Method for producing light olefins containing a modified catalyst

Abstract

The method may include operating a dehydrogenation process in which a hydrocarbon-containing feed is converted to light olefins, and the dehydrogenation process utilizes a fluid process catalyst that circulates between a reactor and a combustor. The method may include recovering the process catalyst from the dehydrogenation process, reforming the process catalyst to form a reformed catalyst, and returning and adding the reformed catalyst to the dehydrogenation process. The process catalyst includes at least one metal selected from 0.1 wt% to 10 wt% of gallium, indium, thallium, or a combination thereof, at least one metal selected from 1 ppmw to 1000 ppmw of platinum, palladium, rhodium, iridium, ruthenium, osmium, or a combination thereof, and at least 85 wt% of a carrier. Reforming the process catalyst may include adding one or more of manganese, iron, chromium, or vanadium.

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims priority to U.S. Provisional Patent Application No. 63 / 352,020, filed on June 14, 2022, which is hereby incorporated by reference in its entirety.

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

Background Art

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

Summary of the Invention

[0004] Some of the methods and related systems used to produce light olefins may utilize a catalyst that can be circulated between a reactor in which the light olefins are produced by an endothermic reaction and a combustor in which the catalyst is heated by at least the exothermic combustion of an auxiliary fuel (sometimes with the combustion of coke). Such a catalyst can 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, conventional catalysts used for dehydrogenation may suffer a decrease in catalytic activity over the period of use as compared to conventional catalysts that have not yet been used in the dehydrogenation process. Such spent catalysts may no longer adequately catalyze the dehydrogenation of alkanes, the combustion of the auxiliary fuel, or both. As described herein, a method of reforming a catalyst that has been partially deactivated by adding a metal such as manganese, iron, chromium, or vanadium has been found to be able to restore the catalytic activity, combustion activity, or both for the dehydrogenation of alkanes as compared to a conventional catalyst that has not been reformed by adding a metal such as manganese, iron, chromium, or vanadium.

[0005] According to one or more embodiments of the present disclosure, the method may include operating a dehydrogenation process in which a hydrocarbon-containing feed is converted to light olefins, the dehydrogenation process utilizing a fluid process catalyst that circulates between a reactor and a combustor. The method may further include recovering the process catalyst from the dehydrogenation process, reforming the process catalyst to form a reformed catalyst, and returning and adding the reformed catalyst to the dehydrogenation process. The process catalyst includes at least one metal selected from 0.1 wt% to 10 wt% of gallium, indium, thallium, or a combination thereof, at least one metal selected from 1 ppmw to 1000 ppmw of platinum, palladium, rhodium, iridium, ruthenium, osmium, or a combination thereof, and at least 85 wt% of a support. Reforming the process catalyst may include adding one or more of manganese, iron, chromium, vanadium, or aluminum.

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

Brief Description of the Drawings

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

[0008]

Figure 1

Figure 2

[0009] When explaining the simplified schematic diagram of FIG. 2, numerous valves, temperature sensors, electronic controllers, etc. that can be used and are well known to those skilled in the art are not included. Further, 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.

[0010] Here, various embodiments are referred to in more detail, some of which are illustrated in the accompanying drawings.

Modes for Carrying Out the Invention

[0011] The present disclosure relates to a method for producing light olefins by dehydrogenation, which may include steps such as operating a dehydrogenation process, recovering a process catalyst from the dehydrogenation process, modifying the process catalyst to form a reformed catalyst, and returning and adding the reformed catalyst back to the dehydrogenation process. The process catalyst may include one or more metals selected from 0.1 wt% to 10 wt% of gallium, indium, thallium, or a combination thereof, one or more metals selected from 1 ppmw to 1000 ppmw of platinum, palladium, rhodium, iridium, ruthenium, osmium, or a combination thereof, and at least 85 wt% of a carrier. As described herein, modifying the process catalyst may include adding one or more of manganese, iron, chromium, or vanadium. In one or more embodiments, such a reformed catalyst provides an improved dual catalyst function for the dehydrogenation of alkanes and the combustion of auxiliary fuel. Such a reformed catalyst is particularly well-suited for the fluidized dehydrogenation of light alkanes to light olefins.

[0012] As described herein, the modification of the process catalyst to the reformed catalyst and its subsequent use in the dehydrogenation process may enable the reuse / recycling continued use of the process catalyst, which may still contain precious materials such as platinum and gallium. However, according to one or more embodiments, the addition of manganese, iron, chromium, or vanadium may improve dehydrogenation activity, combustion activity, or both.

[0013] As used in the present disclosure, the term "process catalyst" refers to the catalyst used in the dehydrogenation process. The process catalyst may have a composition different from that of a new catalyst composition that has not yet been introduced into the dehydrogenation process. The reformed catalyst is a process catalyst that has been modified as described herein and is generally reinserted into the dehydrogenation process.

[0014] Referring to FIG. 1, there is shown a process 100 for producing light olefins according to one or more embodiments described herein. FIG. 1 shows, in sequence, a step 110 of operating a dehydrogenation process, a step 120 of recovering a process catalyst, a step 130 of reforming the process catalyst to form a reformed catalyst, and a step 140 of returning the reformed catalyst back to the dehydrogenation process for filling.

[0015] Step 110 generally includes operating a dehydrogenation process. By operating the dehydrogenation process in step 110, a hydrocarbon-containing feed is converted into light olefins in an olefin-containing effluent. The dehydrogenation process of step 110 can be carried out using a reactor system as schematically shown in FIG. 2. The steps of FIG. 1 may be described in relation to the reactor system of FIG. 2 as described herein. When describing the system of FIG. 2 and the related method, it should be understood that the "catalyst" described, unless otherwise specified, may refer to a process catalyst or a reformed catalyst. Generally, the movement and fluidization of the process catalyst and the reformed catalyst through the system of FIG. 2 are the same.

[0016] Embodiments of the methods disclosed herein are described in detail herein in the context of the reactor system of FIG. 2 operating 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 include a downcomer instead of a riser. Further, it should be understood that not all parts of FIG. 2 should be construed as essential to the claimed subject matter. Further, although the steps of the methods recited in the appended claims are described herein in the context of FIG. 2, 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.

[0017] Next, referring to FIG. 2, an exemplary reactor system 102 that may be suitable for use with the methods and / or apparatuses described herein is schematically shown. 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 when describing, "system components" refers to parts of the reactor system 102, such as reactors, separators, transfer lines, combinations thereof, etc. In the context of FIG. 2 as used herein, the reactor section 200 generally refers to the part of the reactor system 102 where a major process reaction (e.g., dehydrogenation) takes place to form an olefin-containing effluent. A hydrocarbon-containing feed enters the reactor section 200, contacts a catalyst, is converted to an olefin-containing effluent (containing product and unreacted feed), and exits the reactor section 200. The reactor section 200 includes a reactor 202 that may include an upstream reactor section 250 and a downstream reactor section 230. According to one or more embodiments, as shown in FIG. 2, the reactor section 200 may further include a catalyst separation section 210 that functions to separate the catalyst from the olefin-containing effluent formed within the reactor 202. Also, as used herein, the catalyst treatment section 300 generally refers to the part of the reactor system 102 that treats the catalyst in some way, such as by combustion, etc., to improve the catalyst activity, for example, by decoking and / or heating the catalyst. The catalyst treatment section 300 may include a combustor 350 and a riser 330, and may further include a catalyst separation section 310. In one or more embodiments, the catalyst separation section 210 can be in fluid communication with the combustor 350 (e.g., via a water distribution tower 426), and the catalyst separation section 310 can be in fluid communication with the upstream reactor section 250 (e.g., via a water distribution tower 424 and a transfer riser 430).

[0018] Generally, as described herein, in the embodiment shown in FIG. 2, the catalyst is circulated between the reactor section 200 and the catalyst treatment section 300. When "catalysts" are referred to herein, it should be understood that they may refer to solid materials that are catalytically active for the desired reaction. The terms "catalytic activity" and "catalyst activity" refer to the extent to which a catalyst can catalyze the reaction taking place within the reactor system 102. The catalyst exiting the reactor section 200 may be a deactivated catalyst. As used herein, "deactivated" may refer to a catalyst having a lower catalytic activity or a lower temperature compared to the catalyst entering the reactor section 200. However, a deactivated catalyst may maintain some catalytic activity. The decrease in catalytic activity may be due to contamination by substances such as coke. Coke may be formed on the catalyst within the reactor section 200. By reactivation (also sometimes referred to herein as "regeneration"), contaminants such as coke can be removed, the temperature of the catalyst can be increased, or both can be done. In an embodiment, a deactivated catalyst can be reactivated by catalyst reactivation in the catalyst treatment section 300. A 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.

[0019] 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.

[0020] In one or more embodiments, the process catalyst may comprise, consist essentially of, or consist of one or more of gallium, indium, or thallium, one or more of platinum, palladium, rhodium, iridium, ruthenium, or osmium, and a carrier. 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 make up at least 99 wt% of the composition). As described herein, the catalyst can be solid particles suitable for fluidization.

[0021] In one or more embodiments, the process 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 process 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. For example, the process 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 amounts within 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 process 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 describing the amounts of gallium, indium, and thallium represent the ranges of any one of these materials or combinations of these materials. Without being bound by theory, compositions having one or more of gallium, indium, or thallium in an amount less than 0.1 wt% are thought to adversely affect the ability of the process catalyst to catalyze the alkane dehydrogenation process by reducing both the percentage of dehydrogenated alkanes and the percentage of dehydrogenated alkanes that are the intended product. However, compositions having one or more of gallium, indium, or thallium in an amount greater than 10 wt% may adversely affect the ability of the catalyst to catalyze the alkane dehydrogenation process, the selectivity of the catalyst for the intended product, or both.

[0022] In one or more embodiments, the process catalyst may include 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 process 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. For example, the process catalyst may include 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 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 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 range of any one of these materials or a combination 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 process 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 greater than 1000 ppmw is thought to potentially adversely affect either the ability of the catalyst to catalyze the alkane dehydrogenation process, the selectivity of the catalyst for the intended product, or both.

[0023] As described herein, in one or more embodiments, the catalyst may include a support. The support may include one or more of alumina, silica, or a combination thereof. For example, in some embodiments, the support may include one or more of alumina, silica-containing alumina, zirconia-containing alumina, titania-containing alumina, and lanthanum-containing alumina. The support may be present in an amount of at least 85 wt%, 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 support comprises 99.5 wt% or less of the catalyst. Generally, the wt% of the support may fill the remainder of the total catalyst not specified by other materials.

[0024] In one or more embodiments, the process 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 mass of the catalyst. For example, the process 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 process 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 greater than 2.5 wt% may reduce the dehydrogenation activity of the catalyst.

[0025] In one or more embodiments, the process catalyst may contain one or more of iron or manganese in a total amount of 100 ppmw to 5000 ppmw based on the total mass of the catalyst. For example, the process catalyst may contain one or more of iron or manganese in a total amount of 100 ppmw to 500 ppmw, 500 ppmw to 1000 ppmw, 1000 ppmw to 2000 ppmw, 2000 ppmw to 3000 ppmw, 3000 ppmw to 4000 ppmw, 4000 ppmw to 5000 ppmw, or any combination of these ranges. In some embodiments, the process catalyst may contain iron but not manganese, or may contain manganese but not iron. Without being bound by theory, it is believed that compositions having an iron or manganese content in an amount exceeding 5000 ppmw may have an adverse effect on the alkane dehydrogenation performance of the catalyst. However, it is believed that compositions having an iron or manganese content in an amount less than 100 ppmw may not sufficiently improve the catalytic alkane dehydrogenation performance. In some embodiments, the process catalyst may be lacking one or more of iron or manganese.

[0026] In one or more embodiments, the process catalyst may include solid fine particles capable of fluidization. In some embodiments, the process 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.

[0027] Group A of Geldart is understood by those skilled in the art to represent aeratable powders having the following: fluidization in the range without bubbles, high bed expansion, slow and linear degassing rate, divided / recombined bubbles may be dominant, bubble characteristics with maximum bubble size and large wake, high level of solid mixing and gas backmixing 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 ejection except for very shallow beds.

[0028]

Number

[0029] Group B of Geldart is understood by those skilled in the art to represent "sand-like" powders that start foaming at Umf, exhibit moderate bed expansion, rapid degassing, no limitation on bubble size, have a moderate level of solid mixing and gas backmixing assuming equal U-Umf, both axisymmetric and asymmetric slugs; and ejection only in shallow beds. These characteristics tend to improve as the average particle size decreases, but the particle size distribution and, with some uncertainty, the gas pressure, temperature, viscosity, or density do not seem to contribute much to the improvement of the above characteristics. Generally, when the density (ρp) is 1.4 < ρp < 4 g / cm 3 ³, most of the particles

[0030]

Number

[0031]

Number

[0032] Referring again to FIG. 2, 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 through the pipe 420. According to one or more embodiments, the reactor system 102 can be operated by supplying a hydrocarbon-containing feed (e.g., in the feed stream) and a fluid catalyst to the upstream reactor section 250. The hydrocarbon-containing feed contacts the catalyst within the upstream reactor section 250, each flowing 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. 2, the reactor section 200 may include 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, a drum, a barrel, a vat, or other container suitable for a given chemical reaction. As shown in FIG. 2, 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 size of the cross-section of the upstream reactor section 250 towards the size of the cross-section of the downstream reactor section 230 such that the transfer section 258 projects inwards from the upstream reactor section 250 towards the downstream reactor section 230. For example, the transfer section 258 may be a frustum of a cone.

[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 the transfer riser 430 directly from the catalyst separation section 210 via a standpipe 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 standpipe 422 (not shown in FIG. 2). This catalyst may be somewhat deactivated but may still be suitable for reaction 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 3 minutes or less. As used herein, the term "residence time" refers to the average amount of time that a catalyst or other specific material spends within the reactor section 200. Since it is an average, the amount of time that the catalyst can spend within the reactor section 200 during any given cycle has a distribution and may not be equal to the average, but over time averages to approximately the residence time. In some embodiments, the catalyst may have a residence time within the reactor section 200 of 2.5 minutes or less, 2 minutes or less, 1.5 minutes or less, 1 minute or less, 0.5 minutes or less, or 0.1 minutes or less. Without being bound by theory, it is believed that a catalyst residence time exceeding 3 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 not allow the catalyst to sufficiently catalyze the dehydrogenation reaction.

[0036] Referring further to FIG. 2, 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. 2 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 flow from the total upward flow, as is typical of the behavior of fluidized particles. As described herein, a "fast fluidized" reactor may refer to a reactor that utilizes a fluidization regime in which the superficial gas velocity is faster than the choking velocity and may be semi-dense during operation. As described herein, a "turbulent" reactor may refer to a fluidization regime in which the superficial velocity is slower than the choking velocity and has a higher density than the fast fluidization regime. As described herein, a "bubble bed" reactor may 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 in 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. 2, the separated catalyst moves from the catalyst separation section 210 to the combustor 350. In the combustor 350, the catalyst can be treated, for example, by combustion of coke with oxygen. For example, but not limited to, the catalyst can remove coke and / or burn auxiliary fuel to heat the catalyst. Next, the catalyst exits the combustor 350, passes through the riser 330, and is sent to the riser end separator 378, where the gas and solid components from the riser 330 are at least partially separated. The vapor and remaining solids are transferred to the secondary separator 320 within the catalyst separation section 310, where the remaining catalyst is separated from the gas from the catalyst treatment (e.g., the gas released by combustion of the spent catalyst or auxiliary fuel, referred to herein as flue gas). The flue gas can exit the catalyst treatment section 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 processed 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. 2, 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 an auxiliary fuel such as hydrogen, methane, ethane, propane, natural gas, or a combination thereof. Without being bound by any theory, when methane is utilized as the auxiliary fuel, the catalyst described herein that has been reformed may better catalyze the combustion of methane to heat the catalyst. An un-reformed catalyst 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 the flue gas from the catalyst in the riser termination separator 378 and the secondary separation device 320, the treated catalyst is treated with an oxygen-containing gas in the oxygen treatment zone 370. In some embodiments, the oxygen treatment zone 370 includes a fluid-solid contact device. The fluid-solid contact device can include a baffle or grid structure to facilitate contact of the treated catalyst with the oxygen-containing gas. Examples of fluid-solid contact devices are described in more detail in U.S. Patent Nos. 9,827,543 and 9,815,040. The fluidization regime within the oxygen treatment zone may be a bubbling bed type fluidization. The oxygen treatment zone 370 can include an oxygen-containing gas inlet 372 that can feed an oxygen-containing gas into the oxygen treatment zone 370 for 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, the 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 102 of FIG. 2 and may subsequently be processed. As used herein, 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 includes at least 25 wt % light olefins, based on the total weight of the olefin-containing effluent. For example, the olefin-containing effluent can include at least 35 wt % light olefins, at least 45 wt % light olefins, at least 55 wt % light olefins, at least 65 wt % light olefins, or at least 75 wt % light olefins, based on the total weight of the olefin-containing effluent. The olefin-containing effluent may further include unreacted components of the hydrocarbon-containing effluent and other reaction products that are not considered light olefins. The light olefins can be separated from the unreacted components in a subsequent separation step.

[0045] Referring again to FIG. 1, step 120 generally includes recovering the process catalyst from the dehydrogenation process. Over time, the process catalyst can degrade while being used within the dehydrogenation process. This degradation can include loss of catalytically active components such as palladium or platinum from the process catalyst, or deactivation of the catalytic components of the process catalyst. In conventional catalysts, this loss of catalyst material ultimately requires replacing the process catalyst with a new catalyst. Replacing the process catalyst with a new catalyst can be wasteful because many of the components of the process catalyst, such as the catalyst material and the support, remain functional. As described herein, reforming the process catalyst can enable reuse of the functional catalyst material, which can reduce waste generation.

[0046] In one or more embodiments, the process catalyst may be recovered in bulk, thereby stopping the dehydrogenation process and removing a substantial portion of the process catalyst present during the dehydrogenation process. For example, the amount of catalyst recovered may be at least 5% of the total catalyst present, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or even 100% of the total catalyst present may be recovered.

[0047] In one or more embodiments, the process catalyst is continuously recovered. As used in this disclosure, the term "continuously recovered" means that the recovery of the process catalyst is carried out such that it is not necessary to stop the dehydrogenation process to recover the process catalyst, and a portion of the process catalyst is consistently recovered from the dehydrogenation process. For example, continuous recovery can be achieved by the installation of a catalyst recovery system such as the Johnson Matthey INTERCAT™ continuous catalyst recovery system. In some embodiments, the amount of process catalyst continuously recovered and the amount of catalyst returned to the dehydrogenation process are determined by measuring the catalyst loss from the unit due to mechanical wear and the rate of performance as the process catalyst ages, so that the process catalyst can be continuously recovered to maintain performance. In some embodiments, when the process catalyst is continuously recovered, at least 0.05% of the process catalyst can be recovered from the dehydrogenation process. For example, at least 0.1% of the process catalyst may be recovered from the dehydrogenation process, at least 0.25%, at least 0.5%, at least 1.0%, at least 1.5%, at least 2.0%, at least 2.5%, at least 3.0%, at least 3.5%, at least 4.0%, at least 4.5%, or up to 5.0% of the process catalyst may be continuously recovered.

[0048] In one or more embodiments, the process catalyst may be recovered when dehydrogenation or combustion activity has decreased such that the targeted productivity (e.g., olefin production rate) or combustion activity can no longer be achieved, by adding fresh catalyst to compensate for mechanical losses of the catalyst from the unit, or by applying more severe operating conditions such as a higher reaction temperature, a higher regeneration temperature, or a change in the catalyst-to-oil ratio. For example, the process catalyst may be recovered when the combustion activity is not sufficient 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 recovered in bulk 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 end of the concentration range at which a combustible mixture of gas or vapor in air can be ignited at a given temperature and pressure. The LFL of a combustion gas can be determined by reactive chemical testing or as described by Michael G. Zabetakis, Flammability Characteristics of Combustible Gases and Vapors, 627 Bureau of Mines 1 (1965), with pressure regulation as by Coward et al., Limits of Flammability of Gases and Vapors, 503 Bureau of Mines 1 (1952). In some embodiments, if mechanical losses of the catalyst are low and thus do not provide sufficient exchange space to allow for addition of catalyst to compensate for losses in dehydrogenation and combustion activity, the catalyst may be intentionally withdrawn from the unit periodically to provide exchange space to allow for addition of catalyst.

[0049] In one or more embodiments, the process catalyst can be recovered after being used for a predetermined time in the dehydrogenation process. For example, the process catalyst can be recovered after at least 6 months, such as 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 of the dehydrogenation process cycle.

[0050] Referring again to FIG. 1 here, step 130 generally includes reforming the process catalyst to form a reformed catalyst. As used in this disclosure, the term "reformed catalyst" refers to a process catalyst reformed by the addition of one or more metals. In one or more embodiments, the process catalyst can be reformed by adding one or more of manganese, iron, chromium, vanadium, or aluminum to the process catalyst to form a reformed catalyst.

[0051] In one or more embodiments, the reforming catalyst may contain manganese in an amount of 100 ppmw to 5000 ppmw, based on the total mass of the reforming catalyst. For example, the reforming catalyst may contain manganese in an amount of 100 ppmw to 500 ppmw, 500 ppmw to 1000 ppmw, 1000 ppmw to 2000 ppmw, 2000 ppmw to 3000 ppmw, 3000 ppmw to 4000 ppmw, 4000 ppmw to 5000 ppmw, or any combination of these ranges. In some embodiments, the reforming catalyst may contain manganese in an amount of 500 ppmw to 4500 ppmw, 750 ppmw to 4000 ppmw, 1000 ppmw to 3500 ppmw, or 1500 ppmw to 3000 ppmw. Without being bound by theory, compositions having manganese in amounts exceeding 5000 ppmw may adversely affect the ability of the catalyst to catalyze the alkane dehydrogenation process by reducing both the percentage of total dehydrogenated alkanes and the percentage of dehydrogenated alkanes that are the intended product. However, compositions having manganese in amounts less than 100 ppmw are thought to not fully recover the alkane conversion rate and fuel gas combustion activity when compared to the unmodified process catalyst.

[0052] In one or more embodiments, the reforming catalyst may contain iron in an amount of 100 ppmw to 5000 ppmw, based on the total mass of the reforming catalyst. For example, the reforming catalyst may contain iron in an amount of 100 ppmw to 500 ppmw, 500 ppmw to 1000 ppmw, 1000 ppmw to 2000 ppmw, 2000 ppmw to 3000 ppmw, 3000 ppmw to 4000 ppmw, 4000 ppmw to 5000 ppmw, or any combination of these ranges. Some embodiments may have the reforming catalyst contain iron in an amount of 500 ppmw to 4500 ppmw, 750 ppmw to 4000 ppmw, 1000 ppmw to 3500 ppmw, or 1500 ppmw to 3000 ppmw. Without being bound by theory, it is believed that a composition having an amount of iron less than 100 ppmw may not be able to fully recover the alkane conversion rate and fuel gas combustion activity when compared to an unmodified process catalyst. However, a composition having an amount of iron exceeding 5000 ppmw may negatively affect the ability of the catalyst to catalyze the alkane dehydrogenation process, may negatively affect the selectivity of the catalyst for the intended product, or both.

[0053] In one or more embodiments, the reforming catalyst may contain chromium in an amount of 100 ppmw to 5000 ppmw, based on the total mass of the reforming catalyst. For example, the reforming catalyst may contain chromium in an amount of 100 ppmw to 500 ppmw, 500 ppmw to 1000 ppmw, 1000 ppmw to 2000 ppmw, 2000 ppmw to 3000 ppmw, 3000 ppmw to 4000 ppmw, 4000 ppmw to 5000 ppmw, or any combination of these ranges. In some embodiments, the reforming catalyst may contain chromium in an amount of 500 ppmw to 4500 ppmw, 750 ppmw to 4000 ppmw, 1000 ppmw to 3500 ppmw, or 1500 ppmw to 3000 ppmw. Without being bound by theory, it is believed that a composition having an amount of chromium less than 100 ppmw may not be able to fully recover the alkane conversion rate and fuel gas combustion activity when compared to an unmodified process catalyst. However, a composition having an amount of chromium exceeding 5000 ppmw may negatively affect the ability of the catalyst to catalyze the alkane dehydrogenation process, the selectivity of the catalyst for the intended product, or both.

[0054] In one or more embodiments, the reforming catalyst may contain vanadium in an amount of 1 ppmw to 2000 ppmw, based on the total mass of the reforming catalyst. For example, the reforming catalyst may contain vanadium in an amount of 1 ppmw to 100 ppmw, 100 ppmw to 500 ppmw, 500 ppmw to 1000 ppmw, 1000 ppmw to 1500 ppmw, 1500 ppmw to 2000 ppmw, or any combination of these ranges. In some embodiments, the reforming catalyst may contain vanadium in an amount of 100 ppmw to 1900 ppmw, 500 ppmw to 1800 ppmw, 750 ppmw to 1700 ppmw, 1000 ppmw to 1600 ppmw, 1100 ppmw to 1500 ppmw, 1200 ppmw to 1450 ppmw, or 1300 ppmw to 1400 ppmw. Without being bound by theory, it is believed that a composition having an amount of vanadium less than 1 ppmw may not be able to fully recover the alkane conversion rate and fuel gas combustion activity when compared to an unmodified process catalyst. However, a composition having an amount of vanadium greater than 2000 ppmw may negatively affect the ability of the catalyst to catalyze the alkane dehydrogenation process, the selectivity of the catalyst for the intended product, or both.

[0055] In one or more embodiments, the reforming catalyst may be in the form of aluminum oxide that may be present as part of the support and may contain aluminum in an amount of 0.5 wt% to 10 wt% based on the total mass of the aluminum-free reforming catalyst. For example, the reforming catalyst may contain aluminum in an amount of 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. In some embodiments, the reforming catalyst may contain aluminum in 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%. Without being bound by theory, it is believed that a composition having an amount of aluminum less than 0.5 wt% may not be able to fully recover the alkane conversion rate and fuel gas combustion activity when compared to the unmodified process catalyst. However, a composition having an amount of one or more of gallium, indium, or thallium greater than 10 wt% may be considered 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.

[0056] In one or more embodiments, the process catalyst may be modified by adding one or more of platinum or gallium to produce the reforming 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.

[0057] In one or more embodiments, the reforming catalyst may contain platinum in an amount of 5 ppmw to 1000 ppmw, based on the total mass of the reforming catalyst. For example, the reforming catalyst may contain platinum 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 any combination of these ranges. In some embodiments, the reforming catalyst may contain platinum 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. Without being bound by theory, compositions having platinum in an amount less than 5 ppmw 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 platinum in an amount exceeding 1000 ppmw may adversely affect the ability of the catalyst to catalyze the alkane dehydrogenation process, the selectivity of the catalyst for the intended product, or both.

[0058] In one or more embodiments, the reforming catalyst may contain gallium in an amount of 0.1 wt% to 10 wt% based on the total mass of the reforming catalyst. For example, the reforming catalyst may contain 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 in an amount of any combination of these ranges. In some embodiments, the reforming 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%. Without being bound by theory, compositions having gallium in an amount less than 0.1 wt% are thought to adversely affect the ability of the catalyst to catalyze the alkane dehydrogenation process by reducing both the percentage of total dehydrogenated alkanes and the percentage of dehydrogenated alkanes that are the intended product. However, compositions having gallium in an amount greater than 10 wt% may adversely affect the ability of the catalyst to catalyze the alkane dehydrogenation process, the selectivity of the catalyst for the intended product, or both.

[0059] In one or more embodiments, the process catalyst can be modified by incipient wetness impregnation, also known as dry impregnation or capillary impregnation, to form the reforming catalyst. 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 process catalyst can be impregnated using a metal precursor, then dried at a temperature below 200°C, and then calcined at a temperature below 800°C to produce the catalyst. For example, in some embodiments, the process catalyst can be modified to form the reforming 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. Further, as will be known to those skilled in the art, other suitable methods for making the catalysts described herein are contemplated.

[0060] Referring again to FIG. 1, step 140 generally includes returning and adding the reforming catalyst to the dehydrogenation process. The reforming catalyst can then cycle through the steps of method 100 for producing light olefins by being utilized as the process catalyst in step 110, recovered in step 120, reformed to be the reforming catalyst in step 130, and returned and added to the dehydrogenation process in step 140.

Examples

[0061] 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.

[0062] Example 1 - Addition of Platinum and Gallium In Example 1, seven different samples of catalytically active particles were prepared and tested. Performance tests for all samples were carried out in a laboratory-scale fixed-bed reactor using a simulated reaction-combustion-reactivation cycle in a fixed-bed rig. The 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 standard reaction combustion reactivation cycle was carried out in three steps. First, dehydrogenation was carried out at 625 °C for 60 seconds using a feed composition of 90% propane / 10% nitrogen and a weight hourly space velocity “WHSV” of propane of 10 hr -1 Then, combustion was carried out at 730 °C for 3 minutes using 2.5 mol% methane / the remaining air, a total flow rate of 50 standard cubic centimeters per minute (sccm), and a WHSV of methane of 0.1 hr -1 Finally, the reactivation step was carried out at 730 °C for 2 minutes under 100% air with a flow rate of 40 sccm. Dehydrogenation performance data was collected with a running time of 30 seconds, and combustion data was collected with a running time of 60 seconds. The performance data after cycle 25 is reported in Table 1.

[0063] First, a microspherical alumina support was prepared by spray-drying a mixture of hydrated alumina and Ludox® silica, and then the obtained spray-dried particles were heated at a temperature of at least 1000 °C sufficient to achieve particles having a particle size in the range of 5 μm to 300 μm, a pore volume of 0.20 ± 0.10 mL / g, a surface area of 70 ± 20 m 2 / g, and a silica content of 2.5 ± 2.5 wt% to prepare Comparative Example A. Then, the catalyst material was prepared by using the incipient wetness impregnation method to load the specified metal(s) onto the support using a nitrate or amine nitrate metal precursor, 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.

[0064] Comparative Example B was prepared by operating Comparative Example A for 9 months under alkane dehydrogenation, methane combustion, and air regeneration conditions at 600 °C to 800 °C in a fluidized reactor-regenerator. The chemical properties and propane dehydrogenation performance of Comparative Example B are listed in Table 1.

[0065] Samples 1 to 4 were prepared via incipient wetness impregnation by adding the metal(s) specified for Comparative Example B using a nitrate or amine nitrate metal precursor, followed by drying and calcination as in Comparative Example A. The amount of metal added to each of these samples and their dehydrogenation and combustion performances are listed in Table 1. [Table 1]

[0066] Table 1 shows that Comparative Example B has a lower propane conversion rate and methane conversion rate compared to Comparative Example A, which has not undergone aging degradation. Table 1 also shows that samples with added platinum or platinum and gallium, such as Samples 1 to 4, have improved propane conversion rates and methane conversion rates when compared to Comparative Example B. This indicates that the addition of additional platinum and gallium to a used catalyst such as Comparative Example B can recover at least a portion of the decreased methane and propane conversion rates of the used catalyst.

[0067] Example 2 - Addition of Transition Metals In Example 2, eight different samples of catalytically active particles were prepared and tested. Samples 5 to 12 were prepared via incipient wetness impregnation by adding the metal(s) specified for Comparative Example B using a nitrate or amine nitrate metal precursor, followed by drying and calcination as in Comparative Example A. The amount of metal added to each of these samples and their dehydrogenation and combustion performances are listed in Table 2. [Table 2]

[0068] As shown in Table 2, the addition of transition metals that do not exist in the original catalyst can improve the methane conversion rate and propane conversion rate of the catalyst compared with aged catalysts such as Comparative Example B. For example, Samples 5-7, 9, and 12 have improved propane conversion rates and methane conversion rates compared with Comparative Example B. Some samples (i.e., Samples 8 and 10) have only an improved methane conversion rate compared with Comparative Example B. Sample 11 does not improve either the propane conversion rate or the methane conversion rate compared with Comparative Example B. That is, Table 3 shows that the addition of only some transition metals can improve the methane conversion rate, the propane conversion rate, or both of used catalysts such as Comparative Example B.

[0069] Example 3 - Addition of Iron or Manganese In Example 3, seven different samples of catalytic active particles were prepared and tested. Samples 13-19 were prepared via incipient wetness impregnation by adding the metal(s) specified in Comparative Example B using nitrate or amine nitrate metal precursors, followed by drying and calcination as in Comparative Example A. The amount of metal added to each of these samples and their dehydrogenation and combustion performance are listed in Table 3. [Table 3]

[0070] As shown in Table 3, samples modified with one of iron or manganese such as Samples 13-18 have improved propane conversion rates and methane conversion rates when compared with Comparative Example B that does not contain iron or manganese. Table 3 also shows that samples with a high iron loading such as Sample 19 improved the methane conversion rate but did not improve the propane conversion rate when compared with Comparative Example B.

[0071] Example 4 - Addition of Platinum and Another Metal In Example 4, 17 different samples of the catalytically active particles were prepared and tested. Samples 20 - 36 were prepared via incipient wetness impregnation by adding the metal(s) specified in Comparative Example B using a nitrate or amine nitrate metal precursor, followed by drying and calcination as in Comparative Example A. The amount of metal added for each of these samples, as well as their dehydrogenation and combustion performance, are listed in Table 4.

Table 4

[0072] As shown in Table 4, all samples modified by adding both platinum and manganese, such as Samples 20 - 26, have both improved propane conversion and methane conversion when compared to unmodified Comparative Example B over a wide range of possible modifications, such as 50 ppmw - 220 ppmw added platinum and 500 ppmw - 3000 ppmw added manganese.

[0073] 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. Further, both Sample 33, modified by adding platinum, manganese, and iron, and Sample 34, modified by adding manganese and iron, have improved propane conversion and methane conversion when compared to Comparative Example B.

[0074] Table 4 further shows that Sample 32, modified by adding both platinum and chromium, has 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, have improved propane conversion and methane conversion when compared to Comparative Example B.

[0075] In a first aspect of the present disclosure, the method may include operating a dehydrogenation process in which a hydrocarbon-containing feed is converted to light olefins, the dehydrogenation process utilizing a fluid process catalyst that circulates between a reactor and a combustor. Recovering the process catalyst from the dehydrogenation process, reforming the process catalyst to form a reformed catalyst, and returning and adding the reformed catalyst to the dehydrogenation process. The process catalyst includes 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 1 ppmw to 1000 ppmw of platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof, and at least 85 wt% of a support. Reforming the process catalyst includes adding one or more of manganese, iron, chromium, vanadium, or aluminum.

[0076] A second aspect of the present disclosure may include the first aspect, wherein the process catalyst includes 0.1 wt% to 10 wt% of gallium, 1 ppmw to 1000 ppmw of platinum, and at least 85 wt% of a support.

[0077] A third aspect of the present disclosure may include aspect 1 or 2, wherein the process catalyst does not include manganese and iron.

[0078] A fourth aspect of the present disclosure may include any one of aspects 1 to 3, wherein the process catalyst includes manganese, iron, or a combination thereof.

[0079] A fifth aspect of the present disclosure may include any one of aspects 1 to 4, wherein reforming the process catalyst includes adding manganese, and the reformed catalyst includes 100 ppmw to 5000 ppmw of manganese.

[0080] A sixth aspect of the present disclosure may include any one of aspects 1 to 5, wherein reforming the process catalyst includes adding iron, and the reformed catalyst includes 100 ppmw to 5000 ppmw of iron.

[0081] A seventh embodiment of the present disclosure may include any of the embodiments 1-6, wherein modifying the process catalyst includes adding chromium, and the modified catalyst includes between 100 ppmw and 5000 ppmw of chromium.

[0082] An eighth embodiment of the present disclosure may include any of the embodiments 1-7, where modifying the process catalyst includes adding vanadium, and the modified catalyst includes from 100 ppmw to 2000 ppmw of vanadium.

[0083] A ninth embodiment of the present disclosure can include any of the embodiments 1-8, wherein modifying the process catalyst includes adding aluminum, and the modifying catalyst includes 0.5% to 10% by weight aluminum.

[0084] A tenth embodiment of the present disclosure can include any of the embodiments 1-9, wherein modifying the process catalyst further includes adding one or more of platinum or gallium.

[0085] An eleventh embodiment of the present disclosure can include any of the first to tenth embodiments, wherein modifying the process catalyst further includes adding between 10 ppmw and 300 ppmw of platinum.

[0086] A twelfth embodiment of the present disclosure can include any of the first to eleventh embodiments, wherein modifying the process catalyst further includes adding 0.1 wt % to 0.5 wt % gallium.

[0087] A thirteenth aspect of the present disclosure may include any of the preceding aspects, wherein the support comprises one or more of alumina, silica, or a combination thereof.

[0088] A fourteenth embodiment of the present disclosure may include any of the preceding embodiments, wherein recovering the process catalyst occurs after the process catalyst has undergone at least four months of dehydrogenation process cycles.

[0089] A fifteenth aspect of the present disclosure may include any of the foregoing aspects, wherein the process catalyst is recovered from the dehydrogenation process when the combustion activity of the process catalyst has decreased by at least 60%.

[0090] 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 the disclosed embodiments incorporating the spirit and substance of the technology of the present disclosure can be conceived by those skilled in the art, and thus the technology should be construed to include all within the scope of the appended claims and their equivalents. Further, while some aspects of the present disclosure may be specified herein as preferred or particularly advantageous, it is contemplated that the present disclosure is not limited to these aspects.

[0091] 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 herein. Unless so specifically specified, the features disclosed and described herein should not be construed as "essential". The contemplated embodiments of the technology include those that include some or all of the features of the appended claims.

[0092] Note that for the purpose of describing and defining the present disclosure, the term "about" is used in the present disclosure to represent the degree of inherent uncertainty that may result from any quantitative comparison, value, measurement, or other representation. The term "about" is also used in the present disclosure to represent the degree to which a quantitative representation may vary from the reference of the description without causing a change in the basic function of the subject matter in question.

[0093] When relevant, when a composition is described as "comprising" one or more elements, embodiments of the composition "consisting of" or "consisting essentially of" those one or more elements are contemplated herein.

[0094] It should be understood that the flow or the composition range of the chemical components in the reactor may, in some embodiments, contain a mixture of isomers of that component. For example, the composition range specifying butene may include a mixture of various isomers of butene. It should be understood that the examples provide various flow composition ranges and that the total amount of isomers of a particular chemical composition may constitute the range.

[0095] 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".

[0096] It should be understood that any two quantitative values assigned to a property may constitute a range of that property and that all combinations of ranges formed from all the described 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, Operating a dehydrogenation process in which a hydrocarbon-containing feed is converted to a light olefin, wherein the dehydrogenation process utilizes a fluid process catalyst circulating between a reactor and a combustor, and the process catalyst is 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, ranging from 1 ppmW to 1000 ppmW. and comprising at least 85% by weight of a carrier, The process catalyst is recovered from the dehydrogenation process, Modifying the process catalyst to form a modified catalyst, wherein the modification of the process catalyst includes adding one or more of manganese, iron, chromium, or vanadium. A method comprising returning the reforming catalyst to the dehydrogenation process and adding it back in.

2. The process catalyst is 0.1% to 10% by weight of gallium, Platinum from 1 ppmW to 1000 ppmW, The method according to claim 1, comprising and at least 85% by weight of a carrier.

3. The method according to claim 1, wherein the process catalyst does not contain manganese and iron.

4. The method according to claim 1, wherein the process catalyst comprises manganese, iron, or a combination thereof.

5. The method according to claim 1, wherein the modification of the process catalyst includes adding manganese, and the modified catalyst contains 100 ppmw to 5000 ppmw of manganese.

6. The method according to claim 1, wherein the modification of the process catalyst includes adding iron, and the modified catalyst contains 100 ppmw to 5000 ppmw of iron.

7. The method according to claim 1, wherein the modification of the process catalyst includes adding chromium, and the modified catalyst contains 100 ppmw to 5000 ppmw of chromium.

8. The method according to claim 1, wherein the modification of the process catalyst includes adding vanadium, and the modified catalyst contains 100 ppm W to 2000 ppm W of vanadium.

9. The method according to claim 1, wherein modifying the process catalyst further comprises adding aluminum, and the modified catalyst contains 0.5% to 10% by weight of aluminum.

10. The method according to claim 1, further comprising modifying the process catalyst by adding one or more of platinum or gallium.

11. The method according to claim 1, further comprising modifying the process catalyst by adding 10 ppm W to 300 ppm W of platinum.

12. The method according to claim 1, further comprising modifying the process catalyst by adding 0.1% to 0.5% by weight of gallium.

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 any one of claims 1 to 13, wherein the recovery of the process catalyst is performed after the process catalyst has undergone a dehydrogenation process cycle of at least four months.

15. The method according to any one of claims 1 to 13, wherein the process catalyst is recovered from the dehydrogenation process when the combustion activity of the process catalyst decreases by at least 60%.

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