RU2767113C2 - Device and method of converting methane using a supersonic flow reactor - Google Patents

Abstract

FIELD: chemical or physical processes.

SUBSTANCE: invention relates to production of methane by pyrolysis. Device for producing acetylene from a stream of raw material containing methane, including: a supersonic reactor for receiving a methane feed stream and heating the methane feed stream to a pyrolysis temperature; supersonic reactor shell for determining the boundaries of the reactor chamber, wherein the reaction chamber operates at temperature of 1,200 °C to 4,000 °C; supersonic reactor combustion zone for combustion of fuel source to produce high-temperature carrier gas, passing through the reactor space at supersonic speeds to accelerate and heat the flow of methane feedstock to pyrolysis temperature; reactor shell, comprising an inner shell and an outer shell with one or more channels between the inner shell and the outer shell, wherein the inner shell is made of a material, having thermal conductivity from 300 to 450 W/(m·K) to remove heat from the reactor chamber and a melting point of 500 °C to 2,000 °C; wherein the material is at least copper and chromium, or copper, chromium and zinc, or copper, chromium and niobium, or copper and zirconium, or copper, silver and zirconium, or mixtures thereof; and coating containing metallic nickel, nickel alloy, chromium metal, chromium alloy, platinum metal, platinum alloy, palladium or palladium alloy or mixtures thereof, deposited on the inner surface of the inner layer of the reactor shell.

EFFECT: high efficiency of the process of pyrolysis of initial raw material of light alkanes.

10 cl, 14 dwg

Description

This application claims priority over U.S. Patent Application No. 15/629447, filed June 21, 2017, which is a partial continuation of co-pending Application No. 15/491,280, filed April 19, 2017, which is a continuation of Application No. 13/ 967,334, filed Aug. 14, 2013, currently protected by U.S. Patent No. 9,656,229, which claims priority over Provisional Application No. 61/691,317, filed Aug. 21, 2012, now expiring and now expiring, the contents of said applications are incorporated in their entirety to this document by reference.

Field of invention

A device and methods for the conversion of methane in a hydrocarbon stream to acetylene using a supersonic flow reactor are described.

Prerequisites for the creation of the invention

Light olefins, including ethylene and propylene, make up a significant portion of the world's demand in the petrochemical industry. Light olefins are used in the production of many chemical products through polymerization, oligomerization, alkylation and other well known chemical reactions. These light olefins are essential building blocks of today's petrochemical and chemical industries. As a consequence, the petrochemical industry is focusing on the economical production of light olefins in large quantities. The main source of such substances in oil refining is currently steam cracking of crude oil.

The cracking of hydrocarbons by heating feedstock in a furnace has long been used to produce useful products, including, for example, olefinic products. For example, ethylene, which is one of the most important products in the chemical industry, can be produced by pyrolysis of feedstocks ranging from light paraffins such as ethane and propane to heavier fractions such as naphtha. Typically, lighter feedstocks provide higher ethylene yields (50-55% for ethane versus 25-30% for naphtha), but which feedstock is used will likely determine feedstock costs. Historically, naphtha cracking has provided the largest source of ethylene, followed by pyrolysis, cracking or dehydrogenation of ethane and propane. However, due to the high demand for ethylene and other light oleic substances, the cost of these traditional raw materials is steadily increasing.

Energy consumption is another factor affecting the pyrolytic production of chemical products from various feedstocks. Over the past few decades, significant improvements have been made in the efficiency of the pyrolysis process, which has reduced production costs. In a conventional or conventional pyrolysis plant, the feedstock passes through a plurality of heat exchanger tubes where it is heated externally to the pyrolysis temperature by the combustion products of fuel oil or natural gas and air. One of the most important steps taken to keep production costs to a minimum has been to reduce the residence time of raw materials in the heat exchanger tubes of the pyrolysis oven. Reducing the residence time of the raw material increases the yield of the desired product and at the same time reduces the production of heavier by-products that tend to foul the walls of the pyrolysis tubes. However, there remains little room for improvement in terms of feedstock residence time or overall energy consumption with conventional pyrolysis processes.

Recent attempts to reduce the cost of producing light olefins include the use of alternative processes and/or feed streams. In one approach, hydrocarbon oxygenates, and in particular methanol or dimethyl ether (DME), are used as alternative feedstocks for the production of light olefin products. Oxygenates can be obtained from available substances such as coal, natural gas, recycled plastics, various carbon waste streams from industry, and various products and by-products of agricultural production. The production of methanol and other oxygenates from this type of feedstock is well established and typically involves one or more well known processes such as syngas production using a nickel or cobalt catalyst in a steam reforming step followed by a relatively high pressure methanol synthesis step using copper based catalyst.

Once the oxygenates are formed, the process includes the catalytic conversion of oxygenates such as methanol to the desired light olefin products in an oxygenate to olefin (OTO) process. Technologies for converting oxygenates such as methanol to light olefins (MTO) are disclosed in US Pat. No. 4,387,263, which describes a process that uses a catalytic conversion zone containing a zeolite-type catalyst. US 4,587,373 describes the use of a zeolite catalyst such as ZSM-5 to produce light olefins. US Patents 5,095,163; US 5,126,308 and US 5,191,141, on the other hand, describe MTO conversion technology using a non-zeolitic molecular sieve catalyst such as metal aluminophosphate (ELAPO) molecular sieve. The OTO and MTO processes, although useful, use an indirect method to generate the desired hydrocarbon product by first converting the feed to oxygenate and then converting the oxygenate to hydrocarbon product. This indirect production route is often associated with energy and waste costs, which often reduces the benefit of using a less expensive feed.

Recently, attempts have been made to use pyrolysis to convert natural gas to ethylene. US 7,183,451 describes heating natural gas to a temperature at which the fraction is converted to hydrogen and a hydrocarbon product such as acetylene or ethylene. The product stream is then quenched to stop further reaction and then reacted in the presence of a catalyst to form transport liquids. The resulting liquids include naphtha, gasoline or diesel. While this process may be effective for converting some of the natural gas to acetylene or ethylene, this approach is expected to yield only 40% acetylene from the methane feed stream. While it has been found that higher temperatures combined with a shorter residence time can increase yield, the associated technical limitations prevent further improvement of the process.

While the aforementioned conventional pyrolysis systems provide solutions for converting ethane and propane to other useful hydrocarbon products, they have proven to be either inefficient or uneconomical for converting methane to these other products, such as ethylene. While MTO technology is promising, these methods can be costly due to the indirect approach to obtaining the desired product. Due to the continuing rise in feedstock prices, such as ethane and naphtha, for conventional processes, and the oversupply and associated low cost of natural gas and other methane sources, such as the recent greater availability of shale gas, it is desirable to provide commercially feasible and cost-effective ways to use methane as a feedstock for the production of ethylene and other useful hydrocarbons.

Brief description of graphic materials

In FIG. 1 is a cross-sectional side view of a supersonic reactor in accordance with the various embodiments described herein.

In FIG. 2 is a schematic view of a system for converting methane to acetylene and other hydrocarbon products in accordance with the various embodiments described herein.

In FIG. 3 is a partial cross-sectional side view showing portions of the supersonic reactor shown in FIG. 1 in accordance with various embodiments described herein.

In FIG. 4 is a partial cross-sectional side view showing portions of the supersonic reactor shown in FIG. 1 in accordance with various embodiments described herein.

In FIG. 5 is a cross-sectional view showing a supersonic reactor in accordance with various embodiments described herein.

In FIG. 6 is a partial cross-sectional side view showing portions of the supersonic reactor shown in FIG. 1 in accordance with various embodiments described herein.

In FIG. 7 is a partial cross-sectional side view showing portions of the supersonic reactor shown in FIG. 1 in accordance with various embodiments described herein.

In FIG. 8 is a partial cross-sectional side view showing portions of the supersonic reactor shown in FIG. 1 in accordance with various embodiments described herein.

In FIG. 9 is a perspective view of a section of the supersonic reactor shown in FIG. one.

In FIG. 10 is a partial cross-sectional side view showing portions of the supersonic reactor shown in FIG. 1 in accordance with various embodiments described herein.

In FIG. 11 is a partial cross-sectional side view showing portions of the supersonic reactor shown in FIG. 1 in accordance with various embodiments described herein.

In FIG. 12 is a partial cross-sectional side view showing portions of the supersonic reactor shown in FIG. 1 in accordance with various embodiments described herein.

In FIG. 13 is a partial sectional perspective view showing portions of the supersonic reactor shown in FIG. 1 in accordance with various embodiments described herein.

In FIG. 14 is a schematic view of a supersonic reactor in accordance with the various embodiments described herein.

Detailed description

One proposed alternative implementation for prior olefin production processes that have not been widely commercialized involves feeding a hydrocarbon feed to a supersonic reactor and accelerating the feed to supersonic speed to provide kinetic energy that can be converted to heat to allow an endothermic pyrolysis reaction to proceed. Embodiments of this method are set forth in US Pat. Nos. 4,136,015; US 4,724,272 and Russian Patent No. SU 392723A. These methods include burning the feedstock or carrier fluid in an oxygenated environment to raise the temperature of the feedstock and accelerate it to supersonic speeds. A shock wave is created in the reactor to initiate pyrolysis or cracking of the feedstock.

More recently, US Pat. Nos. 5,219,530 and 5,300,216 propose a similar process that uses a shock wave reactor to provide kinetic energy to initiate the pyrolysis of natural gas to produce acetylene. More specifically, this method includes passing steam through a heating section to superheat it and accelerate it to near supersonic speeds. The heated fluid is transferred to a nozzle which acts to cause the carrier fluid to expand, reach supersonic speed and lower the temperature. The ethane feed is passed through a compressor and heater and injected with mixing nozzles with supersonic carrier fluid to turbulently mix with each other at Mach 2.8 at 427°C. The temperature in the mixing section remains low enough to limit premature pyrolysis. The shock wave reactor includes a pyrolysis section with gradually increasing cross-sectional area, in which a standing shock wave is formed due to back pressure in the reactor due to flow restriction at the outlet. The shock wave rapidly reduces the velocity of the fluid, correspondingly rapidly increasing the temperature of the mixture by converting kinetic energy into heat. This immediately initiates the pyrolysis of the ethane feedstock for its conversion to other products. Then, the quench exchanger receives the pyrolysis mixture to quench the pyrolysis reaction mixture.

The following describes in general terms methods and apparatus for converting hydrocarbon components in methane feed streams using a supersonic reactor. As used herein, the term "methane feed stream" includes any feed stream containing methane. The methane feed streams destined for supersonic processing generally include methane and form at least a portion of the process stream. The apparatus and methods provided herein convert at least a portion of the methane to the desired hydrocarbon compound to produce a product stream having a higher concentration of product hydrocarbon compound relative to the feed stream.

As used herein, the term "hydrocarbon stream" refers to one or more streams that provide at least a portion of a methane feed stream entering a supersonic reactor as described herein, or derived from a supersonic reactor from a methane feed stream, regardless of whether whether additional processing or processing of such a hydrocarbon stream is carried out. As shown in the example shown in FIG. 2, the hydrocarbon stream may include methane feed stream 1, supersonic reactor product stream 2, desired product stream 3 from a subsequent hydrocarbon conversion process, or any intermediate or by-product streams generated during the implementation of the methods described herein. The hydrocarbon stream may be carried via process stream line 115 as shown in FIG. 2, which includes lines for carrying each of the portions of the process stream described above. As used herein, the term "process stream" includes "hydrocarbon stream" as described above, and may also include carrier fluid stream, fuel stream 4, oxygen source stream 6, or any streams used in systems and methods. described in this document. The process stream may be transferred via a process stream line 115, which includes lines for transferring each of the portions of the process stream described above. As shown in FIG. 2, any of the methane feed stream 1, fuel stream 4, and oxygen source stream 6 may be preheated, for example, by one or more heaters 7.

Previous attempts to convert light paraffin or alkane feed streams, including ethane and propane feed streams, to other hydrocarbons using supersonic flow reactors have shown promise in providing higher yields of desired products from a particular feed stream compared to other more conventional pyrolysis systems. In particular, the ability of these types of processes to provide very high reaction temperatures with an associated very short residence time provides a significant improvement over conventional pyrolysis processes. It has recently been found that these methods can also convert methane to acetylene and other useful hydrocarbons, while more conventional pyrolysis methods are unsuitable or inefficient for such conversion.

However, most of the previous work with supersonic reactor systems has been of a theoretical or research nature and thus has not solved the problems associated with the practical implementation of this method on a commercial scale. In addition, many of these previous descriptions do not involve the use of supersonic reactors to carry out the pyrolysis of a methane feed stream, and rather focus on the pyrolysis of ethane and propane. One of the problems that has recently been identified with the acceptance of the use of a supersonic flow reactor for the pyrolysis of light alkanes, and more specifically the pyrolysis of methane feedstock to form acetylene and other useful products, includes the detrimental effects that a supersonic flow reactor may be subjected to and other associated equipment due to the harsh operating conditions in the pyrolysis of methane. Previous work has not fully evaluated or addressed these severe operating conditions. For example, a supersonic reactor, along with high pressures, can operate at temperatures up to 3000°C or higher. Such high temperatures and pressures create the risk of mechanical failure of the reactor walls as a result of metal melting, tearing or creep. In particular, it has been found that, at elevated temperatures, hot spots on the walls may indicate shell melting. In addition, even where the walls are cooled, chemical reactions damage can occur, for example due to redox reactions, forming non-passivated products that are carried away with the gas flow, resulting in depressions in the walls. In addition, transient oxidation can occur, creating non-adhesive oxides that are carried away with the gas flow.

In addition, the carrier stream and the feed stream can pass through the reactor at supersonic speeds, which can rapidly wear out many materials that can be used to form the reactor shell. Moreover, certain substances and contaminants that may be present in the hydrocarbon stream may cause corrosion, oxidation and/or thinning of the walls or shell of the reactor and other equipment or components of the reactor. Such components causing corrosion, oxidation, or thinning problems may include, for example, hydrogen sulfide, water, methanethiol, arsine, mercury vapor, cause carbidization due to reaction in the fuel itself, or hydrogen embrittlement. Another problem that can exist at high temperatures is reaction with unstable compounds such as radicals such as hydroxide.

Thus, in accordance with the various embodiments described herein, apparatus and methods are provided for the conversion of methane in hydrocarbon feed streams to acetylene and other products. The apparatus and use thereof described in accordance with the present invention has been found to improve the general process for the pyrolysis of light alkane feedstock, including methane feedstock, into acetylene and other useful products. The apparatus and methods described herein also improve the ability of the apparatus and associated components and equipment to withstand degradation and possible failure due to extreme operating conditions in a reactor.

In one approach, the apparatus and methods described herein are used to process a hydrocarbon process stream to convert at least a portion of the methane in the hydrocarbon process stream to acetylene. The hydrocarbon process stream described herein includes a methane feed stream to the system that contains methane and may also contain ethane or propane. The methane feed stream may also include combinations of methane, ethane and propane at various concentrations and may also contain other hydrocarbon compounds as well as contaminants. In one approach, the hydrocarbon feed stream includes natural gas. Natural gas can be obtained from various sources, including, without limitation, gas fields, oil fields, coal fields, shale fracturing, biomass, and landfill gas. In another approach, the methane feed stream may include a stream from another part of the refinery or refinery. For example, during the processing of crude oil into various products, light alkanes, including methane, are often separated, and a methane feed stream may be obtained from one of these sources. These streams may be provided by the same refinery or another refinery, or refinery off-gas. The methane feed stream may also include combinations of streams from various sources.

In accordance with the methods and systems described herein, the methane feed stream may be supplied from a remote location or from the location or locations of the systems and methods described herein. For example, although the source of the methane feed stream may be located at the same refinery or refinery where the processes and systems are operated, such as the effluent of another on-site hydrocarbon conversion process or a local natural gas field, the methane feed stream may be supplied from a remote source via pipelines or other means of transportation. For example, the feed stream may be obtained from a remote hydrocarbon processing plant or refinery, or a remote natural gas field and provided as feedstock for the systems and methods described herein. The initial processing of the methane stream may occur at a remote source to remove certain contaminants from the methane feed stream. Where such initial processing occurs, it may be considered as part of the systems and processes described herein, or it may precede the systems and processes described herein. Thus, the methane feed stream envisaged for the systems and processes described herein may have different levels of contaminants depending on whether the upstream processing occurs.

In one example, the methane feed stream has a methane content in the range of 65 mole % to 100 mole %. In another example, the concentration of methane in the hydrocarbon feed is in the range of 80 mole % to 100 mole % of the hydrocarbon feed. In another example, the concentration of methane is in the range from 90 mol.% to 100 mol.% hydrocarbon feed.

In one example, the concentration of ethane in the methane feed is in the range from 0 mol.% to 35 mol.%, and in another example, from 0 mol.% to 10 mol.%. In one example, the concentration of propane in the methane feed ranges from 0 mol% to 5 mol%, and in another example, from 0 mol% to 1 mol%.

The methane feed stream may also include heavy hydrocarbons such as aromatic, paraffinic, olefinic and naphthenic hydrocarbons. These heavy hydrocarbons, if present, will likely be present in concentrations from 0 mole % to 100 mole %. In another example, they may be present in concentrations from 0 mol% to 10 mol% and may be present in the range from 0 mol% to 2 mol%.

The apparatus and method for generating acetylene from a methane feed stream described herein uses a supersonic flow reactor to pyrolyze methane in a feed stream to form acetylene. The supersonic flow reactor may include one or more reactors configured to create a supersonic carrier fluid stream and a methane feed stream and expand the carrier fluid to initiate the pyrolysis reaction. In one approach, the method may involve a supersonic reactor, as described essentially in US Pat. No. 4,724,272, the contents of which are incorporated herein by reference in their entirety. In another approach, the method and system may include a supersonic reactor such as that described in US Pat. In yet another approach, a supersonic reactor described as a "shock wave" reactor may include a reactor such as that described by Robert G. Cerff "Supersonic Injection and Mixing in the Shock Wave Reactor", University of Washington Graduate School, 2010.

Although a variety of supersonic reactors can be used in the present process, an example of a reactor 5 is shown in FIG. 1. As shown in FIG. 1, supersonic reactor 5 includes a reactor vessel 10 substantially defining a reactor chamber 15. Although the reactor 5 is shown as a single reactor, it should be understood that it can be made modular or in the form of separate vessels. If they are formed modularly or as separate components, the modules or individual components of the reactor may be connected to each other permanently or temporarily, or may be separated from each other with contained fluids in other ways, such as, for example, by adjusting the pressure difference between them. A combustion zone or chamber 25 is provided for burning fuel to produce a carrier fluid at a desired temperature and flow rate. The reactor 5 may optionally include a carrier fluid inlet 20 for introducing additional carrier fluid into the reactor. One or more fuel injectors 30 are provided to inject combustible fuel, such as hydrogen, into combustion chamber 26. The same or different injectors may be used to inject an oxygen source into combustion chamber 26 to facilitate fuel combustion. Injection of the fuel and oxygen source may be in the axial direction, tangential direction, radial direction, or other direction, including a combination of directions. The fuel and oxygen are combusted to produce a hot carrier fluid stream typically having a temperature of 1200°C to 3500°C in one example, 2000°C to 3500°C in another example, and 2500°C to 3200°C in yet another example. The present document also contemplates generating a hot carrier fluid stream using other known methods, including non-burning methods. According to one example, the carrier fluid flow has a pressure of 1 atm or higher, greater than 2 atm in another example, and greater than 4 atm in yet another example.

The hot carrier fluid stream from combustion zone 25 passes through supersonic expander 51, which includes a convergent-divergent nozzle 50 to increase the velocity of the carrier fluid to over Mach 1.0 in one example, from Mach 1.0 to Mach 4. Mach 0 in another example and Mach 1.5 to Mach 3.5 in another example. At the same time, the residence time of the fluid in the reaction section of the supersonic flow reactor is from 0.5 ms to 100 ms in one example, from 1.0 ms to 50 ms in another example, and from 1.5 ms to 20 ms in another example. The temperature of the carrier fluid stream passing through the supersonic expander is in one example in the range of 1000°C to 3500°C, 1200°C to 2500°C in another example, and 1200°C to 2000°C in yet another. example.

A feed inlet 40 is provided to inject the methane feed stream into the reactor 5 for mixing with the carrier fluid. Feedstock inlet 40 may include one or more feed injectors 45 for injecting feedstock into nozzle 50, mixing zone 55, diffuser zone 60, or reaction zone or chamber 65. Injector 45 may include a manifold containing, for example, a plurality of orifices for injection or nozzles for injecting raw materials into the reactor 5.

In one approach, the reactor 5 may include a mixing zone 55 for mixing the carrier fluid with the feed stream. In one approach, as shown in FIG. 1, reactor 5 may have a separate mixing zone, for example, between supersonic expander 51 and diffuser zone 60, while in another approach, the mixing zone is integrated into the diffuser section and mixing can take place in nozzle 50, expansion zone 60, or reaction zone 65 of reactor 5. The expansion zone 60 includes a divergent wall 70 to rapidly decrease the velocity of the gases passing along it, convert the kinetic energy of the flowing fluid into thermal energy and additionally heat the flow, which causes the reaction of pyrolysis of methane in the feed stream, which can occur in the expansion section 60 and/ or located below the reaction section 65 of the reactor. The fluid is quenched in quench zone 72 to terminate the pyrolysis reaction with further conversion of the desired acetylene product to other compounds. Spray plates 75 can be used to introduce a cooling fluid, such as water or steam, into the quench zone 72.

The reactor product exits the reactor through outlet 80 and, as mentioned above, forms part of the hydrocarbon stream. The product will contain a higher concentration of acetylene than the feed stream and a reduced concentration of methane compared to the feed stream. The reactor product stream may also be referred to herein as an acetylene stream because it contains an increased concentration of acetylene. The acetylene stream may be an intermediate stream in a process to form another hydrocarbon product, or it may be further processed and captured as an acetylene product stream. In one example, the reactor product stream has an acetylene concentration prior to addition of cooling fluid in the range of 2 mole % to 30 mole %. In another example, the concentration of acetylene is in the range from 5 mol.% to 25 mol.% and from 8 mol.% to 23 mol.% in another example.

The reactor body 10 includes a reactor shell 11 . It should be noted that the term "reactor shell" refers to the wall or walls forming the reactor vessel which forms the reactor chamber 15. The reactor shell 11 is typically an annular structure forming a substantially hollow central chamber 15 of the reactor. The reactor shell 11 may include one layer of material, one composite structure, or a plurality of shells with one or more shells located within one or more other shells. The reactor shell 11 also includes various zones, components and/or modules, as described above and further described below for various zones, components and/or modules of the supersonic reactor 5. reactor zones and components, or may be modular, with different modules forming different zones and/or reactor components.

According to one approach, one or more sections of the wall or shell 11 of the reactor is molded by casting. In this case, one or more sections may not be formed by welding or stamping, or other manufacturing methods, however, the casting can be subjected to additional processing, as described below. Without intending to be bound by any theory, it is believed that because welding often retains a residual stress in the metal, forming the reactor wall or walls by welding can produce a reactor that is more susceptible to failure or rupture at high temperatures and pressures. In addition, due to changing microstructure and possible compositional gradients, welds can also be more susceptible to corrosion and cracking. Similarly, it is believed that the fabrication of the reactor walls by stamping can lead to slight residual stresses in the reactor walls, which will cause similar problems when operating at high temperatures and pressures. Thus, a more isotropic microstructure is provided by molding a section of the reactor shell in the form of a casting. The molded section of the reactor shell can provide superior corrosion resistance compared to similar components made by other methods such as welding or stamping. Molding of the reactor shell by casting can also provide more uniform heat flow and more uniform temperatures in this reactor component. Molding a section of the reactor shell by casting can also provide better and more uniform high temperature creep as well as fracture resistance compared to shell molding by other methods.

According to one approach, the casting may have a directional crystallization casting structure to provide improved thermal shock resistance and creep resistance at elevated reaction temperatures and pressures. In one approach, the casting has a columnar crystal structure. In another approach, the casting has a single crystal structure.

The casting may be made from one or more materials, as further described below. The cast section of the reactor can be further processed in various ways known in this field. For example, the cast reactor shell 11 may be coated, as further described herein, heat treated, hardened, carbon cemented, nitrided, or treated in other known ways to improve its properties.

A single crystal casting may be used to form the integral reactor shell 11, or the reactor shell 11 may include, as further described herein, individual molded components or modules that are assembled to form the reactor shell 11. In addition, if the reactor shell 11 comprises various layers, including coatings, inner and outer shells, and the like, as further described herein, these layers can be cast separately or together, and respectively operated separately or connected to each other.

According to various other approaches, one or more sections of the supersonic reactor shell may be fabricated by known methods other than casting, such as, for example, powder metallurgy, whereby sections of the shell can be pressed by hot isostatic pressing, hot isostatic pressing of powder onto substrate or laser sintering, or other suitable sintering methods, or by machining the workpiece.

In one approach, at least a portion of the reactor shell 11 is made of a material having a high melting point to withstand the high operating temperatures of the supersonic reactor 5. In one approach, one or more materials forming the portion of the reactor shell 11 may have a greater low cycle fatigue life. , high yield strength, resistance to creep and mechanical failure, oxidation resistance and compatibility with coolants and fuels. In one example, at least a portion of the shell 11 of the reactor is made of a material having a melting point from 1200°C to 4000°C and in another example from 1800°C to 3500°C. The materials can also exhibit microstructural stability through various heat and mechanical treatments, compatibility with bonding processes, and good adhesion to high oxidation resistance coatings. Some preferred materials for forming at least a portion of the reactor shell include superalloys, nickel aluminide, and gamma titanium aluminide. In one approach, the superalloy is a nickel-based superalloy, and in another approach, the superalloy is an iron-based superalloy.

In one approach, the reactor shell 11 or wall section is made of a superalloy. Meanwhile, the wall can provide excellent mechanical strength and creep resistance at combustion and pyrolysis temperatures in the reactor. Thus, the device can also resist melting or breaking due to the operating temperature and pressure in the reactor chamber 15.

In accordance with another approach, the section of the reactor shell 11 is made of a material selected from the group consisting of carbide, nitride, titanium diboride, sialon ceramic, zirconium dioxide, thorium dioxide, carbon-carbon composite, tungsten, tantalum, molybdenum, chromium, nickel and their alloys.

In yet another approach, the reactor shell portion 11 is injection molded, the casting comprising a component selected from the group consisting of duplex stainless steel, super duplex stainless steel, and a nickel-based low creep high temperature superalloy.

Chrome or nickel can be used to provide good corrosion resistance.

In another aspect, the walls of the reactor are made of a material having a high thermal conductivity. In this way, heat can be quickly removed from the reactor chamber 15. This helps to limit the surface temperature of the inner surface of the reactor shell 11 so that it does not heat up to temperatures equal to or close to the reactor temperature that could cause melting, chemical combustion, or other degradation of the walls of the reactor shell 11. In one example, one or more sections of the reactor are made of a material having a thermal conductivity of 200 to 500 W/(m-K). In another example, the thermal conductivity is between 300 and 450 W/(m-K). In yet another example, the thermal conductivity is between 200 and 346 W/(m-K), and in yet another example, it may be between 325 and 375 W/(m-K).

It has been found that with this approach, the reactor shell can be made from a material having a relatively low melting point, provided that the material has a very high conductivity. Since heat is quickly removed from the reaction chamber 15 in this approach, the reactor shell 11 is not exposed to such a high temperature. In this regard, when forming a section of the reactor shell from a material having high thermal conductivity, the material may have a melting point below the temperature in the reactor chamber 15 . In one example, the section of the shell 11 of the reactor is made of a material having a melting point from 500°C to 2000°C. In another example, the section of the shell 11 of the reactor may be made of a material having a melting point of 800°C to 1300°C, and may be made of a material having a melting point of 1000°C to 1200°C in another example.

According to one approach, a material having a high thermal conductivity includes a metal or a metal alloy. In one approach, one or more sections of the shell 11 of the reactor can be made of copper, silver, aluminum, zirconium, niobium and their alloys. In this regard, it should be noted that one or more of the above materials can also be used to form a coating on the substrate of the reactor shell or to form a layer of the multilayer shell 11 of the reactor. According to one approach, section 11 of the reactor contains copper or a copper alloy. In one example, the section of the reactor shell contains a material selected from the group consisting of copper and chromium; copper, chromium and zinc; copper, chromium and niobium; copper and nickel and copper, nickel and tungsten. In another example, the reactor shell portion includes niobium and silver. To improve heat removal from the reactor chamber, cooling can be used to remove heat more quickly from the reactor chamber so that its temperature is maintained at an acceptable level and below.

According to another approach, the reactor shell 11 may include a plurality of layers. The reactor shell 11 shown in FIG. 3 comprises an inner layer 210 defining the reactor chamber 15 and an outer layer 205 defining the inner layer 210. Although the reactor shell 11 shown in FIG. 3 has two layers for ease of explanation, it should be understood that the reactor shell 11 may include three or more layers as shown in FIG. 8 having one or more intermediate layers 211 between the inner layer 210 and the outer layer 205. In addition, one or more additional outer layers 212 may be located on the outside of the outer layer 212. On the inside of the inner layer 210, one or more additional inner layers.

In one approach, the inner layer 210 comprises a coating made on the inner surface of the outer layer 205 or any additional intermediate layers 211. In this case, the outer layer 205 forms a substrate on which the inner layer 210 is coated. In an alternative embodiment, the inner layers 210 can serve as a substrate, which is coated with the outer layer 205. One or both of the inner layer 210 and the outer layer 205 can be cast as previously described, or molded by other known methods in accordance with this approach.

In one approach, at least a portion of the inner layer 210 contains a material with a high melting point, as described above. In accordance with another approach, the inner layer 210 contains a material selected from the group consisting of carbide, nitride, titanium diboride, sialon ceramic, zirconia, thorium dioxide, carbon-carbon composite, tungsten, tantalum, molybdenum, chromium, nickel, and their alloys. . In yet another approach, inner layer 210 comprises a superalloy, and in another approach, comprises a material selected from the group consisting of duplex stainless steel, super duplex stainless steel, and a nickel-based low creep high temperature superalloy. In this regard, the inner layer 210 may be selected to provide advantageous performance, particularly when the layer is subjected to harsh operating conditions in the reactor chamber 15, including high temperatures therein.

In another approach, at least a portion of the inner layer 210 contains a material with high thermal conductivity, as described above. In accordance with another approach, the inner layer 210 contains a material selected from the group consisting of copper, silver, aluminum, zirconium, niobium and their alloys. In another approach, the inner layer 210 contains a material selected from the group consisting of copper and chromium; copper, chromium and zinc; copper, chromium and niobium; copper and nickel and copper, nickel and tungsten. In another example, the reactor shell portion includes niobium and silver. In this regard, the inner layer 210 may be selected to provide advantageous performance, particularly when the layer is subjected to harsh operating conditions in the reactor chamber 15, including high temperatures therein.

In one approach, the outer layer 205 may be made of a material different from that of the inner layer 210. The material of the outer layer 205 may be chosen to form a support structure or provide other desirable properties for the reactor shell 11. In one example, the outer layer 205 or intermediate layer comprises stainless steel. Other suitable materials for forming the outer layer 205 of the reactor shell 11 include, but are not limited to, duplex stainless steel, super duplex stainless steel, and nickel based low high temperature creep superalloy, nickel based Nimonic™ low high temperature creep superalloy, Inco™ 718, Haynes™, 230 or other nickel alloys such as Mar-M-247.

In one approach, the inner layer 210 includes a thermal barrier coating. Thermal barrier coatings can be made from a material that exhibits the desired properties for use in the reactor chamber 15, such as, for example, a high melting point to withstand high temperatures in the reactor chamber 15. For example, the thermal barrier coating may include yttria stabilized zirconia, lanthanum and rare earth doped lanthanum hexaluminate, hafnium carbide, or tungsten, since both materials have high melting points, good mechanical properties at high operating temperatures, and optionally low thermal conductivity.

In one approach, a tie coat is provided between the inner layer 210 and the surface of the outer layer 205, including a thermal barrier coating, in accordance with one approach. The bond coating may comprise NiCrAlY, NiCoCrAlY alloys deposited on the metal surface by plasma spraying, electron beam physical vapor deposition (PVD), or other methods known in the art. Other bond coatings for copper alloys may include NiAl deposited by vacuum plasma spraying in a low pressure inert gas atmosphere or by other methods known in the art.

The multilayer reactor shell 11 may be formed by any known method known in the art. In one approach, the inner diameter coating formed on the mandrel can be used to form a multilayer reactor shell by coating the substrate material. In another approach, the substrate may be coated by hot isostatic pressing to form a multilayer reactor shell 11 . In yet another approach, cladding can be used to obtain a coating on a substrate. In another approach, the inner layer and outer layers can be formed separately and connected to each other. An example of this approach includes separately casting the inner layer 210 and the outer layer 205 and joining them together by soldering to form a multilayer reactor shell 11 . Double casting can also be used by casting a second alloy of the first alloy.

In another approach, as shown in FIG. 4, at least a portion of the reactor shell 11 may include a separate inner shell 215 and an outer shell 220. Similar to the multilayer reactor shell 11 described above, the reactor shell having a separate inner shell 215 and outer shell 220 may allow the inner shell 215 to withstand operating conditions of the reactor chamber 15, while the outer shell 220 forms a support structure and/or provides other desired properties for the reactor shell 11.

In one approach, at least a portion of the inner shell 215 contains a material with a high melting point, as described above. In accordance with another approach, at least a portion of the inner shell 215 contains a material selected from the group consisting of carbide, nitride, titanium diboride, sialon ceramic, zirconia, thorium dioxide, carbon-carbon composite, tungsten, tantalum, molybdenum, chromium, molybdenum, chromium, nickel and their alloys. In another approach, at least a portion of the inner sheath 210 comprises a superalloy, and in another approach, comprises a material selected from the group consisting of duplex stainless steel, super duplex stainless steel, and a nickel-based low creep high temperature superalloy. However, the inner shell 215 may be selected to provide advantageous performance, particularly when the shell is subjected to harsh operating conditions in the reactor chamber 15.

In another approach, at least a portion of the inner shell 215 contains a material with high thermal conductivity, as described above. In accordance with another approach, the inner shell 215 contains a material selected from the group consisting of copper, silver, aluminum, zirconium, niobium and their alloys. In yet another approach, inner sheath 215 comprises a material selected from the group consisting of copper and chromium; copper, chromium and zinc; copper, chromium and niobium; copper and nickel and copper, nickel and tungsten. In another example, inner sheath 215 includes niobium and silver. In another approach, the inner sheath may comprise a material including a copper alloy that has been hardened with particulate precipitates of secondary phase compounds so that the alloy retains a high thermal conductivity. In this regard, the inner shell 215 may be selected to provide advantageous performance, particularly when the layer is subjected to harsh operating conditions in the reactor chamber 15, including high temperatures therein.

In one approach, outer shell 220 may be made from a material different from inner shell 215. Outer shell 220 may be selected to form a support structure or provide other desirable properties for reactor shell 11. In one example, the outer shell 220 contains stainless steel. Other suitable materials for forming the outer layer 205 of the reactor shell 11 include, but are not limited to, duplex stainless steel, super duplex stainless steel, and nickel based low high temperature creep superalloy, nickel based Nimonic™ low high temperature creep superalloy, Inco™ 718, Haynes™, 230 or other nickel alloys such as Mar-M-247.

According to one approach, one or both of the inner shell 215 and the outer shell 220 are molded as described above.

In one approach, outer shell 220 includes tubesheet 230 as shown in FIG. 5. In accordance with this approach, at least one additional inner shell 235 is located within the outer shell 230 forming the second reactor chamber 240. Thus, a plurality of pyrolysis reactions can take place within a plurality of reactor chambers 240. In this approach, each of the inner shells 235 may include some or all of the components described above in relation to the supersonic reactor 5 shown in FIG. 1, or some of the components of the individual inner shells 235 may be integral. In one approach, some of the inner shells 235 of the reactor may be oriented in opposite directions. In this regard, any jet thrust that may be generated by the high velocity flows through the inner shells will be displaced by the opposingly oriented inner shells 235 of the reactor.

In one approach, inner sheath 215 is spaced from outer sheath 220 to provide a conduit 245 therebetween, as shown in FIG. 4. In this approach, channel 245 may include a pressure zone. The pressure zone is pressurized to maintain the same pressure as the pressure in the reactor chamber 15 . In this case, the inner shell 215 can be made in such a way that it does not have to withstand a large pressure difference between its inner surface 250 and the outer surface 255. Further, the inner shell 215 can be made of a material having a relatively lower pressure rating and/or relatively small wall thickness. In addition, the outer shell 220 may form a supporting structure and also serve as a pressure vessel to withstand the pressure difference between the pressure zone 245 and the outer shell 220. In another approach (not shown), the inner shell 215 may be adjacent to the outer shell 220 .

In one approach, channel 245 further comprises one or more sensors 216. The sensors can detect or measure variables such as one or more parameters or substances in channel 245. Examples of sensors include pressure sensors, temperature sensors, chemical sensors such as gas sensors , hydrogen sensors, hydrocarbon sensors, methane sensors, etc. The sensors may be electrically connected to one or more display, monitoring and/or control systems. In one approach, the channel 245 further accommodates one or more supporting structures 217 to support the inner shell 215 relative to the outer shell 220.

According to another approach, as shown in FIG. 6, a lining 260 may be provided within at least a portion of the reactor shell 11 to prevent wear of the portion of the reactor shell 11 due to operating conditions in the reactor chamber 15. Lining 260 may extend along the inner surface of the reactor shell 11 and may be adjacent to or separate from the reactor shell 11 .

In one approach, lining 260 includes a removable lining. The removable lining may contain carbon in the form of carbon-carbon composite, pyrolytic carbon, vitreous carbon, or other forms of carbon or high temperature alloy, and can be removed and replaced after wear of the lining 260 has been reached. chamber 15 of the reactor.

In accordance with another approach, lining 260 includes a self-healing lining and is capable of being regenerated during supersonic reactor 5 operation and/or when supersonic reactor 5 is taken offline. In one approach, the self-healing lining includes carbon that is catalytically active to facilitate the formation of carbon or coke along the inner surface of the shell 11 of the carbon lining regeneration reactor. In another approach, the self-healing lining includes a self-healing lining having a graphite coke layer. In another approach, the self-healing liner includes a liner having a nanostructured layer of coke. In yet another approach, the self-healing cladding includes a cladding with a nanostructured graphene layer. In one approach, the self-healing lining has directional thermal conduction to rapidly remove heat from the reaction chamber 15 during operation.

In one approach, lining 260 includes a low thermal conductivity coating that functions to protect the metal alloys used and retard heat transfer. In another approach, the liner may be a floating trapped liner made from materials with high temperature resistance and low thermal conductivity. This cladding reduces heat transfer and erosion. A floating trapped liner can be formed by vacuum plasma spraying of HfC or rhenium onto a suitable mandrel machined to the exact dimensions of the mold of the desired outer diameter of the liner. The sputtered HfC or rhenium coating can be followed by a tungsten support layer capable of maintaining this structure at the required temperatures. The tungsten layer may be followed by a molybdenum layer and possibly another support layer of tungsten and/or nickel, cobalt, chromium, yttrium-aluminum. All layers can be applied using vacuum plasma spraying, and they will be one after the other after the inner diameter of the mandrel has been subjected to chemical etching.

In one approach, active cooling is provided in one or more regions of the reactor cladding 11 to remove heat from the reactor chamber 15 and limit meltdown or other degradation of the reactor cladding 11 due to exposure to high temperatures and other operating conditions. In one approach, active cooling includes an active cooling system. As shown in FIG. 7, a cross section of a portion of the reactor shell 11 shows an active cooling system that includes a plurality of cooling channels 300 molded into the reactor shell 11 for flowing a cooling medium along the reactor shell 11 to remove heat from it. The active cooling system may also include a source of coolant for supplying pressurized coolant passing through the cooling channels 300. As shown in FIG. 7, the cooling channels may extend substantially around the circumference of the reactor shell 11, which in one approach includes a substantially annular configuration. Collector tubes may also be provided to supply cooling medium to and from the cooling channels 300.

In one approach, the cooling channels 300 may include one or a plurality of channels formed on the surface of the reactor shell. In another approach, the cooling channels 300 may include one or a plurality of tubes or substantially hollow tunnels molded into the reactor shell 11 for cooling fluid to flow therethrough, as in the configuration shown in FIG. 7. Channels 300 may extend along one or more surfaces of the reactor or may be provided in the walls of the reactor shell 11 as shown in FIG. 9. The channels 300 may be arranged in various orientations and may extend axially along the reactor shell 11, around the circumference of the reactor shell 11, radially through the reactor shell, helically along the annular reactor shell, or in another orientation known in the art.

In yet another approach, cooling channels 300 may include one or more spaces between inner and outer layers, linings, or inner and outer skins, as described above, to provide one or more cooling channels, such as channel 245 in FIG. 4. In addition, a flow manipulator may be provided in the space between the inner and outer layers, liners or shells to direct the cooling fluid in accordance with the desired flow pattern. As shown in FIG. 10, protrusions 315, such as pins, fins, or other protrusions, may be used in the space between the inner and outer layers to increase the surface area for cooling. In addition, the cooling system may include a combination of different types of cooling channels 300 as described herein. For example, the cooling channels 300 may include a cooling channel 300 between the layers 215 and 220 of the reactor shell 11, as well as channels formed on the surface of one of the inner layer 215 and the outer layer 220 so that the coolant flowing through the cooling channels also passes through channels 245 of the reactor shell.

The cooling channels 300 may be formed in various ways. In one approach, cooling channels 300 are machined from the reactor shell. In another approach, partial channels may be formed along the surface(s) of one or more layers, or shells, of the reactor shell 11, as described above, and full channels 300 may be formed between the layers or shells by joining the layers and/or shells, as shown in FIG. 10. Similarly, a partial channel may be formed on the surface of the reactor wall or bed, and a coating or lining may be applied over the partial channel to form a complete channel 300 between the reactor wall or bed and the coating or lining. In yet another approach, the coating or lining may be applied in a pattern defining a full or partial channel. Such partial or complete channels may be formed, as described above, by machining, casting, or during the application of a particular coating, layer, or lining, or by other means. Cooling channels 300 may also be formed by others that are well known in the art. Pins, ribs, or other protrusions may be used in the channels to increase the surface area for cooling. The cladding may be coated with a low thermal conductivity, functioning to provide protection to the metal alloys used, slow down the transfer of heat to active cooling, and increase efficiency. As an example, the coating may be a nickel or copper alloy that has been vacuum plasma sprayed onto an inner lining with a pre-applied bond coating that allows the base metal to adhere to the low thermal conductivity material. The bond coat may contain nickel, chromium, cobalt, aluminum and/or yttrium, followed by molybdenum and tungsten, and finally HfC or HfO ₂ .

The walls forming the cooling channels can facilitate heat transfer to the circulating cooling medium, acting as cooling fins, and also withstand pressure loads from the cooling medium. In one approach, the wall thickness in contact with the hot gas (the portion of the reactor shell 11 between the coolant and the hot combustion gas) is optimized to minimize resistance to heat flow through the lining walls and cooling channels 300, while maintaining structural integrity against pressure and thermal effects. loads. In one approach, the hot gas wall thickness is 0.10 inch to 0.375 inch, and in another example it is 0.15 inch to 0.225 inch. In another approach, the walls between the cooling channels are optimized with ribs to provide low thermal resistance between the hot wall and the cooling medium, as well as maintaining structural integrity.

In another approach, the cooling channels contain flow enhancers to enhance the flow of the cooling medium to increase the heat transfer coefficient of the cooling medium and the heat flow from the wall to the cooling medium. In one approach, the flow enhancers include fins oriented perpendicular to or at a lesser angle to the direction of the coolant flow to renew the coolant boundary layer, resulting in an increase in the heat transfer coefficient of the coolant and an increase in heat flow from the wall to the coolant. The swirl created by fins at less than 90 degrees will generate a swirl velocity component, mixing the coolant and imparting a higher rate of heat transfer from the wall to the coolant.

When the reactor shell 11 is assembled, the collector tubes and the network of cooling channels 300 are combined to form a collector in which the passing cooling medium removes the heat generated during the combustion process in the supersonic reactor 5 to a level necessary to maintain an acceptable temperature of the reactor wall.

In one approach, the coolant is pressurized at a relatively high pressure level such that the coolant flowing through the reactor shell portion 11 has a pressure in the range of 350 psi to 350 psig. inch g up to 3200 psi inch g, and in another approach - from 1000 psi. inch g up to 2000 psi inch g And in another approach - from 1500 to 1600 psi. inch g The relatively high pressure reduces the obstruction of the circulation of the cooling medium by avoiding phase change when using, for example, water as the cooling fluid. Coolant pressure, circulation rate, and temperature are set to provide sufficient coolant flow to sufficiently remove some of the heat generated in reactor chamber 15 to maintain an acceptable reactor wall temperature, particularly during fuel stream combustion and supersonic expansion. In one approach, the coolant has a flow rate through the cooling channels from 28,000 lb/hr to 47,000 lb/hr, and in another example, from 33,500 lb/hr to 80,000 lb/hr. In one example, the coolant inlet temperature is 50°F to 250°F, and in another example it is 85°F to 150°F. In one example, the outlet coolant temperature is 100°F to 700°F, and in another example it is 250°F to 600°F. Various cooling media known in the art can be used. In one example, the cooling medium contains water. In another example, the cooling medium includes steam, hydrogen or methane and may contain a mixture of fluids.

In one approach, injection cooling can be used as active cooling to remove heat from the reactor chamber 15 and limit meltdown or other degradation of the reactor cladding 11 due to exposure to high temperatures and other operating conditions. Injection cooling can be either gas or liquid. In one injection cooling approach, a series of impact jets can be used to provide high heat transfer. For example, high speed jets can be directed at the shell to be cooled. As the cooling jet comes into contact with the shell surface, it radiates in all directions parallel to the shell surface. The jets can be distributed over the shell, for example, randomly or in a pattern. Injection cooling may include technologies such as high impingement systems using steam expansion to cool the hot wall, liquid-to-wall impingement, and gas effusion cooling.

In one approach, a heat pipe can be used as an active cooling mechanism. Heat pipes can conduct up to 250 times more heat energy than a solid copper thermal element.

In one approach, as shown in FIG. 12, a film barrier 350 may be provided along the inner surface of at least a portion of the reactor shell 11 to provide at least a partial barrier in the reactor chamber 15. The film barrier 350 can help limit wear, including melting, erosion, or corrosion of the reactor shell 11 due to high temperatures, high flow rates, and other harsh conditions in the reactor chamber 15.

In one approach, the film barrier 350 includes a cold fluid barrier. As used herein, the term "cold fluid barrier" refers to the temperature of the fluid barrier relative to the temperature in reactor chamber 15. Thus, the cold fluid barrier may have a high temperature but be cold relative to the reactor chamber 15. In one example, the temperature of the cold fluid barrier is between 3000°F and 5000°F. In another example, the temperature of the cold fluid barrier is between 3600°F and 4600°F.

In one example, the cold fluid barrier may include a cold vapor barrier. In another example, the cold fluid barrier includes a molten metal barrier. In another example, the cold fluid barrier includes water or steam. In another approach, the cold fluid barrier includes air or hydrogen. In yet another example, the cold fluid barrier includes methane. The cold fluid barrier may also include other fluids known in the art, or a combination of fluids. According to one approach, the cold fluid barrier includes a fluid that contains at least a portion of the process stream.

The film barrier can be applied to the inner surface of the section of the shell 11 of the reactor in various ways. As shown in FIG. 13, in one approach, the reactor shell 11 includes openings 360 extending through at least a portion of it to allow cold fluid to pass through and form a cold fluid barrier. The holes may be in the form of slots that lead fluid into the core of the flow. In another approach, the reactor shell 11 may include a porous wall 365 that facilitates cold fluid infiltration through it to create a fluid barrier. According to one approach, the reactor shell may include channels (not shown) similar to those described above for the active cooling system, and cold fluid may be introduced through them to form a cold fluid barrier. With this approach, a collection tube may be provided to introduce cold fluid through the channels and orifices. In another approach, the reactor shell 11 may include an inner shell 215 and an outer shell 220, as described above, and the inner shell 215 may contain holes or include a porous wall at least in a portion of the inner shell 215. In this approach, the cold fluid may pass through the channel or channels formed between the outer shell 220 and the inner shell 215 so that it percolates through the porous wall of the inner shell 215 to form a cold fluid barrier over the inner surface of the portion of the inner shell 215. Similarly, where inside the shell 11 The reactor is provided with a lining 260 as described above with reference to FIG. 6, the liner may be a porous or permeable liner that allows cold fluid to pass through the liner and form a cold fluid barrier on its inner surface. The film barrier along the inner surface of the section of the shell 11 of the reactor can also be formed in other ways, including those known in this field.

In another approach, the wall may include a large number of small holes 360 which vent fluid into the film to form a chilled entire surface of the film.

In another approach, the wall may include grooves or slits to which the cooling medium is supplied and which form a cooling film due to the flow of the cooling medium along the wall in the direction of flow. Film barrier 350 may also be formed along the inner surface of the section of the shell 11 of the reactor in other ways, including those known in the field.

In another approach, the injection method can be combined with a full-surface film cooling method, wherein the impact fluid, after being exposed to a hot wall, is discharged through film cooling holes 360 in such wall 365, providing two cooling effects.

Thus, by providing a film barrier 350 on the inner surface of at least a portion of the reactor shell 11, wear of the reactor shell 11 during operation of the supersonic reactor 5 can be limited. The barrier film can reduce the temperature to which the reactor shell 11 is exposed during operation by providing a barrier to the hot reactor core fluid and convectively cooling the wall along with the film to the film cooling temperature.

The cooling system may include the various mechanisms described above to provide the optimum combination to achieve the highest operating efficiency.

In the above description, a number of approaches have been proposed in relation to the shell 11 of the reactor or section of the shell 11 of the reactor. Thus, it should be understood that at least a portion of the reactor shell 11 may refer to the entire reactor shell 11 or may refer to a smaller portion of the reactor shell than the entire shell, as will be described in more detail below. Thus, the foregoing description of methods for improving the design and/or operation of at least a portion of the reactor shell 11 may generally apply to any portion of the reactor shell and/or to the following specifically described portions of the reactor shell.

It has been found that certain sections or components of the reactor shell 11 may experience particularly severe operating conditions or specific problems specific to that section or component. Thus, in accordance with various approaches, certain aspects of the previous description may apply only to those areas or components for which a particular problem is found. The locations around fuel injector(s) 30 and feed injector(s) 45 are examples of locations where local film barriers or film cooling or injection cooling or locally located convective cooling channels may be useful.

One area of the supersonic reactor 5 that faces particularly harsh operating conditions during operation is the combustion area 25 . In the combustion zone 25, the fuel stream is combusted in the presence of oxygen to create a high temperature carrier stream. Temperatures in combustion zone 25 may be the highest temperatures available in reactor chamber 15 and may range from 2000°C to 3500°C in one example and from 2000°C to 3200°C in another example. Thus, a particular problem identified in the combustion zone 25 is the melting of the reactor shell 11 in the combustion zone 25 and the oxidation of the walls of the combustion chamber in the presence of oxygen. The portion of the reactor shell in the combustion zone 25 may be referred to as the combustion chamber 26 .

Another zone of the supersonic reactor 5 that faces particularly harsh operating conditions includes the supersonic expansion zone 60 and in particular the supersonic expander nozzle 50 disposed therein. In particular, because the high temperature carrier gas passes through the expander nozzle 50 at nearly supersonic or supersonic velocities, the expander nozzle 50 and/or other portions of the supersonic expansion zone 60 may be particularly susceptible to erosion.

Similarly, other portions of the supersonic reactor, including diffuser zone 60, mixing zone 55, reaction zone 65, and quench zone, may experience harsh operating conditions during operation of supersonic reactor 5. Additional equipment or components used in conjunction with supersonic reactor 5 may also may face similar challenges and harsh environments, including but not limited to nozzles, piping, mixers and heat exchangers.

Due to the uniqueness of the problems and operating conditions to which individual sections or components of a supersonic reactor may be exposed, these individual sections or components can be formed, operated or used in accordance with various approaches described in this document, while other sections or components are formed, operated or used in accordance with other approaches, which may or may not be described in this document.

Since different components or portions of the supersonic reactor 5 may be formed or operated differently, the supersonic reactor 5 including the reactor shell 11 may be made in separate parts and assembled to form the supersonic reactor 5 or the reactor shell 11. In this regard, supersonic reactor 5 and/or reactor shell 11 may include a modular configuration in which individual modules or components 400 may be assembled together as shown in FIG. 11. According to one approach, at least some sections or components 400 of the assembled supersonic reactor or reactor shell 11 may not be connected, but instead gases or fluids may be contained by adjusting the pressure drop between the components. In other approaches, modules or components 400 may be connected together, such as by flanges 405 sealed at cooled interfaces between components. Likewise, various components, sections, or modules 400 may include various sub-parts as described in the above description. For example, some modules or components 400 may include active cooling, film barrier, inner and outer layers, inner and outer shells, or other components described above, while other sections, modules or components 400 may include other components. .

In accordance with one approach, one or more components or modules 400 may be removed and replaced during the operation of the supersonic reactor 5 or during its downtime. For example, due to possible faster wear of supersonic expansion nozzle 50 than other reactor components, nozzle 50 can be made removable so that it can be replaced with a new nozzle when worn. In one approach, a plurality of supersonic reactors 5 may be provided in parallel or in series with one or more supersonic reactors in operation and one or more supersonic reactors in standby, such that, if maintenance or replacement of one or more components of the operating supersonic reactor 5 is required, the process can be switched to a standby supersonic reactor to continue operation.

In addition, supersonic reactors can be oriented horizontally, as shown in FIG. 1, or vertical (not shown). In cases where the reactor is made in a vertical design, the passage of carrier and feed streams through it in one approach can be carried out vertically from bottom to top. In another approach, carrier and feed streams may flow vertically from top to bottom. In one approach, the supersonic reactor can be oriented so that it can be freely emptied to prevent accumulation of liquid in the quench zone 72. In another approach, the reactor may be oriented vertically (90° from horizontal) or horizontally (0° from horizontal) as above, or may be oriented at an angle of 0° to 90° with the reactor inlet above the reactor outlet. In another embodiment, the outlet 80 may include two or more outlets, including a primary outlet 80 for the main vapor stream and a secondary outlet 81 for draining the liquid. In one approach, the liquid is injected into the quench zone 72 and does not evaporate completely. This may occur during transient or stationary operation. If necessary, the secondary outlet may operate continuously or intermittently.

In one approach, the reactor shell 11 is hermetically sealed at one end and includes a pressurized region at the opposite end.

In accordance with one approach, the reactor shell 11 may include a pressure relief device 218, as shown in FIG. 4. In one approach, pressure relief device 218 includes a rupture disc. In another approach, pressure relief device 218 includes a relief valve.

In one approach, as shown in FIG. 14, the supersonic reactor 5 may include a check valve 450 at the reactor inlet. The supersonic reactor may also include a control system 455 to detect pressure changes in the event of an uncontrolled release. The control system 455 may be configured to isolate the inlet in response to a blowout. In one approach, the inlet is a fuel flow inlet 4.

According to one approach, the supersonic reactor 5 includes a magnetic trap to contain the reactants within the reaction chamber 15.

According to another approach, hydrogen generation may be provided in the supersonic reactor 5 to generate hydrogen from the reactor product stream.

In one example, the reactor product stream after pyrolysis in the supersonic reactor 5 contains a lower methane content than the methane feed stream, in the range of 15 mole % to 95 mole %. In another example, the concentration of methane is in the range from 40 mol.% to 90 mol.% and from 45 mol.% to 85 mol.% in the following example.

In one example, the yield of acetylene produced in a supersonic reactor from methane in the feed stream is between 40% and 95%. In another example, the yield of acetylene produced from methane in the feed stream is between 50% and 90%. The advantage is that this gives a better yield than the estimated 40% yield achieved with previous more conventional pyrolysis approaches.

According to one approach, the reactor product stream is reacted to form another hydrocarbon compound. In this case, a portion of the reactor product from the hydrocarbon stream may be discharged from the reactor outlet into a downstream hydrocarbon conversion process for further processing of the stream. At the same time, it should be understood that the reactor product stream may go through several intermediate process steps, such as, for example, removal of water, adsorption and/or absorption to obtain a concentrated acetylene stream, and these intermediate steps will not be described in detail in this document. .

As shown in FIG. 2, a reactor product stream having a higher concentration of acetylene may be passed to a downstream hydrocarbon conversion zone 100 where the acetylene may be converted to form another hydrocarbon product. The hydrocarbon conversion zone 100 may include a hydrocarbon conversion reactor 105 for converting acetylene to another hydrocarbon product. Although in FIG. 2 is a flow diagram of a process for converting at least a portion of the acetylene in a product stream to ethylene via hydrogenation in hydrogenation reactor 110, it should be understood that many other hydrocarbon conversion methods can be performed in hydrocarbon conversion zone 100 instead of or in addition to those in hydrogenation reactor 110. or a combination of hydrocarbon conversion methods. Similarly, the operations in the pieces of equipment shown in FIG. 2 may be modified or removed and are shown for illustrative purposes and are not limiting to the methods and systems described herein. More specifically, it has been found that several other methods for converting hydrocarbons other than those described in previous approaches can be carried out downstream of the supersonic reactor 5, including methods for converting acetylene to other hydrocarbons, including, without limitation, to: alkenes, alkanes , methane, acrolein, acrylic acid, acrylates, acrylamide, aldehydes, polyacetylenides, benzene, toluene, styrene, aniline, cyclohexanone, caprolactam, propylene, butadiene, butyndiol, butanediol, C2-C4 hydrocarbon compounds, ethylene glycol, diesel fuel, dicarboxylic acids, diols, pyrrolidines and pyrrolidones.

Contaminant removal zone 120 for removing one or more contaminants from a hydrocarbon or process stream may be located at various locations along the hydrocarbon or process stream depending on the effect of the particular contaminant on the product or process and the reason for removing the contaminants, as further described below. For example, specific contaminants have been identified that interfere with the operation of the supersonic flow reactor 5 and/or contaminate components in the supersonic flow reactor 5. Thus, according to one approach, a contaminant removal zone is located upstream of the supersonic flow reactor to remove these contaminants from the feed methane stream before introducing the stream into the supersonic reactor. Other contaminants have been found to interfere with a downstream refining step or hydrocarbon conversion process, in which case the contaminant removal zone may be located upstream of the supersonic reactor or between the supersonic reactor and the particular downstream refining step. Other contaminants have been identified and must be removed according to specific product specifications. If multiple contaminants are to be removed from a hydrocarbon or process stream, different contaminant removal zones may be located at different locations along the hydrocarbon or process stream. In still other approaches, the contaminant removal zone may overlap or be integral with another method in the system, in which case the contaminant may be removed during another part of the process, including, without limitation, the supersonic reactor 5 or the downstream hydrocarbon conversion zone 100. This can be achieved with or without modification of these particular zones, reactors or processes. Although the contaminant removal zone 120 shown in FIG. 2 is shown downstream of the hydrocarbon shift reactor 105, it should be understood that the contaminant removal zone 120 of the present invention may be located upstream of the supersonic flow reactor 5, between the supersonic flow reactor 5 and the hydrocarbon shift zone 100, or below. downstream of hydrocarbon conversion zone 100 as shown in FIG. 2, or along other streams in the process stream, such as, for example, a carrier fluid stream, a fuel stream, an oxygen source stream, or any of the streams used in the systems and methods described herein.

One embodiment of the present disclosure relates to apparatus and methods for converting methane in a hydrocarbon stream to acetylene using a supersonic flow reactor while minimizing the possibility of an explosion due to the formation of copper acetylides in the chemical reaction between the generated acetylene gas and the copper of the reactor core. The methane pyrolysis reaction zone is a strong reducing environment in the presence of hydrogen and at high temperature. It has been found that Cu or CuO readily reacts with acetylene, resulting in the formation of copper acetylenide.

A coating may be applied to the inner surface of the inner layer to provide a barrier between the generated acetylene gas and the copper of the inner layer to prevent the formation of acetylides. Thus, the inner layer 210 may include a coating formed on the inner surface of the inner layer to form a barrier between the copper of the inner layer and the generated acetylene gas. The coating may be a thin coating applied to the inner surface of the inner layer of the reactor shell and may be a material that does not react with acetylene. In one embodiment, examples of suitable coatings include those containing metallic nickel or a nickel alloy, or mixtures thereof. Specific examples of nickel alloys include NiCrAlY, NiCoCrAlY, CoNiCrAlY, and Ni-P. When using a substrate containing copper, the nickel forms a solid solution which, when heat-treated, creates a very strong bond that is resistant to thermal shock cracking. In addition, it is contemplated that the nickel or nickel alloy coating may be supplemented with a thermal barrier coating such as described above to retard heat transfer. Other suitable coatings may consist of chromium containing chromium alloy, platinum containing platinum alloy, palladium containing palladium alloy or mixtures thereof, or mixtures of any of the above metals with nickel or nickel containing alloy.

The metal or alloy or mixture can be deposited on the surfaces of the reactor shell, such as the inner surface of the inner layer, by various known metal deposition methods. Suitable examples include electroplating using electric current, chemical deposition that does not use electric current, or deposition using plasma spray techniques. For example, pure nickel can be deposited using electroplating techniques. Such a coating may not require post-application heat treatment, but adhesion can be improved by heat exposure at 482°C to 538°C for 1 to 3 hours. The coating is dense and prevents contact of copper with acetylene gas. Moreover, the coating can be applied in combination with, for example, a stabilized zirconia coating as described above, in which case the dense coating not only provides a barrier to acetylenide formation, but is also a barrier to heat transfer. In another example, a nickel alloy coating such as NiCrAlY can be applied using plasma spray techniques. Such a coating may not require post-application heat treatment, but adhesion can be improved by heat exposure at 482°C to 538°C for 1 to 3 hours. The coating is dense and prevents contact of copper with acetylene gas. Moreover, the coating can be applied in combination with, for example, a stabilized zirconia coating as described above, in which case the dense coating not only provides a barrier to acetylenide formation, but is also a barrier to heat transfer. In yet another embodiment, the Ni-P coating can be applied by chemical deposition. As stated above, the coating may not require post-application heat treatment, but adhesion can be improved by heat exposure at 482°C to 538°C for 1 to 3 hours. The coating is dense and prevents contact of copper with acetylene gas. Moreover, the coating can be applied in combination with, for example, a stabilized zirconia coating as described above, in which case the dense coating not only provides a barrier to acetylenide formation, but is also a barrier to heat transfer.

Although specific embodiments and aspects have been illustrated and described, it is to be understood that numerous changes and modifications will be devised by those skilled in the art, and it is intended that the appended claims embrace all such changes and modifications that fall within the true spirit. and the scope of the present description and the appended claims.

Claims (15)

1. A device for producing acetylene from a feed stream containing methane, including: a supersonic reactor for receiving the methane feed stream and heating the methane feed stream to a pyrolysis temperature; a shell of a supersonic reactor for defining the boundaries of the reactor chamber, and the reaction chamber operates at a temperature of from 1200°C to 4000°C; a combustion zone of the supersonic reactor for burning the fuel source to produce a high-temperature carrier gas passing through the reactor space at supersonic speeds to accelerate and heat the methane feed stream to the pyrolysis temperature; a reactor shell comprising an inner shell and an outer shell with one or more channels between the inner shell and the outer shell, wherein the inner shell is made of a material having a thermal conductivity of 300 to 450 W/(m⋅K) to remove heat from the reactor chamber and a melting point from 500°C to 2000°C; wherein the material is at least copper and chromium, or copper, chromium and zinc, or copper, chromium and niobium, or copper and zirconium, or copper, silver and zirconium, or mixtures thereof; And a coating containing nickel metal, nickel alloy, chromium metal, chromium alloy, platinum metal, platinum alloy, palladium or palladium alloy or mixtures thereof deposited on the inner surface of the inner layer of the reactor shell. 2. The device according to claim. 1, in which the coating contains NiCrAlY, or NiCoCrAlY, or CoNiCrAlY, or Ni-P, or mixtures thereof. 3. Device according to claim 1, wherein the coating contains NiCrAlY. 4. The device according to claim. 1, in which the coating is electrodeposited on the inner surface of the inner layer, or applied to the inner surface of the inner layer using plasma spraying technologies; or applied to the inner surface of the inner layer using a chemical deposition method and thermally treated at a temperature of 482°C to 538°C for 1 to 3 hours. 5. The apparatus of claim. 4, wherein the coating is applied by electrolytic deposition on the inner surface of the inner layer and the coating contains metallic nickel. 6. The apparatus of claim. 4, wherein the coating is applied to the inner surface of the inner layer using plasma spraying techniques and the coating contains NiCrAlY. 7. The apparatus of claim. 4, wherein the coating is applied to the inner surface of the inner layer using a chemical deposition method and the coating contains Ni-P. 8. The device of claim 1, wherein the coating further comprises a material capable of providing a thermal barrier. 9. The apparatus of claim 1, wherein the coating further comprises yttria-stabilized zirconia, lanthanum hexaluminate, rare earth-doped lanthanum hexaluminate, hafnium carbide, tungsten, or compositions thereof. 10. A method for producing acetylene from a feed stream containing methane, comprising introducing the feed stream into a supersonic flow reactor, the supersonic reactor comprising a supersonic reactor shell to define the boundaries of the reactor chamber, the reaction chamber operating at a temperature of from 1200°C to 4000°C; a combustion zone of the supersonic reactor for burning the fuel source to produce a high-temperature carrier gas passing through the reactor space at supersonic speeds to accelerate and heat the methane feed stream to the pyrolysis temperature; a reactor shell comprising an inner shell and an outer shell with one or more channels between the inner shell and the outer shell, wherein the inner shell is made of a material having a thermal conductivity of 300 to 450 W/(m K) to remove heat from the reactor chamber and a melting point from 500°C to 2000°C; wherein the material is at least copper and chromium, or copper, chromium and zinc, or copper, chromium and niobium, or copper and zirconium, or copper, silver and zirconium, or mixtures thereof; and a coating including a coating comprising nickel metal, nickel alloy, chromium metal, chromium alloy, platinum metal, platinum alloy, palladium or palladium alloy, or compositions thereof, deposited on the inner surface of the inner layer of the reactor shell; burning the fuel source to produce a high temperature carrier gas passing through the reactor at supersonic speeds to accelerate and heat the methane feed stream to a pyrolysis temperature; moreover, when heating and accelerating the methane stream, acetylene is obtained; and preventing the formation of acetylenides in the reactor by using a coating that prevents acetylene from coming into contact with the copper of the inner layer of the reactor.

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