Methods for processing hydrocarbons that include four particulate solids beds and bubble breakers

Abstract

Hydrocarbons may be processed by a method including contacting a hydrocarbon feed stream with a particulate solid in a first particulate solids bed to form a product stream. The method may further including passing a portion or all of the particulate solid from the first particulate solids bed to a second particulate solids bed, from the second particulate solids bed to a third particulate solids bed, from the third particulate solids bed to a fourth particulate solids bed, and from the fourth particulate solids bed to the first particulate solids bed. The fourth particulate solids bed may fluctuate between a low-level state and a high-level state. A first particulate solids outlet may be positioned at or near the bottom of the fourth particulate solids bed. A second particulate solids outlet may be positioned in the top half of the fourth particulate solids bed during the low-level state. One or more bubble breakers may be positioned within the fourth particulate solids bed and above the second particulate solids outlet, wherein the fourth particulate solids bed may have a height of from 0-3 feet above the uppermost of the one or more bubble breakers in the low-level state, and wherein the fourth particulate solids bed may have a height of from 3-7 feet above the uppermost of the one or more bubble breakers in the high-level state.

Description

86068-WO-PCT / DOW 86068 WO1METHODS FOR PROCESSING HYDROCARBONS THAT INCLUDE FOUR PARTICULATE SOLIDS BEDS AND BUBBLE BREAKERSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 713,825 filed October 30, 2024, the contents of which are incorporated in their entirety herein.TECHNICAL FIELD

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

[0003] Fluidized bed reactors are used in a wide variety of industrial processes, such as those that utilized a circulating catalyst or other particulate solid. For example, olefinic materials may produced in processes that utilize fluidized bed reactors. Olefinic materials, such as ethylene, butene, propylene, and styrene, may be used as base materials to produce many different materials, such as polystyrene, polyethylene, polypropylene, isopropanol, and acrylic acid, which may be used in, e.g., packaging, construction, and textiles. As a result of this utility, there is a worldwide demand for olefinic materials, among other materials that may be produced by circulating fluidized bed processes. However, methods for efficiently producing such products are challenging, and improvements in technology for such purposes are desired by industry.SUMMARY

[0004] Described herein, according to one or more embodiments, are methods for processing hydrocarbons that comprise passing particulate solids between at least four particulate solid beds, where a feed is contacted with a particulate solid (such as a catalyst) in the first particulate solid bed, and the particulate solid circulates from the first to second, second to third, third to fourth, and fourth to first particulate solids beds. As described in greater detail herein, the fourth particulate solids bed may operate as a dense phase fluidized bed, and may fluctuate between a low-level state and a high-level state. For example, the high-level state may be utilized when extra particulate solids inventors is kept in the fourth particulate solids bed. Embodiments herein include a bubble breaker that is positioned within the fourth particulate solids bed and above a particulate solids outlet that is positioned in the top half of the fourth particulate solids86068-WO-PCT / DOW 86068 WO2 bed. It has been discovered that fluidization in the fourth fluidized bed, as described herein, may be enhanced when the fourth fluidized bed operates such that the top of the fourth fluidized bed is no more than 7 feet above the bubble breaker. Such positioning of the bubble breaker in conjunction with operating of the fourth particulate solids bed at specified low-level and high- level states may enhance regularity of fluidization and / or flow at or near, or through, the particulate solids outlet that is positioned in the top half of the fourth particulate solids bed.

[0005] According to one or more embodiments, hydrocarbons may be processed by a method comprising contacting a hydrocarbon feed stream with a particulate solid in a first particulate solids bed to form a product stream. The method may further comprising passing a portion or all of the particulate solid from the first particulate solids bed to a second particulate solids bed, from the second particulate solids bed to a third particulate solids bed, from the third particulate solids bed to a fourth particulate solids bed, and from the fourth particulate solids bed to the first particulate solids bed. The fourth particulate solids bed may fluctuate between a low- level state and a high-level state. A first particulate solids outlet may be positioned at or near the bottom of the fourth particulate solids bed. A second particulate solids outlet may be positioned in the top half of the fourth particulate solids bed during the low-level state. One or more bubble breakers may be positioned within the fourth particulate solids bed and above the second particulate solids outlet, wherein the fourth particulate solids bed may have a height of from 0-3 feet above the uppermost of the one or more bubble breakers in the low-level state, and wherein the fourth particulate solids bed may have a height of from 3-7 feet above the uppermost of the one or more bubble breakers in the high-level state.

[0006] It is to be understood that both the preceding general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter. Additional features and advantages of the embodiments will be set forth in the detailed description and, in part, will be readily apparent to persons of ordinary skill in the art from that description, which includes the accompanying drawing and claims, or recognized by practicing the described embodiments. The drawing is included to provide a further understanding of the embodiments and, together with the detailed description, serves to explain the principles and operations of the claimed subject matter. However, the embodiment depicted in the drawing is illustrative and exemplary in nature, and not intended to limit the claimed subject matter.86068-WO-PCT / DOW 86068 WO3BRIEF DESCRIPTION OF THE DRAWINGS

[0007] The following detailed description may be better understood when read in conjunction with the following drawing, in which:

[0008] FIG. 1 schematically depicts a hydrocarbon processing system, according to one or more embodiments of the present disclosure;

[0009] FIG. 2A schematically depicts a particulate solids bed at a low-level state, according to one or more embodiments of the present disclosure;

[0010] FIG. 2B schematically depicts a particulate solids bed at a high-level state, according to one or more embodiments of the present disclosure; and

[0011] FIG. 3 schematically depicts a hydrocarbon processing system, according to one or more embodiments of the present disclosure.

[0012] When describing the simplified schematic illustration of FIGS. 1-3, the numerous valves, temperature sensors, electronic controllers, and the like, which may be used and are well known to a person of ordinary skill in the art, are not included. Further, accompanying components that are often included in such reactor systems, such as air supplies, heat exchangers, surge tanks, and the like are also not included. However, it should be understood that these components are within the scope of the present disclosure.

[0013] Reference will now be made in greater detail to various embodiments, some of which are illustrated in the accompanying drawing.DETAILED DESCRIPTION

[0014] Described herein are methods and apparatuses utilizing fluidized bed technology which, generally, may include four solid particulate beds. According to one or more embodiments, and as described herein in detail in the context of a dehydrogenation process for making olefinic materials, the first particulate solids bed may be the main reactor where system product is produced, and the particulate solid may circulate between the four particulate solids beds. The fourth particulate solids bed may operate as a dense phase fluidized bed, such as a bubbling bed.86068-WO-PCT / DOW 86068 WO4

[0015] According to one or more embodiments, the fourth particulate solids bed may fluctuate in height from a low-level state (sometimes interchangeably referred to as a “normal” state) to a high-level state. Such fluctuation may be intentional or unintentional, and may be from a wide variety of factors. For example, it may be desirable to allow for particulate solids to build up in the fourth particulate solids bed since, in some embodiments, the amount of particulate solids in this bed has little or no effect on the overall process. For example, when the first particulate solids bed is a reactor and the third particulate solids bed is a combustor, where both operate in a fast fluidized or turbulent fluidization regime, the amount of particulate solid pushed into such units may affect overall system efficiencies. Too little particulate solid in the reactor may cause lower conversion than desired, and too much particulate solid in the reactor may affect desired fluidization and / or catalyst deactivation. In other embodiments, the height of the fourth particulate solids bed may vary from low-level conditions during startup or shutdown. In summary, in various system designs, the fourth particulate solids bed may be the best place to store excess particulate solids inventory, according to some embodiments disclosed herein.

[0016] According to embodiments, particulate solids may exit the fourth particulate solids bed through two different particulate solids outlets. One outlet may be near the bottom of the fourth particulate solids bed and may pass the particulate solid to the first particulate solids bed. The other outlet may be positioned in the top half of the fourth particulate solids bed, which may recycle particulate solids back to the third particulate solids bed, according to some embodiments.

[0017] It has been observed that when the fourth particulate solids bed operates in the low- level state, particulate solids flow through the upper outlet may be relatively standard with relatively good distribution and flow. However, when the fourth particulate solids bed has extra catalyst inventory and is operating in the high-level state, the accumulation of particulate solids in the fourth particulate solids bed may result in undesirable flow patterns, such as streaming and / or maldistribution, within the fourth particulate solids bed near the inlet of the upper outlet.

[0018] It has presently been discovered that positioning one or more bubble breakers above the particulate solids outlet and within the fourth particulate solids bed during the low-level state and the high-level state may prevent undesirable flow patterns in the fourth particulate solids bed during the high-level state. This may increase the capacity of the fourth particulate solids bed for containing particulate solids displaced from the other particulate solids beds during startup,86068-WO-PCT / DOW 86068 WO5 shutdown, or system upsets of the hydrocarbon processing system by allowing for relatively steady flow of particulate solid through the upper outlet.

[0019] According to additional embodiments, it has been found that, for effective fluidization to occur in the fourth particulate solids bed, the fourth particulate solids bed should operate at heights of no greater than 7 feet above the uppermost bubble breaker positioned above the upper outlet. It is believed that operation above 7 feet with respect to the uppermost bubble breaker may result in maldistribution of the particulate solid. As such, according to embodiments, the low level state may be defined as when the fourth particulate solids bed has a height of from 0-3 feet above the uppermost of the one or more bubble breakers, and the high-level state may be defined as when the fourth particulate solids bed has a height of from 3 -7 feet above the uppermost of the one or more bubble breakers. Surprisingly, it is discovered and presently observed that suitable fluidization is maintained when the fourth particulate solids bed does not operate such that it has a height of greater than 7 feet above the uppermost of the one or more bubble breakers in the high-level state.

[0020] Now describing some specific embodiments of the methods described herein, methods for processing hydrocarbons described herein may comprise contacting a hydrocarbon feed stream with a particulate solid to form a product stream. Embodiments of methods for processing hydrocarbons described herein may comprise passing particulate solid between four particulate solids beds in a hydrocarbon processing system. FIG. 1 depicts such a hydrocarbon processing system, which includes four particulate solids beds.

[0021] Referring now to FIG. 1, the hydrocarbon processing system 100 may comprise a first particulate solids bed 101, a second particulate solids bed 102, a third particulate solids bed 103, and a fourth particulate solids bed 104. In one or more embodiments, particulate solids may circulate from the first particulate solids bed 101 to the second particulate solids bed 102, from the second particulate solids bed 102 to the third particulate solids bed 103, from the third particulate solids bed 103 to the fourth particulate solids bed 104, and from the fourth particulate solids bed 104 to the first particulate solids bed 101. In one or more embodiments, particulate solids may be recycled from the second particulate solids bed 102 to the first particulate solids bed 101. In one or more embodiments, particulate solids may be recycled from the fourth particulate solids bed 104 to the third particulate solids bed 103.86068-WO-PCT / DOW 86068 WO6

[0022] Each of the first particulate solids bed 101, the second particulate solids bed 102, the third particulate solids bed 103, and the fourth particulate solids bed 104 may be contained within separate vessels. The vessels may be any suitable vessels, including but not limited to drums, barrels, vats, tanks, and any other container suitable for containing a bed of particulate solids. The vessels may be generally cylindrical in shape (i.e., having a substantially circular diameter), or may alternately be non-cylindrically shaped, such as prism shaped with cross-sectional shaped of triangles, rectangles, pentagons, hexagons, octagons, ovals, or other polygons or curved closed shapes, or combinations thereof. The vessels may be fluidly coupled to allow particulate solids to pass between the particulate solids beds.

[0023] In one or more embodiments, each of the first particulate solids bed 101 and the third particulate solids bed 103 may be a turbulent fluidized bed or a fast fluidized bed. In one or more embodiments the fourth particulate solids bed 104 may be a dense fluidized bed. In one or more embodiments, the second particulate solids bed 102 may be a dense fluidized bed.

[0024] As described herein, a “dense fluidized bed” refers to a fluidized bed having a clearly defined upper limit or surface. For example, a dense fluidized bed may include such fluidization regimes as smooth fluidization, bubbling fluidization, and slugging fluidization. In a dense fluidized bed, the particle entrainment rate may be low, but may increase as the velocity of the gas flowing through the bed increases. It should be understood that in some embodiments, a freeboard region may be positioned above a “dense fluidized bed.” As described herein, a “freeboard region” refers to a dilute phase region where gas and particles disengage. Accordingly, particulate solids may pass through the freeboard region and enter the dense fluidized bed below the freeboard region.

[0025] As described herein, a “fast fluidized bed” refers to a fluidized bed where there is no clear upper limit to the fluidized bed. Instead, particles are dispersed throughout the vessel containing the fluidized bed. The particles in a fast fluidized bed are transported out of the fluidized bed with the gas flowing through the fluidized bed, and particles are generally added to the fast fluidized bed to replace the particles transported out of the bed.

[0026] As described herein, “turbulent fluidized bed” may refer to a fluidized bed that is in a transition state between a dense fluidized bed and a fast fluidized bed. In some cases, turbulent fluidized beds may exhibit no clear upper limit, like fast fluidized beds. In some cases, turbulent86068-WO-PCT / DOW 86068 WO7 fluidized beds may exhibit bubbling, like dense fluidized beds; however, the bubbles in turbulent fluidized beds may consistently break, resulting in a more even distribution of particles than is observed in bubbling or slugging fluidized beds.

[0027] In one or more embodiments, the fourth particulate solids bed 104 may fluctuate between a low-level state, depicted in FIG. 2 A, and a high-level state, depicted in FIG. 2B. Referring now to FIGS 2A and 2B, the fourth particulate solids bed 104 may be contained within a vessel 210. The fourth particulate solids bed may have an upper surface 204. In the high-level state, a distance between the bottom 212 of the vessel 210 and the upper surface 204 of the fourth particulate solids bed 104 is greater than the distance between the bottom 212 of the vessel 210 and the upper surface 204 of the fourth particulate solids bed 104 in the low-level state. Without intending to be bound by theory, the fourth particulate solids bed 104 may be in a low-level state when the hydrocarbon processing system 100 is at steady state operation. The fourth particulate solids bed 104 may be in a high-level state at other points during the operation of the hydrocarbon processing system 100 including, but not limited to, startup, shutdown, and during some system upsets. For example, during startup of the hydrocarbon processing system 100 particulate solids may be removed from the first particulate solids bed 101, as the rate of gas fed to the first particulate solids bed 101 is increased. The particulate solids removed from the first particulate solids bed 101 may accumulate in the fourth particulate solids bed 104 increasing the height of the upper surface 204 of the fourth particulate solids bed 104.

[0028] The vessel 210 may comprise a first particulate solids outlet 220 positioned at or near the bottom of the fourth particulate solids bed 104. As described herein, a position “at or near” the bottom of the fourth particulate solids bed 104 refers to a position in the bottom 10%, 5%, 3%, or even 1% of the fourth particulate solids bed 104. In one or more embodiments, particulate solids may exit the fourth particulate solids bed 104 through the first particulate solids outlet 220 and pass to the first particulate solids bed 101.

[0029] In one or more embodiments, the vessel 210 may comprise a second particulate solids outlet 230 positioned in the top half of the fourth particulate solids bed 104 during the low- level state. In one or more embodiments, the second particulate solids outlet 230 may be positioned in the top third of the fourth particulate solids bed 104 during the low-level state. In some embodiments, the second particulate solids outlet 230 may be positioned in the top 20% of the fourth particulate solids bed 104 during the low-level state. In one or more embodiments,86068-WO-PCT / DOW 86068 WO8 particulate solids may exit the fourth particulate solids bed 104 through the second particulate solids outlet 230 and pass to the third particulate solids bed 103.

[0030] Referring now to FIG. 2B, one or more bubble breakers 240 may be positioned above the second particulate solids outlet 230 and within the fourth particulate solids bed 104. For example, in the embodiments depicted in FIGS. 2A and 2B, first bubble breaker 240a and second bubble breaker 240b are both positioned above the second particulate solids outlet 230 and below the upper surface 204 of the fourth particulate solids bed 104. In low-level state operation, the distance between bubble breaker 240b and upper surface 204 of the fourth particulate solids bed 104 may be 0-3 feet, and the high-level state operation, the distance between bubble breaker 240b and upper surface 204 of the fourth particulate solids bed 104 may be 3-7 feet.

[0031] In one or more embodiments, a “bubble breaker” as described herein, may include a wide variety of system internals that function to break bubbles in a fluidization regime. In one or more embodiments, the one or more bubble breakers 240 may comprise a grating, a plurality of chevrons, structured packing suck as KFBETM (available from Koch-Glitsch) or similar, and a plurality of rods. In some embodiments, the bubble breaker 240 may comprise a grating. The grating may include a plurality of openings. The plurality of openings may be through a substantially horizontal surface portion of the grating in a substantially horizontal plane. Each of the plurality of openings may have any suitable shape, such as a square, rectangle, hexagon, diamond, circle, oval, elipse, or any other suitable shape. In some embodiments, the grating may comprise a plurality of rectangular openings, sometimes called “subway grating” in industry. The plurality of openings may be from 0.5 inches to 10 inches in width or diameter, or from 1 inch to 4 inches in width or diameter, such that the plurality of openings are smaller in width or diameter than the plurality of gas bubbles moving through the fourth particulate solids bed 104. Thus, the plurality of openings may break up the plurality of gas bubbles flowing through the fourth particulate solids bed 104. Without intending to be bound by theory, breaking up the gas bubbles may prevent streaming or other undesirable flow conditions, while promoting smooth fluidization of the fourth particulate solids bed 104.

[0032] In some embodiments, the bubble breakers 240 may comprise a plurality of chevrons or a plurality of bars. Similar to the gratings described hereinabove, the plurality of chevrons or the plurality of bars may extend through the fluidized bed in a substantially horizontal plane. Openings between adjacent chevrons or bars may have a width such that the plurality of openings86068-WO-PCT / DOW 86068 WO9 are smaller in width the plurality of gas bubbles moving through the fourth particulate solids bed 104. Thus, the plurality of openings may break up the plurality of gas bubbles flowing through the fourth particulate solids bed 104.

[0033] In one or more embodiments, the one or more bubble breakers 240 may have an open area ratio from 50% to 99%. For example, in the embodiment of grating bubble breakers, the one or more bubble breakers 240 may have an open area ratio from 50% to 90%, from 60% to 90%, from 70% to 90%, from 80% to 90%, from 50% to 80%, from 50% to 70%, from 50% to 60%, or any range or combination of ranges formed from these endpoints. As described herein, an “open area ratio” refers to the percentage of the bubble breaker that is occupied by holes or openings.

[0034] Referring again to FIG. 2B, in one or more embodiments, the upper surface 204 of the fourth particulate solids bed 104 may be less than or equal to 7 feet above the one or more bubble breakers 240 positioned above the second particulate solids outlet 230 during the high- level state. For example, the upper surface 204 of the fourth particulate solids bed 104 may be less than or equal to 7 feet, 6 feet, 5 feet, or even 4 feet above the one or more bubble breakers 240 positioned above the second particulate solids outlet 230 during the high-level state. In such embodiments the upper surface 204 of the fourth particulate solids bed 104 is less than or equal to 7 feet above the uppermost bubble breaker 240 positioned above the second particulate solids outlet 230. Without intending to be bound by theory, if the distance between the upper surface 204 of the fourth particulate solids bed 104 and the bubble breaker 240b is too great, then streaming may occur in the fourth particulate solids bed 104. This may prevent the flow of particulate solids from the fourth particulate solids bed 104 to the third particulate solids bed 103. In one or more embodiments where particulate solids are regenerated in the third particulate solids bed 103 by combusting coke on the particulate solids, a reduction in particulate solids being recycled from the fourth particulate solids bed 104 to the third particulate solids bed 103 may result in insufficient particulate solid inventory in the third particulate solids bed for the combustion to occur, which may disrupt operation of the hydrocarbon processing system 100. Appropriate spacing between the bubble breakers 240 may expand the capacity of the fourth particulate solids bed 104 and prevent streaming within the fourth particulate solids bed 104.

[0035] In one or more embodiments, one or more additional bubble breakers 250 may be positioned between the first particulate solids outlet 220 and the second particulate solids outlet 230. It should be understood that the description of the structure of the one or more bubble86068-WO-PCT / DOW 86068 WO10 breakers 240 positioned above the second particulate solids outlet 230 also applies to the one or more bubble breakers 250 positioned between the first particulate solids outlet 220 and the second particulate solids outlet 230. Any suitable number of bubble breakers 250 may be positioned between the first particulate solids outlet 220 and the second particulate solids outlet 230. For example, 1, 2, 3, 4, 5, or more bubble breakers 250 may be positioned between the first particulate solids outlet 220 and the second particulate solids outlet 230. In one or more embodiments, the vertical distance between adjacent bubble breakers 250 may be less than or equal to 7 feet. For example, the vertical distance between adjacent bubble breakers 250 may be less than or equal to 7 feet, 6 feet, 5 feet or even 4 feet. In one or more embodiments, a bubble breaker may be positioned about 1 foot above the second particulate solids outlet 230. Without intending to be bound by theory, positioning one or more bubble breakers 250 between the first particulate solids outlet 220 and the second particulate solids outlet 230 may promote smooth fluidization within the fourth particulate solids bed 104 and may prevent streaming or other such undesirable flow patterns.

[0036] Methods for processing hydrocarbons described hereinabove may comprise contacting a hydrocarbon feed stream with a particulate solid to form a product stream. In one or more embodiments, the product stream may comprise olefinic materials. As described herein, olefinic materials refer to compounds that include at least one alkene moiety (i.e., a C=C double bond). In some embodiments, the olefinic materials may be “light olefins” such as ethylene, propylene, butene, or styrene. These olefinic materials can be produced from a variety of hydrocarbon feed streams by utilizing different reaction mechanisms. For example, light olefins may be produced by at least dehydrogenation reactions, cracking reactions, dehydration reactions, and methanol-to-olefm reactions. These reaction types may utilize different feed streams and different particulate solids to produce olefinic materials.

[0037] According to one or more embodiments, the reaction may be a dehydrogenation reaction. According to such embodiments, the hydrocarbon feed stream may comprise one or more of ethylbenzene, ethane, propane, n-butane, and i-butane. In one or more embodiments, the hydrocarbon feed stream may comprise at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.% or even at least 99 wt.% of ethane. In additional embodiments, the hydrocarbon feed stream may comprise at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.% or even at least 99 wt.% of propane. In additional embodiments, the hydrocarbon feed stream may comprise at least 50 wt.%,86068-WO-PCT / DOW 86068 WO11 at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.% or even at least 99 wt.% of n-butane. In additional embodiments, the hydrocarbon feed stream may comprise at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.% or even at least 99 wt.% of i-butane. In additional embodiments, the hydrocarbon feed stream may comprise at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.% or even at least 99 wt.% of ethylbenzene. In additional embodiments, the hydrocarbon feed stream may comprise at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.% or even at least 99 wt.% of the sum of ethylbenzene, ethane, propane, n-butane, and i-butane.

[0038] In one or more embodiments, the dehydrogenation reaction may utilize gallium and / or platinum particulate solids as a catalyst. In such embodiments, the particulate solids may comprise a gallium and / or platinum catalyst. As described herein, a gallium and / or platinum catalyst comprises gallium, platinum, or both. The gallium and / or platinum catalyst may be carried by an alumina or alumina silica support, and may optionally comprise potassium. Such gallium and / or platinum catalysts are disclosed in U.S. Pat. No. 8,669,406, which is incorporated herein by reference in its entirety. However, it should be understood that other suitable catalysts may be utilized to perform the dehydrogenation reaction.

[0039] In one or more embodiments, the reaction mechanism may be dehydrogenation followed by combustion (in the same chamber). In such embodiments, a dehydrogenation reaction may produce hydrogen as a byproduct, and an oxygen carrier material may contact the hydrogen and promote combustion of the hydrogen, forming water. Examples of such reaction mechanisms, which are contemplated as possible reactions mechanisms for the systems and methods described herein, are disclosed in WO 2020 / 046978, the teachings of which are incorporated by reference in their entirety herein.

[0040] According to one or more embodiments, the reaction may be a cracking reaction. According to such embodiments, the hydrocarbon feed stream may comprise one or more of naphtha, n-butane, or i-butane. According to one or more embodiments, the hydrocarbon feed stream may comprise at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.% or even at least 99 wt.% of naphtha. In additional embodiments, the hydrocarbon feed stream may comprise at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.% or even at least 99 wt.% of n-butane. In additional86068-WO-PCT / DOW 86068 WO12 embodiments, the hydrocarbon feed stream may comprise at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.% or even at least 99 wt.% of i- butane. In additional embodiments, the hydrocarbon feed stream may comprise at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.% or even at least 99 wt.% of the sum of naphtha, n-butane, and i-butane.

[0041] In one or more embodiments, the cracking reaction may utilize one or more zeolites as a catalyst. In such embodiments, the particulate solids may comprise one or more zeolites. In some embodiments, the one or more zeolites utilized in the cracking reaction may comprise a ZSM-5 zeolite. However, it should be understood that other suitable catalysts may be utilized to perform the cracking reaction. For example, suitable catalysts that are commercially available may include Intercat Super Z Excel or Intercat Super Z Exceed. In additional embodiments, the cracking catalyst may comprise, in addition to a catalytically active material, platinum. For example, the cracking catalyst may include from 0.001 wt.% to 0.05 wt.% of platinum. The platinum may be sprayed on as platinum nitrate and calcined at an elevated temperature, such as around 700°C. Without being bound by theory, it is believed that the addition of platinum to the catalyst may allow for easier combustion of supplemental fuels, such as methane.

[0042] According to one or more embodiments, the reaction may be a dehydration reaction. According to such embodiments, the hydrocarbon feed stream may comprise one or more of ethanol, propanol, or butanol. According to one or more embodiments, the hydrocarbon feed stream may comprise at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.% or even at least 99 wt.% of ethanol. In additional embodiments, the hydrocarbon feed stream may comprise at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.% or even at least 99 wt.% of propanol. In additional embodiments, the hydrocarbon feed stream may comprise at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.% or even at least 99 wt.% of butanol. In additional embodiments, the hydrocarbon feed stream or may comprise at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.% or even at least 99 wt.% of the sum of ethanol, propanol, and butanol.

[0043] In one or more embodiments, the dehydration reaction may utilize one or more acid catalysts. In such embodiments, the particulate solids may comprise one or more acid catalysts. In some embodiments, the one or more acid catalysts utilized in the dehydration reaction may86068-WO-PCT / DOW 86068 WO13 comprise a zeolite (such as ZSM-5 zeolite), alumina, amorphous aluminosilicate, acid clay, or combinations thereof. For example, commercially available alumina catalysts which may be suitable, according to one or more embodiments, include SynDol (available from Scientific Design Company), V200 (available from UOP), or P200 (available from Sasol). Commercially available zeolite catalysts which may be suitable include CBV 8014, CBV 28014 (each available from Zeolyst). Commercially available amorphous aluminosilicate catalysts which may be suitable include silica-alumina catalyst support, grade 135 (available from Sigma Aldrich). However, it should be understood that other suitable catalysts may be utilized to perform the dehydration reaction.

[0044] According to one or more embodiments, the reaction may be a methanol-to-olefin reaction. According to such embodiments, the hydrocarbon feed stream may comprise methanol. According to one or more embodiments, the hydrocarbon feed stream may comprise at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.% or even at least 99 wt.% of methanol.

[0045] In one or more embodiments, the methanol-to-olefin reaction may utilize one or more zeolites as a catalyst. In such embodiments, the particulate solids may comprise one or more zeolites. In some embodiments, the one or more zeolites utilized in the methanol-to-olefin reaction may comprise a one or more of a ZSM-5 zeolite or a SAPO-34 zeolite. However, it should be understood that other suitable catalysts may be utilized to perform the methanol-to-olefin reaction.

[0046] In one or more embodiments, the product stream may comprise olefinic materials. The olefinic materials may comprise one or more of styrene, ethylene, propylene, or butene. As described herein, butene many include any isomer of butene, such as u-butylene, cis-[3-butylene, trans-[3-butylene, and isobutylene. In some embodiments, the product stream may comprise at least 20 wt.% olefinic material. For example, the product stream may comprise at least 20 wt.%, 30 wt.%, 40 wt.%, 50 wt.%, 60 wt.%, or 70 wt.% olefinic material.

[0047] Embodiments of the methods presently disclosed are described in detail herein in the context of the hydrocarbon processing system 100 of FIG. 3 operating as a fluidized dehydrogenation reactor system to produce olefinic materials, such as propylene. However, it should be understood that the principles disclosed and taught herein may be applicable to other systems which utilize different system components oriented in different ways. For example, the86068-WO-PCT / DOW 86068 WO14 concepts described herein may be equally applied to other systems with alternate reactor units and regeneration units, such as those that include downers rather than risers. It should be further understood that not all portions of FIG. 3 should be construed as essential to the claimed subject matter. Moreover, while the recited method steps in the appended claims are described herein in the context of FIG. 3, such recited method steps should be understood as adaptable to other systems, as would be understood by those skilled in the art.

[0048] Referring now to FIG. 3, the hydrocarbon processing system 100 may comprise a reactor portion 400 and a particulate solid processing portion 500. As used herein in the context of FIG. 3, a reactor portion 400 generally refers to the portion of the hydrocarbon processing system 100 in which the major process reaction takes place (e.g., dehydrogenation, cracking, dehydration, methanol to olefin, etc.), and the particulate solid is separated from the olefin containing product stream of the reaction. In one or more embodiments, the particulate solid may be spent, meaning that the particulate solid is at least partially deactivated. As used herein, “deactivated” may refer to a particulate solid which has reduced catalytic activity or is cooler as compared to particulate solid entering the reactor portion 400. However, deactivated particulate solid may maintain some catalytic activity. Reduced catalytic activity may result from contamination with a substance such as coke. Coke may form on the particulate solid within the reactor portion 400. Also, as used herein, the particulate solid processing portion 500 generally refers to the portion of the hydrocarbon processing system 100 where the particulate solid is regenerated and the regenerated particulate solid is separated from the other process material. The deactivated particulate solid may be reactivated by, but not limited to, oxidizing the particulate solid by contact with an oxygen containing gas, combusting coke present on the particulate solid, combusting a supplemental fuel to heat the particulate solid, or combinations thereof. The reactivated particulate solid from the particulate solid processing portion 500 is then passed back to the reactor portion 400. The particulate solid may be heated during regeneration to aid with regeneration and also because heated particulate solid serves as a heat carrier to carry heat from the combustor 550 to the reactor portion 400 to facilitate the reaction.

[0049] Still referring to FIG. 3, the hydrocarbon feed stream may enter feed inlet 634 into the reactor 402, and the product stream may exit the hydrocarbon processing system 100 via pipe 620. According to one or more embodiments, the hydrocarbon processing system 100 may be operated by feeding a hydrocarbon feed stream and a fluidized particulate solid into the upstream reactor section 450. The hydrocarbon feed stream contacts the particulate solid in the upstream86068-WO-PCT / DOW 86068 WO15 reactor section 450, and each flow upwardly into and through the downstream reactor section 430 to produce an olefin-containing product stream. The reactor 402 may operate at relatively high temperatures, such as from 500 °C to 800 °C (e.g., from 500 °C to 550 °C, from 550 °C to 600 °C, from 600 °C to 650 °C, from 650 °C to 700 °C, from 700 °C to 750 °C, from 750 °C to 800 °C, or any combination of one or more of these ranges).

[0050] Now referring to FIG. 3 in detail, the reactor portion 400 may comprise an upstream reactor section 450, a transition section 458, and a downstream reactor section 430, such as a riser. The transition section 458 may connect the upstream reactor section 450 with the downstream reactor section 430. As depicted in FIG. 3, the upstream reactor section 450 may be positioned below the downstream reactor section 430. Such a configuration may be referred to as an upflow configuration in the reactor 402. The upstream reactor section 450 may include a vessel, drum, barrel, vat, or other container suitable for a given chemical reaction. As depicted in FIG. 3, the upstream reactor section 450 may be connected to the downstream reactor section 430 via the transition section 458. The upstream reactor section 450 may generally comprise a greater cross- sectional area than the downstream reactor section 430. The transition section 458 may be tapered from the size of the cross-section of the upstream reactor section 450 to the size of the crosssection of the downstream reactor section 430 such that the transition section 458 projects inwardly from the upstream reactor section 450 to the downstream reactor section 430. For example, the transition section 458 may be a frustum.

[0051] The upstream reactor section 450 may be connected to a transport riser 630, which, in operation may provide reactivated particulate solid in a feed stream to the reactor portion 400. The reactivated particulate solid and / or reactant chemicals may be mixed with a distributor 460 housed in the upstream reactor section 450. The particulate solid entering the upstream reactor section 450 via transport riser 630 may be passed through standpipe 624 to a transport riser 630, thus arriving from the particulate solid processing portion 500. In some embodiments, particulate solid may come directly from the particulate solid separation section 410 via standpipe 622 and into a transport riser 630, where it enters the upstream reactor section 450, where in such embodiments some of the particulate solid is not passed through the particulate solid processing portion 500. The particulate solid can also be fed via standpipe 622 directly to the upstream reactor section 450 (not depicted in FIG. 3). This particulate solid may be somewhat deactivated, but may still, in some embodiments, be suitable for reaction in the upstream reactor section 250, particularly when used in combination with reactivated particulate solid.86068-WO-PCT / DOW 86068 WO16

[0052] As depicted in FIG. 3, the first particulate solids bed 101 may be in the reactor 402. In one or more embodiments, the first particulate solids bed 101 may be a turbulent or fast fluidized bed and may occupy substantially the entire volume of the reactor 402. As described herein, “substantially the entire volume” may refer to at least 95% of the volume, at least 97% of the volume, or even at least 99% of the volume.

[0053] According to embodiments, the product stream and the particulate solid may be passed out of the downstream reactor section 430 to a separation device 420 in the particulate solid separation section 410, where the particulate solid is at least partially separated from the olefm-containing product, which is transported out of the particulate solid separation section 410. According to one or more embodiments, following separation from vapors in the separation device 420, the particulate solid may generally move through the stripper 424 to the particulate solid outlet port 422 where the particulate solid is transferred out of the reactor portion 400 via standpipe 626 and into the particulate solid processing portion 500.

[0054] The second particulate solids bed 102 may be in the particulate solid separation section 410. In one or more embodiments, the second particulate solids bed 102 may be a dense fluidized bed having an upper surface 122 and occupying at least a portion of the particulate solid separation section 410. In some embodiments, the second particulate solids bed 102 may be positioned at least partially within the stripper 424.

[0055] According to one or more embodiments, the separation device 420 may be a cyclonic separation system, which may include two or more stages of cyclonic separation. In embodiments where the separation device 420 comprises more than one cyclonic separation stages, the first separation device into which the fluidized stream enters is referred to a primary cyclonic separation device. The fluidized effluent from the primary cyclonic separation device may enter into a secondary cyclonic separation device for further separation. Primary cyclonic separation devices may include, for example, primary cyclones, and systems commercially available under the names VSS (commercially available from UOP), LD2 (commercially available from Stone and Webster), and RS2 (commercially available from Stone and Webster). Primary cyclones are described, for example, in U.S. Patent Nos. 4,579,716; 5,190,650; and 5,275,641, which are each incorporated by reference in their entirety herein. In some separation systems utilizing primary cyclones as the primary cyclonic separation device, one or more set of additional cyclones, e.g. secondary cyclones and tertiary cyclones, are employed for further separation of the catalyst from86068-WO-PCT / DOW 86068 WO17 the product gas. It should be understood that any primary cyclonic separation device may be used in embodiments of the present disclosure.

[0056] Still referring to FIG. 3, the separated particulate solid is passed from the particulate solid separation section 410 to the combustor 550. In some embodiments, the particulate solid may be exposed to another oxy gen-containing gas, such as air, downstream of the reactor 402 and upstream of the combustor 550, such as in a standpipe leading to the combustor 550. Such oxygen exposure may serve to oxidize the particulate solid prior to combustion, which may improve combustion catalytic functionality.

[0057] In the combustor 550, the particulate solid may be processed by, for example, combustion of coke with oxygen (if coke is present) and with combustion of supplemental fuel. For example, and without limitation, the particulate solid may be de-coked and / or supplemental fuel may be combusted to heat the particulate solid. The particulate solid is then passed out of the combustor 550 and through the riser 530 to a riser termination separator 578, where the gas and solid components from the riser 530 are at least partially separated. The vapor and remaining solids are transported to a secondary separation device 520 in the particulate solid separation section 510 where the remaining particulate solid is separated from the gases from the particulate solid processing (e.g., gases emitted by combustion of spent particulate solid or supplemental fuel, referred to herein as flue gas). The flue gas may pass out of the particulate solid processing portion 500 via outlet pipe 632. The separated particulate solid is then passed through the oxygen treatment zone 580 within the particulate solid separation section 510 to the upstream reactor section 450 via standpipe 624 and transport riser 630, where it is further utilized in a reaction. Thus, the particulate solid, in operation, may cycle between the reactor portion 400 and the particulate solid processing portion 500.

[0058] Referring now to the particulate solid processing portion 500, as depicted in FIG. 3, the combustor 550 of the particulate solid processing portion 500 may include one or more lower reactor portion inlet ports 552 and may be in fluid communication with the riser 530. Oxygen-containing gas, such as air, may be passed through pipe 628 into the combustor 550. In general, the oxygen-containing gas may comprise at least 10 mol.% oxygen. The combustor 550 may be in fluid communication with the particulate solid separation section 410 via standpipe 626, which may supply spent particulate solid from the reactor portion 400 to the particulate solid processing portion 500 for regeneration. The combustor 550 and riser 530 may collectively be86068-WO-PCT / DOW 86068 WO18 referred to as the particulate solid combustion reactor 502. Geometries as described with respect to the upstream reactor section 450 and downstream reactor section 430 may equally apply to the combustor 550 and riser 530.

[0059] Still referring to FIG. 3, the third particulate solids bed 103 may be in the particulate solid combustion reactor 502. In one or more embodiments, the third particulate solids bed may be a turbulent or bubbling fluidized bed and may occupy substantially the entire volume of the particulate solid combustion reactor 502.

[0060] In one or more embodiments, the combustor 550 may also include a fuel inlet 554, which may supply a fuel, such as a hydrocarbon stream, to the combustor 550. The particulate solid may be heated in the particulate solid processing portion 500 by combustion of supplemental fuels. Supplemental fuels may combust with oxygen to heat the catalyst, and supplemental fuels such as a supplemental fuel, such as hydrogen, methane, ethane, propane, natural gas, or combinations thereof.

[0061] Referring again to FIG. 3, as described in one or more embodiments, following separation of flue gas from particulate solid in the riser termination separator 578 and secondary separation device 520, treatment of the processed particulate solid with an oxy gen-containing gas, such as air, is conducted in the oxygen treatment zone 580. In general, the oxygen-containing gas in the oxygen treatment zone 580 may comprise at least 10 mol.% oxygen, and is substantially void of combustible gaseous hydrocarbons that are present in the combustor 550. The oxygen treatment zone 580 may include an oxygen-containing gas inlet 572, which may supply an oxygen-containing gas to the oxygen treatment zone 580 for oxygen treatment of the particulate solid.

[0062] As is disclosed herein, in one or more embodiments, the particulate solid may be exposed to an oxygen-containing gas in oxygen treatment zone 580. For example, the particulate solid may be exposed to an oxygen-containing gas for from 2 min. to 20 min., such as from 2 min. to 4 min., from 4 min. to 6 min., from 6 min. to 8 min., from 8 min. to 10 min., from 10 min. to 12 min., from 12 min. to 14 min., from 14 min. to 16 min., from 16 min. to 18 min., from 18 min. to 20 min., or any combination of these ranges. In some embodiments the catalyst may be exposed to an oxygen containing gas from 4 min. to 18 min., from 6 min. to 17 min., from 8 min. to 16 min., or from 10 min. to 15 min. Without being bound by theory, it is believed that exposure of86068-WO-PCT / DOW 86068 WO19 the particulate solid to an oxygen-containing gas for more than 20 minutes may increase equipment costs without a matching increase in particulate solid regeneration efficiency. However, it is believed that oxygen-containing gas exposure for less than 2 minutes may lead to less efficient regeneration of the particulate solid which may reduce the particulate solid’s dehydrogenation activity. In one or more embodiments, the particulate solid may be exposed to the oxygen-containing gas at a temperature of at least 650 °C, such as from 650 °C to 800 °C.

[0063] The fourth particulate solids bed 104 may be in the particulate solid separation section 510. In one or more embodiments, the fourth particulate solids bed 104 may be a dense fluidized bed having an upper surface 204 and occupying at least a portion of the particulate solid separation section 510. In one or more embodiments, at least a portion of the fourth particulate solids bed 104 may be within the oxygen treatment zone 580. In some embodiments, the entirety of the fourth particulate solids bed 104 may be within the oxygen treatment zone 580.

[0064] The particulate solid separation section 510 may comprise the oxygen treatment zone 580, described hereinabove, in which at least a portion of the fourth particulate solids bed 104 may be contained. In one or more embodiments, the oxygen treatment zone 580 may have a substantially constant cross sectional area. As described herein, a “substantially constant cross sectional area” refers to a cross sectional area that does not vary by more than 10%, 5%, 3%, 2%, or even 1%. In one or more embodiments, the oxygen treatment zone 580 may be generally cylindrical in shape (i.e., having a substantially circular diameter), or may alternately be non- cylindrically shaped, such as prism shaped with cross-sectional shaped of triangles, rectangles, pentagons, hexagons, octagons, ovals, or other polygons or curved closed shapes, or combinations thereof. In one or more embodiments, the riser 530 may pass through the oxygen treatment zone 580 and at least a portion of the particulate solid separation section 510. In such embodiments, at least a portion of the fourth particulate solids bed 104 may have a substantially annular shape.

[0065] In one or more embodiments, the oxygen treatment zone 580 may not have a constant cross sectional area. In such embodiments, the cross sectional area of the oxygen treatment zone 580 may vary over a height of the particulate solid separation section 510. For example, the oxygen treatment zone 580 may comprise a conical section, a frusticonical section, a bulbous section, a curved section, or a section having any other suitable shape. In one or more embodiments, the oxygen treatment zone 580 may comprise a section having a substantially constant cross sectional area and a section having a non-constant cross sectional area.86068-WO-PCT / DOW 86068 WO20

[0066] Referring still to FIG. 3, the particulate solid separation section 510 may comprise a cylindrical section 516 and a frusticonical section 514 (while noting that not all embodiments may include such a frusticonical geometry). The frusticonical section 514 may be positioned above the cylindrical section 516. In one or more embodiments, the frusticonical section 514 may be directly connected to the cylindrical section 516 such that the cross sectional area of the frusticonical section 514 is substantially the same as the cross sectional area of the cylindrical section 516. In one or more embodiments, the cross sectional area of the frusticonical section 514 increases over the height of the frusticonical section 514. In such embodiments, the frusticonical section 514 may have an average cross sectional area that is larger than the cross sectional area of the cylindrical section 516. In one or more embodiments, one or more bubble breakers 240 may be positioned within the particulate solid separation section 510. The bubble breakers 240 may be positioned in the cylindrical section 516, the frusticonical section 514, or both. Without intending to be bound by theory, including bubble breakers 240 in the particulate solid separation section 510 may prevent streaming or other undesirable flow conditions, while promoting smooth fluidization of the fourth particulate solids bed 104. Additionally, including multiple bubble breakers 240 above the second particulate solids outlet 230 may increase the capacity of the particulate solid separation section 510 such that the fourth particulate solids bed 104 may comprise a greater amount of particulate solids without undesirable flow conditions, such as streaming, during startup, shutdown, or other system upsets.

[0067] Numerous technical aspects are presently disclosed, some of which are specifically described hereinbelow as Aspects 1-15.

[0068] Aspect 1. A method of processing hydrocarbons, the method comprising: contacting a hydrocarbon feed stream with a particulate solid in a first particulate solids bed to form a product stream; passing a portion or all of the particulate solid from the first particulate solids bed to a second particulate solids bed, from the second particulate solids bed to a third particulate solids bed, from the third particulate solids bed to a fourth particulate solids bed, and from the fourth particulate solids bed to the first particulate solids bed; wherein: the fourth particulate solids bed fluctuates between a low-level state and a high-level state; a first particulate solids outlet is positioned at or near the bottom of the fourth particulate solids bed; a second particulate solids outlet is positioned in the top half of the fourth particulate solids bed during the low-level state; and one or more bubble breakers are positioned within the fourth particulate solids bed and above the second particulate solids outlet, wherein the fourth particulate solids bed has a86068-WO-PCT / DOW 86068 WO21 height of from 0-3 feet above the uppermost of the one or more bubble breakers in the low-level state, and wherein the fourth particulate solids bed has a height of from 3-7 feet above the uppermost of the one or more bubble breakers in the high-level state.

[0069] Aspect 2. The method of aspect 1, wherein the one or more bubble breakers comprise grating, a plurality of chevrons, a plurality of rods, structured packing, or combinations thereof.

[0070] Aspect 3. The method of aspect 1 or aspect 2, wherein the one or more bubble breakers have an open area ratio from 50% to 99%.

[0071] Aspect 4. The method of any of aspects 1-3, wherein the fourth particulate solids bed is a dense phase fluidized bed.

[0072] Aspect 5. The method of any of aspects 1-4, wherein the first particulate solids outlet leads to the first particulate solids bed, and wherein the second particulate solids outlet leads to the third particulate solids bed.

[0073] Aspect 6. The method of any one of aspects 1-5, further comprising passing a portion of the particulate solid from the fourth particulate solids bed, through the second particulate solids outlet, to the third particulate solids bed.

[0074] Aspect 7. The method of any one of aspects 1-6, wherein one or more additional bubble breakers are positioned between the first particulate solids outlet and the second particulate solids outlet.

[0075] Aspect 8. The method of any one of aspects 1-7, wherein the first particulate solids bed and the third particulate solids bed are each a turbulent fluidized bed or a fast fluidized bed.

[0076] Aspect 9. The method of any one of aspects 1-8, wherein the fourth particulate solids bed comprises a greater volume of particulate solid than the second particulate solids bed.

[0077] Aspect 10. The method of any one of aspects 1-9, wherein: the hydrocarbon feed stream comprises one or more of ethylbenzene, ethane, propane, n-butane, and i-butane; the particulate solid comprises one or more of gallium and platinum; and the product stream comprises one or more of styrene, ethylene, propylene, or butene.86068-WO-PCT / DOW 86068 WO22

[0078] Aspect 11. The method of any one of aspects 1-10, further comprising regenerating the particulate solid in the third particulate solids bed by one or more of: oxidizing the particulate solid by contact with an oxygen containing gas; combusting coke present on the particulate solid; and combusting a supplemental fuel to heat the particulate solid.

[0079] Aspect 12. The method of any one of aspects 1-11, wherein the fourth particulate solid bed is in a particulate solid separation vessel comprising a cylindrical section and a frustoconical section, wherein the frustoconical section is positioned above the cylindrical section, and wherein the frustoconcial section has an average cross sectional area larger than a cross sectional area of the cylindrical section.

[0080] Aspect 13. The method of aspect 12, wherein a top of the fourth particulate solid bed is in the frustoconical section during the overflow state.

[0081] Aspect 14. The method any of aspects 1-3, wherein the fourth particulate solids bed does not ever operate such that it has a height of greater than 7 feet above the uppermost of the one or more bubble breakers in the high-level state.

[0082] Aspect 15. The method of any one of aspects 1-14, wherein a riser passes through the fourth particulate solids bed such that at least a portion of the fourth particulate solids bed has an annular shape.

[0083] For the purposes of describing and defining the present disclosure it is noted that the term “about” are utilized in this disclosure to represent the inherent degree of uncertainty that may be attributed to any quantitative comparison, value, measurement, or other representation. The term “about” are also utilized in this disclosure to represent the degree by which a quantitative representation may vary from a stated reference without resulting in a change in the basic function of the subject matter at issue. Additionally, the term “consisting essentially of’ is used in this disclosure to refer to quantitative values that do not materially affect the basic and novel characteristic(s) of the disclosure. For example, a chemical stream “consisting essentially” of a particular chemical constituent or group of chemical constituents should be understood to mean that the stream includes at least about 99.5% of a that particular chemical constituent or group of chemical constituents.86068-WO-PCT / DOW 86068 WO23

[0084] It is noted that one or more of the following claims utilize the term “wherein” as a transitional phrase. For the purposes of defining the present technology, it is noted that this term is introduced in the claims as an open-ended transitional phrase that is used to introduce a recitation of a series of characteristics of the structure and should be interpreted in like manner as the more commonly used open-ended preamble term “comprising.”

[0085] It should be understood that any two quantitative values assigned to a property may constitute a range of that property, and all combinations of ranges formed from all stated quantitative values of a given property are contemplated in this disclosure. It should be appreciated that compositional ranges of a chemical constituent in a stream or in a reactor should be appreciated as containing, in some embodiments, a mixture of isomers of that constituent. For example, a compositional range specifying butene may include a mixture of various isomers of butene. It should be appreciated that the examples supply compositional ranges for various streams, and that the total amount of isomers of a particular chemical composition can constitute a range.

[0086] Having described the subject matter of the present disclosure in detail and by reference to specific embodiments, it is noted that the various details described in this disclosure should not be taken to imply that these details relate to elements that are essential components of the various embodiments described in this disclosure, even in cases where a particular element is illustrated in each of the drawings that accompany the present description. Rather, the claims appended hereto should be taken as the sole representation of the breadth of the present disclosure and the corresponding scope of the various embodiments described in this disclosure. Further, it will be apparent that modifications and variations are possible without departing from the scope of the appended claims.

Claims

86068-WO-PCT / DOW 86068 WO24CLAIMS1. A method of processing hydrocarbons, the method comprising: contacting a hydrocarbon feed stream with a particulate solid in a first particulate solids bed to form a product stream; passing a portion or all of the particulate solid from the first particulate solids bed to a second particulate solids bed, from the second particulate solids bed to a third particulate solids bed, from the third particulate solids bed to a fourth particulate solids bed, and from the fourth particulate solids bed to the first particulate solids bed; wherein: the fourth particulate solids bed fluctuates between a low-level state and a high- level state; a first particulate solids outlet is positioned at or near the bottom of the fourth particulate solids bed; a second particulate solids outlet is positioned in the top half of the fourth particulate solids bed during the low-level state; and one or more bubble breakers are positioned within the fourth particulate solids bed and above the second particulate solids outlet, wherein the fourth particulate solids bed has a height of from 0-3 feet above the uppermost of the one or more bubble breakers in the low-level state, and wherein the fourth particulate solids bed has a height of from 3-7 feet above the uppermost of the one or more bubble breakers in the high-level state.

2. The method of claim 1, wherein the one or more bubble breakers comprise grating, a plurality of chevrons, a plurality of rods, structured packing, or combinations thereof.

3. The method of claim 1 or claim 2, wherein the one or more bubble breakers have an open area ratio from 50% to 99%.

4. The method of any one of claims 1-3, wherein the fourth particulate solids bed is a dense phase fluidized bed.86068-WO-PCT / DOW 86068 WO255. The method of any one of claims 1 -4, wherein the first particulate solids outlet leads to the first particulate solids bed, and wherein the second particulate solids outlet leads to the third particulate solids bed.

6. The method of any one of claims 1-5, further comprising passing a portion of the particulate solid from the fourth particulate solids bed, through the second particulate solids outlet, to the third particulate solids bed.

7. The method of any one of claims 1-6, wherein one or more additional bubble breakers are positioned between the first particulate solids outlet and the second particulate solids outlet.

8. The method of any one of claims 1-7, wherein the first particulate solids bed and the third particulate solids bed are each a turbulent fluidized bed or a fast fluidized bed.

9. The method of any one of claims 1-8, wherein the fourth particulate solids bed comprises a greater volume of particulate solid than the second particulate solids bed.

10. The method of any one of claims 1-9, wherein: the hydrocarbon feed stream comprises one or more of ethylbenzene, ethane, propane, n- butane, and i-butane; the particulate solid comprises one or more of gallium and platinum; and the product stream comprises one or more of styrene, ethylene, propylene, or butene.

11. The method of any one of claims 1-10, further comprising regenerating the particulate solid in the third particulate solids bed by one or more of: oxidizing the particulate solid by contact with an oxygen containing gas; combusting coke present on the particulate solid; and combusting a supplemental fuel to heat the particulate solid.

12. The method of any one of claims 1-11, wherein the fourth particulate solid bed is in a particulate solid separation vessel comprising a cylindrical section and a frustoconical section, wherein the frustoconical section is positioned above the cylindrical section, and wherein the86068-WO-PCT / DOW 86068 WO26 frustoconcial section has an average cross sectional area larger than a cross sectional area of the cylindrical section.

13. The method of claim 12, wherein a top of the fourth particulate solid bed is in the frustoconical section during the overflow state.

14. The method any one of claims 1-13, wherein the fourth particulate solids bed does not ever operate such that it has a height of greater than 7 feet above the uppermost of the one or more bubble breakers in the high-level state.

15. The method of any one of claims 1-14, wherein a riser passes through the fourth particulate solids bed such that at least a portion of the fourth particulate solids bed has an annular shape.

Images