combination thereof, and the like. As used herein, Figure 2 As used in the context of , reactor section 200 generally refers to the portion of reactor system 102 where the primary process reaction (e.g., dehydrogenation) occurs to form an olefin-containing effluent. A hydrocarbon-containing feed enters reactor section 200, contacts the catalyst, is converted into an olefin-containing effluent (containing product and unreacted feed), and exits reactor section 200. Reactor section 200 includes reactor 202, which may include an upstream reactor section 250 and a downstream reactor section 230. According to one or more embodiments, as Figure 2As depicted, the reactor section 200 can additionally include a catalyst separation section 210 for separating the catalyst from the olefin-containing effluent formed in the reactor 202. Additionally, as used herein, the catalyst treatment section 300 generally refers to a portion of the reactor system 102 in which the catalyst is treated in some manner, such as by combustion, to improve catalytic activity, for example, by decoking and / or heating the catalyst. The catalyst treatment section 300 can include a burner 350 and a riser 330, and can additionally include a catalyst separation section 310. In one or more embodiments, the catalyst separation section 210 can be in fluid communication with the burner 350 (e.g., via a standpipe 426), and the catalyst separation section 310 can be in fluid communication with the upstream reactor section 250 (e.g., via a standpipe 424 and a transport riser 430).

[0020] Generally, as described in this article, Figure 2 In the embodiment shown, the catalyst circulates between the reactor section 200 and the catalyst treatment section 300. It should be understood that when "catalyst" is mentioned in this article, 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 the catalyst can catalyze the reaction carried out in the reactor system 102. The catalyst leaving the reactor section 200 can be a deactivated catalyst. As used herein, "deactivated" can refer to a catalyst with reduced catalytic activity or cooler than the catalyst entering the reactor section 200. However, the deactivated catalyst can retain some catalytic activity. The reduced catalytic activity can be caused by contamination of substances such as coke. Coke can be formed on the catalyst in the reactor section 200. Reactivation (sometimes referred to as "regeneration" in this article) can remove pollutants such as coke, increase 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 not limited to, removing coke by combustion, oxidizing the catalyst, other reactivation processes, or a combination thereof. In some embodiments, the catalyst may be heated during reactivation by burning a supplemental fuel such as methane, ethane, propane, natural gas, or a combination thereof. The reactivated catalyst from the catalyst treatment section 300 is then transferred back to the reactor section 200.

[0021] In a non-limiting example, the reactor system 102 described herein can be used to produce light olefins from a hydrocarbonaceous feed. According to one or more embodiments, the reaction can be a dehydrogenation reaction. According to such embodiments, the hydrocarbonaceous feed can include one or more of ethane, propane, normal butane and isobutane. In one or more embodiments, the hydrocarbonaceous feed can include at least 50wt.%, at least 60wt.%, at least 70wt.%, at least 80wt.%, at least 90wt.%, at least 95wt.% or even at least 99wt.% of ethane. In other embodiments, the hydrocarbonaceous feed can include at least 50wt.%, at least 60wt.%, at least 70wt.%, at least 80wt.%, at least 90wt.%, at least 95wt.% or even at least 99wt.% of propane. In other embodiments, the hydrocarbon-containing feed can comprise at least 50wt.%, at least 60wt.%, at least 70wt.%, at least 80wt.%, at least 90wt.%, at least 95wt.% or even at least 99wt.% of normal butane. In other embodiments, the hydrocarbon-containing feed can comprise at least 50wt.%, at least 60wt.%, at least 70wt.%, at least 80wt.%, at least 90wt.%, at least 95wt.% or even at least 99wt.% of isobutane. In other embodiments, the hydrocarbon-containing feed can comprise at least 50wt.%, at least 60wt.%, at least 70wt.%, at least 80wt.%, at least 90wt.%, at least 95wt.% or even at least 99wt.% of the sum of ethane, propane, normal butane and isobutane.

[0022] In one or more embodiments, the process catalyst may include, consist essentially of, or consist of one or more of gallium, indium, or thallium, one or more of platinum, palladium, rhodium, iridium, ruthenium, or osmium, and a support. As described herein, "consisting essentially of" means a material having less than 1 wt.% of an unrecited material (i.e., consisting essentially of A and B means that the combination of A and B constitutes at least 99 wt.% of the composition). As described herein, the catalyst may be a solid particle suitable for fluidization.

[0023] In one or more embodiments, the process catalyst can include 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 process catalyst. Such materials can catalyze the dehydrogenation of alkanes to olefins, particularly when used in combination with one or more of platinum, palladium, rhodium, iridium, ruthenium, or osmium. For example, the process catalyst may include 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 include one or more of gallium, indium or thallium in an amount of 0.1wt.% to 9wt.%, 0.1wt.% to 8wt.%, 0.1wt.% to 7wt.%, 0.1wt.% to 6wt.% or 0.1wt.% to 5wt.%. In some embodiments, the process catalyst contains only gallium but not indium or thallium, only indium but not gallium or thallium, or only thallium but not gallium or indium. It should be understood that the composition range describing the amount of gallium, indium and thallium represents the range of any one of these materials or the combination of these materials. Without being bound by theory, it is believed that the composition having an amount of less than 0.1wt.% of one or more of gallium, indium or thallium negatively affects the ability of the process catalyst to catalyze the dehydrogenation process of alkanes by reducing both the percentage of total dehydrogenated alkanes and the percentage of dehydrogenated alkanes as the expected product. However, it is believed that compositions having one or more of gallium, indium, or thallium in an amount exceeding 10 wt. % may negatively affect the ability of the catalyst to catalyze an alkane dehydrogenation process, negatively affect the selectivity of the catalyst to the desired product, or both.

[0024] In one or more embodiments, based on the total mass of the process catalyst, the process catalyst may include one or more of platinum, palladium, rhodium, iridium, ruthenium or osmium in an amount of 5ppmw to 1000ppmw. Such materials can catalyze the dehydrogenation of alkanes to olefins, particularly when used in combination with one or more of gallium, indium or thallium. For example, the process catalyst may include one or more of platinum, palladium, rhodium, iridium, ruthenium or osmium in an amount of 5ppmw to 50ppmw, 50ppmw to 100ppmw, 100ppmw to 200ppmw, 200ppmw to 300ppmw, 300ppmw to 400ppmw, 400ppmw to 500ppmw, 500ppmw to 600ppmw, 600ppmw to 700ppmw, 700ppmw to 800ppmw, 800ppmw to 900ppmw, 900ppmw to 1000ppmw or any combination of these ranges. In some embodiments, the process catalyst may include 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 700 ppmw, 5 ppmw to 600 ppmw, 5 ppmw to 500 ppmw, or 10 ppmw to 400 ppmw. In some embodiments, the process catalyst includes only platinum but not palladium, rhodium, iridium, ruthenium, or osmium, only palladium but not platinum, rhodium, iridium, ruthenium, or osmium, only rhodium but not platinum, palladium, iridium, ruthenium, or osmium, only iridium but not platinum, palladium, rhodium, ruthenium, or osmium, only ruthenium but not platinum, palladium, rhodium, iridium, or osmium, or only osmium but not platinum, palladium, rhodium, iridium, or ruthenium. It should be understood that the composition range describing the amount of platinum, palladium, rhodium, iridium, ruthenium and osmium represents the range of any one of these materials or the combination of these materials. Without being bound by theory, it is believed that the composition with an amount less than one or more of the platinum, palladium, rhodium, iridium, ruthenium or osmium of 5ppmw negatively affects the ability of the process catalyst to catalyze the alkane dehydrogenation process by reducing the percentage of total dehydrogenated alkanes and the percentage of dehydrogenated alkanes as the expected product. However, it is believed that the composition with an amount exceeding one or more of the platinum, palladium, rhodium, iridium, ruthenium or osmium of 1000ppmw can negatively affect the ability of the catalyst to catalyze the alkane dehydrogenation process, negatively affect the selectivity of the catalyst to the expected product, or both.

[0025] 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, alumina containing silica, alumina containing zirconium oxide, alumina containing titania, and alumina containing lanthanum. Relative to the gross weight of the catalyst, the carrier may be present in an amount of at least 85wt.%, such as at least 85wt.%, at least 90wt.%, or at least 95wt.%. In some embodiments, the carrier accounts for less than or equal to 99.5wt.% of the catalyst. Typically, the wt.% of the carrier can fill the remainder of the entire catalyst that is not specified by other materials.

[0026] In one or more embodiments, the process catalyst can optionally include 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 mass of the catalyst. For example, the process catalyst can include 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 of one or more alkali metals, one or more alkaline earth metals, or both. In some embodiments, the process catalyst may contain 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.% of one or more alkali metals, one or more alkaline earth metals, or both. In some embodiments, the one or more alkali metals or one or more alkaline earth metals may be potassium. Without being bound by theory, it is believed that compositions having an alkali metal or alkaline earth metal in an amount less than 0.01 wt.% may cause undesirable products to be produced during the dehydrogenation reaction. However, it is believed that compositions having an alkali metal or alkaline earth metal in an amount exceeding 2.5 wt.% may reduce the dehydrogenation activity of the catalyst.

[0027] In one or more embodiments, based on the total mass of catalyst, process catalyst can include one or more of the iron or manganese of 100ppmw to 5000ppmw in combination amount.For example, process catalyst can contain one or more of the iron or manganese of 100ppmw to 500ppmw, 500ppmw to 1000ppmw, 1000ppmw to 2000ppmw, 2000ppmw to 3000ppmw, 3000ppmw to 4000ppmw, 4000ppmw to 5000ppmw or any combination of these ranges.In some embodiments, process catalyst can include iron but not include manganese or can include manganese but not include iron.Not bound by theory, it is believed that the composition with the iron or manganese content exceeding 5000ppmw in amount can negatively affect the alkane dehydrogenation performance of catalyst.However, it is believed that the composition with the iron or manganese content less than 100ppmw in amount may not be enough to improve the alkane dehydrogenation performance of catalyst.In some embodiments, process catalyst can be free of one or more of iron or manganese.

[0028] In one or more embodiments, the process catalyst may include solid particles capable of fluidization. In some embodiments, the process catalyst may exhibit characteristics known in the industry as "Geldart A" or "Geldart B" characteristics. According to D. Geldart, "Gas Fluidization Technology", John Wiley & Sons (New York, 1986), pp. 34-37; and D. Geldart, "Types of Gas Fluidization", Powder Technol. 7 (1973) 285-292, the disclosure of which is incorporated herein by reference in its entirety, catalyst types may be classified as "Group A" or "Group B".

[0029] The Geldart A group is understood by those skilled in the art to represent aerated powders with fluidization in the bubble-free range; high bed expansion; slow and linear degassing rates; bubble characteristics, which may include a predominance of splitting / recoalescing bubbles, with maximum bubble size and large wakes; high levels of solid mixing and gas backmixing, assuming that U-umf are equal (U is the velocity of the carrier gas, and Umf is the minimum fluidizing velocity, usually but not necessarily measured in meters per second (m / s), i.e., excessive gas velocities exist); axisymmetric lump characteristics; and no spurting except in very shallow beds. The listed characteristics tend to improve with decreasing average particle size, assuming that The particles may be equal; or increase with a ratio of <45 microns (μm); or increase with the pressure, temperature, viscosity and density of the gas. In general, the particles may exhibit a small average particle size and / or a low particle density (<1.4 g / cm3, g / cm 3 ); easy fluidization, with smooth fluidization at low gas velocities; and controlled bubbling with small bubbles can be exhibited at higher gas velocities.

[0030] The Geldart B group is understood by those skilled in the art to represent "sand-like" powders that begin bubbling at Umf; that exhibit moderate bed expansion; rapid degassing; no restrictions on bubble size; moderate levels of solid mixing and gas backmixing, assuming equal U-umf; both axisymmetric and asymmetric lumps; and spurting only in shallow beds. These properties tend to improve as the average particle size decreases, but the particle size distribution and some uncertainty in the gas, pressure, temperature, viscosity or density appear to play little role in improving these properties. In general, when the density (ρp) is 1.4<ρp<4 g / cm 3 When the particle size of most particles is for

[0031] Still refer to it again Figure 2 , a hydrocarbon-containing feed can enter feed inlet 434, enter reactor 202, and an olefin-containing effluent can exit reactor system 102 via pipe 420. According to one or more embodiments, reactor system 102 can be operated by feeding a hydrocarbon-containing feed (e.g., in a feed stream) and a fluidized catalyst into an upstream reactor section 250. The hydrocarbon-containing feed contacts the catalyst in the upstream reactor section 250, and each hydrocarbon-containing feed flows upwardly into and through the downstream reactor section 230 to produce an olefin-containing effluent.

[0032] Now refer to the detailed Figure 2 , the reactor portion 200 may include an upstream reactor section 250, a transition section 258, and a downstream reactor section 230, such as a riser. The transition section 258 may connect the upstream reactor section 250 with the downstream reactor section 230. Figure 1 As depicted, the upstream reactor section 250 can be positioned 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 can include a container, a drum, a barrel, a barrel, or other container suitable for a given chemical reaction. Figure 2As depicted, the upstream reactor section 250 may be connected to the downstream reactor section 230 via a transition section 258. The upstream reactor section 250 may generally include a larger cross-sectional area than the downstream reactor section 230. The transition section 258 may taper from the size of the cross-section of the upstream reactor section 250 to the size of the cross-section of the downstream reactor section 230 such that the transition section 258 protrudes inwardly from the upstream reactor section 250 to the downstream reactor section 230. For example, the transition section 258 may be a frustum.

[0033] The upstream reactor section 250 can be connected to a transfer riser 430, which in operation can provide the reactivated catalyst in the feed stream to the reactor portion 200. The reactivated catalyst and / or reactant chemicals can be mixed with a distributor 260 contained in the upstream reactor section 250. Catalyst entering the upstream reactor section 250 via the transfer riser 430 can be transferred to the transfer riser 430 via a standpipe 424, thereby arriving from the catalyst treatment section 300. In some embodiments, catalyst can enter the transfer riser 430 directly from the catalyst separation section 210 via a standpipe 422, wherein the catalyst enters the upstream reactor section 250, wherein in such embodiments, some of the catalyst is not transferred through the catalyst treatment section 300. Catalyst can also be fed directly to the upstream reactor section 250 via the standpipe 422 (at Figure 2 250). This catalyst may be somewhat deactivated, but in some embodiments may still be suitable for reaction in the upstream reactor section 250, particularly when used in combination with a reactivated catalyst.

[0034] In one or more embodiments, the residence time of the catalyst in the reactor portion 200 may be less than or equal to 3 minutes. As used herein, the term "residence time" refers to the average amount of time that the catalyst or other specified material spends in the reactor portion 200. Because the residence time is an average value, the amount of time that the catalyst can spend in the reactor portion 200 during any given cycle may have a certain distribution and may not be equal to the average value, but will average about the residence time over time. In some embodiments, the residence time of the catalyst in the reactor portion 200 may be less than or equal to 2.5 minutes, less than or equal to 2 minutes, less than or equal to 1.5 minutes, less than or equal to 1 minute, less than or equal to 0.5 minutes or less than or equal to 0.1 minutes. Without being bound by theory, it is believed that a catalyst residence time greater than 3 minutes can increase equipment costs without a matching increase in catalyst dehydrogenation performance. However, it is believed that a catalyst residence time less than 0.1 minutes may not allow the catalyst to fully catalyze the dehydrogenation reaction.

[0035] Still refer to Figure 2In one or more embodiments, based on the shapes, dimensions, and other process conditions (such as temperature and pressure) in the upstream reactor section 250 and the downstream reactor section 230, the upstream reactor section 250 can be operated as a fluidized bed, such as in a fast fluidized, turbulent, or bubbling bed flow reactor, while the downstream reactor section 230 can be operated in a more plug flow manner, such as in a riser reactor. For example, Figure 2 The reactor 202 may include an upstream reactor section 250 operated as a fast fluidization, turbulent or bubbling bed reactor and a downstream reactor section 230 operated as a dilute phase riser reactor, resulting in an average catalyst and gas flow moving upward simultaneously. As used herein, the term "average flow" refers to the net flow, i.e., the total upward flow minus the reverse or reverse flow, which is generally the typical behavior of fluidized particles. As described herein, a "fast fluidization" reactor may refer to a reactor utilizing a fluidization scheme in which the superficial velocity of the gas phase is greater than the choke velocity and can be semi-dense in operation. As described herein, a "turbulent" reactor may refer to a fluidization scheme in which the superficial velocity is less than the choke velocity and is denser than a fast fluidization scheme. As described herein, a "bubbling bed" reactor may refer to a fluidization morphology in which well-defined bubbles in a high-density bed are present in two well-divided phases. "Choke 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 operated at the above-mentioned choke velocity.

[0036] According to embodiments, the olefin-containing effluent and catalyst may be passed from the downstream reactor section 230 to a separation device 220 in the catalyst separation section 210 where the catalyst is at least partially separated from the olefin-containing effluent that is conveyed from the catalyst separation section 210. After the catalyst is separated from the vapor in the separation device 220, the catalyst may generally move through a stripper 224 to a catalyst outlet port 222 where the catalyst is transferred out of the reactor portion 200 via a standpipe 426 and into the catalyst treatment section 300, according to one or more embodiments.

[0037] According to one or more embodiments, the separation device 220 may be a cyclonic separation system, which may include two or more stages of cyclonic separation. In the embodiment where the separation device 220 includes more than one cyclonic separation stage, the first separation device in which the fluidized stream enters is referred to as a primary cyclonic separation device. The fluidized effluent from the primary cyclonic separation device can enter a secondary cyclonic separation device for further separation. The primary cyclonic separation device may include, for example, a primary cyclonic separator and a system commercially available under the name VSS (commercially available from UOP), LD2 (commercially available from Stone and Webster) and RS2 (commercially available from Stone and Webster). Primary cyclonic separators are described in, for example, U.S. Patents 4,579,716, 5,190,650 and 5,275,641, each of which is incorporated herein by reference in its entirety. In some separation systems utilizing a primary cyclone separator as a primary cyclone separation device, one or more additional cyclone separators, e.g., a secondary cyclone separator and a tertiary cyclone separator, are used to further separate the catalyst from the product gas. It should be understood that any primary cyclone separation device may be used in embodiments of the present disclosure.

[0038] Still refer to Figure 2 , the separated catalyst is transferred from the catalyst separation section 210 to the burner 350. In the burner 350, the catalyst can be treated by, for example, burning coke with oxygen. For example, but not limited to, the catalyst can be decoked and / or supplementary fuel can be burned to heat the catalyst. Then, the catalyst is transferred from the burner 350 and passed through the riser 330 to the riser terminal separator 378, where the gas and solid components from the riser 330 are at least partially separated. The steam and the remaining solids are transported to the secondary separation device 320 in the catalyst separation section 310, where the remaining catalyst is separated from the gas from the catalyst treatment (for example, the gas emitted by burning the spent catalyst or supplementary fuel, referred to as flue gas in this article). The flue gas can be transferred from the catalyst treatment section 300 via the outlet pipe 432. The separated catalyst is then transferred to the upstream reactor section 250 via the vertical pipe 424 and the transport riser 430 through the oxygen treatment zone 370 in the catalyst separation section 310, where the catalyst is further used for catalytic reaction. Thus, the catalyst may be circulated during operation between the reactor section 200 and the catalyst treatment section 300. Generally speaking, the processed chemical stream comprising the hydrocarbon-containing feed and the olefin-containing effluent may be gaseous, and the catalyst may be a fluidized particulate solid.

[0039] Referring now to the catalyst treatment section 300, as shown Figure 2As depicted, the burner 350 of the catalyst treatment section 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 (e.g., air) may be delivered to the burner 350 via a pipe 428. The burner 350 may be in fluid communication with the catalyst separation section 210 via a riser 426, which may supply spent catalyst from the reactor section 200 to the catalyst treatment section 300 for regeneration. The burner 350 and the riser 330 (collectively referred to as the catalyst combustion reactor 302) may be operated in a fluidized manner similar to or the same as disclosed with respect to the upstream reactor section 250 and the downstream reactor section 230 of the reactor section 200. That is, the burner 350 may be operated as a fluidized bed, such as in a fast fluidized, turbulent, or bubbling bed flow reactor, while the riser 330 may be operated in a more plug flow manner, such as in a riser reactor. The geometries as described with respect to the upstream reactor section 250 and the downstream reactor section 230 may be equally applicable to the burner 350 and the riser 330. In addition, the burner 350 may also include a fuel inlet 354 that may supply a fuel, such as a hydrocarbon stream, to the burner 350.

[0040] As described herein, the catalyst can be heated by the combustion of a supplemental fuel in the catalyst treatment section 300. The supplemental fuel can be burned with oxygen and a supplemental fuel to heat the catalyst, such as a supplemental fuel such as hydrogen, methane, ethane, propane, natural gas, or a combination thereof. Without being bound by any theory, when methane is used in the supplemental fuel, a catalyst that has been modified as described herein can better catalyze the combustion of methane to heat the catalyst. When methane is used in the supplemental fuel, an unmodified catalyst may be defective by not promoting the heating of the catalyst to the temperature required for dehydrogenation.

[0041] As described in one or more embodiments, after the catalyst is separated from the flue gas in the riser terminal separator 378 and the secondary separation device 320, the processed 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 may include a baffle or a grid structure to promote contact between the processed catalyst and the oxygen-containing gas. Examples of fluid-solid contact devices are further described in detail in U.S. Patents Nos. 9,827,543 and 9,815,040. The fluidization mode in the oxygen treatment zone can be a bubbling bed type fluidization. The oxygen treatment zone 370 may include an oxygen-containing gas inlet 372, which can supply oxygen-containing gas to the oxygen treatment zone 370 for oxygen treatment of the catalyst.

[0042] As disclosed herein, in one or more embodiments, the catalyst can be exposed to oxygen-containing gas in oxygen treatment zone 370. For example, the catalyst can be exposed to oxygen-containing gas for 2 minutes to 20 minutes, such as 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 can be exposed to oxygen-containing gas for 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 exposing the catalyst to oxygen-containing gas for more than 20 minutes can increase equipment costs without the matching increase of catalyst regeneration efficiency. However, it is believed that exposure to oxygen-containing gas less than 2 minutes can lead to less efficient regeneration of the catalyst, which can reduce the dehydrogenation activity of the catalyst.

[0043] In one or more embodiments, light olefins may be present in a "product stream" sometimes referred to as an "olefin-containing effluent" and include light olefins. Figure 2 The reactor system 102 of the present invention can be processed subsequently. As used in the present disclosure, the term "light olefins" refers to one or more of ethylene, propylene and butene. The term butene includes any butene isomers, such as α-butene, cis-β-butene, trans-β-butene and isobutylene. In some embodiments, based on the gross weight of the olefin-containing effluent, the olefin-containing effluent comprises at least 25wt.% of light olefins. For example, based on the gross weight of the olefin-containing effluent, the olefin-containing effluent can comprise at least 35wt.% of light olefins, at least 45wt.% of light olefins, at least 55wt.% of light olefins, at least 65wt.% of light olefins or at least 75wt.% of light olefins. The olefin-containing effluent can also include unreacted components of the hydrocarbon-containing effluent and other reaction products that are not considered to be light olefins. The light olefins can be separated from the unreacted components in the subsequent separation step.

[0044] Now refer to it again Figure 1 , step 120 typically includes extracting the process catalyst from the dehydrogenation process. Over time, the process catalyst may degrade when used in the dehydrogenation process. This degradation may include the loss of catalytically active components such as palladium or platinum in the process catalyst or the deactivation of the catalytic components of the process catalyst. For conventional catalysts, this loss of catalytic material will eventually require the replacement of the process catalyst with a fresh catalyst. Replacing the process catalyst with a fresh catalyst may be wasteful because many components of the process catalyst (such as catalytic materials and carriers) remain functional. As will be described herein, modification of the process catalyst may allow the reuse of functional catalyst materials, which can reduce the generation of waste.

[0045] In one or more embodiments, the extraction of process catalyst can be performed in batches such that the dehydrogenation process is stopped and a significant portion of the process catalyst present during the dehydrogenation process is removed. For example, the amount of catalyst extracted can be at least 5% of the total catalyst present, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or even 100% of the total catalyst present can be extracted.

[0046] In one or more embodiments, the process catalyst is continuously extracted. As used in this disclosure, the term "continuous extraction" means that extraction of the process catalyst occurs such that some process catalyst is continuously extracted from the dehydrogenation process so that the dehydrogenation process does not need to be stopped in order to extract the process catalyst. For example, continuous extraction can be achieved by installing a catalyst extraction system (such as the Johnson Matthey INTERCAT TM The amount of process catalyst continuously withdrawn and added back to the dehydrogenation process is determined by measuring the catalyst loss from the unit due to mechanical wear and the performance rate of the process catalyst as it ages, so the process catalyst can be continuously withdrawn to maintain performance. In some embodiments, when the process catalyst is continuously withdrawn, at least 0.05% of the process catalyst can be withdrawn from the dehydrogenation process. For example, at least 0.1% of the process catalyst can be withdrawn from the dehydrogenation process, at least 0.25% of the process catalyst, at least 0.5% of the process catalyst, at least 1.0% of the process catalyst, at least 1.5% of the process catalyst, at least 2.0% of the process catalyst, at least 2.5% of the process catalyst, at least 3.0% of the process catalyst, at least 3.5% of the process catalyst, at least 4.0% of the process catalyst, at least 4.5% of the process catalyst, or even up to 5.0% of the process catalyst can be continuously withdrawn.

[0047] In one or more embodiments, the process catalyst may be withdrawn when the dehydrogenation or combustion activity decreases such that the target productivity (e.g., olefin production rate) or combustion activity can no longer be achieved by adding fresh catalyst to compensate for mechanical losses of catalyst from the unit or by applying high severity operating conditions such as higher reaction temperatures, higher regeneration temperatures, or changing the catalyst to oil ratio. For example, the process catalyst may be withdrawn when the combustion activity is insufficient to reach at least 5% of the lower flammable limit (LFL), at least 10% of the LFL, at least 20% of the LFL, or at least 40% of the LFL, or the process catalyst may be withdrawn in batches when the productivity drops to 95% of the nameplate productivity, 90% of the nameplate productivity, 85% of the nameplate productivity, or 80% of the nameplate productivity. As used in this disclosure, the term "lower flammable limit" refers to the lower limit of the concentration range of a flammable mixture of gas or vapor in air that can be ignited at a given temperature and pressure. The LFL of the combustion gases may be determined by reactive chemistry testing, or as described by Michael G. Zabetakis, Flammability Characteristics of Combustible Gases and Vapors, 627 Bureau of Mines 1 (1965), with the pressure adjusted according to Coward et al., Limits of Flammability of Gases and Vapors, 503 Bureau of Mines 1 (1952). In some embodiments, when mechanical losses of catalyst are low and thus do not provide sufficient replacement space to allow catalyst to be added to compensate for the loss of dehydrogenation and combustion activity, catalyst may be intentionally withdrawn from the unit on a routine basis to provide replacement space to allow catalyst addition.

[0048] In one or more embodiments, the process catalyst can be withdrawn after being used in the dehydrogenation process for a given amount of time. For example, the process catalyst can be withdrawn after at least 6 months of the dehydrogenation process cycle, such as after at least 2 weeks, at least 1 month, at least 2 months, at least 3 months, at least 4 months, at least 5 months, at least 7 months, at least 8 months, at least 9 months, at least 10 months, at least 11 months, or at least 1 year.

[0049] Now refer to it again Figure 1, step 130 generally includes modifying the process catalyst to form a modified catalyst. As used in this disclosure, the term "modified catalyst" refers to a process catalyst that has been modified by adding one or more metals. In one or more embodiments, the process catalyst can be modified by adding one or more of manganese, iron, chromium, vanadium, or aluminum to the process catalyst to form a modified catalyst.

[0050] In one or more embodiments, based on the gross mass of the modified catalyst, the modified catalyst may include an amount of manganese of 100ppmw to 5000ppmw. For example, the modified catalyst may include an amount of manganese of 100ppmw to 500ppmw, 500ppmw to 1000ppmw, 1000ppmw to 2000ppmw, 2000ppmw to 3000ppmw, 3000ppmw to 4000ppmw, 4000ppmw to 5000ppmw or any combination of these ranges. In some embodiments, the modified catalyst may include an amount of manganese of 500ppmw to 4500ppmw, 750ppmw to 4000ppmw, 1000ppmw to 3500ppmw or 1500ppmw to 3000ppmw. Without wishing to be bound by theory, it is believed that compositions having manganese in an amount exceeding 5000 ppmw may negatively 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 as desired products. However, it is believed that compositions having manganese in an amount less than 100 ppmw may not be sufficient to restore alkane conversion and fuel gas combustion activity when compared to an unmodified process catalyst.

[0051] In one or more embodiments, based on the gross mass of modified catalyst, modified catalyst can include the iron of 100ppmw to 5000ppmw.For example, modified catalyst can include the iron of 100ppmw to 500ppmw, 500ppmw to 1000ppmw, 1000ppmw to 2000ppmw, 2000ppmw to 3000ppmw, 3000ppmw to 4000ppmw, 4000ppmw to 5000ppmw or any combination of these scopes.In some embodiments, modified catalyst can include the iron of 500ppmw to 4500ppmw, 750ppmw to 4000ppmw, 1000ppmw to 3500ppmw or 1500ppmw to 3000ppmw.Not bound by theory, it is believed that when compared with unmodified process catalyst, the composition with the iron of amount less than 100ppmw may be insufficient to recover alkane conversion and fuel gas combustion activity. However, it is believed that compositions having iron in an amount exceeding 5000 ppmw may negatively affect the ability of the catalyst to catalyze an alkane dehydrogenation process, negatively affect the selectivity of the catalyst to the desired product, or both.

[0052] In one or more embodiments, based on the gross mass of modified catalyst, modified catalyst can include the chromium of 100ppmw to 5000ppmw.For example, modified catalyst can include the chromium of 100ppmw to 500ppmw, 500ppmw to 1000ppmw, 1000ppmw to 2000ppmw, 2000ppmw to 3000ppmw, 3000ppmw to 4000ppmw, 4000ppmw to 5000ppmw or any combination of these scopes.In some embodiments, modified catalyst can include the chromium of 500ppmw to 4500ppmw, 750ppmw to 4000ppmw, 1000ppmw to 3500ppmw or 1500ppmw to 3000ppmw.Not bound by theory, it is believed that when compared with unmodified process catalyst, the composition with the chromium of amount less than 100ppmw may not be enough to recover alkane conversion and fuel gas combustion activity. However, it is believed that compositions having chromium in an amount exceeding 5000 ppmw may negatively affect the ability of the catalyst to catalyze an alkane dehydrogenation process, negatively affect the selectivity of the catalyst to the desired product, or both.

[0053] In one or more embodiments, based on the gross mass of the modified catalyst, the modified catalyst can include an amount of 1ppmw to 2000ppmw vanadium. For example, the modified catalyst can include an amount of 1ppmw to 100ppmw, 100ppmw to 500ppmw, 500ppmw to 1000ppmw, 1000ppmw to 1500ppmw, 1500ppmw to 2000ppmw or any combination of these scopes. In some embodiments, the modified catalyst can include an amount of 100ppmw to 1900ppmw, 500ppmw to 1800ppmw, 750ppmw to 1700ppmw, 1000ppmw to 1600ppmw, 1100ppmw to 1500ppmw, 1200ppmw to 1450ppmw or 1300ppmw to 1400ppmw vanadium. Without being bound by theory, it is believed that compositions having less than 1 ppmw of vanadium may not be sufficient to restore alkane conversion and fuel gas combustion activity when compared to an unmodified process catalyst. However, it is believed that compositions having more than 2000 ppmw of vanadium may negatively affect the ability of the catalyst to catalyze the alkane dehydrogenation process, negatively affect the selectivity of the catalyst to the desired product, or both.

[0054] In one or more embodiments, based on the total mass of the modified catalyst excluding aluminum in the form of aluminum oxide that may be present as part of the support, the modified catalyst may include an amount of 0.5 wt.% to 10 wt.% aluminum. For example, the modified catalyst may include 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.%, 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 of aluminum. In some embodiments, the modified catalyst may include an amount of 0.75 wt.% to 8 wt.%, 1 wt.% to 7 wt.%, 1.5 wt.% to 6 wt.%, or 2 wt.% to 5 wt.% aluminum. Without being bound by theory, it is believed that compositions having an amount of less than 0.5 wt.% aluminum may not be sufficient to restore alkane conversion and fuel gas combustion activity when compared to an unmodified process catalyst. However, it is believed that compositions having an amount of more than 10 wt.% aluminum may negatively affect the ability of the catalyst to catalyze the alkane dehydrogenation process, negatively affect the selectivity of the catalyst to the desired product, or both.

[0055] In one or more embodiments, the process catalyst may be modified by adding one or more of platinum or gallium to produce a modified catalyst. In some embodiments, one or more of platinum or gallium may be added to the process catalyst in addition to one or more of manganese, iron, chromium, vanadium, or aluminum. For example, in some embodiments, the process catalyst may be modified by adding platinum and iron; platinum and manganese; platinum and chromium; platinum and vanadium; platinum and aluminum; gallium and iron; gallium and manganese; gallium and chromium; gallium and vanadium; gallium and aluminum; platinum, gallium and iron; platinum, gallium and manganese; platinum, gallium and chromium; platinum, gallium and vanadium; or platinum, gallium and aluminum.

[0056] In one or more embodiments, based on the gross mass of the modified catalyst, the modified catalyst may include an amount of 5ppmw to 1000ppmw of platinum. For example, the modified catalyst may include an amount of 5ppmw to 50ppmw, 50ppmw to 100ppmw, 100ppmw to 200ppmw, 200ppmw to 300ppmw, 300ppmw to 400ppmw, 400ppmw to 500ppmw, 500ppmw to 600ppmw, 600ppmw to 700ppmw, 700ppmw to 800ppmw, 800ppmw to 900ppmw, 900ppmw to 1000ppmw or any combination of these ranges of platinum. In some embodiments, the modified catalyst may include an amount of 5ppmw to 900ppmw, 5ppmw to 800ppmw, 5ppmw to 600ppmw, 5ppmw to 500ppmw or 10ppmw to 400ppmw of platinum. Without being bound by theory, it is believed that compositions having platinum in an amount less than 5 ppmw negatively impact the ability of the catalyst to catalyze an alkane dehydrogenation process by reducing both the percentage of total dehydrogenated alkanes and the percentage of dehydrogenated alkanes that are desired products. However, it is believed that compositions having platinum in an amount greater than 1000 ppmw may negatively impact the ability of the catalyst to catalyze an alkane dehydrogenation process, negatively impact the selectivity of the catalyst to the desired product, or both.

[0057] In one or more embodiments, the modified catalyst can include gallium in an amount of 0.1 wt.% to 10 wt.%, based on the total mass of the modified catalyst. For example, the modified catalyst can include gallium 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 modified catalyst may include 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.%. Without being bound by theory, it is believed that compositions with an amount of less than 0.1 wt.% of gallium negatively 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 as the desired product. However, it is believed that compositions with an amount of more than 10 wt.% of gallium may negatively affect the ability of the catalyst to catalyze the alkane dehydrogenation process, negatively affect the selectivity of the catalyst to the desired product, or both.

[0058] In one or more embodiments, the process catalyst can be modified via incipient wetness impregnation (also known as dry impregnation or capillary impregnation) to form a modified catalyst. For example, such a process is described in Marceau et al., Impregnation and Drying, Synthesis of Solid Catalysts 59 (2008), which is incorporated herein by reference in its entirety. For example, a process catalyst can be impregnated with a metal precursor, then dried at a temperature below 200° C., and then calcined at a temperature below 800° C. to produce a catalyst. For example, in some embodiments, a process catalyst can be modified to form a modified catalyst by impregnating the process catalyst with one or more of gallium, platinum, iron, manganese, chromium, vanadium, or aluminum, drying the support, and calcining the support. In addition, as will be appreciated by those skilled in the art, other suitable methods for preparing the catalyst as described herein are contemplated.

[0059] Reference again Figure 1, step 140 generally includes adding the modified catalyst back into the dehydrogenation process. The modified catalyst can then be recycled through the steps of the method for producing light olefins 100 by being used in step 110 to become a process catalyst, withdrawn in step 120, modified in step 130 to become a modified catalyst, and added back into the dehydrogenation process in step 140.

[0060] Example

[0061] Various embodiments of the present disclosure will be further illustrated by the following examples. The examples are illustrative in nature and should not be construed as limiting the subject matter of the present disclosure.

[0062] Example 1 - Addition of platinum and gallium

[0063] In Example 1, seven different samples of catalytically active particles were prepared and tested. Performance testing of all samples was performed in a fixed bed bench using a simulated reaction-combustion-reactivation cycle in a laboratory-scale fixed bed reactor. The samples were tested under ambient pressure under the condition that 0.5 grams (g) of sample was mixed with 1.0 g of inert silicon carbide and loaded into a quartz reactor. The standard reaction combustion reactivation cycle was carried out in three steps. First, the feed composition of 90% propane / 10% nitrogen and 10 hours at 625°C were used. -1 The dehydrogenation was carried out at a propane weight hourly space velocity "WHSV" of 1.000 mol / s for 60 seconds. Next, 2.5 mol% methane / balance air was used at a total flow rate of 50 standard cubic centimeters per minute (sccm) and 0.1 hr -1 Combustion was performed at 730°C for 3 minutes at a methane WHSV of 1.5 wt%. Finally, a reactivation step was performed at 730°C for 2 minutes at 100% air with a flow rate of 40 sccm. Dehydrogenation performance data were collected at 30 seconds run time and combustion data were collected at 60 seconds run time. Performance data after the 25th cycle are recorded in Table 1.

[0064] Comparative Example A was prepared by first spray drying hydrated alumina and The microspheroidal alumina support is prepared by mixing a mixture of silica and then heating the resulting spray-dried particles at a temperature of at least 1000° C., which is sufficient to obtain a particle size range of 5 μm to 300 μm, a pore volume of 0.20 ml / g ± 0.10 ml / g, and a surface area of ​​70 m 2 / g±20m 2 / g and a silica content of 2.5 wt.% ± 2.5 wt.%. The catalyst material was then prepared using an incipient wetness impregnation method to load the specified metal or metals onto the support using a nitrate or nitrate amine metal precursor, followed by drying at a temperature below 200°C and then calcining at a temperature below 800°C. Table 1 provides the exact composition of the samples.

[0065] Comparative Example B was produced by operating Comparative Example A in a fluidized reactor-regenerator between 600°C and 800°C for 9 months under alkane dehydrogenation, methane combustion and air regeneration conditions. The chemical properties and propane dehydrogenation performance of Comparative Example B are listed in Table 1.

[0066] Samples 1-4 were prepared via incipient wetness impregnation by adding the indicated metal(s) to Comparative Example B using nitrate or nitrate ammine metal precursors, followed by drying and calcining as Comparative Example A. The metal additions for each of these samples and their dehydrogenation and combustion performance are listed in Table 1.

[0067] Table 1

[0068]

[0069] Table 1 shows that Comparative Example B has reduced propane conversion and methane conversion when compared to the unaged Comparative Example A. Table 1 also shows that samples with added platinum or platinum and gallium, such as Samples 1-4, have improved propane conversion and methane conversion when compared to Comparative Example B. This shows that adding additional platinum and gallium to a used catalyst, such as Comparative Example B, can recover at least a portion of the methane and propane conversion lost by the used catalyst.

[0070] Example 2 - Addition of transition metals

[0071] In Example 2, eight different samples of catalytically active particles were prepared and tested. Samples 5-12 were prepared via incipient wetness impregnation by adding the specified metal or metals to Comparative Example B using nitrate or nitrate ammine metal precursors, followed by drying and calcining as in Comparative Example A. The metal additions for each of these samples and their dehydrogenation and combustion performance are listed in Table 2.

[0072] Table 2

[0073]

[0074] As shown in Table 2, when compared to an aged catalyst such as Comparative Example B, adding a transition metal that is not present in the initial catalyst can improve the methane conversion and propane conversion of the catalyst. For example, when compared to Comparative Example B, Samples 5-7, 9, and 12 have increased propane conversion and methane conversion. When compared to Comparative Example B, some samples (i.e., Samples 8 and 10) only have increased methane conversion. When compared to Comparative Example B, Sample 11 does not have an increase in propane conversion or methane conversion. That is, Table 3 shows that adding only some transition metals improves the methane conversion, propane conversion, or both of the spent catalyst (such as Comparative Example B).

[0075] Example 3 - Addition of Iron or Manganese

[0076] In Example 3, seven different samples of catalytically active particles were prepared and tested. Samples 13-19 were prepared via incipient wetness impregnation by adding the specified metal or metals to Comparative Example B using nitrate or nitrate ammine metal precursors, followed by drying and calcining as in Comparative Example A. The metal additions for each of these samples and their dehydrogenation and combustion performance are listed in Table 3.

[0077] Table 3

[0078]

[0079]

[0080] As shown in Table 3, samples modified with one of iron or manganese, such as Samples 13-18, had improved propane conversion and methane conversion when compared to Comparative Example B, which did not contain iron or manganese. Table 3 also shows that samples with high iron loading, such as Sample 19, had improved methane conversion, but not improved propane conversion, when compared to Comparative Example B.

[0081] Example 4 - Addition of Platinum and Another Metal

[0082] In Example 4, seventeen different samples of catalytically active particles were prepared and tested. Samples 20-36 were prepared via incipient wetness impregnation by adding the specified metal or metals to Comparative Example B using nitrate or nitrate ammine metal precursors, followed by drying and calcining as in Comparative Example A. The metal additions for each of these samples and their dehydrogenation and combustion performance are listed in Table 4.

[0083] Table 4

[0084]

[0085] As shown in Table 4, all samples modified by the addition of both platinum and manganese (such as samples 20-26) have improved propane conversion and methane conversion over a wide range of possible modifications (such as 50 ppmw to 220 ppmw of platinum and 500 ppmw to 3000 ppmw of manganese) when compared to the unmodified Comparative Example B.

[0086] Table 4 also shows that all samples modified by adding both platinum and iron (such as samples 27-31) have improved methane conversion when compared to unmodified Comparative Example B. Some samples modified by adding both platinum and iron (such as samples 27 and 28) have improved methane conversion and propane conversion when compared to Comparative Example B. In addition, sample 33 modified by adding platinum, manganese and iron and sample 34 modified by adding manganese and iron both have improved propane conversion and methane conversion when compared to Comparative Example B.

[0087] Table 4 also shows that Sample 32, which was modified by adding both platinum and chromium, had improved propane conversion and methane conversion when compared to Comparative Example B. Finally, Table 4 shows that samples modified by adding both platinum and aluminum, such as Samples 35 and 36, had improved propane conversion and methane conversion when compared to Comparative Example B.

[0088] In a first aspect of the present disclosure, a method may include operating a dehydrogenation process whereby a hydrocarbon-containing feed is converted into light olefins, wherein the dehydrogenation process utilizes a fluidized process catalyst that circulates between a reactor and a combustor. The process catalyst is extracted from the dehydrogenation process, the process catalyst is modified to form a modified catalyst, and the modified catalyst is added back into the dehydrogenation process. Wherein the process catalyst comprises 0.1 wt.% to 10 wt.% of one or more metals selected from gallium, indium, thallium, or a combination thereof, 1 ppmw to 1000 ppmw of one or more metals selected from platinum, palladium, rhodium, iridium, ruthenium, osmium, or a combination thereof, and at least 85 wt.% of a carrier. Wherein the process catalyst modification comprises adding one or more of manganese, iron, chromium, vanadium, or aluminum.

[0089] A second aspect of the disclosure may include the first aspect, wherein the process catalyst comprises 0.1 wt.% to 10 wt.% gallium, 1 ppmw to 1000 ppmw platinum, and at least 85 wt.% of a support.

[0090] A third aspect of the present disclosure may include any of the preceding aspects, wherein the process catalyst is free of manganese and iron.

[0091] A fourth aspect of the present disclosure may include any of the preceding aspects, wherein the process catalyst comprises manganese, iron, or a combination thereof.

[0092] A fifth aspect of the present disclosure may include any of the preceding aspects, wherein modifying the process catalyst comprises adding manganese and wherein the modified catalyst comprises 100 ppmw to 5000 ppmw manganese.

[0093] A sixth aspect of the present disclosure may include any of the preceding aspects, wherein modifying the process catalyst comprises adding iron and wherein the modified catalyst comprises from 100 ppmw to 5000 ppmw iron.

[0094] A seventh aspect of the present disclosure may include any of the preceding aspects, wherein modifying the process catalyst comprises adding chromium and wherein the modified catalyst comprises 100 ppmw to 5000 ppmw chromium.

[0095] An eighth aspect of the present disclosure may include any of the preceding aspects, wherein modifying the process catalyst comprises adding vanadium and wherein the modified catalyst comprises 100 ppmw to 2000 ppmw vanadium.

[0096] A ninth aspect of the present disclosure may include any of the preceding aspects, wherein modifying the process catalyst comprises adding aluminum and wherein the modified catalyst comprises 0.5 wt.% to 10 wt.% aluminum.

[0097] A tenth aspect of the present disclosure may include any of the preceding aspects, wherein modifying the process catalyst further comprises adding one or more of platinum or gallium.

[0098] An eleventh aspect of the present disclosure may include any of the preceding aspects, wherein modifying the process catalyst further comprises adding 10 ppmw to 300 ppmw of platinum.

[0099] A twelfth aspect of the present disclosure may include any of the preceding aspects, wherein modifying the process catalyst further comprises adding 0.1 wt. % to 0.5 wt. % gallium.

[0100] A thirteenth aspect of the present disclosure may include any of the preceding aspects, wherein the support includes one or more of alumina, silica, or a combination thereof.

[0101] A fourteenth aspect of the present disclosure may include any of the preceding aspects, wherein the extracting of the process catalyst occurs after the process catalyst has been subjected to at least 4 months of dehydrogenation process cycles.

[0102] A fifteenth aspect of the present disclosure may include any of the preceding aspects, wherein the process catalyst is withdrawn from the dehydrogenation process when the combustion activity of the process catalyst decreases by at least 60%.

[0103] It will be apparent to those skilled in the art that various modifications and variations may be made to the technology disclosed in the present invention without departing from the spirit and scope of the technology. Because those skilled in the art may make modifications, combinations, sub-combinations and variations of the disclosed embodiments that incorporate the spirit and essence of the technology disclosed in the present invention, the technology should be interpreted as including everything within the scope of the attached claims and their equivalents. In addition, 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.

[0104] It should be noted that the various details described in the present disclosure should not be considered to imply that these details relate to elements that are essential components of the various embodiments described in the present disclosure, even in the case where specific elements are shown in each of the drawings attached to this specification. Unless so explicitly stated, the features disclosed and described herein should not be interpreted as "essential". Contemplated embodiments of the present technology include those that include some or all of the features of the appended claims.

[0105] For purposes of describing and defining the present disclosure, it is noted that the term "about" is used herein to represent the inherent degree of uncertainty that may be attributed to any quantitative comparison, value, measurement, or other representation. The term "about" is also utilized herein to represent the degree by which a quantitative representation may vary from a stated reference without resulting in a change in the basic function of the subject matter at issue.

[0106] Where relevant, where 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.

[0107] It should be understood that in some embodiments, the composition range of the chemical composition in a stream or reactor should be understood as a mixture of isomers containing the composition. For example, a composition range specifying butenes can include a mixture of various isomers of butenes. It should be understood that the embodiments provide composition ranges for various streams, and the total amount of isomers of a specific chemical composition can constitute a range.

[0108] It should be noted that one or more of the following claims and detailed description utilize the term "wherein" or "wherein" as a transition phrase. For purposes of defining the present technology, it should be noted that this term is introduced in the claims as an open transition phrase that is used to introduce a recitation of a series of features of a structure and should be interpreted in a manner similar to the more commonly used open-ended preamble term "comprising."

[0109] It should be understood that any two quantitative values ​​assigned to a characteristic may constitute a range for that characteristic, and all combinations of ranges formed by all said quantitative values ​​for a given characteristic are considered in the present disclosure. Where multiple ranges of quantitative values ​​are provided, these ranges may be combined to form a wider range, which is contemplated in the embodiments described herein.

Claims

1. A method for preparing light olefins by dehydrogenation, the method comprising: A dehydrogenation process is operated whereby a hydrocarbonaceous feed is converted to light olefins, wherein the dehydrogenation process utilizes a fluidized process catalyst that circulates between a reactor and a combustor, wherein the process catalyst comprises: 0.1 wt.% to 10 wt.% of one or more metals selected from gallium, indium, thallium or a combination thereof; 1 ppmw to 1000 ppmw of one or more metals selected from platinum, palladium, rhodium, iridium, ruthenium, osmium or a combination thereof; and at least 85 wt.% of a carrier; withdrawing said process catalyst from said dehydrogenation process; modifying the process catalyst to form a modified catalyst, wherein the modification of the process catalyst comprises adding one or more of manganese, iron, chromium or vanadium; and The modified catalyst is added back to the dehydrogenation process.

2. The method of claim 1, wherein the process catalyst comprises: 0.1 wt. % to 10 wt. % gallium; 1 ppmw to 1000 ppmw platinum; and at least 85 wt. % of a carrier.

3. The process according to any one of the preceding claims, wherein the process catalyst is free of manganese and iron.

4. The process according to any one of the preceding claims, wherein the process catalyst comprises manganese, iron or a combination thereof.

5. A process according to any one of the preceding claims, wherein the modification of the process catalyst comprises the addition of manganese, and wherein the modified catalyst comprises from 100 ppmw to 5000 ppmw manganese.

6. A process according to any one of the preceding claims, wherein the modification of the process catalyst comprises the addition of iron, and wherein the modified catalyst comprises from 100 ppmw to 5000 ppmw iron.

7. A method according to any one of the preceding claims, wherein the modification of the process catalyst comprises the addition of chromium, and wherein the modified catalyst comprises from 100 ppmw to 5000 ppmw chromium.

8. A process according to any one of the preceding claims, wherein the modification of the process catalyst comprises the addition of vanadium, and wherein the modified catalyst comprises from 100 ppmw to 2000 ppmw vanadium.

9. The method according to any one of the preceding claims, wherein modifying the process catalyst further comprises adding aluminum, wherein the modified catalyst comprises 0.5 wt.% to 10 wt.% aluminum.

10. The method according to any one of the preceding claims, wherein modifying the process catalyst further comprises adding one or more of platinum or gallium.

11. The method according to any one of the preceding claims, wherein modifying the process catalyst further comprises adding 10 ppmw to 300 ppmw of platinum.

12. The method of any one of the preceding claims, wherein modifying the process catalyst further comprises adding 0.1 wt.% to 0.5 wt.% gallium.

13. The method of any one of the preceding claims, wherein the support comprises one or more of alumina, silica, or a combination thereof.

14. The method according to any one of the preceding claims, wherein the extraction of the process catalyst occurs after the process catalyst has been subjected to at least 4 months of dehydrogenation process cycles.

15. A method according to any one of the preceding claims, wherein the process catalyst is withdrawn from the dehydrogenation process when the combustion activity of the process catalyst decreases by at least 60%.

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