Olefinic material production systems that include metal components, Anti-coking coatings, and refractory materials, and methods for operating the same

Abstract

An olefinic material production system may include a metal component comprising an outer surface, an anti-coking coating positioned over the metal component, and a refractory material layer positioned over the anti-coking coating, such that the anti-coking coating is positioned between the metal component and the refractory material layer. Also disclosed are methods for operating such an olefinic material production system.

Description

OLEFINIC MATERIAL PRODUCTION SYSTEMS THAT INCLUDE METAL COMPONENTS, ANTI-COKING COATINGS, AND REFRACTORY MATERIALS, AND METHODS FOR OPERATING THE SAMECROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 665,550 filed June 28, 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, particular, to methods and system for making olefinic materials.BACKGROUND

[0003] Olefinic materials, such as ethylene, butene, propylene, and styrene, may be used as base materials to produce many different materials, such as 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. However, methods for efficiently producing such olefinic materials are challenging, and improvements in technology for such purposes are desired by industry.SUMMARY

[0004] Described herein, according to one or more embodiments, are olefinic material production systems that include metal components, where such metal components can be a wide variety of portions of the olefinic material production system. In particular, according to one or more embodiments, such metal components may be in regions of the olefinic material production system that experience relatively high temperatures (such as at least 550 °C) in the presence of hydrocarbons, such as a hydrocarbon feed. As described herein, anti-coking coatings may be positioned between the metal components and a refractory material layer. Surprisingly, it has been discovered that despite coverage of the metal components by refractory material layers, substantial coking may take place, which is believed to be caused by contact of the hydrocarbon with the material of the metal components. The incorporation of an anti-coking coating can mitigate coking and, in some embodiments, greatly enhance olefinic material production efficiency.

[0005] According to one or more embodiments, an olefinic material production system may comprise a metal component comprising an outer surface, an anti -coking coating positioned over the metal component, and a refractory material layer positioned over the anti-coking coating, such that the anti-coking coating is positioned between the metal component and the refractory material layer.

[0006] According to one or more additional embodiments, a method for operating the olefinic material production system may comprise exposing a refractory material layer to temperatures of at least 550 °C in the presence of hydrocarbons. The olefinic material production system may comprise a metal component comprising an outer surface, an anti-coking coating positioned over the metal component, and the refractory material layer positioned over the anticoking coating, such that the anti-coking coating is positioned between the metal component and the refractory material layer.

[0007] 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.BRIEF DESCRIPTION OF THE DRAWINGS

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

[0009] FIG. 1 schematically depicts a cross-sectional view of a coated metal component, according to one or more embodiments of the present disclosure;

[0010] FIG. 2 schematically depicts a hexagonally-shaped anchor system that may be coated, according to one or more embodiments of the present disclosure;

[0011] FIG. 4 schematically depicts a combustor of an olefinic material production system, according to one or more embodiments of the present disclosure; and

[0012] FIG. 5 schematically depicts a portion of a particulate solids separation section, according to one or more embodiments of the present disclosure.

[0013] When describing the simplified schematic illustration of FIGS. 3-5, 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.

[0014] Reference will now be made in greater detail to various embodiments, some of which are illustrated in the accompanying drawing.DETAILED DESCRIPTION

[0015] Described herein are olefinic material production systems that include metal components, anti-coking coatings, and refractory material layers, where the anti-coking coatings are positioned between the metal components and the refractory material layers. Also described herein are methods for using such systems. Embodiments of such systems and methods are examples of the presently disclosed technology, and are not encompassing of all embodiments contemplated by the present disclosure.

[0016] According to one or more embodiments, the coated metal components described herein may mitigate coking. For example, the fluidized bed dehydrogenation reactors of light alkanes may be operated at, e.g., a temperature ranging from 550 °C to 850 °C. In these reactors, coking precursors such as ethylene and propylene are formed and transported downstream. Metal surfaces consisting of chrome, iron and other metal components that function as catalyst for coking are prone to catalytic coke formation and deposition of pyrolytic coke. Such metal surfaces may include vessel metal surfaces, internal mechanical structures (e.g., gratings, structured packing) and refractory metal anchors. Coking is especially an issue for low velocity and stagnant zones, where prolonged gas residence time together with lack of sand blast effect from catalyst particle movement further increases the risk of coke formation. In embodiments, coked metal surfaces cancause issues such as plugging of flow passages, metal carburization and additional stresses on mechanical structures, which is especially an issue where there are thermal cycles. The presently disclosed embodiments may provide a way to mitigate the risk of coke formation for fluidized bed dehydrogenation reactors of light alkanes and the downstream equipment.

[0017] According to embodiments described herein, such propensity for coking may be reduced by the use of anti-coking coatings positioned over the metal components. Despite the presence of refractory material over the metal component, it has been discovered that coking is still an issue. Thus, the use of an anti-coking coating between the refractory and the metal component, while thought conventionally as unneeded, can provide benefits as described herein.

[0018] Referring now to FIG. 1, a coated metal component 102 that is component of an olefinic material production system 100. The coated metal component 102, as is described in detail herein, may be a wide variety of components of the olefinic material production system 100, one embodiment of which is described generally in the context of the olefinic material production system 100 FIG. 3.

[0019] According to one or more embodiments, the coated metal component 102 may comprise a metal component 110, an anti-coking coating 120, and refractory material layer 130. As is depicted, the metal component 110 may include an outer surface 112, the anti -coking coating 120 may include an inner surface 122 and an outer surface 124, and the refractory material layer 130 may include an inner surface 132 and an outer surface 134 (i.e., an air-facing surface). The anti-coking coating 120 may be positioned over the outer surface 112 of the metal component 110, and the refractory material layer 130 may be positioned over the anti-coking coating 120. According to some embodiments, such as that depicted in FIG. 1, the metal component 110 may be in direct contact with the anti-coking coating 120, and the refractory may be in direct contact with the refractory material layer 130. However, in additional embodiments, other layers may be present between, for example, the metal component 110 and the anti-coking coating 120, or between the anti-coking coating 120 and the refractory material layer 130. Generally, the anticoking coating 120 and the refractory material layer 130 may be disposed as coatings, and may have thicknesses that are relatively uniform over an area of the outer surface 112 of the metal component 110.

[0020] According to one or more embodiments, the metal component 110 may be steel, such as structural steel (e.g. carbon steel), aluminum, stainless steel, or other metal alloys. For example, stainless steel may include chromium, molybdenum, carbon, nickel, and / or nitrogen. Generally, in some embodiments, the stainless steel may include chromium in amounts of at least 5 wt.%. Examples of metals that may be utilized include, without limitation, stainless steel (304H, 321H, 347H), alloy 800 (H or HT), and alloy 617. The metal component 110 may have an oxidation layer on its outer surface 112, or may have pure metal or metal alloy on the outer surface 112. According to some embodiments, the metal component 110 may include nickel, iron, and / or chromium, which may promote coking of hydrocarbons at relatively high temperatures, such as 550 °C or above.

[0021] According to one or more embodiments, the refractory material layer 130 may comprises, without limitation, one or more of alumina, silica, lime, iron oxide (any oxidation state), titania, phosphorus pentoxide, silicon carbide, zirconia, chromium oxide, magnesium oxide, calcium oxide, graphite, yttria-stabilized zirconia, MgAhCU (spinnel), calcium aluminate, hafnium carbide, or compounds having refractory metals such as tungsten and / or molybdenum. Such refractory materials may be coated by spraying, dipping, paint application, etc., and is not necessarily limited for the embodiments herein. According to one or more embodiments, the refractory material may have a fired density of from 80 lb / ft3to 250 lb / ft3, such as from 130 lb / ft3to 210 lb / ft3. Some suitable refractory materials that are commercially available include, without limitation Actchem 85, Rescobond AA-22S, R-Max MP, and Thermbond 7018.

[0022] According to some embodiments, the refractory material layer 130 may comprise less than or equal to 1.5 wt.% iron, such as 1.0 wt.% iron, or 0.5 wt.% iron (as measured on an elemental basis). It is believed that iron may effectuate coking, and so its incorporation may be limited in the refractory material layer 130.

[0023] In one or more embodiments, the refractory material layer 130 may have a thickness of from 0.25 inches to 2 feet, such as from 0.25 inches to 0.5 inches, from 0.5 inches to 1 inch, 0.75 inches to 1 inches, 0.75 inches to 2 inches, from 1 inch to 2 inches, from 2 inches to 3 inches, from 3 inches to 6 inches, from 6 inches to 1 foot, from 1 foot to 2 feet, or any combination of these ranges. Generally, the thickness of the refractory may depend on the operational temperatures in the olefinic material production system 100 and the materialcomposition of the refractory material layer 130. In some embodiments, the thickness of the refractory may depend on the desired erosion resistance and run length targets.

[0024] As described herein, the anti-coking coating 120 is disposed between the metal component 110 and the refractory material layer 130. The anti-coking coating 120 refers to any coating that reduces coking of hydrocarbons at elevated temperatures, as compared with exposure of the hydrocarbons to the raw surface of the metal component 110. A variety of compositions may be utilized as the anti -coking coating, some of which are described hereinbelow.

[0025] According to one or more embodiments, the anti-coking coating 120 may comprise a ceramic material. Such coatings may include, without limitation, metal oxides and / or metal carbides, such as SiC and AI2O3. Contemplated commercially available coating compositions that may be suitable for use as the anti-coking coating 120 include, without limitation, Cerakote V- Series, Cerablak HTP-100, and Emisshield M-l or M-6 sintered coatings. According to some embodiments, the coatings may be applied as ceramic particles suspended in an inorganic binder matrix, which may be painted onto the metal component 110. In some other embodiments, the coatings may be applied by spray gun application. Curing may be needed to remove solvents and / or chemically change the coating composition following application.

[0026] According to one or more embodiments, the anti-coking coating 120 that is positioned over the metal component 110 may comprise one or more of aluminum, silicon, chromium, or cerium. In some embodiments, the anti -coking coating 120 may include aluminum, silicon, chromium, and cerium. In some embodiments, the anti-coking coating is a ceramic material that comprises aluminum, silicon, chromium, and cerium. The aluminum, silicon, chromium, and / or cerium may be present as oxides, nitrides, alloys of other metals (such as those in the composition of the metal component 110), or as elemental constituents. For example, the anti-coking coating 120 may include one or more of AIN, Cr3Si, AlNi, AlFe, CeFeSi, and Ce.

[0027] According to one or more embodiments, the anti-coking coating 120 that includes one or more of aluminum, silicon, chromium, or cerium may be fabricated over the metal component by a variety of techniques. For example, pack cementation coatings from intermetallic compounds may be applied. Two application methods for this technique include chemical vapor deposition (CVD) and thermal diffusion. Without being bound by any particular theory, it is believed that these methods may ensure the anti-coking coating 120 completely covers thesubstrate surface and prevents any direct contact between hydrocarbons and the substrate. In utilizing this fabrication technique to apply the anti-coking coating 120 to the metal component 110, the constituent elements of the anti-coking coating 120 in the solid phase may be reacted in activators such as sodium chloride and ammonium chloride. This reaction may generate gaseous metal halides that are capable of diffusing to the substrate surface, where they undergo disproportionate reaction. As the resulting permeating source material accumulates on the substrate surface, it may further diffuse into the substrate, forming a diffusion coating. The diffusion coating may comprise of aluminum nitrides, chromium silicate, aluminum nickel, silicon dioxide, cerium, cerium iron silicide, and aluminum iron, which may create three regions. The three regions may include an outer layer, an inter-diffusion layer, and a transitional layer. The outer layer may contain relatively large amounts of aluminum and chromium in the form of aluminum nitrides and chromium silicates, as well as relatively small amounts of silicon, cerium, nitrogen, oxygen, iron, and nickel.

[0028] According to one or more embodiments, without being bound by any particular theory, it is believed that, at high temperatures, the aluminum and chromium may oxidize on the substrate surface, which still may offer protection. The inter-diffusion layer may be composed of aluminum, iron, and nickel in the form of aluminum nickel and aluminum iron. Additionally, the transitional layer may be comprised of high amounts of chromium, iron, and nickel.

[0029] To produce one or more of the embodiments described herein, uncoated samples may be encapsulated in a retort with composite powder, which may include aluminum, chromium, silicon, and cerium (IV) oxide. Then an activator, such as ammonium chloride, and an inert filler, such as aluminum oxide, may be added. The retort may be sealed with refractory mud and placed in an oven for about 2 hours. Following this, the retort may be heat treated for eight hours at about 1000 °C in a preheated muffle furnace in the air atmosphere. After being heat treated, the sample may be cooled to room temperature, polished with sandpaper, and ultrasonically cleaned with ethanol for about three minutes.

[0030] According to other embodiments, the anti-coking coating 120 may comprise a metalized surface, whereby a portion of the metal component 110 is metalized. In some embodiments, the metallization is an aluminized surface, such that the anti-coking coating 120 comprises aluminum. In one or more embodiments, morphology of the aluminized surfacedepends upon the conditions which are used to perform the coating, but may involve the alloying of aluminum with the underlying substrate across a thin band within the coating. Total thickness of this type of coating may be from 50 microns to 150 microns. Aluminization may be performed via pack cementation (PC), though may also be performed via vapor phases aluminizing (VP A), chemical vapor deposition (CVD), or other methods. In PC, the metal substrate will be surrounded by a “pack”, consisting of an inert filler (e.g. AI2O3 powder), the coating material (aluminum metal), and a halide salt “activator” (e.g. ammonium chloride). The substrate and surrounding packing will then be heated (commonly in either an inert or hydrogen atmosphere) to high temperature (e.g. 800-1100 °C). At this point a gaseous metal halide (e.g. aluminum chloride) will form from the coating material and the activator. The metal halide deposits the aluminum onto the substrate surface forming a layer with thicknesses commonly ranging 50-150 um. The aluminum diffuses into the substrate with prolonged heat treatment. The ultimate morphology and thickness (commonly 50-150 um) of this layer depends on the conditions and the packing. Upon exposure to atmosphere, and inert aluminum oxide layer is formed.

[0031] In one or more embodiments, and according to the composition of the anti -coking coating 120, the anti-coking coating 120 may be applied in a variety of thicknesses. For example, in some embodiments, the anti-coking coating may have a thickness of from 25 microns to 500 microns, such as at least 25 microns and less than 400 microns, less than 300 microns, less than 200 microns, less than 100 microns, or less than 50 microns, or such as less than or equal to 500 microns and at least 50 microns, at least 100 microns, at least 200 microns, at least 300 microns, or at least 400 microns.

[0032] Now described are non-limiting embodiments of metal components 110 that may utilize the anti-coking coating 120 and refractory material layers 130 described herein. Some metal components 110 are described with respect to the embodiment of FIG. 3, which is described in detail herein. In general, the metal component 110 may be any apparatus in the reactor portion 200 of the olefinic material production system 100 of FIG. 3, particularly those that experience hydrocarbons at relatively high temperatures, such as 550 °C or greater, which cause coking.

[0033] According to one or more embodiments, the metal component 110 may be a reactor sidewall. For example, as is described in more detail in the context of the embodiment of FIG. 3 that follows, the metal component 100 may be the interior sidewall of the upstream reactor portion250, the interior sidewall of the transition section 258, or the interior sidewall of the downstream reactor section 230. In some embodiments, a reactor sidewall may include shroud, such as that disclosed in PCT Publication WO / 2024 / 092196, the contents of which are incorporated by reference in their entirety.

[0034] According to additional embodiments, the metal component 110 may be a reactor internal (i.e., an internal within the reactor 202). Reactor internals include, without limitation, bubble breakers such as chevrons, gratings, beams, support apparatuses, etc.

[0035] According to additional embodiments, the metal component 110 may be other downstream components of the reactor section 200, such as, without limitation, the outer surface of the downstream reactor section 230, the wall of the catalyst separation section 210, the wall defining the stripper 224, or a separation device 220, in FIG. 3. Referring now to FIG. 5, also discussed in detail herein, in one or more embodiments, the metal component 110 may be the inlet 522 of a primary separation device 520, a primary separation device 520 (e.g., a cyclone), a crossover duct 570, a secondary separation device 540 (e.g., a cyclone), one or more portions forming a plenum 546, or a downstream heat exchanger (not depicted but downstream of products effluent pipe 420).

[0036] According to additional embodiments, the metal component 110 may be a metal anchor such as that depicted in FIG. 2. FIG. 2 depicts a metal anchor system that is affixed to a back surface, that could be any of the metal components 110 described herein, where the refractory material layer 130 is not shown. According to one or more embodiments, the metal anchor may be a hexagonally-shaped frame metal anchor (sometimes referred to in industry and / or commercially as Hex-mesh). As is known in the art, such metal anchors may be utilized as a stabilizing frame onto which refractory material layer 130 may be applied. For example, metal anchors may be positioned on a wall and refractory material may be deposited into the openings, such as the hexagonal openings as shown in FIG. 2. While hex -mesh is depicted in FIG. 2, other metal anchors with different geometric configurations are contemplated, such as comer tabs, flex metal, S-bar, radius tabs, hexcells, monster tabs, speedhex™ and other general refractory anchor systems used in industry. Any surface of the metal anchor may have the anti-coking coating.

[0037] Now described are methods for making olefinic materials may utilize olefinic material production systems, and such methods are described in the context of such olefinicmaterial production systems. As described herein, an olefinic material production system is any system that can produce 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 via dehydrogenation from ethane, propane, butane, and ethylbenzene, respectively, which may be included as the feed into the reactor.

[0038] According to embodiments described herein, particulate solids may be utilized in the process to form olefinic materials, whereby the particulate solids continuously circulate between a reactor and a combustor during normal steady-state operation during olefinic material production. The olefinic materials are produced in the reactor, and the particulate solids are heated in the combustor by combustion of a supplemental fuel, burning of coke, or both. Various reaction mechanisms, and associated reactants, may be utilized to form the olefinic materials. For example, dehydrogenation may be utilized to convert paraffins to olefins, such as ethane to ethylene, butane to butylene, and propane to propylene, or to convert ethylbenzene to styrene. Such dehydrogenation reactions may utilize a catalyst, which may be the solid particulate. In additional embodiments, olefinic materials may be produced by cracking reactions, dehydration reactions, and methanol-to-olefin reactions. These reaction types may utilize different hydrocarbon feed streams and different catalytic particulate solids to produce the olefinic materials from hydrocarbon feeds. In additional embodiments, it is contemplated that the particulate solids may be non-catalytic solids such as, for example, materials capable of carrying oxygen (referred to sometimes herein as “oxygen carrier materials”). For example, such oxygen carrier materials may be utilized along with catalyst whereby hydrogen produced in a dehydrogenation reactor is combusted by contact with oxygen supplied from the oxygen carrier materials. In additional embodiments, oxygen carrier materials may be utilized without catalyst, where thermal dehydrogenation may from hydrogen that is combusted by contact with the oxygen from the oxygen carrier materials.

[0039] According to some embodiments, the chemical processing may comprise a dehydrogenation reaction that utilizes circulating a catalyst between the chemical processing vessel and a regeneration unit, where alkanes are converted to alkenes in the chemical processing vessel and where the catalyst is heated by a supplemental fuel in the regeneration unit. Such aprocess may convert propane to propylene, such as is described in U.S. Pat. No. 10,227,271, the entirety of which is incorporated by reference in this disclosure.

[0040] In additional embodiments, chemical processing may comprise a dehydrogenation reaction that utilizes circulating a solid particulate oxygen carrier material between the chemical processing vessel and a regeneration unit, where alkanes are converted to alkenes in the chemical processing vessel by thermal dehydrogenation, and where the produced hydrogen gas is converted to water by contact with oxygen released from the oxygen carrier material. Such a process may convert ethane to ethylene, such as is described in WO 2024 / 059554 Al, the entirety of which is incorporated by reference in this disclosure.

[0041] In additional embodiments, chemical processing may comprise a dehydrogenation reaction that utilizes circulating both a catalyst and a solid particulate oxygen carrier material between the chemical processing vessel and a regeneration unit, where alkanes are converted to alkenes in the chemical processing vessel by catalytic dehydrogenation, and where the produced hydrogen gas is converted to water by contact with oxygen released from the oxygen carrier material. Such a process may convert ethane to ethylene, such as is described in U.S. Patent No. 11,724,974, the entirety of which is incorporated by reference in this disclosure.

[0042] Embodiments of the methods presently disclosed are described in detail herein in the context of the olefinic material production 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, the concepts described herein may be equally applied to other systems with alternate reactor units and regeneration units, such as those that operate under non-fluidized conditions or 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.

[0043] Referring now to FIG. 3, an example olefinic material production system 100 that may be suitable for use with the methods and / or apparatuses described herein is schematically depicted. The olefinic material production system 100 generally comprises multiple systemcomponents that are included in a reactor portion 200 and a catalyst processing portion 300. As described herein, “system components” refer to portions of the olefinic material production system 100, such as reactors, separators, transfer lines, combinations thereof, and the like. As used herein in the context of FIG. 3, the reactor portion 200 generally refers to the portion of the olefinic material production system 100 in which the major process reaction takes place (e.g., dehydrogenation) to form an olefinic material-containing effluent. A hydrocarbon-containing feed enters the reactor portion 200, is contacted with a catalyst, converted to an olefinic materialcontaining effluent (containing product and unreacted feed), and exits the reactor portion 200. The reactor portion 200 comprises a reactor 202 which may include an upstream reactor section 250 and a downstream reactor section 230. According to one or more embodiments, as depicted in FIG. 3, the reactor portion 200 may additionally include a catalyst separation section 210, which serves to separate the catalyst from the olefinic material-containing effluent formed in the reactor 202. Also, as used herein, the catalyst processing portion 300 generally refers to the portion of the olefinic material production system 100 where the catalyst is in some way processed, such as by combustion, to, e.g., improve catalytic activity by decoking and / or heating the catalyst. The catalyst processing portion 300 may comprise a combustor 350 and a riser 330, and may additionally comprise a catalyst separation section 310. In one or more embodiments, the catalyst separation section 210 may be in fluid communication with the combustor 350 (e.g., via standpipe 426) and the catalyst separation section 310 may be in fluid communication with the upstream reactor section 250 (e.g., via standpipe 424 and transport riser 430).

[0044] Generally, as is described herein, in embodiments illustrated in FIG. 3, catalyst is circulated between the reactor portion 200 and the catalyst processing portion 300. It should be understood that when “catalysts” are referred to herein, they may refer to solid materials that are catalytically active for a desired reaction. The terms “catalytic activity” and “catalyst activity” refer to the degree to which the catalyst is able to catalyze the reactions conducted in the olefinic material production system 100. The catalyst that exits the reactor portion 200 may be deactivated catalyst. As used herein, “deactivated” may refer to a catalyst which has reduced catalytic activity or is cooler as compared to catalyst entering the reactor portion 200. However, deactivated catalyst may maintain some catalytic activity. Reduced catalytic activity may result from contamination with a substance such as coke. Coke may form on the catalyst within the reactor portion 200. Reactivation (sometimes called “regeneration” herein) may remove the contaminant such as coke,raise the temperature of the catalyst, or both. In embodiments, deactivated catalyst may be reactivated by catalyst reactivation in the catalyst processing portion 300. The deactivated catalyst may be reactivated by, but not limited to, removing coke by combustion, oxidizing the catalyst, other reactivation process, or combinations thereof. In some embodiments, the catalyst may be heated during reactivation by combustion of a supplemental fuel, such as hydrogen, methane, ethane, propane, natural gas, or combinations thereof. The reactivated catalyst from the catalyst processing portion 300 is then passed back to the reactor portion 200. The catalyst is heated during regeneration to aid with regeneration and also because heated catalyst serves as a heat carrier to carry heat from the combustor 350 to the reactor portion 200 to facilitate the dehydrogenation reaction.

[0045] In non -limiting examples, the olefinic material production system 100 described herein may be utilized to produce light olefins from a hydrocarbon-containing feed. According to one or more embodiments, the reaction may be a dehydrogenation reaction. According to such embodiments, the hydrocarbon-containing feed may comprise one or more of ethane, propane, butane, and ethylbenzene. In one or more embodiments, the hydrocarbon-containing feed 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 one or more embodiments, the hydrocarbon- containing feed 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-containing feed 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-containing feed 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, i-butane, or combinations thereof.

[0046] In one or more embodiments, the catalyst may comprise, consist essentially of, or consist of one or more of gallium, indium, or thallium; one or more of platinum, palladium, rhodium, iridium, ruthenium, or osmium; and a support. As described herein, “consisting essentially of’ refers to materials with less than 1 wt.% of the non-recited materials (i.e., consisting essentially of A and B means A and B combined are at least 99 wt.% of the composition). In additional embodiments, the catalyst may comprise, consist essentially of, or consist of one or more of gallium, indium, or thallium; one or more of platinum, palladium, rhodium, iridium,ruthenium, or osmium; a support; and one or both of alkali or alkaline earth metals. As is described herein, the catalyst may be solid particles suitable for fluidization.

[0047] Still referring to FIG. 3, the hydrocarbon-containing feed may enter feed inlet 434 into the reactor 202, and the olefinic material -containing effluent may exit the olefinic material production system 100 via pipe 420. According to one or more embodiments, the olefinic material production system 100 may be operated by feeding a hydrocarbon-containing feed (e.g., in a feed stream) and a fluidized catalyst into the upstream reactor section 250. The hydrocarbon-containing feed contacts the catalyst in the upstream reactor section 250, and each flow upwardly into and through the downstream reactor section 230 to produce an olefin-containing effluent. The reactor 202 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).

[0048] Now referring to FIG. 3 in detail, the reactor portion 200 may comprise an upstream reactor section 250, a transition section 258, and a downstream reactor section 230, such as a riser. The transition section 258 may connect the upstream reactor section 250 with the downstream reactor section 230. As depicted in FIG. 3, the upstream reactor section 250 may be positioned below the downstream reactor section 230. Such a configuration may be referred to as an upflow configuration in the reactor 202. The upstream reactor section 250 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 250 may be connected to the downstream reactor section 230 via the transition section 258. The upstream reactor section 250 may generally comprise a greater cross- sectional area than the downstream reactor section 230. The transition section 258 may be tapered from the size of the cross-section of the upstream reactor section 250 to the size of the crosssection of the downstream reactor section 230 such that the transition section 258 projects inwardly from the upstream reactor section 250 to the downstream reactor section 230. For example, the transition section 258 may be a frustum.

[0049] The upstream reactor section 250 may be connected to a transport riser 430, which, in operation may provide reactivated catalyst in a feed stream to the reactor portion 200. The reactivated catalyst and / or reactant chemicals may be mixed with a distributor 260 housed in the upstream reactor section 250. The catalyst entering the upstream reactor section 250 via transportriser 430 may be passed through standpipe 424 to a transport riser 430, thus arriving from the catalyst processing portion 300. In some embodiments, catalyst may come directly from the catalyst separation section 210 via standpipe 422 and into a transport riser 430, where it enters the upstream reactor section 250, where in such embodiments some of the catalyst is not passed through the catalyst processing portion 300. The catalyst can also be fed via standpipe 422 directly to the upstream reactor section 250 (not depicted in FIG. 3). This catalyst 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 catalyst.

[0050] In one or more embodiments, the catalyst may have a residence time within the reactor portion 200 of less than or equal to 5 minutes. As the term is used herein, “residence time” refers to the average amount of time the catalyst or other specified material spends within the reactor portion 200 in contact with the feed (e.g., time from first contact with feed to time of separation from product). As it is an average, the amount of time the catalyst may spend within the reactor portion 200 during any given cycle may not be equal to the average, but over time will average out to be equal to about the residence time. In some embodiments, the catalyst may have a residence time within the reactor portion 200 of less than or equal to 4.5 min., less than or equal to 4 min., less than or equal to 3.5 min., less than or equal to 3 min., less than or equal to 2.5 min., less than or equal to 2 min., less than or equal to 1.5 min., less than or equal to 1 min., less than or equal to 0.5, or less than or equal to 0.1 min. Without being bound by theory, it is believed that catalyst residence time greater than 3 minutes may increase equipment costs without a matching increase in catalyst dehydrogenation performance. However, it is believed that catalyst residence time less than 0.1 minutes may not allow the catalyst to sufficiently catalyze the dehydrogenation reaction.

[0051] Still referring to FIG. 3, in one or more embodiments, based on the shape, size, and other processing conditions (such as temperature and pressure) in the upstream reactor section 250 and the downstream reactor section 230, the upstream reactor section 250 may operate as a fluidized bed, such as in a fast fluidized, turbulent, or bubbling bed upflow reactor, while the downstream reactor section 230 may operate in more of a plug flow manner, such as in a riser reactor. For example, the reactor 202 of FIG. 3 may comprise an upstream reactor section 250 operating as a fast fluidized, turbulent, or bubbling bed reactor and a downstream reactor section 230 operating as a dilute phase riser reactor, with the result that the average catalystand gas flow moves concurrently upward. As the term is used herein, “average flow” refers to the net flow, i.e., the total upward flow minus the retrograde or reverse flow, as is typical of the behavior of fluidized particles in general. As described herein, a “fast fluidized” reactor may refer to a reactor utilizing a fluidization regime wherein the superficial velocity of the gas phase is greater than the choking velocity and may be semi-dense in operation. As described herein, a “turbulent” reactor may refer to a fluidization regime where the superficial velocity of less than the choking velocity and is more dense than the fast fluidized regime. As described herein, a “bubbling bed” reactor may refer to a fluidization regime wherein well defined bubbles in a highly dense bed are present in two distinct phases. The “choking velocity” refers to the minimum velocity required to maintain solids in the dilute-phase mode in a vertical conveying line. As described herein, a “dilute phase riser” may refer to a riser reactor operating at above choking velocity.

[0052] According to embodiments, the olefinic material-containing effluent and the catalyst may be passed out of the downstream reactor section 230 to a separation device 220 in the catalyst separation section 210, where the catalyst is at least partially separated from the olefin- containing effluent, which is transported out of the catalyst separation section 210. According to one or more embodiments, following separation from vapors in the separation device 220, the catalyst may generally move through the stripper 224 to the catalyst outlet port 222 where the catalyst is transferred out of the reactor portion 200 via standpipe 426 and into the catalyst processing portion 300.

[0053] According to one or more embodiments, the separation device 220 may be a cyclonic separation system, which may include two or more stages of cyclonic separation. In embodiments where the separation device 220 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 systemsutilizing 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 from the product gas. It should be understood that any primary cyclonic separation device may be used in embodiments of the present disclosure.

[0054] Now referring to FIG. 5, an embodiment of a catalyst separation section 210 suitable for use in the olefinic material production system 100 of FIG. 3 is schematically depicted. In the embodiment of FIG. 5, two cyclonic separation devices are utilized in series. As depicted, the catalyst separation section 210 may include a primary separation device 520. The primary separation device 520 is contained within a shell 530 and has a body 521, an inlet 522 from the downstream reactor section 230 (i.e., a riser in FIGS. 3 and 5), an outlet 524 and a solids discharge dipleg 526. A fluidized solid stream enters the primary separation device 520 through inlet 522. In the primary separation device 520, a major part of entrained solids, e.g. catalyst particles, are separated from the fluidized solid stream. The separated solids exit the primary separation device through discharge dipleg 526 leaving a primary separation device effluent which comprises solids not removed by the primary separation device 520 and fluid, e.g. gaseous product. The primary separation device effluent passes vertically upward and out of the primary separation device 520 through outlet 524 and into the secondary separation device 540 through primary separation device outlet tube 542 and then through crossover duct 570. The secondary separation device 540 further comprises a body 541, an outlet 544 and a solids discharge dipleg 546. The secondary separation device 540 further separates out solids from the primary separation device effluent. Solids separated out in the secondary separation device 540 exit downward through dipleg 546. The products may be passed through the outlet 544 and out of the catalyst separation section 210 via the pipe 420, passing through a plenum.

[0055] As depicted in FIG. 5, quench stream 296 may enter the upper portion of the primary separation device outlet tube 542, which is positioned directly above the primary separation device 520. It is believed that such an arrangement may be desirable for proper mixing of the quench stream with the effluent of the primary separation device 540 and to reduce residence time between the exit of the primary separation device 540 and the mixing with the quench stream 296.

[0056] Still referring to FIG. 3, the separated catalyst is passed from the catalyst separation section 210 to the combustor 350. In some embodiments, the catalyst may be exposed to another oxygen-containing gas, such as air, downstream of the reactor 202 and upstream of the combustor 350, such as in a standpipe leading to the combustor 350. Such oxygen exposure may serve to oxidize the catalyst prior to combustion, which may improve combustion catalytic functionality.

[0057] In the combustor 350, the catalyst 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 catalyst may be de-coked and / or supplemental fuel may be combusted to heat the catalyst. The catalyst is then passed out of the combustor 350 and through the riser 330 to a riser termination separator 378, where the gas and solid components from the riser 330 are at least partially separated. The vapor and remaining solids are transported to a secondary separation device 320 in the catalyst separation section 310 where the remaining catalyst is separated from the gases from the catalyst processing (e.g., gases emitted by combustion of spent catalyst or supplemental fuel, referred to herein as flue gas). The flue gas may pass out of the catalyst processing portion 300 via outlet pipe 432. The separated catalyst is then passed through the oxygen treatment zone 370 within the catalyst separation section 310 to the upstream reactor section 250 via standpipe 424 and transport riser 430, where it is further utilized in a catalytic reaction. Thus, the catalyst, in operation, may cycle between the reactor portion 200 and the catalyst processing portion 300. In general, the processed chemical streams, including the hydrocarbon-containing feed and olefinic material -containing effluent may be gaseous, and the catalyst may be fluidized particulate solid.

[0058] Referring now to the catalyst processing portion 300, as depicted in FIG. 3, the combustor 350 of the catalyst processing portion 300 may include one or more lower reactor portion inlet ports 352 and may be in fluid communication with the riser 330. Oxygen-containing gas, such as air, may be passed through pipe 428 into the combustor 350. In general, the oxygencontaining gas may comprise at least 10 mol.% oxygen. The combustor 350 may be in fluid communication with the catalyst separation section 210 via standpipe 426, which may supply spent catalyst from the reactor portion 200 to the catalyst processing portion 300 for regeneration. The combustor 350 and riser 330, collectively referred to as the catalyst combustion reactor 302, may operate with similar or identical fluidization regimes as to what was disclosed with respect to the upstream reactor section 250 and downstream reactor section 230 of the reactor portion 200.That is, the combustor 350 may operate as a fluidized bed, such as in a fast fluidized, turbulent, or bubbling bed upflow reactor, while the riser 330 may operate in more of a plug flow manner, such as in a riser reactor. Geometries as described with respect to the upstream reactor section 250 and downstream reactor section 230 may equally apply to the combustor 350 and riser 330. Additionally, the combustor 350 may also include a fuel inlet 354, which may supply a fuel, such as a hydrocarbon stream, to the combustor 350.

[0059] Still referring to olefinic material operation mode in steady state, as described herein, the catalyst may be heated in the catalyst processing portion 300 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.

[0060] Now referring to FIG. 4, one embodiment of a combustor 350 suitable with the system and methods of FIG. 3 is schematically depicted. As shown in FIG. 3, the combustor 350 may comprise a vessel 360 whereby catalyst may enter the vessel 360 through downcomer 362. Alternatively or additionally, in embodiments, the catalyst may enter the vessel 102 from a side inlet (not shown) or from a bottom feed (not shown), passing upward through the air distributor 364. The catalyst may impinge upon and may be distributed by a splash guard. The combustor 350 may include the air distributor 364, which may be a plate distributor and may be located at or slightly below the height of the splash guard. Above the air distributor 364 and the outlet of the downcomer 362 may one or more grids 366. The girds may operate as bubble breakers to promote even fluidization within the combustor 350.

[0061] Still referring to FIG. 4, the combustor 350 may also include a plurality of gas distributors 368 through which the supplemental fuel is fed into the combustor 350, which may be in fluid communication with the fuel inlet 354. Additionally, liquid fuel used for system startup may be fed through inlet 380.

[0062] Turning back to FIG. 3, as described in one or more embodiments, following separation of flue gas from catalyst in the riser termination separator 378 and secondary separation device 320, treatment of the processed catalyst with an oxygen-containing gas, such as air, is conducted in the oxygen treatment zone 370. In general, the oxygen-containing gas in the oxygen treatment zone 370 may comprise at least 10 mol.% oxygen, and is substantially void ofcombustable gaseous hydrocarbons that are present in the combustor 350. In some embodiments, the oxygen treatment zone 370 includes a fluid solids contacting device. The fluid solids contacting device may include baffles or grid structures to facilitate contact of the processed catalyst with the oxygen-containing gas. Examples of fluid solid contacting devices are described in further detail in U.S. Patent Nos. 9,827,543 and 9,815,040. The fluidization regime within the oxygen treatment zone may be bubbling bed type fluidization. The oxygen treatment zone 370 may include an oxygen-containing gas inlet 372, which may supply an oxygen-containing gas to the oxygen treatment zone 370 for oxygen treatment of the catalyst.

[0063] As is disclosed herein, in one or more embodiments the catalyst may be exposed to an oxygen-containing gas in oxygen treatment zone 370. For example, the catalyst 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 of the catalyst to an oxygen-containing gas for more than 20 minutes may increase equipment costs without a matching increase in catalyst regeneration efficiency. However, it is believed that oxygen-containing gas exposure for less than 2 minutes may lead to less efficient regeneration of the catalyst which may reduce the catalyst’s dehydrogenation activity. In one or more embodiments, the catalyst may be exposed to the oxygen-containing gas at a temperature of at least 650 °C, such as from 650 °C to 800 °C.

[0064] In one or more embodiments, the olefinic material may be present in a “product stream” sometimes called an “olefin product-containing effluent” and include light olefins. Such a stream exits the olefinic material production system 100 of FIG. 3 and may be subsequently processed.

[0065] The present disclosure describes numerous technical aspects, including aspects 1- 15 below.

[0066] Aspect 1. An olefinic material production system comprising: a metal component comprising an outer surface; an anti-coking coating positioned over the metal component; and arefractory material layer positioned over the anti -coking coating, such that the anti-coking coating is positioned between the metal component and the refractory material layer.

[0067] Aspect 2. The method of aspect 1, wherein the anti -coking coating comprises a ceramic material.

[0068] Aspect 3. The method of aspect 2, wherein the ceramic material comprises metal carbides, metal oxides, or both.

[0069] Aspect 4. The method of aspect 2, wherein the ceramic material comprises alumina.

[0070] Aspect 5. The method of aspect 2, wherein the ceramic material comprises compounds containing one or more of aluminum, silicon, chromium, and cerium.

[0071] Aspect 6. The method of aspect 1, wherein the anti-coking coating comprises a metalized surface.

[0072] Aspect 7. The method of aspect 1, wherein the anti -coking coating comprises aluminum.

[0073] Aspect 8. The olefinic material production system of any previous aspect, wherein the anti -coking coating has a thickness of from 25 microns to 500 microns.

[0074] Aspect 9. The olefinic material production system of aspect 1, wherein the metal component is a reactor sidewall.

[0075] Aspect 10. The olefinic material production system of aspect 1, wherein the metal component is a crossover duct, a cyclone, a riser, a reactor internal, a plenum, a downstream heat exchanger, or a stripper.

[0076] Aspect 11. The olefinic material production system of aspect 1, wherein the metal component is a metal anchor.

[0077] Aspect 12. The olefinic material production system of any previous aspect, wherein the metal component is in direct contact with the anti-coking coating, and the anti-coking coating is in direct contact with the refractory material layer.

[0078] Aspect 13. The olefinic material production system of any previous aspect, wherein the refractory material layer comprises one or more of alumina, silica, lime, iron oxide, titania, phosphorus pentoxide, silicon carbide, zirconia, chromium oxide, magnesium oxide, calcium oxide, graphite, yttria-stabilized zirconia, MgA12O4, calcium aluminate, hafnium carbide, or compounds having tungsten or molybdenum.

[0079] Aspect 14. The olefinic material production system of any previous aspect, wherein the metal component comprises stainless steel, structural steel, metal alloys, or aluminum.

[0080] Aspect 15. A method for operating the olefinic material production system of any previous aspect, the method comprising exposing the refractory material layer to temperatures of at least 550 °C in the presence of hydrocarbons.

[0081] EXAMPLES

[0082] The following examples illustrate features of the present disclosure but are not intended to limit the scope of the disclosure. The following experiments analyzed the performance of embodiments described herein.

[0083] Example 1: Preparation and Analysis of Aluminization Coatings

[0084] Coating samples A and B, respectively, were prepared by depositing two different commercially available metallic aluminum coatings onto 304H stainless steel tubes. The coatings were estimated to be from about 10 pm to 100 pm in thickness. The metallic aluminum was allowed to diffuse into the steel, forming an aluminum rich alloy near the surface. Comparative Sample C was a 304H stainless steel tube that was uncoated.

[0085] These samples were tested for their ability to inhibit coke formation immediately following coating (no additional processing). All samples were tested by forming coke by a coking procedure, and then measuring the coking rate. Specifically, the coke was formed on each sample by exposure to a temperature of 750 °C and pressure of 50 psig over pure ethane as the carbon feed source with a flowrate set to produce about 12 seconds of residence time within the tube. The coking rate was measured using a mass spectrometer carried out at a temperature of 750 °C with 5% O2 in balance Argon. The results are displayed in Table 1. These results are described as “fresh coking” herein.Table 1

[0086] Next, following the de-coking by the coking measuring by mass spectrometer, the coking rates of Samples A, B, and C were again measured by an identical coking and measurement process as described above. These results are described as “post-decoke” herein.Table 2

[0087] The aluminized surface from both Samples A and B reduces coking rates both in fresh and post-coking testing. In fresh samples, the coking rate of aluminized surfaces is about 10- times lower than for bare 304H surfaces. Furthermore, the coking rate on aluminized steel does not appear to increase upon decoking. After decoke, the coking rate of aluminized surfaces is about 50-times lower than for bare 304H surfaces.

[0088] Example 2: Preparation and analysis of aluminophosphate bonded ceramic spray coating

[0089] In Example 2, Sample D was prepared by directly applying a commercially available aluminophosphate bonded ceramic spray coating to a 304H stainless steel coupon. The coating consisted of silicon carbide and alumina particles suspended in an alumino-phosphate matrix. This coating was tested for its capability to inhibit coke formation.

[0090] Sample D was analyzed alongside Comparative Sample E, which was a bare, uncoated 304H stainless steel coupon. Sample D was analyzed only for fresh coupons, not postdecoke as was done in Example 1. The coking rates of each sample were tested at a temperature of 750 °C and pressure of 50 psig. Pure ethane was used as the feed source with a flowrate set to produce about 12 seconds of residence time within the coupon. Coking rate was measured using a mass spectrometer carried out at a temperature of 750 °C with 5% O2 in balance Argon. The results are displayed in Table 3.Table 3

[0091] The fresh coking rate of Sample D is about 8 times lower than Comparative Sample E. This shows an improved capability to inhibit coke formation from the aluminophosphate bonded ceramic spray coating as compared to uncoated 304H steel.

[0092] For the purposes of describing and defining the present disclosure it is noted that the term “about” is 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” is 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 novelcharacter! stic(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.

[0093] 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.”

[0094] 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.

[0095] 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

CLAIMS1. An olefinic material production system comprising: a metal component comprising an outer surface; an anti -coking coating positioned over the metal component; and a refractory material layer positioned over the anti-coking coating, such that the anticoking coating is positioned between the metal component and the refractory material layer.

2. The method of claim 1, wherein the anti -coking coating comprises a ceramic material.

3. The method of claim 2, wherein the ceramic material comprises metal carbides, metal oxides, or both.

4. The method of claim 2, wherein the ceramic material comprises alumina.

5. The method of claim 2, wherein the ceramic material comprises compounds containing one or more of aluminum, silicon, chromium, and cerium.

6. The method of claim 1, wherein the anti -coking coating comprises a metalized surface.

7. The method of claim 1, wherein the anti -coking coating comprises aluminum.

8. The olefinic material production system of any previous claim, wherein the anti -coking coating has a thickness of from 25 microns to 500 microns.

9. The olefinic material production system of claim 1, wherein the metal component is a reactor sidewall.

10. The olefinic material production system of claim 1, wherein the metal component is a crossover duct, a cyclone, a riser, a reactor internal, a plenum, a downstream heat exchanger, or a stripper.

11. The olefinic material production system of claim 1, wherein the metal component is a metal anchor.

12. The olefinic material production system of any previous claim, wherein the metal component is in direct contact with the anti-coking coating, and the anti-coking coating is in direct contact with the refractory material layer.

13. The olefinic material production system of any previous claim, wherein the refractory material layer comprises one or more of alumina, silica, lime, iron oxide, titania, phosphorus pentoxide, silicon carbide, zirconia, chromium oxide, magnesium oxide, calcium oxide, graphite, yttria-stabilized zirconia, MgAhCU, calcium aluminate, hafnium carbide, or compounds having tungsten or molybdenum.

14. The olefinic material production system of any previous claim, wherein the metal component comprises stainless steel, structural steel, metal alloys, or aluminum.

15. A method for operating the olefinic material production system of any previous claim, the method comprising exposing the refractory material layer to temperatures of at least 550 °C in the presence of hydrocarbons.

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