CN110769926B - Methane conversion apparatus and process using supersonic flow reactor - Google Patents

Abstract

An apparatus and process for converting methane in a feed stream to acetylene is provided. A hydrocarbon stream is introduced into a supersonic reactor and pyrolyzed to convert at least a portion of the methane to acetylene. The reactor effluent stream may be treated to convert acetylene to another hydrocarbon process.

Description

Methane conversion apparatus and process using supersonic flow reactor

Priority declaration

This application claims priority to U.S. application 15/629447 filed on day 6, 21, 2017, which is a continuation-in-part application to co-pending application 15/491,280 filed on day 19, 4, 2017, which is a continuation application to now U.S. patent 9,656,229 of application 13/967,334 filed on day 14, 8, 2013, which claims priority to now expired provisional application 61/691,317 filed on day 21, 8, 2012, all of the contents of the referenced applications being hereby incorporated by reference in their entirety.

Technical Field

An apparatus and process for converting methane in a hydrocarbon stream to acetylene using a supersonic flow reactor is disclosed.

Background

Light olefin materials, including ethylene and propylene, account for a significant portion of the global demand in the petrochemical industry. Light olefins are used to produce a variety of chemical products via polymerization, oligomerization, alkylation, and other well-known chemical reactions. These light olefins are an essential and important component of the modern petrochemical and chemical industries. Therefore, the economic production of large quantities of light olefin materials is an important point of the petrochemical industry. The major source of these materials in today's refining is steam cracking of petroleum feeds.

The cracking of hydrocarbons produced by heating feedstock materials in a furnace has long been used to produce useful products, including, for example, olefin products. For example, ethylene is one of the more important products in the chemical industry, which can be produced by pyrolysis of feedstocks ranging from light paraffins (such as ethane and propane) to heavier fractions (such as naphtha). Generally, lighter feedstocks will result in higher ethylene yields (50-55% for ethane versus 25-30% for naphtha); however, the cost of the raw materials is more likely to determine which one is used. Historically, naphtha cracking provided the largest source of ethylene, followed by ethane and propane pyrolysis, cracking, or dehydrogenation. However, the cost of these conventional feeds has steadily increased due to the large demand for ethylene and other light olefin materials.

Energy consumption is another cost factor affecting the pyrolytic production of chemical products from various feedstocks. Over the past decades, the efficiency of the pyrolysis process has increased significantly, thereby reducing production costs. In a typical or conventional pyrolysis unit, the feedstock is passed through a plurality of heat exchanger tubes, where the feedstock is externally heated to pyrolysis temperatures by fuel oil or combustion products of natural gas and air. One of the more important steps taken to minimize production costs is to reduce the residence time of the feedstock in the heat exchanger tubes of the pyrolysis furnace. The reduction in residence time increases the yield of desired product while reducing the production of heavier by-products that tend to foul the walls of the pyrolysis tube. However, in conventional pyrolysis processes, there is little room for improvement in residence time or overall energy consumption.

Recent attempts to reduce the cost of light olefin production have included the use of alternative processes and/or feed streams. In one process, a hydrocarbon oxygenate, and more specifically methanol or dimethyl ether (DME), is used as an alternative feedstock to produce light olefin products. Oxygenates can be produced from useful materials such as coal, natural gas, recycled plastics, various carbon waste streams from industry and various products, and by-products from agricultural production. The production of methanol and other oxygenates from these types of feedstocks is well known and typically involves one or more commonly known processes, such as the production of synthesis gas in a steam reforming step using a nickel or cobalt catalyst followed by a methanol synthesis step at relatively high pressure using a copper-based catalyst.

Once the oxygenate is formed, the process includes catalytically converting the oxygenate, such as methanol, to the desired light olefin product in an Oxygenate To Olefin (OTO) process. Technology for converting oxygenates such as methanol to light olefins (MTO) is described in US4,387,263, which discloses a process utilizing a catalytic conversion zone containing a zeolite-type catalyst. US4,587,373 discloses the use of zeolite catalysts such as ZSM-5 to produce light olefins. On the other hand, US 5,095,163, US 5,126,308 and US 5,191,141 disclose MTO conversion techniques utilizing non-zeolitic molecular sieve catalytic materials such as metalloaluminophosphate (ELAPO) molecular sieves. Although useful, OTO and MTO processes utilize an indirect process to form the desired hydrocarbon product by first converting the feed to oxygenates and then converting the oxygenates to the hydrocarbon product. This indirect production route is generally associated with energy and cost losses, generally reducing the advantages gained by using less expensive feed materials.

More recently, attempts have been made to convert natural gas to ethylene using pyrolysis. US 7,183,451 discloses heating natural gas to a temperature that converts the distillate into hydrogen and hydrocarbon products such as acetylene or ethylene. The product stream is then quenched to stop further reaction, and subsequently reacted in the presence of a catalyst to form a liquid to be transported. The liquids ultimately produced include naphtha, gasoline or diesel. While this process can effectively convert a portion of the natural gas to acetylene or ethylene, it is estimated that this process will only provide a 40% yield of acetylene from the methane feed stream. Although higher temperatures in combination with short residence times have been found to increase yield, technical limitations prevent further improvement of the process in this regard.

While the aforementioned conventional pyrolysis systems provide solutions for converting ethane and propane into other useful hydrocarbon products, they have proven ineffective or economically inefficient for converting methane into these other products, such as, for example, ethylene. Although MTO technology is promising, these processes can be expensive due to the indirect method of forming the desired product. Due to the continuing increase in feed prices for traditional processes, such as ethane and naphtha, as well as the availability of adequate supplies of natural gas and other sources of methane that are available and the corresponding low costs, such as the recent ready availability of shale gas, it is desirable to provide a commercially viable and economically efficient process for using methane as a feed for the production of ethylene and other useful hydrocarbons.

Drawings

FIG. 1 is a cross-sectional side view of a supersonic reactor according to various embodiments described herein;

FIG. 2 is a schematic diagram of a system for converting methane to acetylene and other hydrocarbon products, according to various embodiments described herein;

FIG. 3 is a partial cross-sectional side view illustrating a portion of the supersonic reactor of FIG. 1 according to various embodiments described herein;

FIG. 4 is a partial cross-sectional side view illustrating a portion of the supersonic reactor of FIG. 1 according to various embodiments described herein;

FIG. 5 is a cross-sectional view illustrating a supersonic reactor according to various embodiments described herein;

FIG. 6 is a partial cross-sectional side view illustrating a portion of the supersonic reactor of FIG. 1 according to various embodiments described herein;

FIG. 7 is a partial cross-sectional side view illustrating a portion of the supersonic reactor of FIG. 1 according to various embodiments described herein;

FIG. 8 is a partial cross-sectional side view illustrating a portion of the supersonic reactor of FIG. 1 according to various embodiments described herein;

FIG. 9 is a perspective view of a portion of the supersonic reactor of FIG. 1;

FIG. 10 is a partial cross-sectional side view illustrating a portion of the supersonic reactor of FIG. 1 according to various embodiments described herein;

FIG. 11 is a partial cross-sectional side view illustrating a portion of the supersonic reactor of FIG. 1 according to various embodiments described herein;

FIG. 12 is a partial cross-sectional side view illustrating a portion of the supersonic reactor of FIG. 1 according to various embodiments described herein;

FIG. 13 is a partial cross-sectional perspective view illustrating portions of the supersonic reactor of FIG. 1 according to various embodiments described herein;

fig. 14 is a schematic view of a supersonic reactor according to various embodiments described herein.

Detailed Description

One proposed alternative to previous methods for producing olefins that have not gained a large commercial attraction includes passing a hydrocarbon feedstock into a supersonic reactor and accelerating it to a supersonic velocity to provide kinetic energy that can be converted to heat such that an endothermic pyrolysis reaction takes place. Variations of this process are found in US4,136,015, US4,724,272 and russian patent SU 392723 a. These processes involve combusting the feedstock or carrier liquid in an oxygen-rich environment to increase the feed temperature and accelerate the feed to supersonic velocities. Shock waves are generated within the reactor to initiate pyrolysis or cracking of the feed.

More recently, US 5,219,530 and US 5,300,216 propose similar processes that utilize a shockwave reactor to provide kinetic energy to initiate pyrolysis of natural gas to produce acetylene. More specifically, the process includes passing steam through a heater section to become superheated and accelerate to near supersonic velocities. The heated fluid is delivered to a nozzle for expanding the carrier liquid to a supersonic velocity and a lower temperature. The ethane feed passes through a compressor and heater and is injected through a nozzle to mix with the supersonic carrier liquid, turbulently mixing together at a velocity of mach 2.8 and a temperature of 427 ℃. The temperature in the mixing section is kept low enough to limit premature pyrolysis. The shock wave reactor comprises a pyrolysis section with a gradually increasing cross-sectional area, wherein a vertical shock wave is formed by the back pressure in the reactor due to the flow restriction at the outlet. The shock wave rapidly reduces the velocity of the fluid and correspondingly rapidly increases the temperature of the mixture by converting kinetic energy into heat. This immediately initiates pyrolysis of the ethane feed to convert it to other products. The quench heat exchanger then receives the pyrolysis mixture to quench the pyrolysis reaction.

Generally disclosed are methods and apparatus for converting hydrocarbon components in a methane feed stream using a supersonic reactor. As used herein, the term "methane feed stream" includes any feed stream comprising methane. The methane feed stream provided for processing in the supersonic reactor typically comprises methane and forms at least a portion of the process stream. The apparatuses and methods provided herein convert at least a portion of the methane to desired product hydrocarbon compounds to produce a product stream having a higher concentration of product hydrocarbon compounds relative to the feed stream.

As used herein, the term "hydrocarbon stream" refers to at least a portion of a methane feed stream entering a supersonic reactor or one or more streams produced from a methane feed stream from a supersonic reactor as described herein, regardless of whether such hydrocarbon stream is further treated or processed. Referring to the example shown in fig. 2, a "hydrocarbon stream" may include a methane feed stream 1, a supersonic reactor effluent stream 2, a desired product stream 3 exiting a downstream hydrocarbon conversion process, or any intermediate or byproduct streams formed during the processes described herein. The hydrocarbon stream may be carried via a process stream line 115, as shown in fig. 2, which includes lines for carrying each of the various portions of the process stream described above. As used herein, the term "process stream" includes a "hydrocarbon stream" as described above, and it may include a carrier liquid stream, a fuel stream 4, an oxygen source stream 6, or any stream used in the systems and processes described herein. The process stream may be carried via a process stream line 115 that includes lines for carrying each of the portions of the process stream described above. As shown in fig. 2, any of 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 a desire to provide higher yields of desired products from particular feed streams than other more traditional pyrolysis systems. In particular, these types of processes can provide significant improvements over conventional pyrolysis processes by providing very high reaction temperatures and very short associated residence times. It has recently been recognized that these processes may also be capable of converting methane to acetylene and other useful hydrocarbons, while more traditional pyrolysis processes are ineffective or inefficient for such conversion.

However, much of the work previously done with supersonic reactor systems is theoretical or research based and therefore does not address the problems associated with practicing the process on a commercial scale. Moreover, many of these prior disclosures do not contemplate the use of supersonic reactors to effect pyrolysis of methane feed streams, and tend to focus primarily on the pyrolysis of ethane and propane. It has recently been discovered that one problem with the use of supersonic flow reactors for mild alkane pyrolysis, more particularly pyrolysis of methane feed to form acetylene and other useful products therefrom, includes that the harsh operating conditions of methane pyrolysis can have a damaging effect on the supersonic flow reactor and other associated equipment. Previous work has not fully understood or addressed these harsh operating conditions. For example, supersonic reactors may operate at temperatures up to 3000 ℃ or more, and at elevated pressures. These high temperatures and pressures can pose a risk of mechanical failure within the reactor walls of the reactor due to melting, cracking or creep. In particular, at high temperatures, it has been found that hot spots on the walls may indicate melting of the shell. Furthermore, even when the wall is cooled, chemical type damage may occur, such as for example redox reactions forming non-passivating products that are lost due to gas flow, leading to dishing. In addition, conversion oxidation may occur, resulting in non-adherent oxides that are lost due to gas flow.

In addition, the carrier stream and the feed stream may travel through the reactor at supersonic velocities, which may rapidly erode many materials that may be used to form the reactor shell. In addition, certain substances and contaminants that may be present in the hydrocarbon stream may cause corrosion, oxidation, and/or reduction of the reactor walls or shell, as well as other instrumentation or components of the reactor. Such components that cause corrosion, oxidation or reduction problems may include, for example, hydrogen sulfide, water, methyl mercaptan, arsine, mercury vapor, carbonization via reactions within the fuel itself, or hydrogen embrittlement. Another problem that may exist at high temperatures is the reaction with transient species such as free radicals, e.g. hydroxides.

Thus, according to various embodiments disclosed herein, an apparatus and process for converting methane in a hydrocarbon stream to acetylene and other products is provided. It has been found that the apparatus according to the invention and its use will improve the overall process for the pyrolysis of light alkane feeds, including methane feeds, to acetylene and other useful products. The apparatus and processes described herein also improve the ability of the apparatus and its associated components and instrumentation to withstand degradation and possible failure due to extreme operating conditions within the reactor.

According to one method, the apparatus and methods disclosed herein are used to treat a hydrocarbon process stream to convert at least a portion of the methane in the hydrocarbon process stream to acetylene. The hydrocarbon process streams described herein include a methane feed stream provided to the system that includes methane and may also include ethane or propane. The methane feed stream may also include a combination of various concentrations of methane, ethane, and propane, and may also include other hydrocarbon compounds as well as contaminants. In one process, the hydrocarbon feed stream comprises natural gas. Natural gas may be provided from a variety of sources, including, but not limited to, gas fields, oil fields, coal fields, shale field fracturing, biomass, and landfill gas. In another approach, the methane feed stream may comprise a stream from another part of the refinery or processing plant. For example, during processing of crude oil into various products, light alkanes, including methane, are typically separated, and a methane feed stream may be provided from one of these sources. These streams may be provided from the same refinery or from different refineries or from refinery off-gases. The methane feed stream may also include streams from a combination of different sources.

In accordance with the processes and systems described herein, the methane feed stream may be provided at a remote location or at one or more locations of the systems and processes described herein. For example, while the source of the methane feed stream may be located at the same refinery or processing plant that performs the processes and systems, such as produced from another on-site hydrocarbon conversion process or a local natural gas field, the methane feed stream may be provided from a remote source via pipeline or other transportation method. For example, the feed stream may be provided from a remote hydrocarbon processing plant or refinery or a remote natural gas field and provided as a feed to the systems and methods described herein. Initial treatment of the methane stream may be performed at a remote source to remove certain contaminants from the methane feed stream. In making such initial treatment, it may be considered part of the systems and processes described herein, or it may occur upstream of the systems and processes described herein. Thus, the methane feed stream provided for the systems and processes described herein may have different levels of contaminants depending on whether the initial treatment is performed upstream thereof.

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

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

The methane feed stream may also include heavy hydrocarbons such as aromatics, paraffins, olefins, and naphthenes. These heavy hydrocarbons, if present, may be present in concentrations between 0 mol% and 100 mol%. In another example, they can be present at a concentration between 0 and 10 mole%, and can be present at a concentration between 0 and 2 mole%.

The apparatus and methods for forming acetylene from a methane feed stream described herein utilize a supersonic flow reactor to pyrolyze methane in the feed stream to form acetylene. The supersonic flow reactor may comprise one or more reactors capable of generating a supersonic flow of the carrier liquid and the methane feed stream and expanding the carrier liquid to initiate the pyrolysis reaction. In one approach, the process may comprise a supersonic reactor as generally described in US4,724,272, which is incorporated herein by reference in its entirety. In another approach, the process and system may include a supersonic reactor such as described as a "shockwave" reactor in US 5,219,530 and US 5,300,216, which are incorporated herein by reference in their entirety. In another approach, the Supersonic Reactor described as a "shockwave" Reactor may comprise a Reactor such as described in "Supersonic Injection and Mixing in the Shock Wave Reactor" of Robert g.ceff, washington university, 2010.

Although a variety of supersonic reactors may be used in the process of the present invention, an exemplary reactor 5 is shown in FIG. 1. Referring to fig. 1, supersonic reactor 5 comprises a reactor vessel 10 generally defining a reaction chamber 15. Although reactor 5 is shown as a single reactor, it should be understood that the reactor may be formed modularly or as a separate vessel. If formed modularly or as separate components, the modules or separate components of the reactor may be joined together permanently or temporarily, or may be separated from one another with the fluids contained by other means, such as, for example, pressure differential regulation between them. A combustion zone or chamber 25 is provided for combusting a fuel to produce a carrier liquid having a desired temperature and flow rate. The reactor 5 may optionally include a carrier liquid inlet 20 for introducing supplemental carrier liquid into the reactor. One or more fuel injectors 30 are provided for injecting a combustible fuel, such as hydrogen, into the combustion chamber 26. The same or other injectors may be provided for injecting a source of oxygen into the combustion chamber 26 to facilitate combustion of the fuel. The fuel and oxygen source injection may be in the axial, tangential, radial, or other directions including combinations of directions. The fuel and oxygen are combusted to produce a hot carrier fluid stream, typically having a temperature of 1200 ° to 3500 ℃ in one example, between 2000 ° and 3500 ℃ in another example, and between 2500 ° and 3200 ℃ in another example. It is also contemplated herein that the hot carrier liquid stream is generated by other known methods, including non-combustion methods. According to one example, the carrier liquid stream has a pressure of 1atm and higher, in another example greater than 2atm, and in another example greater than 4 atm.

The hot carrier fluid stream from the combustion zone 25 passes through a supersonic expander 51 comprising a converging-diverging nozzle 50 to accelerate the velocity of the carrier fluid to be higher than mach 1.0 in one example, between mach 1.0 and mach 4.0 in another example, and between mach 1.5 and mach 3.5 in another example. In this regard, the residence time of the fluid in the reactor portion of the supersonic flow reactor is between 0.5ms and 100ms in one example, between 1.0ms and 50ms in another example, between 1.5ms and 20ms in another example. By way of one example, the temperature of the carrier liquid stream passing through the supersonic expander is between 1000 ℃ and 3500 ℃, in another example between 1200 ℃ and 2500 ℃, and in another example between 1200 ℃ and 2000 ℃.

A feedstock inlet 40 is provided for injecting a methane feed stream into the reactor 5 for mixing with the carrier liquid. The feedstock inlet 40 may include one or more injectors 45 for injecting feedstock into the nozzle 50, the mixing zone 55, the diffusion zone 60, or the reaction zone or chamber 65. Injector 45 may comprise a manifold including, for example, a plurality of injection ports or nozzles for injecting feed into reactor 5.

In one approach, reactor 5 may include a mixing zone 55 for mixing the carrier liquid and the feed stream. In one approach, as shown in FIG. 1, reactor 5 may have a separate mixing zone between, for example, supersonic expander 51 and diffusion zone 60, while in another approach, the mixing zone is integrated into the diffuser portion and mixing may occur in nozzle 50, expansion zone 60, or reaction zone 65 of reactor 5. The expansion zone 60 includes an expanding wall 70 to produce a rapid reduction in the velocity of the gas flowing therethrough to convert the kinetic energy of the flowing fluid into thermal energy to further heat the stream to cause pyrolysis of methane in the feed, which may occur in the expansion section 60 and/or the downstream reaction section 65 of the reactor. The fluid is rapidly quenched in the quench zone 72 to stop the pyrolysis reaction from further conversion of the desired acetylene product to other compounds. Spray bars 75 may be used to introduce a quenching fluid (e.g., water or steam) into the quenching zone 72.

The reactor effluent exits the reactor via outlet 80 and forms a portion of the hydrocarbon stream as described above. The effluent will include a greater concentration of acetylene than the feed stream and a reduced concentration of methane relative to the feed stream. The reactor effluent stream may also be referred to herein as an acetylene stream because it contains an increased acetylene concentration. In a process to form another hydrocarbon product, the acetylene stream can be an intermediate stream, or it can be further processed and captured as an acetylene product stream. In one example, the reactor effluent stream has an acetylene concentration in the range of 2 to 30 mole percent prior to addition of the quenching fluid. In another example, the concentration of acetylene is in a range of 5 to 25 mole percent, and in another example, in a range of 8 to 23 mole percent.

The reactor vessel 10 includes a reactor shell 11. It should be noted that the term "reactor housing" refers to one or more walls forming a reactor vessel defining the reaction chamber 15. The reactor housing 11 will generally be an annular structure defining a generally hollow central reaction chamber 15. The reactor shell 11 may comprise a single layer of material, a single composite structure, or multiple shells, with one or more shells being positioned within one or more other shells. Reactor housing 11 also includes various zones, components, and/or modules as described above and further described below with respect to the different zones, components, and/or modules of supersonic reactor 5. The reactor housing 11 may be formed as a single piece defining all of the individual reactor zones and components, or it may be modular, with different modules defining different reactor zones and/or components.

By one approach, one or more portions of the reactor wall or shell 11 are formed as castings. In this regard, one or more portions may not be formed by welding or forming or other manufacturing methods, although the casting may be otherwise processed as described below. Without intending to be bound by theory, it is believed that forming one or more reactor walls by welding may result in a reactor that is more prone to failure or fracture at high temperatures and pressures because welds typically include residual stresses. Furthermore, welds may also be more prone to corrosion and cracking due to their different microstructures and possible compositional gradients. Similarly, it is believed that forming the reactor wall will result in the formation of non-negligible residual stresses on the reactor wall, leading to similar operational problems at high temperatures and pressures. Thus, a more isotropic microstructure is provided by forming a portion of the reactor shell as a casting. The cast portion of the reactor shell may provide corrosion resistance over similar components formed by other methods such as welding or forming. Shaping the reactor shell from a casting may also provide a more uniform heat flux and more uniform temperature in the component. Forming the portion of the reactor shell from a casting may also provide better and more uniform high temperature creep and failure resistance than forming the shell by other methods.

By one approach, casting may include directional casting to provide improved thermal shock and creep resistance at elevated reaction temperatures and pressures. In one method, the casting includes a columnar grain structure. In another method, the casting includes a single crystal structure.

The casting may be formed from one or more materials as described further below. The cast portion of the reactor may be further processed by a variety of methods known in the art. For example, the casting reactor shell 11 may be coated, heat treated, tempered, carbonized, nitrided, or otherwise treated in known ways as further described herein to improve its properties.

A single casting may be used to form the entire reactor shell 11, or the reactor shell 11 may comprise individual casting components or modules that are assembled to form the reactor shell 11 as further described herein. Furthermore, where reactor shell 11 includes various layers (including coatings, inner and outer shells, etc.) as further described herein, these layers may be cast separately or together, and then held or joined together separately.

According to various other methods, one or more portions of the supersonic reactor shell may be formed by known methods other than casting, such as, for example, powder metallurgy, which may be densified by hot isostatic pressing, hot isostatic pressing of powders into a substrate, or laser sintering, or other suitable sintering method, or machined from a billet.

By one approach, at least a portion of reactor shell 11 is constructed of a material having a high melting temperature to withstand the high operating temperatures of supersonic reactor 5. In one approach, one or more of the materials forming a portion of the reactor shell 11 may have long low cycle fatigue life, high yield strength, creep and stress rupture resistance, oxidation resistance, and compatibility with coolant and fuel. In one example, at least a portion of reactor shell 11 is formed from a material having a melting temperature between 1200 ° and 4000 ℃, and in another example 1800 ° to 3500 ℃. The material may also exhibit microstructural stability through different thermal and mechanical processing procedures, compatibility with the bonding process, and good adhesion of the oxidation-resistant coating. Some preferred materials for forming at least a portion of the reactor shell include superalloys and nickel and gamma Ti aluminides. By one approach, the superalloy is a nickel-based superalloy, and by another approach, the superalloy is an iron-based superalloy.

In one approach, the reactor shell 11 or wall portion is formed of a superalloy. In this regard, the walls may provide excellent mechanical strength and creep resistance at the combustion and pyrolysis temperatures occurring within the reactor. In this way, the apparatus may also limit melting or failure due to operating temperatures and pressures in the reaction chamber 15.

According to another method, portions of the reactor shell 11 are made of a material selected from the group consisting of carbides, nitrides, titanium diboride, sialon, zirconia, thoria, carbon-carbon composites, tungsten, tantalum, molybdenum, chromium, nickel, and alloys thereof.

According to another method, portions of reactor shell 11 are formed into a casting, wherein the casting includes a component selected from the group consisting of duplex stainless steel, super duplex stainless steel, and nickel-based high temperature low creep superalloy.

Chromium or nickel may be included to provide good corrosion resistance.

In another aspect, the reactor wall is constructed of a material having a high thermal conductivity. In this way, heat from the reaction chamber 15 can be quickly removed from the reaction chamber. This may limit the skin temperature of the inner surface of the reactor housing 11 from being heated to temperatures at or near reactor temperatures that may cause melting, chemical fire, or other degradation to the reactor housing 11 walls. In one example, one or more portions of the reactor are formed from a material having a thermal conductivity between 200 and 500W/m K. In another example, the thermal conductivity is between 300 and 450W/m K. In yet another example, the thermal conductivity is between 200 and 346W/m K, and in another example may be between 325 and 375W/m K.

It has been found that according to this method, the reactor shell can be formed from a material having a relatively low melting temperature, as long as the material has a very high electrical conductivity. Because heat from the reaction chamber 15 is removed rapidly in this process, the reactor shell 11 is not exposed to relatively high temperatures. In this regard, by forming the reactor housing portion from a material having a high thermal conductivity, the material may have a melting temperature that is lower than the temperature in the reaction chamber 15. In one example, portions of reactor shell 11 are formed from a material having a melting temperature between 500 ° and 2000 ℃. In another example, the reactor shell 11 portion may be formed of a material having a melting temperature between 800 ° and 1300 ℃, and in another example may be formed of a material having a melting temperature between 1000 ° and 1200 ℃.

By one approach, the material having high thermal conductivity comprises a metal or metal alloy. In one approach, one or more portions of the reactor shell 11 may be formed from copper, silver, aluminum, zirconium, niobium, and alloys thereof. In this regard, it should be noted that one or more of the above materials may also be used to form a coating on the reactor shell substrate or to form a layer of the multilayer reactor shell 11. By one approach, the reactor shell 11 portion comprises copper or a copper alloy. In one example, the reactor housing portion comprises a material selected from the group consisting of copper chromium, copper chromium zinc, copper chromium niobium, copper nickel, and copper nickel tungsten. In another example, the reactor housing portion comprises niobium silver. To enhance the removal of heat from the reaction chamber, cooling may be used to more rapidly remove heat from the reaction chamber so that its temperature remains below and at an allowable temperature.

By another approach, the reactor shell 11 may comprise multiple layers. The reactor housing 11 shown in fig. 3 includes an inner layer 210 defining the reaction chamber 15 and an outer layer 205 forming the interior 210. While 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 with one or more intermediate layers 211 between the inner layer 210 and the outer layer 205, as shown in fig. 8. Further, one or more additional outer layers 212 may be positioned outside of the outer layers 212. One or more additional inner layers may be positioned inside inner layer 210.

In one approach, the inner layer 210 includes a coating formed on the inner surface of the outer layer 205 or on any intervening intermediate layer 211. In this regard, the outer layer 205 forms a substrate coated with a coating of the inner layer 210. Alternatively, the inner layer 210 may provide a substrate coated with a coating of the outer layer 205. One or both of inner layer 210 and outer layer 205 may be formed as a casting as previously described or in other known manners in accordance with the method.

In one approach, at least a portion of inner layer 210 includes a high melting temperature material as described above. According to another approach, the inner layer 210 includes a material selected from the group consisting of carbides, nitrides, titanium diboride, sialon, zirconia, thoria, carbon-carbon composites, tungsten, tantalum, molybdenum, chromium, nickel, and alloys thereof. By another approach, inner layer 210 comprises a superalloy, and by another approach, inner layer 210 comprises a material selected from the group consisting of duplex stainless steel, super duplex stainless steel, and nickel-based high temperature low creep superalloy. In this regard, the inner layer 210 can be selected to provide beneficial operating characteristics, particularly when exposed to the harsh operating conditions within the reaction chamber 15, including its elevated temperatures.

In another approach, at least a portion of the inner layer 210 includes a high thermal conductivity material as described above. According to another approach, inner layer 210 includes a material selected from the group consisting of copper, silver, aluminum, zirconium, niobium, and alloys thereof. By another approach, the inner layer 210 comprises a material selected from the group consisting of copper chromium, copper chromium zinc, copper chromium niobium, copper nickel, and copper nickel tungsten. In another example, the reactor housing portion comprises niobium silver. In this regard, the inner layer 210 can be selected to provide beneficial operating characteristics, particularly when exposed to the harsh operating conditions within the reaction chamber 15 (including its high temperatures).

In one method, the outer layer205 may be formed of a different material than inner layer 210. The outer layer 205 material may be selected to provide structural support or other desired properties to the reactor shell 11. In one example, the outer layer 205 or intermediate layer comprises corrosion resistant 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 high temperature low creep superalloy, Nimonic^TMNickel-based high temperature low creep superalloy, Inco^TM718、Haynes ^TM230, or other nickel alloys such as Mar-M-247.

In one approach, inner layer 210 includes a thermal barrier coating. The thermal barrier coating may be formed of a material that exhibits desirable properties for the reaction chamber 15, such as a high melting temperature, to withstand the high temperatures in the reaction chamber 15. For example, the thermal barrier coating may comprise Yttria stabilized zirconia, lanthanum and rare earth doped lanthanum hexaaluminate, hafnium carbide or tungsten, as these two materials have high melting temperatures, good mechanical properties at high operating temperatures, and optionally low thermal conductivity.

In one approach, a bond coat comprising a thermal barrier coating is provided between the surfaces of the inner layer 210 and the outer layer 205 by one method. The bond coat may comprise a NiCrAlY, NiCoCrAlY alloy applied to the metal surface by plasma spray, electron beam PVD, or other methods known in the art. Other bond coats for copper alloys may include NiAl applied by low pressure, vacuum plasma spray, or other methods known in the art.

The layered reactor shell 11 may be formed in any known manner known in the art. In one approach, an inner diameter coating formed on a mandrel may be used to provide a layered reactor shell by providing a coating on a substrate material. By another approach, the coating may be formed on the substrate by hot isostatic pressing to provide a layered reactor shell 11. By another approach, a cladding layer can be used to provide a coating on a substrate. In another approach, the inner and outer layers may be formed separately and joined together. One example of such a method includes casting the inner layer 210 and the outer layer 205 separately and brazing them together to form the layered reactor shell 11. A double casting may also be used by casting the second alloy and the first alloy.

In another approach, as shown in FIG. 4, at least a portion of the reactor shell 11 may include separate inner and outer shells 215, 220. Similar to the layered reactor shell 11 previously described, a reactor shell having separate inner and outer shells 215, 220 may allow the inner shell 215 to withstand the operating conditions of the reaction chamber 15 while the outer shell 220 provides structural support and/or other desirable properties to the reactor shell 11.

In one approach, at least a portion of the inner shell 215 includes a high melting temperature material as described above. According to another approach, at least a portion of the inner shell 215 includes a material selected from the group consisting of carbides, nitrides, titanium diboride, sialon, zirconia, thoria, carbon-carbon composites, tungsten, tantalum, molybdenum, chromium, nickel, and alloys thereof. By another approach, at least a portion of the inner shell 210 comprises a superalloy, and by another approach, at least a portion of the inner shell 210 comprises a material selected from the group consisting of duplex stainless steel, super duplex stainless steel, and nickel based high temperature low creep superalloy. In this regard, the inner shell 215 can be selected to provide beneficial operating characteristics, particularly when exposed to the harsh operating conditions within the reaction chamber 15.

In another approach, at least a portion of the inner shell 215 includes a high thermal conductivity material as described above. According to another approach, the inner shell 215 includes a material selected from the group consisting of copper, silver, aluminum, zirconium, niobium, and alloys thereof. By another approach, the inner shell 215 comprises a material selected from the group consisting of copper chromium, copper chromium zinc, copper chromium niobium, copper nickel, and copper nickel tungsten. In another example, the inner shell 215 comprises niobium silver. In another method, the inner shell may include a material comprising a copper alloy that has been precipitation hardened with a second phase compound that maintains a high thermal conductivity alloying. In this regard, the inner shell 215 can be selected to provide beneficial operating characteristics, particularly when exposed to the harsh operating conditions within the reaction chamber 15 (including its high temperatures).

In one approach, the outer shell 220 may be formed of a different material than the inner shell 215. The outer shell 220 may be selected to provide structural support or other benefits to the reactor shell 11The nature of inspection. In one example, the enclosure 220 comprises corrosion resistant 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 high temperature low creep superalloy, Nimonic^TMNickel-based high temperature low creep superalloy, Inco^TM718、Haynes ^TM230, or other nickel alloys such as Mar-M-247.

By one approach, one or both of the inner and outer shells 215, 220 are formed as castings as previously described.

In one approach, the housing 220 includes a piece of tubing 230 as shown in FIG. 5. According to the method, at least one additional inner shell 235 is positioned within the outer shell 230 defining the second reaction chamber 240. In this manner, multiple pyrolysis reactions may occur within multiple reaction chambers 240. In this way, each of the inner shells 235 may include some or all of the components described above with respect to the supersonic reactor 5 shown in fig. 1, or some of the components of the separate inner shells 235 may be integrated. In one approach, some of the internal reactor shells 235 may be oriented in opposite directions. In this regard, any thrust that may be generated by the high velocity stream flowing through the inner shell will be offset by the relatively inward facing reactor shell 235.

In one approach, as shown in FIG. 4, the inner shell 215 is spaced apart from the outer shell 220 to provide a channel 245 therebetween. In this approach, the channel 245 may include a pressure region. The pressure zone is pressurized to maintain the pressure therein at the same pressure as the pressure in the reaction chamber 15. In this regard, the inner shell 215 may be configured such that it does not have to withstand high pressure differentials between its inner and outer surfaces 250, 255. The inner shell 215 may then be formed from a material having a relatively low pressure rating and/or having a relatively thin wall thickness. The housing 220 may then provide structural support and act as a pressure vessel to withstand the pressure differential between the pressure zone 245 and the exterior of the housing 220. In another approach (not shown), the inner shell 215 may abut the outer shell 220.

In one approach, the channel 245 also houses one or more sensors 216. The sensor may detect or measure a variable, such as one or more parameters or materials within the channel 245. Examples of sensors include pressure sensors, temperature sensors, chemical sensors such as gas sensors, hydrogen sensors, hydrocarbon sensors, methane sensors, and the like. The sensors may be electronically connected to one or more displays to monitor and/or control the system. In one approach, the channel 245 also receives one or more support structures 217 to support the inner shell 215 relative to the outer shell 220.

According to another approach, as shown in FIG. 6, an inner liner 260 may be provided within at least a portion of the reactor shell 11 to resist degradation of some of the reactor shell 11 due to operating conditions within the reaction chamber 15. The liner 260 may extend along the inner surface of the reactor shell 11 and may abut or be spaced apart from the reactor shell 11.

In one approach, the liner 260 comprises a disposable liner. The disposable liner may comprise carbon/carbon composites, pyrolytic carbon, glassy carbon, or other forms of carbon or carbon in the form of superalloys, and may be removed and replaced after degradation of the liner 260. In this regard, the disposable liner may protect the reactor shell from the harsh operating conditions within the reaction chamber 15.

According to another method, liner 260 comprises a self-regenerating liner and is capable of regeneration during operation of supersonic reactor 5 and/or while supersonic reactor 5 is offline. In one approach, the self-regenerating lining comprises carbon that is catalyzed to promote the formation of carbon or coke along the inner surface of the reactor shell 11 to regenerate the carbon lining. In another method, the self-regenerating liner comprises a self-regenerating liner having a coke graphite layer. In another method, the self-regenerating liner comprises a liner having a coke nanostructured layer. In another approach, a self-regenerating liner includes a liner having a graphene nanostructured layer. In one approach, the self-regenerating liner includes a directional thermal conductivity to remove heat from the reaction chamber 15 very quickly during operation.

In one approach, the liner 260 includes a low thermal conductivity coating that is used to provide protection to the metal alloy used and to slow heat transfer. In another approach, the liner may be a floating capture liner made of a high temperature resistant low thermal conductivity material. Such liners will reduce heat transfer and erosion. The floating capture liner may be formed by vacuum plasma spraying HfC or rhenium onto a suitable mandrel that is machined to the net shape dimensions of the desired liner outer diameter. The spraying of HfC or rhenium will be followed by a tungsten structural layer capable of supporting the structure at the necessary temperature. The tungsten layer will be followed by a molybdenum and possibly another tungsten and/or nickel, cobalt, chromium, aluminum yttrium structure layer. All layers will be applied using vacuum plasma spray and will protrude after the inner diameter of the mandrel is chemically etched.

In one approach, one or more portions of the reactor shell 11 include active cooling to dissipate heat from the reaction chamber 15 and limit melting or other degradation of the reactor shell 11 due to high temperatures and other operating conditions. In one approach, the active cooling includes an active cooling system. As shown in fig. 7, a cross-section of a portion of the reactor shell 11 is shown, which illustrates an active cooling system including a plurality of cooling channels 300 formed in the reactor shell 11 to flow a coolant along the reactor shell 11 to remove heat therefrom. The active cooling system may also include a coolant source for providing pressurized coolant through the cooling passages 300. As shown in fig. 7, the cooling channels may extend generally circumferentially along the reactor shell 11, which in one approach includes a generally annular configuration. Manifold tubing may also be present for providing coolant to and from the cooling channels 300.

In one approach, the cooling channel 300 may include one or more channels formed in a surface of the reactor shell. In another approach, as shown in FIG. 7, the cooling passages 300 may comprise one or more tubes or substantially hollow tunnels formed in the reactor shell 11 for the cooling fluid to flow therethrough. The channels 300 may extend along one or more surfaces of the reactor, as shown in fig. 9, or they may be formed in the walls of the reactor shell 11. The channels 300 may be provided in a variety of orientations and may extend axially along the reactor shell 11, circumferentially around the reactor shell 11, radially through the reactor shell, helically around the annular reactor shell, or in other orientations known in the art.

In another approach, the cooling passage 300 may include one or more spaces between the inner and outer layers, the inner liner, or the inner and outer shells as previously described to provide one or more cooling channels, such as in the channel 245 of FIG. 4. Further, a flow manipulator may be provided in the space between the inner and outer layers, the inner liner or the housing to direct the cooling fluid along a desired flow pattern. As shown in fig. 10, projections 315, such as pins, fins, or other projections, may be used in the space between the inner and outer layers to increase the surface area for cooling. Further, the cooling system may include a combination of different types of cooling passages 300 as described herein. For example, the cooling channels 300 may include cooling channels 300 between the layers 215 and 220 of the reactor shell 11 and channels formed in a surface of one of the inner layer 215 and the outer layer 220 such that coolant flowing through the cooling channels also passes through the reactor shell channels 245.

The cooling channel 300 may be formed by a variety of methods. In one approach, the cooling channel 300 is machined into the reactor shell. In another approach, partial channels may be formed along one or more layers of the reactor shell 11 or one or more surfaces of the shell as described above, and a complete channel 300 may be formed between the layers or shells after the layers and/or shells are joined together as shown in fig. 10. Similarly, partial channels may be formed on the surface of the reactor wall or layer, and a coating or lining may be applied over the partial channels to provide complete channels 300 between the reactor wall or layer and the coating or lining. In another approach, the coating or lining can be applied in a pattern that defines complete or partial channels. Such partial or complete channels may be formed by machining, casting, as described above, or during application of a particular coating, layer or liner, or by other methods. The cooling channel 300 may also be formed by other methods generally known in the art. Pins, fins or other protrusions may be used within the channels to increase the surface area for cooling. A low thermal conductivity coating may be applied to the liner that serves to provide protection to the metal alloy used and to slow the transfer of heat to the active cooling and increase efficiency. By way of example, the coating may be a nickel or copper alloy that is first plasma sprayed onto the liner from a vacuum with a bond coat that allows the structural metal to bond with the low thermal conductivity material. The bond coat may comprise nickel, chromium, cobalt, aluminum, and/or yttrium, followed by molybdenum and tungsten, and finally HfC or HfO 2.

The walls defining the cooling channels may facilitate heat transfer into the circulating coolant by acting as cooling fins and also supporting the coolant pressure load. In one approach, the thickness of the hot gas wall (the portion of the reactor shell 11 wall between the coolant and the hot combustion gases) is optimized to minimize resistance to heat flow through the wall of the liner and into the coolant channels 300 while providing structural integrity with respect to pressure and heat loads. In one approach, the thickness of the hot gas wall is between 0.10 inches and 0.375 inches, and in another example between 0.15 inches and 0.225 inches. In another approach, the walls between the cooling passages are optimized as fins to provide low thermal resistance from the hot walls to the coolant and to maintain structural integrity.

In another approach, the coolant passages contain a flow enhancer to enhance the flow of the coolant to increase the coolant heat transfer coefficient and heat flux from the wall to the coolant. In one approach, the flow enhancer includes ribs oriented at a perpendicular or relatively small angle to the direction of coolant flow to restart the coolant boundary layer, increase the coolant heat transfer coefficient, and increase the heat flux from the wall to the coolant. The rotation imparted by the ribs positioned at an angle less than 90 degrees will impart a swirling velocity component, mixing the coolant and resulting in a higher heat transfer rate from the wall to the coolant.

When the reactor housing 11 is assembled, the network of manifold tubing and coolant channels 300 cooperate to form a manifold for flowing coolant to remove heat generated during the combustion process in the supersonic reactor 5 to the extent necessary to maintain acceptable reactor wall temperatures.

In one method, the cooling fluid is pressurized to a relatively high pressure such that the coolant flowing through a portion of reactor shell 11 has a pressure between 350psig and 3200psig, and in another method between 1000psig and 2000 psig. And in another method between 1500 and 1600 psig. The relatively high pressure reduces the complexity of the coolant circulation by avoiding phase changes when using, for example, water as the cooling fluid. The coolant pressure, circulation rate, and temperature are set to provide sufficient coolant flow to sufficiently remove a portion of the heat generated in reaction chamber 15 to maintain an acceptable reactor wall temperature, particularly during combustion and supersonic expansion of the fuel stream. In one approach, the coolant has a flow rate of between 28,000 and 47,000, and in another example between 33,500 and 80,000 coolant channels. In one example, the coolant has an inlet temperature between 50 ° F to 250 ° F, and in another example between 85 ° F to 150 ° F. In one example, the outlet temperature of the coolant is 100 ° F to 700 ° F, and in another example 250 ° F to 600 ° F. A variety of coolants known in the art may be used. In one example, the coolant includes water. In another example, the coolant comprises steam, hydrogen, or methane, and may comprise a mixture of fluids.

In one approach, impingement cooling may be used as active cooling to dissipate heat from the reaction chamber 15 and limit melting or other degradation of the reactor shell 11 due to high temperatures and other operating conditions. Impingement cooling may be employed with a gas or a liquid. In one approach, impingement cooling may employ a series of impingement jets to affect high heat transfer. For example, a high velocity jet may be directed onto the housing to be cooled. When the cooling jet contacts the surface of the housing, it is dispersed in all directions parallel to the surface of the housing. The jets may be arranged on the housing, such as randomly or in a pattern. Impingement cooling may include techniques such as high impingement systems using steam expansion for hot wall cooling, liquid wall impingement, and gas effusion cooling.

In one approach, the heat pipe may be used as an active cooling mechanism. The heat pipe may conduct up to 250 times as much thermal energy as the solid copper conductive member.

In one approach, as shown in fig. 12, a membrane barrier 350 may be provided along an inner surface of at least a portion of the reactor shell 11 to provide at least a partial barrier to the reaction chamber 15. Due to the high temperatures, flow rates, and other harsh conditions within the reaction chamber 15, the membrane barrier 350 may help limit degradation of the reactor shell 11, including melting, erosion, or corrosion.

In one approach, the membrane barrier 350 comprises a cold fluid barrier. As used herein, cold fluid barrier refers to the temperature of the fluid barrier relative to the temperature in the reaction chamber 15. Thus, the cold fluid barrier may have a high temperature, but be cool relative to the reaction chamber 15. In one example, the cold fluid barrier has a temperature between 3000 ° F and 5000 ° F. In another example, the cold fluid barrier has a temperature between 3600 ° and 4600 ° F.

By way of one example, the cold fluid barrier may comprise a cold gas phase barrier. In another example, the cold fluid barrier comprises a molten metal barrier. In another example, the cold fluid barrier comprises water or steam. In another approach, the cold fluid barrier comprises air or hydrogen. In another example, the cold fluid barrier comprises methane. The cold fluid barrier may also comprise other fluids or combinations of fluids known in the art. By one approach, the cold fluid barrier comprises a fluid comprising at least a portion of the process stream.

The membrane barrier may be provided on the inner surface of the portion of the reactor shell 11 in various ways. Referring to fig. 13, in one method, the reactor shell 11 includes an opening 360 through at least a portion thereof to allow the cold fluid to pass therethrough and form a cold fluid barrier. This may take the form of a slot discharging into the core stream. In another approach, the reactor shell 11 may include a porous wall 365 that facilitates leakage of cold fluid therethrough to provide a fluid barrier. By one approach, the reactor shell may include channels (not shown) similar to those described above with respect to the active cooling system, and a cooling fluid for forming a cooling fluid barrier may be provided therein. In this method, manifold tubing may be provided to introduce cold fluid into the channels and openings. 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 include openings or porous walls contained on at least a portion of the inner shell 215. In this method, the cold fluid may pass through channels or passages defined between the outer shell 220 and the inner shell 215 such that it leaks through the porous wall inner shell 215 to form a cold fluid barrier on the inner surface of the portion of the inner shell 215. Also, where the liner 260 is provided inside the reactor shell 11 as described above with respect to fig. 6, the liner may be a porous or permeable liner to allow cold fluid to pass through the liner and form a cold fluid barrier on its inner surface. The membrane barrier may also be formed along the inner surface of the portion of the reactor shell 11 by other methods, including methods known in the art.

In another approach, the wall may contain a plurality of small holes 360 that expel fluid in the film, thereby forming a fully covered film cooling surface.

In another approach, the wall may contain slots or grids that are supplied with coolant and form a cooling film by discharging the coolant in a downstream direction along the wall. The membrane barrier 350 may also be formed along the inner surface of the portion of the reactor shell 11 by other methods, including methods known in the art.

In another approach, the impingement approach may be combined with a full film coverage cooling approach, where impingement fluid after impinging the hot wall is discharged through film cooling holes 360 in such wall 365, thereby providing two cooling effects.

In this manner, by providing membrane barrier 350 on an inner surface of at least a portion of reactor housing 11, degradation of reactor housing 11 may be limited during operation of supersonic reactor 5. The membrane barrier may reduce the temperature to which the reactor shell 11 is exposed during operation by providing a barrier to the hot core fluid and convectively cooling the walls if the membrane is at a membrane cooling temperature.

The cooling system may incorporate various mechanisms as described above to provide the best combination for maximum operating efficiency.

The above description provides several approaches to the reactor shell 11 or a portion of the reactor shell 11. In this manner, it should be understood that at least a portion of the reactor shell 11 may refer to the entire reactor shell 11, or it may refer to less than the entire reactor shell, as will now be described in more detail. Accordingly, the foregoing description of a method for improving the construction and/or operation of at least a portion of reactor shell 11 may be generally applicable to any portion of a reactor shell and/or may be applicable to portions of a reactor shell specifically described below.

It has been found that certain parts or components of the reactor shell 11 may be subject to particularly harsh operating conditions or specific problems specific to that part or component. Thus, according to various approaches, certain aspects of the foregoing description may apply only to those portions or components where a particular problem has been discovered. The locations around the one or more fuel injectors (30) and the one or more feedstock injectors 45 are examples of locations where convective cooling pathways may benefit from localized film barrier or film cooling or impingement or localized positioning.

One zone of supersonic reactor 5 that encounters particularly severe operating conditions during its operation is combustion zone 25. In the combustion zone 25, the fuel stream is combusted in the presence of oxygen to produce a high temperature carrier stream. The temperature in the combustion zone 25 may be the highest temperature present in the reaction chamber 15, and may reach temperatures between 2000 ° and 3500 ℃ in one example, and between 2000 and 3200 ℃ in another example. Thus, a particular problem that has been found in the combustion zone 25 is the melting of the reactor shell 11 at the combustion zone 25 in the presence of oxygen and the oxidation of the combustor walls. The portion of the reactor housing in the combustion zone 25 may be referred to as a combustion chamber 26.

Another zone of supersonic reactor 5 that encounters particularly severe operating conditions comprises supersonic expansion zone 60, and in particular supersonic expander nozzle 50 located therein. In particular, as the high temperature carrier gas travels through the expander nozzle 50 at or near 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 the diffuser zone 60, the mixing zone 55, the reactor zone 65, and the quench zone, may encounter harsh operating conditions during operation of the supersonic reactor 5. Additional equipment or components used in conjunction with supersonic reactor 5 may also face similar problems and harsh operating conditions including, but not limited to, nozzles, lines, mixers, and exchangers.

Because of the unique problems and operating conditions to which individual portions or components of the supersonic reactor may be exposed, these individual portions or components may be formed, operated, or used according to the various methods described herein, while other portions or components are formed, operated, or used according to other methods that may or may not be described herein.

Because different components or portions of the supersonic reactor 5 can be formed or operated in different ways, the supersonic reactor 5 (including the reactor housing 11) can be made as separate pieces and assembled to form the supersonic reactor 5 or the reactor housing 11. In this regard, as shown in fig. 11, the supersonic reactor 5 and/or the reactor housing 11 may comprise a modular configuration in which individual modules or components 400 may be assembled together. By one approach, at least some portions or components 11 of the assembled supersonic reactor or reactor shell 400 may not be attached, instead, a gas or fluid may be contained therein by pressure differential regulation between the components. In other approaches, the modules or components 400 may be joined together, for example, by a flange 405 sealed at a cooling location at an interface between the components. Similarly, different components, portions or modules 400 may include different aspects provided in the description above. For example, some modules or components 400 may include active cooling, membrane barriers, inner and outer layers, inner and outer shells, or other aspects described above, while other portions, modules, or components 400 may include different aspects.

According to one approach, one or more components or modules 400 may be removed and replaced during operation of supersonic reactor 5 or during shutdown thereof. For example, because the supersonic expansion nozzle 50 may degrade faster than other components of the reactor, the nozzle 50 may be removable so that it may be replaced with a new nozzle after it has degraded. In one approach, a plurality of supersonic reactors 5 may be provided in parallel or in series with one or more operating supersonic reactors and one or more backup supersonic reactors, such that when maintenance or replacement of one or more components of an operating supersonic reactor 5 is required, the process may switch to a backup supersonic reactor to continue operation.

Further, the supersonic reactor may be oriented horizontally as shown in FIG. 1, or vertically (not shown). In a vertical configuration of the reactor, the carrier stream feed stream therethrough may be directed vertically upward in one process. In another approach, the carrier stream and the feed stream may be directed vertically downward. In one approach, the supersonic reactor may be oriented such that it is free draining to prevent liquid from accumulating in the quench zone 72. In another approach, the reactor may be oriented vertically (from 90 ° horizontal) or horizontally (from 0 ° horizontal) as described above, or may be oriented at an angle between 0 ° and 90 ° from the reactor inlet at some height above the reactor outlet. In another embodiment, the outlet 80 may include two or more outlets, including a primary outlet 80 for the primary vapor phase stream and a secondary outlet 81 for discharging liquid. In one method, the liquid is injected into the quench zone 72 and does not completely evaporate. This may occur during transient or steady state operating modes. The secondary outlet may be operated continuously or intermittently as desired.

In one approach, reactor shell 11 is sealed at one end and includes a plenum chamber at the end opposite thereof.

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

In one approach, as shown in fig. 14, the supersonic reactor 5 may include an isolation valve 450 at its inlet. The supersonic reactor may also include a control system 455 to detect pressure changes in the ejection event. The control system 455 may be configured to isolate the inlet in response to an ejection event. In one approach, the inlet is a fuel stream 4 inlet.

According to one method, the supersonic reactor 5 comprises a magnetic seal to contain the reactants within the reaction chamber 15.

According to another approach, the supersonic reactor 5 may include hydrogen generation to generate hydrogen from the reactor effluent stream.

In one example, the pyrolyzed reactor effluent stream in supersonic reactor 5 has a reduced methane content in the range of from 15 mol% to 95 mol% relative to the methane feed stream. In another example, the concentration of methane is in a range of 40 mol% to 90 mol% and 45 mol% to 85 mol%.

In one example, the acetylene yield produced from methane in the feed in the supersonic reactor is between 40% and 95%. In another example, the acetylene yield from methane in the feed stream is between 50% and 90%. Advantageously, this provides a better yield than the estimated 40% yield obtained from the more traditional pyrolysis process.

By one approach, the reactor effluent stream is reacted to form another hydrocarbon compound. In this aspect, the reactor effluent portion of the hydrocarbon stream may be passed from the reactor outlet to a downstream hydrocarbon conversion process for further processing of the stream. Although it is understood that the reactor effluent stream may undergo several intermediate process steps, such as dehydration, adsorption and/or absorption to provide a concentrated acetylene stream, these intermediate steps will not be described in detail herein.

Referring to fig. 2, the reactor effluent stream having a higher acetylene concentration may be forwarded to a downstream hydrocarbon conversion zone 100 where acetylene may be converted to form another hydrocarbon product. The hydrocarbon conversion zone 100 can include a hydrocarbon conversion reactor 105 for converting acetylene to another hydrocarbon product. Although fig. 2 illustrates a process flow diagram for converting at least a portion of the acetylene in the effluent stream to ethylene by hydrogenation in the hydrogenation reactor 110, it should be understood that the hydrocarbon conversion zone 100 may include a variety of other hydrocarbon conversion processes in place of or in addition to the hydrogenation reactor 110 or a combination of hydrocarbon conversion processes. Similarly, the unit operations illustrated in FIG. 2 may be modified or removed and are illustrated for exemplary purposes and are not intended to limit the processes and systems described herein. In particular, it has been found that several other hydrocarbon conversion processes may be positioned downstream of supersonic reactor 5 in addition to those disclosed in the previous processes, including processes for converting acetylene to other hydrocarbons, including but not limited to: olefins, alkanes, methane, acrolein, acrylic acid, acrylates, acrylamides, aldehydes, polyacetylenes, benzene, toluene, styrene, aniline, cyclohexanone, caprolactam, propylene, butadiene, butynediol, butanediol, C2-C4 hydrocarbons, ethylene glycol, diesel, diacids, diols, pyrrolidine, and pyrrolidone.

As described further below, the contaminant removal zone 120 for removing one or more contaminants from the hydrocarbon or process stream can 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 contaminant removal. For example, it has been found that certain contaminants can interfere with the operation of the supersonic flow reactor 5 and/or foul components in the supersonic flow reactor 5. Thus, according to one approach, a contaminant removal zone is positioned upstream of the supersonic flow reactor to remove these contaminants from the methane feed stream prior to introducing the stream into the supersonic reactor. Other contaminants have been found to interfere with downstream processing steps or hydrocarbon conversion processes, in which case the contaminant removal zone may be positioned upstream of the supersonic reactor, or between the supersonic reactor and the particular downstream processing step in question. It has also been found that other contaminants should be removed to meet specific product specifications. Where it is desired to remove multiple contaminants from a hydrocarbon or process stream, various contaminant removal zones may be positioned at different locations along the hydrocarbon or process stream. In other methods, the contaminant removal zone may overlap or be integrated with another process within the system, in which case the contaminants may be removed during another portion of the process, including but not limited to supersonic reactor 5 or downstream hydrocarbon conversion zone 100. This may be accomplished with or without modification of these specific zones/reactors or processes. While the contaminant removal zone 120 shown in fig. 2 is shown as being positioned downstream of the hydrocarbon conversion reactor 105, it should be understood that the contaminant removal zone 120 according to the present invention may be positioned upstream of the supersonic flow reactor 5, between the supersonic flow reactor 5 and the hydrocarbon conversion zone 100, or downstream of the hydrocarbon conversion zone 100 as shown in fig. 2, or along other streams within the process stream, such as, for example, a carrier fluid stream, a fuel stream, an oxygen source stream, or any stream used in the systems and methods described herein.

One embodiment of the present disclosure relates to an apparatus and method for converting methane in a hydrocarbon stream to acetylene using a supersonic flow reactor while minimizing the potential for explosions due to the formation of copper acetylene from chemical reactions between the generated acetylene gas and the copper of the inner layer. The methane pyrolysis reactor zone exhibits a strong reducing environment in the presence of hydrogen and elevated temperatures. Cu or CuO was found to interact readily with acetylene, resulting in the formation of copper acetylide.

A coating may be applied to the inner surface of the inner layer to provide a barrier between the acetylene gas produced and the copper of the inner layer to prevent the formation of acetylene. Accordingly, the inner layer 210 may include a coating formed on an 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 coatings comprising nickel metal or nickel alloys or mixtures thereof. Specific examples of nickel include NiCrAlY, NiCoCrAlY, CoNiCrAlY, and Ni-P. In the case of copper-containing substrates, nickel forms a solid solution which, by means of a thermal treatment, forms a very strong bond which is resistant to thermal shock stress. Nickel or nickel alloy coatings may be envisaged in addition to thermal barrier coatings such as those described above in order to slow heat transfer. Other suitable coatings may be comprised of chromium, chromium-containing alloys, platinum-containing alloys, palladium-containing alloys, or mixtures thereof, or mixtures of any of the foregoing with nickel or nickel-containing alloys.

The metal or alloy or mixture may be applied to a surface of the reactor shell, such as the inner surface of the inner layer, by a variety of known metallization processes. Suitable examples include electroplating using electric current, electroless plating without electric current, or coating by using plasma spray techniques. For example, pure nickel may be applied using electroplating techniques. The coating may not require a post-coating heat treatment, but adhesion may be improved by heat exposure at 482 ℃ to 538 ℃ for 1 to 3 hours. The coating is dense and prevents the copper from contacting the acetylene gas. Furthermore, the coating may be applied in combination with a stabilized zirconia coating such as described above, in which case the dense coating not only provides a barrier to acetylene formation, but also provides a heat transfer barrier. In another example, a coating of a nickel alloy (such as NiCrAlY) may be applied using a plasma spray technique. The coating may not require a post-coating heat treatment, but adhesion may be improved by heat exposure at 482 ℃ to 538 ℃ for 1 to 3 hours. The coating is dense and prevents the copper from contacting the acetylene gas. Furthermore, the coating may be applied in combination with a stabilized zirconia coating such as described above, in which case the dense coating not only provides a barrier to acetylene formation, but also provides a heat transfer barrier. In another embodiment, electroless plating may be used to apply the Ni-P coating. As above, the coating may not require a post-coating heat treatment, but adhesion may be improved by heat exposure at 482 ℃ to 538 ℃ for 1 to 3 hours. The coating is dense and prevents the copper from contacting the acetylene gas. Furthermore, the coating may be applied in combination with a stabilized zirconia coating such as described above, in which case the dense coating not only provides a barrier to acetylene formation, but also provides a heat transfer barrier.

While particular embodiments and aspects have been shown and described, it will be understood that numerous changes and modifications will occur to those skilled in the art, and it is intended in the appended claims to cover all those changes and modifications which fall within the true spirit and scope of the disclosure and appended claims.

Claims (10)

1. An apparatus for producing acetylene from a feed stream comprising methane, the apparatus comprising:

a supersonic reactor for receiving the methane feed stream and heating the methane feed stream to a pyrolysis temperature;

a reactor housing of the supersonic reactor, the reactor housing for defining a reaction chamber, wherein the reaction chamber operates at a temperature of 1200 ℃ to 4000 ℃;

a combustion zone of the supersonic reactor for combusting a source of fuel to provide a high temperature carrier gas at a supersonic velocity through the supersonic reactor space to heat and accelerate the methane feed stream to a pyrolysis temperature;

the reactor housing comprises an inner shell and an outer shell with one or more channels therebetween, wherein the inner shell is composed of a material having a thermal conductivity between 300 and 450W/m-K for conducting heat from the reaction chamber and a melting temperature between 500 ℃ and 2000 ℃; the material is at least copper chromium, or copper chromium zinc, or copper chromium niobium, or copper zirconium or copper silver zirconium; or mixtures thereof; and

a coating comprising nickel metal, nickel alloy, chromium metal, chromium alloy, platinum metal, platinum alloy, palladium, or palladium alloy, or mixtures thereof, applied to the inner surface of the inner layer of the reactor shell.

2. The apparatus of claim 1, wherein the coating comprises NiCrAlY, or NiCoCrAlY, or CoNiCrAlY, or Ni-P, or mixtures thereof.

3. The apparatus of claim 1, wherein the coating comprises NiCrAlY.

4. The apparatus of claim 1, wherein the coating:

is electroplated onto said inner surface of said inner layer, or

Is applied to the inner surface of the inner layer using a plasma spray technique; or

Applying to the inner surface of the inner layer using an electroless plating process;

and heat-treated at a temperature of 482 ℃ to 538 ℃ for 1 to 3 hours.

5. The apparatus of claim 4, wherein the coating is electroplated onto the inner surface of the inner layer, and the coating comprises nickel metal.

6. The apparatus of claim 4, wherein the coating is applied to the inner surface of the inner layer using a plasma spray technique and the coating comprises NiCrAlY.

7. The apparatus of claim 4, wherein the coating is applied to the inner surface of the inner layer using an electroless process, the coating comprising Ni-P.

8. The apparatus of claim 1, wherein the coating further comprises a material capable of providing a thermal barrier layer.

9. The apparatus of claim 1, wherein the coating further comprises yttrium stabilized zirconia, lanthanum hexaaluminate, rare earth doped lanthanum hexaaluminate, hafnium carbide, tungsten, or mixtures thereof.

10. A process for producing acetylene from a feed stream comprising methane, the process comprising:

introducing the feed stream into a supersonic reactor, wherein the supersonic reactor comprises:

a reactor housing of the supersonic reactor, the reactor housing for defining a reaction chamber, wherein the reaction chamber operates at a temperature of 1200 ℃ to 4000 ℃;

a combustion zone of the supersonic reactor for combusting a source of fuel to provide a high temperature carrier gas at a supersonic velocity through the supersonic reactor space to heat and accelerate the methane feed stream to a pyrolysis temperature;

the reactor housing comprises an inner shell and an outer shell with one or more channels therebetween, wherein the inner shell is comprised of a material having a thermal conductivity between 300 and 450W/m-K for conducting heat from the reaction chamber and a melting temperature between 500 ℃ and 2000 ℃; the material is at least copper chromium, or copper chromium zinc, or copper chromium niobium, or copper zirconium or copper silver zirconium; or mixtures thereof; and

a coating comprising nickel metal, nickel alloy, chromium metal, chromium alloy, platinum metal, platinum alloy, palladium, or palladium alloy, or mixtures thereof, applied to the inner surface of the inner layer of the reactor shell;

combusting a fuel source to provide a high temperature carrier gas at a supersonic velocity through the reactor to heat and accelerate the methane feed stream to a pyrolysis temperature, wherein acetylene is generated after heating and accelerating the methane stream; and

acetylene formation in the reactor is prevented by using a coating that prevents acetylene from contacting the copper of the inner layer of the reactor.

Images