WO2014031516A1 - Appareil de conversion du méthane et procédé qui utilise un réacteur à écoulement supersonique - Google Patents

Appareil de conversion du méthane et procédé qui utilise un réacteur à écoulement supersonique Download PDF

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Publication number
WO2014031516A1
WO2014031516A1 PCT/US2013/055529 US2013055529W WO2014031516A1 WO 2014031516 A1 WO2014031516 A1 WO 2014031516A1 US 2013055529 W US2013055529 W US 2013055529W WO 2014031516 A1 WO2014031516 A1 WO 2014031516A1
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WIPO (PCT)
Prior art keywords
stream
heat exchanger
reactor
heat
methane
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PCT/US2013/055529
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English (en)
Inventor
Robert L. Bedard
Christopher Naunheimer
Gavin P. Towler
Laura E. Leonard
Mark C. Morris
Alexander Mirzamoghadam
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Uop Llc
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Priority to EP13831716.9A priority Critical patent/EP2888038A4/fr
Priority to EA201500260A priority patent/EA201500260A1/ru
Publication of WO2014031516A1 publication Critical patent/WO2014031516A1/fr
Priority to ZA2015/01931A priority patent/ZA201501931B/en

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10H—PRODUCTION OF ACETYLENE BY WET METHODS
    • C10H17/00—High-pressure acetylene gas generators
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/06—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies
    • B01J3/08—Application of shock waves for chemical reactions or for modifying the crystal structure of substances
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00004—Scale aspects
    • B01J2219/00006—Large-scale industrial plants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00027—Process aspects
    • B01J2219/0004—Processes in series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
    • B01J2219/00081—Tubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
    • B01J2219/00083—Coils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00121—Controlling the temperature by direct heating or cooling
    • B01J2219/00123—Controlling the temperature by direct heating or cooling adding a temperature modifying medium to the reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/02—Apparatus characterised by their chemically-resistant properties
    • B01J2219/0204—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components
    • B01J2219/0227—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components of graphite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/02—Apparatus characterised by their chemically-resistant properties
    • B01J2219/025—Apparatus characterised by their chemically-resistant properties characterised by the construction materials of the reactor vessel proper
    • B01J2219/0263—Ceramic

Definitions

  • Light olefin materials including ethylene and propylene, represent a large portion of the worldwide demand in the petrochemical industry.
  • Light olefins are used in the production of numerous chemical products via polymerization, oligomerization, alkylation and other well-known chemical reactions. These light olefins are essential building blocks for the modern petrochemical and chemical industries. Producing large quantities of light olefin material in an economical manner, therefore, is a focus in the petrochemical industry.
  • the main source for these materials in present day refining is the steam cracking of petroleum feeds.
  • ethylene which is among the more important products in the chemical industry, can be produced by the pyrolysis of feedstocks ranging from light paraffins, such as ethane and propane, to heavier fractions such as naphtha.
  • the lighter feedstocks produce higher ethylene yields (50-55% for ethane compared to 25-30% for naphtha); however, the cost of the feedstock is more likely to determine which is used.
  • More recent attempts to decrease light olefin production costs include utilizing alternative processes and/or feed streams.
  • hydrocarbon oxygenates and more specifically methanol or dimethylether (DME) are used as an alternative feedstock for producing light olefin products.
  • Oxygenates can be produced from available materials such as coal, natural gas, recycled plastics, various carbon waste streams from industry and various products and by-products from the agricultural industry.
  • Making methanol and other oxygenates from these types of raw materials is well established and typically includes one or more generally known processes such as the manufacture of synthesis gas using a nickel or cobalt catalyst in a steam reforming step followed by a methanol synthesis step at relatively high pressure using a copper-based catalyst.
  • the process includes catalytically converting the oxygenates, such as methanol, into the desired light olefin products in an oxygenate to olefin (OTO) process.
  • oxygenates such as methanol to light olefins (MTO)
  • MTO oxygenate to olefins
  • United States Patent No. 4,387,263 discloses a process that utilizes a catalytic conversion zone containing a zeolitic type catalyst.
  • United States Patent No. 4,587,373 discloses using a zeolitic catalyst like ZSM-5 for purposes of making light olefins.
  • 5,095,163; 5,126,308 and 5,191,141 disclose an MTO conversion technology utilizing a non-zeolitic molecular sieve catalytic material, such as a metal aluminophosphate (ELAPO) molecular sieve.
  • OTO and MTO processes while useful, utilize an indirect process for forming a desired hydrocarbon product by first converting a feed to an oxygenate and subsequently converting the oxygenate to the hydrocarbon product. This indirect route of production is often associated with energy and cost penalties, often reducing the advantage gained by using a less expensive feed material.
  • FIG. 1 is a side cross-sectional view of a supersonic reactor in accordance with various embodiments described herein;
  • FIG. 2 is a schematic view of a system for converting methane into acetylene and other hydrocarbon products in accordance with various embodiments described herein;
  • FIG. 3 is a side cross-sectional view of a supersonic reactor in accordance with various embodiments described herein. DETAILED DESCRIPTION
  • One proposed alternative to the previous methods of producing olefins that has not gained much commercial traction includes passing a hydrocarbon feedstock into a supersonic reactor and accelerating it to supersonic speed to provide kinetic energy that can be transformed into heat to enable an endothermic pyrolysis reaction to occur. Variations of this process are set out in U.S. Pat. Nos. 4,136,015 and 4,724,272, and Russian Patent No. SU 392723 A. These processes include combusting a feedstock or carrier fluid in an oxygen-rich environment to increase the temperature of the feed and accelerate the feed to supersonic speeds. A shock wave is created within the reactor to initiate pyrolysis or cracking of the feed.
  • US Patent Nos. 5,219,530 and 5,300,216 have suggested a similar process that utilizes a shock wave reactor to provide kinetic energy for initiating pyrolysis of natural gas to produce acetylene. More particularly, this process includes passing steam through a heater section to become superheated and accelerated to a nearly supersonic speed. The heated fluid is conveyed to a nozzle which acts to expand the carrier fluid to a supersonic speed and lower temperature. An ethane feedstock is passed through a compressor and heater and injected by nozzles to mix with the supersonic carrier fluid to turbulently mix together at a speed of Mach 2.8 and a temperature of 427°C. The temperature in the mixing section remains low enough to restrict premature pyrolysis.
  • the Shockwave reactor includes a pyrolysis section with a gradually increasing cross-sectional area where a standing shock wave is formed by back pressure in the reactor due to flow restriction at the outlet.
  • the shock wave rapidly decreases the speed of the fluid, correspondingly rapidly increasing the temperature of the mixture by converting the kinetic energy into heat. This immediately initiates pyrolysis of the ethane feedstock to convert it to other products.
  • a quench heat exchanger then receives the pyrolized mixture to quench the pyrolysis reaction.
  • methane feed stream includes any feed stream comprising methane.
  • the methane feed streams provided for processing in the supersonic reactor generally include methane and form at least a portion of a process stream.
  • the apparatus and methods presented herein convert at least a portion of the methane to a desired product hydrocarbon compound to produce a product stream having a higher concentration of the product hydrocarbon compound relative to the feed stream.
  • hydrocarbon stream refers to one or more streams that provide at least a portion of the methane feed stream entering the supersonic reactor as described herein or are produced from the supersonic reactor from the methane feed stream, regardless of whether further treatment or processing is conducted on such hydrocarbon stream.
  • the "hydrocarbon stream” may include the 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 by- product 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 portions of the process stream described above.
  • process stream includes the "hydrocarbon stream” as described above, as well as it may include a carrier fluid stream, a fuel stream 4, an oxygen source stream 6, or any streams used in the systems and the processes described herein.
  • the process stream may be carried via a process stream line 115, which includes lines for carrying each of the portions of the process stream described above.
  • 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.
  • a carrier stream and feed stream may travel through the reactor at supersonic speeds, which can quickly erode many materials that could be used to form the reactor shell, even after a short amount of time.
  • certain substances and contaminants that may be present in the hydrocarbon stream can cause corrosion, oxidation, and/or reduction of the reactor walls or shell and other equipment or components of the reactor.
  • Such components causing corrosion, oxidation, or reduction problems may include, for example hydrogen sulfide, water, methanethiol, arsine, mercury vapor, carbidization via reaction with the fuel itself, or hydrogen embrittlement.
  • apparatus and methods for converting methane in hydrocarbon streams to acetylene and other products is provided.
  • Apparatus in accordance herewith, and the use thereof, have been identified to improve the overall process for the pyrolysis of light alkane feeds, including methane feeds, to acetylene and other useful products.
  • the apparatus and methods disclosed herein are used to treat a hydrocarbon process stream to convert at least a portion of methane in the hydrocarbon process stream to acetylene.
  • the hydrocarbon process stream described herein includes the methane feed stream provided to the system, which includes methane and may also include ethane or propane.
  • the methane feed stream may also include combinations of methane, ethane, and propane at various concentrations and may also include other hydrocarbon compounds as well as contaminants.
  • the hydrocarbon feed stream includes natural gas.
  • the natural gas may be provided from a variety of sources including, but not limited to, gas fields, oil fields, coal fields, fracking of shale fields, biomass, and landfill gas.
  • the methane feed stream can include a stream from another portion of a refinery or processing plant.
  • light alkanes, including methane are often separated during processing of crude oil into various products and a methane feed stream may be provided from one of these sources.
  • These streams may be provided from the same refinery or different refinery or from a refinery off gas.
  • the methane feed stream may include a stream from combinations of different sources as well.
  • a methane feed stream may be provided from a remote location or at the location or locations of the systems and methods described herein.
  • the methane feed stream source may be located at the same refinery or processing plant where the processes and systems are carried out, such as from production 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 pipelines or other transportation methods.
  • a 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 processes described herein.
  • Initial processing of a methane stream may occur at the remote source to remove certain contaminants from the methane feed stream.
  • the methane feed stream provided for the systems and processes described herein may have varying levels of contaminants depending on whether initial processing occurs upstream thereof.
  • the methane feed stream has a methane content ranging from 65 mol-% to 100 mol-%.
  • the concentration of methane in the hydrocarbon feed ranges from 80 mol-% to 100 mol-% of the hydrocarbon feed.
  • the concentration of methane ranges from 90 mol-% to 100 mol-% of the hydrocarbon feed.
  • the concentration of ethane in the methane feed ranges from 0 mol-% to 35 mol-% and in another example from 0 mol-% to 10 mol-%.
  • 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 aromatics, paraffinic, olefmic, and naphthenic hydrocarbons. These heavy hydrocarbons if present will likely be present at concentrations of between 0 mol-% and 100 mol-%. In another example, they may be present at concentrations of between 0 mol-% and 10 mol-% and may be present at between 0 mol-% and 2 mol-%.
  • heavy hydrocarbons such as aromatics, paraffinic, olefmic, and naphthenic hydrocarbons.
  • the apparatus and method for forming acetylene from the methane feed stream described herein utilizes a supersonic flow reactor for pyrolyzing methane in the feed stream to form acetylene.
  • the supersonic flow reactor may include one or more reactors capable of creating a supersonic flow of a carrier fluid and the methane feed stream and expanding the carrier fluid to initiate the pyrolysis reaction.
  • the process may include a supersonic reactor as generally described in U.S. Patent No. 4,724,272, which is incorporated herein by reference, in its entirety.
  • the process and system may include a supersonic reactor such as described as a "shock wave" reactor in U.S. Patent Nos.
  • the supersonic reactor described as a "shock wave” reactor may include a reactor such as described in "Supersonic Injection and Mixing in the Shock Wave Reactor” Robert G. Cerff, University of Washington graduate School, 2010.
  • the supersonic reactor 5 includes a reactor vessel 10 generally defining a reactor chamber 15. While the reactor 5 is illustrated as a single reactor, it should be understood that it may be formed modularly or as separate vessels. 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 separate from one another with fluids contained by other means, such as, for example, differential pressure adjustment between them.
  • a combustion zone or chamber 25 is provided for combusting a fuel to produce a carrier fluid with the desired temperature and flowrate.
  • the reactor 5 may optionally include a carrier fluid inlet 20 for introducing a supplemental carrier fluid into the reactor.
  • One or more fuel injectors 30 are provided for injecting a combustible fuel, for example hydrogen, into the combustion chamber 25.
  • the same or other injectors may be provided for injecting an oxygen source into the combustion chamber 25 to facilitate combustion of the fuel.
  • the fuel and oxygen are combusted to produce a hot carrier fluid stream typically having a temperature of from 1200 to 3500°C in one example, between 2000 and 3500°C in another example, and between 2500 and 3200°C in yet another example. It is also contemplated herein to produce the hot carrier fluid stream by other known methods, including non-combustion methods.
  • the carrier fluid stream has a pressure of 1 arm or higher, greater than 2 atm in another example, and greater than 4 atm in another example.
  • the hot carrier fluid stream from the combustion zone 25 is passed through a supersonic expander 51 that includes a converging-diverging nozzle 50 to accelerate the flowrate of the carrier fluid to above mach 1.0 in one example, between mach 1.0 and mach 4.0 in another example, and between mach 1.5 and 3.5 in another example.
  • the residence time of the fluid in the reactor portion of the supersonic flow reactor is between 0.5 - 100 ms in one example, 1.0 - 50 ms in another example, and 1.5 - 20 ms in another example.
  • the temperature of the carrier fluid stream through the supersonic expander by one example is between 1000°C and 3500°C, between 1200°C and 2500°C in another example, and between 1200°C and 2000°C in another example.
  • a feedstock inlet 40 is provided for injecting the methane feed stream into the reactor 5 to mix with the carrier fluid.
  • the feedstock inlet 40 may include one or more injectors 45 for injecting the feedstock into the nozzle 50, a mixing zone 55, a diffuser zone 60, or a reaction zone or chamber 65.
  • the injector 45 may include a manifold, including for example a plurality of injection ports or nozzles for injecting the feed into the reactor 5.
  • the reactor 5 may include a mixing zone 55 for mixing of the carrier fluid and the feed stream.
  • the reactor 5 may have a separate mixing zone, between for example the supersonic expander 51 and the diffuser zone 60, while in another approach, the mixing zone is integrated into the diffuser section is provided, and mixing may occur in the nozzle 50, expansion zone 60, or reaction zone 65 of the reactor 5.
  • An expansion zone 60 includes a diverging wall 70 to produce a rapid reduction in the velocity of the gases flowing therethrough, to convert the kinetic energy of the flowing fluid to thermal energy to further heat the stream to cause pyrolysis of the methane in the feed, which may occur in the expansion section 60 and/or a downstream reaction section 65 of the reactor.
  • the fluid is quickly quenched in a 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, for example water or steam into the quench zone 72.
  • the reactor effluent exits the reactor via outlet 80 and as mentioned above forms a portion of the hydrocarbon stream.
  • the effluent will include a larger 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 as it includes an increased concentration of acetylene.
  • the acetylene stream may be an
  • the reactor effluent stream has an acetylene concentration prior to the addition of quenching fluid ranging from 2 mol-% to 30 mol-%. In another example, the concentration of acetylene ranges from 5 mol-% to 25 mol-% and from 8 mol-% to 23 mol-% in another example.
  • the reactor vessel 10 includes a reactor shell 11.
  • reactor shell refers to the wall or walls forming the reactor vessel, which defines the reactor chamber 15.
  • the reactor shell 11 will typically be an annular structure defining a generally hollow central reactor chamber 15.
  • the reactor shell 11 may include a single layer of material, a single composite structure or multiple shells with one or more shells positioned within one or more other shells.
  • the reactor shell 11 also includes various zones,
  • the reactor shell 11 may be formed as a single piece defining all of the various reactor zones and components or it may be modular, with different modules defining the different reactor zones and/or components.
  • At least one heat exchanger 200 is provided for transferring heat from at least a portion of the supersonic reactor pyrolysis or effluent stream to one or more other portions of the process stream.
  • the process stream may include any of the process streams described above, or may include other process streams, including, for example, dedicated heat transfer process streams.
  • the dedicated heat transfer process streams may comprise any phase or combination of phases, as further described herein.
  • the heat exchanger 200 may be generally downstream of the supersonic reactor 5 such that a reactor effluent line carrying at least a portion of the reactor effluent provides fluid to the heat exchanger 200.
  • the heat exchanger 200 may be integrated with the supersonic reactor 5, including adding a portion thereof within the reactor chamber.
  • the heat exchanger 200 may include a stab-in heat exchanger 500.
  • the stab-in heat exchanger 500 may include any number of tubes and tube configurations, including, but not limited to, straight single pass 505 as shown in FIG. 5, U-tube as shown in FIG. 6, coils, or other configurations, and combinations thereof.
  • the heat exchanger 200 or a portion thereof may be positioned within various locations of the supersonic reactor, including, for example, within the reaction zone 65 or the quench zone 70 to transfer heat from at least one of the pyrolysis stream and the effluent stream flowing through the reactor chamber 15.
  • the stab-in heat exchanger includes a heat transfer fluid flowing therethrough.
  • the heat transfer fluid may include various heat transfer fluids known in the art, including, but not limited to molten metal, raising stream, superheating steam, hot oil, and liquid sodium
  • the heat exchanger in order to withstand harsh operating conditions within the reactor chamber 15, at least a portion of the heat exchanger may include a ceramic tube heat exchanger.
  • the ceramic tube heat exchanger comprises a material selected from the group of a carbide, a nitride, titanium diboride, a sialon ceramic, zirconia, or thoria.
  • the heat exchanger 200 includes highly inert coated tubes to restrict corrosion of the tubes within the reactor chamber 15.
  • the highly-inert tubes include highly-sulfided tubes that are formed by sulfiding.
  • the highly- inert tubes include carbon-carbon tubes. Carbon-carbon tubes may be formed by providing a carbon coating on one or more tubes.
  • the heat exchanger 200 includes tubes formed of a material having a melting temperature of above at least 800 C.
  • the tubes may be formed of a superalloy.
  • the tubes may be formed of nickel-based high- temperature low creep superalloy and chromium.
  • the heat exchanger 200 provides heat to a circulating heat exchange fluid 310.
  • the heat exchanger 200 includes a transport bed heat exchanger for transferring heat between one or more fluid streams as described above and a high heat capacity bulk solid 310 flowing through the heat exchanger 200.
  • the transport bed heat exchanger 200 may include direct heat exchange in which at least one of the pyrolysis stream and the effluent stream directly contacts the bulk solid material to provide a heated bulk solid 320.
  • the transport bed heat exchanger may include indirect heat exchange in which at least one of a pyrolysis stream and an effluent stream flows through one set of passageways of the heat exchanger 200 and a bulk solid material flows through another set of passageways of the heat exchanger 200 so that heat is transferred from the pyrolysis stream and/or the effluent stream to the bulk solid through components of the heat exchanger to provide the heated bulk solid 320.
  • the heated bulk solid material 320 may then be transferred to another downstream zone 300 wherein the heat is recovered or utilized.
  • the bulk solid may then be returned to the heat exchanger 200 via line 350.
  • the heat exchanger 200 includes a thermoelectric heat exchanger for converting a portion of the heat from one of the pyrolysis stream and the effluent stream to electricity.
  • the thermoelectric heat exchanger may include a high temperature thermoelectric heat exchanger for operating in the presence of high temperature fluids.
  • the heat exchanger 200 may use a phase transformation fluid capable of transferring energy from the one of the pyrolysis stream and the effluent stream to the phase transformation fluid by transformation of the phase thereof.
  • the phase transformation fluid includes a eutectic-eutectic fluid capable of phase transformation upon receiving energy from the pyrolysis stream or the effluent stream.
  • the eutectic-eutectic fluid may operate at or near the eutectic point thereof. Heat transfer may also be achieved via alloy transformations in so lid- liquid eutectic mixtures and in eutectic molten salts.
  • heat exchanger 200 may provide heat to a circulating heat exchange fluid 310.
  • the circulating heat exchange fluid may include water, steam, super-heated steam, and a hydrocarbon heat transfer fluid.
  • the hydrocarbon heat transfer fluid is part of a hot oil loop used for carrying heat to other unit operations in zone 300 by stream 320.
  • Hot oil loops may be used for providing high temperature heat to process users in applications where fired heaters are not appropriate.
  • the so called hot oil is circulated in a loop that includes a fired heater to supply heat to the heat transfer fluid and process which use heat.
  • the heat exchanger fluid for the hot oil loop may be a synthetic heat transfer fluid which is hydrocarbon fluid that is specially designed to be thermally stable or a non-synthetic heat transfer fluid.
  • Examples of commercially available synthetic heat transfer fluids include, for example, Therminol 66 by Solutia, Dowtherm RP by Dow, and Marlotherm SH by Sasol.
  • Examples of non-synthetic heat transfer fluids include for example diesel fuel or heavy gas oil or any other suitable hydrocarbon stream commonly available and known in the art.
  • the hot oil from heat exchanger 200 may be circulated to process users in zone 300 to provide heat directly or to a boiler to produce steam which in turn may be used to generate electricity, drive compressors, provide heat to process users, or any other use of steam known in the art.
  • the heat exchange fluid may be water and preferably water preheated to its bubble point.
  • steam is raised directly from the pyrolysis stream or effluent stream in heat exchanger 200.
  • this directly produces steam, which may be used in other unit operations as described above.
  • the circulating water rate may be set to minimize the temperature rise of the heat transfer fluid such that saturated steam is produced.
  • the water may be provided from one or more cooling channels incorporated into reactor 5 for the purpose of cooling the reactor vessel walls. The water may be preheated in the said channels, but not vaporized. The preheated water from the cooling channels may then be directed to heat exchanger 200 to produce steam.
  • the pressure of the circulating water may be increased or reduced as desired to maximize steam production at the desired temperature and pressure.
  • heat exchanger 200 consists of a series of two or more heat exchangers 200 and/or steam drums 400 to produce steam of varying grades.
  • Each heat exchanger in series will produce lower pressure, lower grade steam than the upstream exchangers and steam drums.
  • high pressure steam 410 at 600 psig high pressure steam 410 at 600 psig
  • medium pressure steam 420 at 150 psig medium pressure steam 420 at 150 psig
  • low pressure steam 430 at 50 psig.
  • the grades of steam may be optimized to produce power, as heat exchange media, or drive other process operations such as a compressor, a turbine, or any combination thereof as desired and understood by one skilled in the art in zone 300.
  • the steam may be provided in a stream to a power generation device 440 or other process operation.
  • the condensate from the various process users in zone 300 may be recycled back to the cooling channels of reactor 5 or heat exchanger 200 via line 450.
  • the heat exchange fluid directed to heat exchanger 200 is steam which is superheated in the subject heat exchanger.
  • the steam may be produced by one of a series of heat exchangers 200 as described above or provided from elsewhere in the process.
  • the fluid heated in heat exchanger 200 may be selected from process streams available in the process described with regard to FIG 1 and FIG 2.
  • one or more of the fuel and oxygen injected into combustion zone 25 via nozzle(s) 30 and feedstock provided to the reactor 5 via feedstock inlet 40 may be preheated in one or more heat exchangers 200 of FIG 3.
  • Preheating the fuel, oxygen, and feedstock as described above will improve the efficiency of the methane pyrolysis reactor by decreasing the amount of fuel that needs to be burned to achieve a desired level of conversion. In this way heat may be provided directly to the process streams rather than to a utility stream.
  • the reactor effluent stream after pyrolysis in the supersonic reactor 5 has a reduced methane content relative to the methane feed stream ranging from 15 mol-% to 95 mol-%.
  • the concentration of methane ranges from 40 mol-% to 90 mol-% and from 45 mol-% to 85 mol-% in another example.
  • the yield of acetylene produced from methane in the feed in the supersonic reactor is between 40% and 95%.
  • the yield of acetylene produced from methane in the feed stream is between 50%> and 90%>.
  • this provides a better yield than the estimated 40% yield achieved from previous, more traditional, pyrolysis approaches.
  • the reactor effluent stream is reacted to form another hydrocarbon compound.
  • 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. While it should be understood that the reactor effluent stream may undergo several intermediate process steps, such as, for example, water removal, adsorption, and/or absorption to provide a concentrated acetylene stream, these intermediate steps will not be described in detail herein.
  • the reactor effluent 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 the acetylene to another hydrocarbon product. While FIG. 2 illustrates a process flow diagram for converting at least a portion of the acetylene in the effluent stream to ethylene through hydrogenation in hydrogenation reactor 110, it should be understood that the hydrocarbon conversion zone 100 may include a variety of other hydrocarbon conversion processes instead of or in addition to a hydrogenation reactor 110, or a combination of hydrocarbon conversion processes. Similarly, unit operations illustrated in FIG.
  • hydrocarbon conversion processes may be positioned downstream of the supersonic reactor 5, including processes to convert the acetylene into other hydrocarbons, including, but not limited to: alkenes, alkanes, methane, acrolein, acrylic acid, acrylates, acrylamide, aldehydes, polyacetylides, benzene, toluene, styrene, aniline, cyclohexanone, caprolactam, propylene, butadiene, butyne diol, butandiol, C2-C4 hydrocarbon compounds, ethylene glycol, diesel fuel, diacids, diols, pyrrolidines, and pyrrolidones.
  • a contaminant removal zone 120 for removing one or more contaminants from the hydrocarbon or process stream may be located at various positions along the hydrocarbon or process stream depending on the impact of the particular contaminant on the product or process and the reason for the contaminants removal, as described further below. For example, particular contaminants have been identified to interfere with the operation of the supersonic flow reactor 5 and/or to 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 in order to remove these contaminants from the methane feed stream prior to introducing the stream into the supersonic reactor.
  • contaminant removal zone may be positioned upstream of the supersonic reactor or between the supersonic reactor and the particular downstream processing step at issue. Still other contaminants have been identified that should be removed to meet particular product specifications. Where it is desired to remove multiple contaminants from the hydrocarbon or process stream, various contaminant removal zones may be positioned at different locations along the hydrocarbon or process stream. In still other approaches, a contaminant removal zone may overlap or be integrated with another process within the system, in which case the contaminant may be removed during another portion of the process, including, but not limited to the supersonic reactor 5 or the downstream hydrocarbon conversion zone 100. This may be accomplished with or without modification to these particular zones, reactors or processes.
  • the contaminant removal zone 120 illustrated in FIG. 2 is shown positioned downstream of the hydrocarbon conversion reactor 105, it should be understood that the contaminant removal zone 120 in accordance herewith 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 illustrated 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 streams used in the systems and the processes described herein.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente invention se rapporte à un appareil et à des procédés permettant de convertir le méthane présent dans un flux d'alimentation en acétylène. Un courant d'hydrocarbures est introduit dans un réacteur supersonique et pyrolysé pour convertir au moins une partie du méthane en acétylène. Le courant d'effluent de réacteur peut être traité pour convertir l'acétylène selon un autre traitement des hydrocarbures.
PCT/US2013/055529 2012-08-21 2013-08-19 Appareil de conversion du méthane et procédé qui utilise un réacteur à écoulement supersonique WO2014031516A1 (fr)

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EP13831716.9A EP2888038A4 (fr) 2012-08-21 2013-08-19 Appareil de conversion du méthane et procédé qui utilise un réacteur à écoulement supersonique
EA201500260A EA201500260A1 (ru) 2012-08-21 2013-08-19 Устройство и способ для конверсии метана посредством сверхзвукового проточного реактора
ZA2015/01931A ZA201501931B (en) 2012-08-21 2015-03-20 Methane conversion apparatus and process using a supersonic flow reactor

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US61/691,303 2012-08-21
US13/964,396 2013-08-12
US13/964,396 US20140056766A1 (en) 2012-08-21 2013-08-12 Methane Conversion Apparatus and Process Using a Supersonic Flow Reactor

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EP3013469B1 (fr) * 2013-06-28 2020-06-03 Uop Llc Système et procédé d'extinction à haute température
US20150361010A1 (en) * 2014-06-11 2015-12-17 Uop Llc Apparatus and process for the conversion of methane into acetylene
TWI617536B (zh) 2015-06-12 2018-03-11 薩比克環球科技公司 藉由甲烷之非氧化偶合製造烴類之方法
WO2018069837A1 (fr) * 2016-10-10 2018-04-19 King Abdullah University Of Science And Technology Brûleurs pour conversion de méthane en oléfines, composés aromatiques et nanoparticules

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EA201500260A1 (ru) 2015-07-30
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EP2888038A1 (fr) 2015-07-01
US20140056766A1 (en) 2014-02-27

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