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WO2015117166A1 - Procédé de production de composés aromatiques à partir de méthane comprenant une étape intermédiaire d'alimentation simultanée en cox - Google Patents

Procédé de production de composés aromatiques à partir de méthane comprenant une étape intermédiaire d'alimentation simultanée en cox Download PDF

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Publication number
WO2015117166A1
WO2015117166A1 PCT/US2015/014735 US2015014735W WO2015117166A1 WO 2015117166 A1 WO2015117166 A1 WO 2015117166A1 US 2015014735 W US2015014735 W US 2015014735W WO 2015117166 A1 WO2015117166 A1 WO 2015117166A1
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Prior art keywords
aromatics
stream
methane
reactor
product stream
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Inventor
Yaming Jin
Majed M. MUSSA
Flaiyh AL-ANAZI
Syed A. HASHMI
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Saudi Basic Industries Corp
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Saudi Basic Industries Corp
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
    • C01B3/586—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction the reaction being a methanation reaction
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/68—Aromatisation of hydrocarbon oil fractions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08—Production of synthetic natural gas
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2523/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of germanium, tin or lead
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/26—Chromium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/28—Molybdenum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/30—Tungsten
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    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/46—Ruthenium, rhodium, osmium or iridium
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/48—Silver or gold
    • C07C2523/50—Silver
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/72—Copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/745—Iron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/75—Cobalt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/755—Nickel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock

Definitions

  • the present invention relates to systems and methods for producing aromatics and other chemicals, and more specifically, to a process for producing aromatics and other chemicals from methane-containing feedstocks.
  • Embodiments of the present invention solve many of the problems and/or overcome many of the drawbacks and disadvantages of the prior art by providing systems and methods for producing aromatics and recycling unconverted methane in an integrated process.
  • Embodiments of the present invention may include systems and methods for producing aromatics and other chemicals in an integrated process.
  • the systems and methods can include a process for producing aromatics and other chemicals.
  • the method can include providing methane feedstock to a first reactor to produce a first product stream comprising aromatics and hydrogen, wherein the methane feedstock is contacted with a catalyst;
  • Embodiments of the present invention can include systems and methods for producing aromatics and other chemicals from recycled methane feedstock.
  • the method can include receiving recycled methane from a methanation reaction; mixing the recycled methane and methane feedstock to form a combined methane feedstock; providing the combined methane feedstock to a first reactor to produce a first product stream comprising aromatics and hydrogen, wherein the combined methane feedstock is contacted with a catalyst; recovering aromatics from the first product stream to create an aromatics depleted resulting stream; mixing the aromatics depleted resulting stream with a feed stream to create a combined product stream; and providing the combined product stream to a second reactor to produce a second product stream comprising synthetic methane or unconverted methane, and water.
  • Embodiments of the present invention can include systems and methods for producing a methane-rich gas.
  • the method can include receiving a first resulting stream from one or more dehydroaromatization reactions; extracting aromatics from the first resulting stream, wherein the resulting stream is converted to an aromatic depleted resulting stream; mixing the aromatics depleted resulting stream with a carbon dioxide feed or steam feed stream to create a combined stream; mixing the combined stream with one or more methanation catalysts in a methanation reactor to produce a second resulting stream; and extracting water from the second resulting stream.
  • FIGS. 1 and 2 show exemplary integrated systems for producing aromatics from a methane-containing feed stock and recycling synthetic methane or unconverted methane for use in future aromatic production.
  • FIG. 1 is a flow diagram illustrating an exemplary integration process of the current invention.
  • methane- containing feedstock from feed line 102 can be converted to aromatics and hydrogen via a dehydroaromatization reaction, and/or other hydrocarbons via dehydrogenation-coupling reactions in reactor 103.
  • conversion of the methane-containing feedstock can involve contacting the methane-containing feedstock with one or more catalysts at the dehydromatization reactor 103.
  • the one or more catalysts can include a bifunctional Zeolite supported metal catalyst.
  • the metal function can include but is not limited to any of the following individually or in a combination: molybdenum, tungsten, ruthenium, iron, cobalt, nickel, copper, silver, zinc, chromium, or tin.
  • the zeolite function can include but is not limited to pentasil type zeolite family, modified pentasil type zeolites family, or other medium pore zeolites such as zeolite beta and zeolite MCM-22.
  • the integrated process 101 can include one or more simultaneous dehydrogenation and cyclization
  • the dehydrocyclization steps can be conducted over a wide range of conditions, such as temperature, pressure or gaseous hourly space velocity (GHSV) of the feed gas.
  • GHSV gaseous hourly space velocity
  • the dehydrocyclization steps can be conducted at a temperature of about 400°C to about 1000°C, about 500°C to about 850°C, or about 700°C to about 750°C.
  • the dehydrocyclization steps can be conducted at an absolute pressure of 0.2 - 5 atmosphere (0.02 to 0.5 MegaPascals (MPa)), and more preferably 0.5 - 2 atmosphere (0.05 to 0.2 MPa).
  • the dehydrocyclization steps can be conducted at a GHSV of the feed gas in terms of volumes of gas per volume of catalyst per hour can be about 400 to about 8,000 GHSV or about 500 to about 7,000 GHSV.
  • the product stream coming from the reactor 103 via line 104 can be fed to a condenser or separator 105.
  • the condenser or separator 105 can be a cryogenic separator where the aromatics can be recovered from the condenser or separator 105 via line 106.
  • the aromatics can include benzene, toluene, naphthalene, and/or other aromatics.
  • the aromatic depleted reaction product of the dehydroaromatization reaction can then be sent via transfer line 107.
  • a feed containing carbon dioxide and steam (water) can be added via line 108 and can be mixed with the aromatic depleted reaction product of the dehydroaromatization reaction in transfer line 107.
  • the volume ratio of steam to carbon dioxide can be increased from 0 up to 1.
  • This combined feed of carbon dioxide, steam and the aromatic depleted reaction product in transfer line 107 can be fed to a Methanation reactor 109 to produce a product stream.
  • the combined feed in methanation reactor 109 can be contacted with one or more methanation catalysts to produce a product stream.
  • the product stream can contain high concentration of unconverted methane 115.
  • unconverted methane can be separated from aromatic depleted stream from line 107 using separator 201 and can be mixed with line 116 via line 202.
  • the resulting stream from separator 201 can then be sent via transfer line 203.
  • a feed containing carbon dioxide and steam (water) can be added via line 108 and can be mixed with the resulting stream in transfer line 203 to create a combined stream.
  • the combined stream can then be mixed with one or more methanation catalysts in a methanation reactor 109 to produce a second resulting stream consisting of synthetic methane.
  • Water 113 can be extracted from the synthetic methane stream via line 112.
  • methanation catalysts can include ruthenium, cobalt, nickel or iron.
  • the product stream coming from reactor 109 via line 110 can be fed to a separator 111.
  • Water 113 can be recovered from the separator 111 via line 112. In some alternatives, the recovered water 113 can be used for other reactions.
  • Recycled methane 115 can be recovered from the separator 111 via line 114. Recycled methane 115 can be sent via line 116 to be combined in line 102 with methane-containing feedstock from feed line 102 for producing aromatics and other chemicals in the future using the exemplary integrated process 101.
  • the methanation reactions can be conducted over a range of conditions, such as temperature, pressure and GHSV of combined feed gas.
  • the methanation reactions temperature can be about 200°C to about 600° C, and more preferably about 300°C to about 575°C, and most preferably about 550°C.
  • the methanation reactions pressure can be about 0 to about 10,000 pound per square inch (psi) (about 0 MPa to about 70 MPa).
  • the methanation reactions GHSV of combined feed gas in terms of volumes of gas per volume of catalyst per hour can be about 200 to about 10,000 GHSV or about 600 to about 5,000 GHSV.
  • Elimination of the need to separate the hydrogen by-product from the output stream of the dehydroaromatization reaction adds significant value to the exemplary integrated process by reducing time, cost and energy requirements.
  • the integrated process 101 brings considerable savings by avoiding costly hydrogen separation steps and improving energy/site efficiency by producing other valuable downstream products, such as methanol, Dimethyl Ether (DME) and other aromatics.
  • DME Dimethyl Ether
  • a feed stock of methane can be introduced via feed line 102 into a first reactor 103.
  • Any methane-containing feedstock can be used in the present process but, in general, the present process can be used with a natural gas feedstock.
  • Other suitable methane- containing feedstocks can include those obtained from sources such as coal beds, landfills, agricultural or municipal waste fermentation, or refinery gas streams.
  • Methane-containing feedstocks, such as natural gas typically contain carbon dioxide and ethane in addition to methane. Ethane and other aliphatic hydrocarbons that can be present in the feedstock can, of course, be converted to desired aromatic products in a dehydroaromatization step.
  • the feed to the dehydroaromatization step can contain less than approximately 100 parts per million (ppm), less than approximately 10 ppm, or less than approximately 1 ppm each of nitrogen and sulfur compounds.
  • the feedstock lower molecular weight hydrocarbon of the present invention can include methane or natural gas containing Q to C 4 hydrocarbons.
  • the feed to the dehydroaromatization step in 103 can include approximately 95 to approximately 99.9 mol , more preferably 97 to approximately 99 mol % methane.
  • the first reactor 103 can convert the methane-containing feedstock to benzene and hydrogen via a dehydroaromatization reaction.
  • the dehydroaromatization step can be conducted in one or more fixed beds, moving beds, or fluidized bed reactors, with catalyst regeneration being conducted in-situ or ex-situ with air, oxygen, carbon dioxide, carbon monoxide, water, H 2 , or combinations thereof.
  • the dehydroaromatization reaction is endothermic and, hence when the reaction is conducted in a plurality of stages, it can be necessary to employ inter-stage heating to return the feed to the required reaction temperature.
  • the fuel required to provide the interstage heating can be obtained by removing and combusting a side stream from the
  • dehydroaromatization effluent after separation of the aromatic components and/or alkylated aromatic components.
  • a portion or all of the heat can be supplied by withdrawing a portion of the catalyst from the bed, heating the catalyst by, for example, combustion of coke on the catalyst and then returning the heated catalyst to the moving catalyst bed.
  • the major components of the effluent from the dehydroaromatization step are H 2 , benzene, napthalene, and unconverted methane. Small amounts of ethylene, propylene, toluene, and carbon monoxide can also exist in the effluent.
  • the effluent can contain a concentration of aromatic rings which is at least 5 weight percent (wt ), or at least 10 wt , or at least 15 wt , or preferably at least 20 wt % greater than the concentration of aromatic rings in the feed.
  • dehydroaromatization effluent for example, by solvent extraction followed by fractionation.
  • the hydrogen in the effluent can be reacted with C0 2 , and/or H 2 0, to produce a new effluent gas mixture, which can contain synthetic or unconverted methane 115, hydrogen, carbon monoxide, carbon dioxide, and water.
  • synthetic or unconverted methane 115 can come from the methanation step above and can be recycled back to the dehydroaromatization reactor feed stream preheater together with the fresh methane coming from feed line 102. Most of the synthetic or unconverted methane 115 can be recycled under pressure to the feed line 116 of the dehydroaromatization reactor 103 without a compressor, and thus with no energy loss. The synthetic or unconverted methane 115 can be recycled at a temperature of 300°C to 600°C, and a pressure of 300 to 3000 kiloPascals (kPa).
  • the aromatics depleted reaction product contains unreacted methane, hydrogen and ethylene, and approximately 225 moles/hr of carbon dioxide.
  • Carbon dioxide is fed via line 108.
  • the methanation reactor 109 is operated at a temperature of 425°C and a pressure of 2500 kPa. The conversion of carbon dioxide can be greater than ninety- nine percent.
  • Line 110 exiting the methanation reactor 109 contains approximately 225 moles/hr steam (water), and 600 moles/hr of methane, comprising synthetic methane, unreacted methane, and other fuel gas components.
  • recycled methane 115 is recovered from the separator 111 via line 114 and recycled back to dehydroaromatization reactor 103 via feed line 116.
  • the water (steam) 113 is removed via line 112. The recovered water 113 can be used for other reactions after appropriate purification to acceptable levels.
  • Embodiment 1 A process for producing aromatics and other chemicals, comprising: providing methane feedstock to a first reactor to produce a first product stream comprising aromatics and hydrogen, wherein the methane feedstock is contacted with a catalyst; recovering aromatics from the first product stream to create an aromatics depleted resulting stream; mixing the aromatics depleted resulting stream with a feed stream to create a combined product stream; and providing the combined product stream to a second reactor to produce a second product stream comprising water and unconverted methane.
  • Embodiment 2 The process of Embodiment 1, wherein the first reactor produces the first product stream by dehydroaromatization.
  • Embodiment 3 The process of Embodiment 1 or Embodiment 2, wherein the second reactor is a methanation reactor.
  • Embodiment 4 The process of any of Embodiments 1 to 3, wherein the aromatics are recovered from the first product stream prior to entering the second reactor.
  • Embodiment 5 The process of any of Embodiments 1 to 4, wherein the feed stream is selected from a carbon dioxide feed stream, a steam feed stream, and combinations thereof.
  • Embodiment 6 The process of any of Embodiments 1 to 5, wherein the aromatics are selected from benzene, toluene, naphthalene, other aromatics, and combinations thereof.
  • Embodiment 7 The process of any of Embodiments 1 to 6, wherein the catalyst is a bifunctional Zeolite supported metal catalyst.
  • Embodiment 8 The process of Embodiment 7, wherein the metal is selected from molybdenum, tungsten, ruthenium, iron, cobalt, nickel, copper, silver, zinc, chromium, or tin, and combinations thereof.
  • Embodiment 9 A process for producing aromatics and other chemicals from recycled methane feedstock, comprising: receiving recycled methane from a methanation reaction; mixing the recycled methane and methane feedstock to form a combined methane feedstock; providing the combined methane feedstock to a first reactor to produce a first product stream comprising aromatics and hydrogen, wherein the combined methane feedstock is contacted with a catalyst; recovering aromatics from the first product stream to create an aromatics depleted resulting stream; mixing the aromatics depleted resulting stream with a feed stream to create a combined product stream; and providing the combined product stream to a second reactor to produce a second product stream comprising synthetic or unconverted methane, and water.
  • Embodiment 10 The process of Embodiment 9, wherein the first reactor produces the first product stream by dehydroaromatization.
  • Embodiment 11 The process of Embodiment 9 or Embodiment 10, wherein the second reactor is a methanation reactor.
  • Embodiment 12 The process of any of Embodiments 9 to 11, wherein the carbon dioxide or steam feed stream is a carbon dioxide feed stream.
  • Embodiment 13 The process of any of Embodiments 9 to 12, wherein the feed stream is selected from a carbon dioxide feed stream, a steam feed stream, and combinations thereof.
  • Embodiment 14 The process of any of Embodiments 9 to 13, wherein the aromatics are selected from a group consisting of: benzene, toluene, naphthalene, other aromatics and combinations thereof.
  • Embodiment 15 The process of any of Embodiments 9 to 14, wherein the catalyst is a bifunctional Zeolite supported metal catalyst.
  • Embodiment 16 The process of any of Embodiments 9 to 15, wherein the metal is selected from molybdenum, tungsten, ruthenium, iron, cobalt, nickel, copper, silver, zinc, chromium, or tin, and combinations thereof.
  • Embodiment 17 A process for producing a methane-rich gas, comprising: receiving a first resulting stream from one or more dehydroaromatization reactions; extracting aromatics from the first resulting stream, wherein the resulting stream is converted to an aromatic depleted resulting stream; mixing the aromatics depleted resulting stream with a carbon dioxide feed or steam feed stream to create a combined stream; mixing the combined stream with one or more methanation catalysts in a methanation reactor to produce a second resulting stream; and extracting water from the second resulting stream.
  • Embodiment 18 The process of Embodiment 17, wherein the aromatics are selected from benzene, toluene, naphthalene, other aromatics, and combinations thereof.
  • Embodiment 19 The process of Embodiment 17 or Embodiment 18, wherein the methanation catalysts are selected from ruthenium, cobalt, nickel or iron, and
  • the invention may alternately comprise, consist of, or consist essentially of, any appropriate components herein disclosed.
  • the invention may additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any components, materials, ingredients, adjuvants or species used in the prior art compositions or that are otherwise not necessary to the achievement of the function and/or objectives of the present invention.
  • the endpoints of all ranges directed to the same component or property are inclusive and independently combinable (e.g., ranges of "less than or equal to 25 wt , or 5 wt to 20 wt%," is inclusive of the endpoints and all intermediate values of the ranges of "5 wt to 25 wt%,” etc.).

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Abstract

L'invention porte sur des systèmes et des procédés pour la production intégrée de composés aromatiques. Les systèmes et procédés peuvent comprendre un procédé de production de composés aromatiques, tels que le benzène, le toluène, le naphtalène, ou d'autres composés aromatiques consistant à alimenter un premier réacteur en méthane afin de produire un premier courant de produits comprenant des composés aromatiques, tels que le benzène, le toluène, le naphtalène, ou d'autres composés aromatiques et l'hydrogène; à récupérer les composés aromatiques du premier courant de produits et à mélanger le premier courant de produits avec un courant d'alimentation en dioxyde de carbone et/ou en vapeur d'eau; à alimenter un second réacteur en un courant combiné comprenant le premier courant de produits appauvri en composés aromatiques et le courant d'alimentation en dioxyde de carbone afin de produire un second courant de produits contenant de l'eau et du méthane de synthèse ou non converti; et à ajouter le méthane recyclé à une nouvelle charge d'alimentation contenant du méthane destinée à une future production intégrée de composés aromatiques.
PCT/US2015/014735 2014-01-30 2015-02-06 Procédé de production de composés aromatiques à partir de méthane comprenant une étape intermédiaire d'alimentation simultanée en cox Ceased WO2015117166A1 (fr)

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US61/933,619 2014-01-30
US201461941803P 2014-02-19 2014-02-19
US61/941,803 2014-02-19

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2017136490A1 (fr) * 2016-02-02 2017-08-10 Sabic Global Technologies B.V. Conversion de gaz de schiste en hydrocarbures aromatiques

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WO2006083409A2 (fr) * 2004-12-22 2006-08-10 Exxonmobil Chemical Patents, Inc. Production d'hydrocarbures liquides a partir de methane
US20070260098A1 (en) * 2004-12-22 2007-11-08 Iaccino Larry L Production Of Aromatic Hydrocarbons From Methane
US8138384B2 (en) 2004-12-22 2012-03-20 Exxonmobil Chemical Patents Inc. Production of alkylated aromatic hydrocarbons from methane

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006083409A2 (fr) * 2004-12-22 2006-08-10 Exxonmobil Chemical Patents, Inc. Production d'hydrocarbures liquides a partir de methane
US20070260098A1 (en) * 2004-12-22 2007-11-08 Iaccino Larry L Production Of Aromatic Hydrocarbons From Methane
US8138384B2 (en) 2004-12-22 2012-03-20 Exxonmobil Chemical Patents Inc. Production of alkylated aromatic hydrocarbons from methane

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017136490A1 (fr) * 2016-02-02 2017-08-10 Sabic Global Technologies B.V. Conversion de gaz de schiste en hydrocarbures aromatiques
US10532962B2 (en) 2016-02-02 2020-01-14 Sabic Global Technologies B.V. Conversion of shale gas to aromatics

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