WO2008157047A1 - Procédés pour produire de l'hydrogène à partir de sources d'alimentation en hydrocarbures - Google Patents

Procédés pour produire de l'hydrogène à partir de sources d'alimentation en hydrocarbures Download PDF

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Publication number
WO2008157047A1
WO2008157047A1 PCT/US2008/065839 US2008065839W WO2008157047A1 WO 2008157047 A1 WO2008157047 A1 WO 2008157047A1 US 2008065839 W US2008065839 W US 2008065839W WO 2008157047 A1 WO2008157047 A1 WO 2008157047A1
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WIPO (PCT)
Prior art keywords
metal halide
combining
methane
hydrocarbon feed
producing
Prior art date
Application number
PCT/US2008/065839
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English (en)
Inventor
George W. Cook
Joe D. Sauer
Allen M. Beard
Joseph E. Coury
Mario A. Garcia
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Albemarle Corporation
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Publication of WO2008157047A1 publication Critical patent/WO2008157047A1/fr

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Classifications

    • 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
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06—Catalytic processes
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/08—Halides
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/125—Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/125—Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium
    • C07C2527/126—Aluminium chloride

Definitions

  • Hydrogen is useful in the production of ammonia, methanol, gasoline, heating oil, and rocket fuel. It is also used to make fertilizers, glass, refined metals, vitamins, cosmetics, semiconductor circuits, soaps, lubricants, cleaners, and even margarine and peanut butter.
  • This invention meets the above-described needs by providing processes for producing H 2 .
  • H 2 can be produced directly from methane and/or other hydrocarbon feed sources by processes that comprise combining at least gaseous methane and/or a hydrocarbon feed source and a metal halide suitable for catalyzing polymerization of the methane.
  • a benefit of processes of this invention is that usable H 2 is produced, as is described in greater detail below.
  • a component suitable for absorbing hydrogen can be used in processes of this invention for recovery of the usable H 2 .
  • H 2 can be recovered by techniques familiar to those skilled in the art, such as by pressure swing absorption, distillation, and the like.
  • the availability of usable H 2 is advantageous in that it can be used as a clean-burning fuel with reduced CO 2 emissions as compared to traditional fuels.
  • haiide an olefin, or a metal haiide comprising Li, Na, K, Mg, Ca, Sc, Y, Zr, Cu, Hf, V, Nb, Ta 1 Fe, Ru, Co, Ni, Pb, B, Ga, Ge 9 Sn, or Sb and bromine, chlorine, fluorine, or iodine; and such processes further comprising combining gaseous methane with the at least hydrocarbon feed source and metal halide.
  • Also provided are processes for producing H 2 comprising: combining at least a hydrocarbon feed source and a metal halide at at least about 350 0 C, cracking at least some of the hydrocarbon feed source to Ci or higher hydrocarbons; and polymerizing at least some of the Ci or higher hydrocarbons; yielding at least H 2 and C 2 and higher hydrocarbons.
  • Also provided are processes for producing H 2 the processes comprising combining at least a gas stream comprising methane and a metal halide at a temperature of at least 100 0 C and yielding at least H 2 ; such processes wherein the gas stream comprises at least about 50 vol% methane; such processes wherein the gas stream comprises at least about 75 vol% methane; such processes wherein the metal halide comprises aluminum bromide, aluminum chloride, aluminum fluoride, titanium bromide, or aluminum iodide; such processes wherein the metal halide comprises aluminum bromide; and such processes wherein the process comprises combining at least the gas stream comprising methane, the metal halide, and a component suitable for absorbing hydrogen.
  • processes for producing H 2 comprising: (a) heating a metal halide to a melt temperature at least high enough to melt the metal halide; (b) combining at least a gas stream comprising methane and the heated metal halide; (c) producing C 2 and higher hydrocarbons; and (d) producing H 2 .
  • processes for producing H2 comprising: (a) heating a metal halide to a melt temperature at least high enough to melt the metai haiide; (b) combining at least a gas stream comprising methane, a halogen, and the heated metal halide; (c) producing C 2 and higher hydrocarbons; and (d) producing H2.
  • Suitable Lewis acids include, without limitation, metal halides such as aluminum bromide.
  • a Lewis acid is defined as a compound capable of accepting an electron pair.
  • Also provided are processes comprising combining at least gaseous methane and a Lewis acid at at least a temperature at which at least some of the Lewis acid is gaseous, yielding at least H 2 and C2 and higher hydrocarbons.
  • Also provided are processes comprising combining at least gaseous methane, a Lewis acid, and a Bronsted acid, e.g., HBr, at at least 100 0 C, yielding at least H 2 and
  • a Bronsted acid is defined as a compound capable of donating a proton.
  • Also provided are processes comprising combining at least gaseous methane, a Lewis acid, and a Bronsted acid, e.g., HBr 1 at at least a temperature at which at least some of the Lewis acid is gaseous, yielding at least H 2 and C2 and higher hydrocarbons.
  • a Bronsted acid e.g., HBr 1
  • C 2 and higher hydrocarbons produced according to processes of this invention can include without limitation C2 to C30 hydrocarbons, particularly C2 to C12 hydrocarbons or C 4 to Ce hydrocarbons.
  • the C 2 and higher hydrocarbons produced according to this invention can include normal and ⁇ so alkanes (CnHan+a), cyclic alkanes (C n H 2n ), alkenes (C n H 2n ), alkynes (C n H 2n _ 2 ), aromatics, and the like.
  • the gaseous methane can be provided by a natural gas stream co-produced with oil or otherwise produced, or a natural gas stream from any other suitable source.
  • the gas stream can be produced from coal beds (e.g., anthracite or bituminous), biogas produced by the anaerobic decay of non-fossil organic materia! from swamps, marshes, landfills, and the like, biogas produced from sewage sludge and manure by way of anaerobic digesters, biogas produced by enteric fermentation particularly in cattle and termites, and from other gas sources.
  • H 2 can be added with the gas stream
  • the gas stream can comprise at least about 50 vol% methane, or at least about 75 vol% methane
  • Other components can be present in the gas stream, for example, ethane, butane, propane, carbon dioxide, nitrogen, helium, hydrogen sulfide, water, odorants, mercury, organosulfur compounds, etc.
  • Such components can be removed as needed from the gas stream prior to, during, or after processing according to this invention using techniques familiar to those skilled in the art
  • the gas stream can consist essentially of methane, e g , can be zero grade, or essentially pure, methane
  • This invention also provides processes for producing C 2 and higher hydrocarbons comprising combining at least a hydrocarbon feed source and a metal halide within a temperature range in which at least some of the metal halide is gaseous
  • Suitable hydrocarbon feed sources include without limitation, paraffin waxes, high density polyethylene, plastic grocery bags, C ⁇ straight chain paraffins, isopentane, cyclohexane, heptane, acetylene, ethylene, etc.
  • the metal halide or other Lewis acid can be suitable for catalyzing polymerization of methane and can comprise aluminum bromide (e g , AIBrs or AlaBr ⁇ ), aluminum chloride, aluminum fluoride, aluminum iodide, titanium bromide, and the like, including mixtures thereof
  • metal halides comprising a metal such as Li, Na, K, Mg Ca, Sc, Y, Zr, Cu, Hf, V,
  • Impurities can be present on the surface of the metal halide(s); and such impurities can participate in reactions that occur during processes of this invention.
  • the metal halide can be heated such that it is at a temperature, or is within a temperature range, that is at least high enough to gasify at least some of the metal halide.
  • the temperature can be at least about 100 0 C, and can be from about 100 0 C to about 400 0 C, or about 250 0 C to about 350 0 C.
  • any suitable hydrogen halide can be used, for example hydrogen bromide.
  • a hydrogen halide such as hydrogen bromide for example, it can have a purity of about 100% or less than about 100%.
  • the hydrogen halide can be of a commercial grade, can have a purity of at least about 95%, or at least about 98%, or at least about 99%, or at least about 99.9%.
  • the hydrogen halide can have a purity of at least about 50% or at least about 90% and can comprise various impurities such as H 2 O, CO, CO 2 , O 2 , HCI, HF, Br 2 , Cl 2 , fluorine, or iodine, to name a few.
  • impurities such as H 2 O, CO, CO 2 , O 2 , HCI, HF, Br 2 , Cl 2 , fluorine, or iodine, to name a few.
  • another hydrogen halide such as hydrogen fluoride, or hydrogen chloride, or hydrogen iodide.
  • the component suitable for absorbing hydrogen can comprise Raney nickel, platinum, paladium, tantalum, niobium, yttrium, platinum on carbon, paladium on carbon, platinum on activated carbon, paladium on activated carbon, etc.
  • Raney nickel can be comprised of aluminum-nickel alloy. Given the teachings of this disclosure, one skilled in the art can select an suitable component for absorbing hydrogen.
  • Processes according to this invention for producing C 2 and higher hydrocarbons can comprise combining at least gaseous methane, a meta! halide, and an additional component.
  • the additional component (sometimes referred to herein as a promoter) can comprise a halogen such as bromine, chlorine, fluorine, or iodine; methyl iodide; titanium bromide; metal halides comprising a metal such as Li, Na, K, Mg, Ca, Sc, Y, Zr, Cu, Hf, V, Nb, Ta, Fe, Ru, Co, Ni, Pb, B, Ga, Ge, Sn, or Sb and a halogen such as bromine, chlorine, fluorine, or iodine; branched hydrocarbons such as isopentane, neopentane, and the like; ethane; hydrogen; alkyl halides such as methyl bromide, ethyl bromide, and the like; and/or olefins such as propene, butene, and the like.
  • a halogen such as bromine, chlorine, fluorine, or iodine
  • Such additional components can be generated in situ.
  • combined methane and bromine can generate methyl bromide in situ; combined hydrogen bromide and ethylene can generate ethylene bromide in situ, etc..
  • the metal halide 114 can catalyze polymerization of methane in gaseous methane stream 118 to C 2 and higher hydrocarbons.
  • Gaseous methane stream 118 can comprise ethane, butane, olefins, etc., in addition to the methane.
  • the metal halide 114 can be in a container 112.
  • the container 112 can be heated by any suitable means, e.g., by a heated sand bed 116, so that the metal halide 114 is heated, e.g., at least to its melting temperature.
  • the gaseous methane stream 118 can be injected into (or otherwise put into) the container 112 such that the metal halide 114 catalyzes polymerization of the methane.
  • the residence time of methane in the gaseous methane stream 118 within the container 112 and other conditions, such as temperature can be adequate to initiate polymerization of the methane.
  • the residence time of methane in the gaseous methane stream 118 within the container 112 and other conditions, such as temperature, can be adequate to initiate polymerization of the methane.
  • residence time can be up to about one minute. Longer residence times can be used.
  • residence time of methane in the gaseous methane stream 118 within the container 112 can be longer than about one minute, for example from about one minute to about five minutes, or up to about two minutes.
  • a substantial portion of the polymerization can occur in vapor phase 119. Simultaneously with the polymerization in vapor phase 119, some of the polymerized higher hydrocarbons can be cracked, e.g., by thermal cracking, acid cracking, etc..
  • olefins are formed and hydrogen given off can assist in the cracking process.
  • the temperature can be above about 350 0 C, or can be from about 350 0 C to about 1000 0 C, or from about 35O 0 C to about 400 0 C.
  • cracking can be achieved without the assistance of olefins by addition of hydrogen.
  • a temperature of up to about 350 0 C, or at about 11 O 0 C cracking can be assisted by addition of hydrogen under pressure.
  • Thermal reforming of hydrocarbons, isomerization of hydrocarbons, and other reactions can also occur in vapor phase 119 and/or elsewhere in container 112. Skeletel or bond isomerization can occur.
  • the metal halide can catalyze polymerization of the methane by action as a Lewis acid.
  • hydrogen given off during the polymerization of the methane can be recovered for sale or use, e.g., by being absorbed by a component suitable for absorbing hydrogen, which component may be in the container 112 with the metal halide 114 or may be in a separate container through which the gaseous methane stream 118 (or a resulting product/product stream (not shown in Figure 1)) is subsequently passed.
  • Produced C 2 and higher hydrocarbons can be recovered from container 112 by means known to those skiiSed in the art (not illustrated in Figure 1). Given the teachings of this disclosure, those skilled in the art can determine appropriate temperatures, pressures, and other process parameters as desired to achieve desired results using processes of this invention. [0027] Referring, for example, to Figure 2, in processes of this invention, metal halide
  • component 215 can be put into container 212, e.g., for the purpose of increasing surface area within container 212 and/or for supporting the metal halide 214.
  • component 215 is that additional surface area is provided for surface activated polymerization reactions. Gas/vapor phase polymerization reactions can also occur.
  • suitable packing materials will be well known to those skilled in the art, given the teachings of this disclosure, and can include, for example, glass beads, aluminum oxides, and zeolites.
  • the container 212 can be heated by any suitable means, e.g., by a heated sand bed 216, so that the metal halide 214 is heated, e.g., to at least its melting temperature.
  • the gaseous methane stream 218 can be injected into (or otherwise put into) the container 212 such that the metal halide 214 catalyzes polymerization of the methane.
  • the residence time of methane in the gaseous methane stream 218 within the container 212 and other conditions, such as temperature can be adequate to initiate polymerization of the methane.
  • a substantial portion of the polymerization can occur on the surface of component 215 and/or in vapor phase 219. Simultaneously with the polymerization on the surface of component
  • the vapor phase (e.g., 119 in Figure 1 or 219 in Figure 2) can comprise ionic species in that the pressure and temperature conditions allow a substantial portion of the metal halide to remain available as a salt in the vapor phase.
  • a vapor phase containing such ionic species can be conducive to reactions such as alkylation, isomerization, and the like,
  • Red oil is a clathrate of at least oiefinic hydrocarbon(s), aluminum haiide(s), and, in some cases, Bronsted acid(s) and/or other Lewis acid(s).
  • a benefit of processes of this invention is that components having a catalytic effect on the polymerization reactions taking place, e.g., aluminum bromide and hydrogen bromide, for example, either do not require regeneration, e.g., when conditions are maintained to minimize tar formation during processes of this invention, or can be regenerated in situ with hydrogen pressure at the appropriate temperature.
  • components having a catalytic effect on the polymerization reactions taking place e.g., aluminum bromide and hydrogen bromide, for example, either do not require regeneration, e.g., when conditions are maintained to minimize tar formation during processes of this invention, or can be regenerated in situ with hydrogen pressure at the appropriate temperature.
  • natural gas comprising at least about 50 vol% methane is being co-produced with oil. Given the remote location of the production site and limited available space on the offshore platform, the natural gas is being flared.
  • a process according to the present invention is used to produce higher hydrocarbons from the methane.
  • the higher hydrocarbons as well as the hydrogen produced during the process are utilized as fuel at the platform, thus providing a substantial economic benefit to the site.
  • natural gas stream 318 comprises on average from about 70 vol% to about 85 vol% methane, and also includes other components such as ethane, butane, propane, carbon dioxide, nitrogen, helium, and hydrogen sulfide.
  • inert material 313 is made from glass, an inert material.
  • Inert material 310 is glass beads; and in addition to supporting device 313, inert material 310 fills at least some of the otherwise empty space in container 312.
  • inert materials 310 used in this invention can include glass and other suitable inert materials.
  • a slurry 317 of about 3 grams to about 5 grams of aluminum bromide 314 and about 0.5 grams to about 2 grams platinum-on-activated-charcoal 315 is in device 313.
  • the temperature inside container 312 is maintained between about 250 0 C and 400 0 C by heated sand bed 316. Residence time of methane (in natural gas stream 318) within container 312 is from about 1 minute to about 30 minutes.
  • container 312 The conditions in container 312 are adequate to catalyze polymerization of methane to C 2 and higher hydrocarbons. A substantial portion of the polymerization occurs in vapor phase 319. Simultaneously with the polymerization in vapor phase 319, some of the polymerized higher hydrocarbons are thermally cracked. During the polymerization, produced hydrogen is absorbed by piatinum-on-activated-charcoai 315, or another suitable hydrogen absorber. Outlet gas stream 320, exiting container 312 and comprising produced C 2 and higher hydrocarbons and any unreacted methane, is input to device 330. Within device 330, recycle stream 334 comprising any unreacted methane is separated from product stream 332 comprising liquefied C 2 and higher hydrocarbons.
  • Recycle stream 334 comprising methane is input into container 312 along with natural gas stream 318.
  • Product stream 332 comprising liquefied C 2 and higher hydrocarbons is removed from device 330 and is put into storage containers (not illustrated in Figure 3) for use as fuel and for chemical feedstock needed at the offshore production site, or is used directly without being stored.
  • platinum-on-activated-charcoal 315 is removed from device 313 in container 312 and replaced with fresh platinum-on-activated- charcoal 315. Hydrogen is recovered as removed platinum-on-acfivated-charcoal 315 is regenerated for reuse within container 312, using means known to those skilled in the art.
  • gaseous feedstock in container 500 comprises gaseous methane, HBr, ethane and hydrogen.
  • the gaseous feedstock is fed via conduit 510 to conduit 520.
  • Pressure regulator 530 is used to regulate the pressure within container 500.
  • Flow valve 540 is used to control flow through rotometer 545.
  • Container 550 contains aluminum bromide 560.
  • Aluminum bromide 560 is heated to about 100 0 C by heat provided by a heating source, e.g., a heating mantle (not shown in Figure 4) with heat from the heating source being transferred through a heat transfer materia! 555, e.g., sand.
  • Nitrogen from a nitrogen source (not shown in Figure 4) is fed through conduit 570 (via flow valve 572 and rotometer 574) through the aluminum bromide in container 550.
  • Pressure indicator 565 indicates the pressure within container 550.
  • Gaseous nitrogen and aluminum bromide exit container 550 via conduit 580. Both the gaseous feedstock from conduit 510 and the gaseous nitrogen and aluminum bromide from conduit 580 flow into conduit 520 in container 521.
  • conduits 580 and 520 is insulated, e.g., with heating tape.
  • the contents of conduit 520 are fed to stainless capillary coil 590, which is heated to a temperature of about 325°C by heat provided by a heating source, e.g., a heating mantle (not shown in Figure 4) with heat from the heating source being transferred through sand bed 592 in container 591.
  • Stainless capillary coil 590 is about 100 yards long.
  • Product comprising C 2 and higher hydrocarbons exits container 591 (coil 590) via conduit 600.
  • Device 610 is an all-in-one condenser, separator, collector, and sight glass).
  • Flow valve 611 is used to control flow of product comprising C 2 and higher hydrocarbons to storage and/or end use facilities (not shown in Figure 4).
  • Flow valve 620 in conduit 625 controls flow of gaseous fluid through rotometer 640 that is used to regulate flow through continuous process system 599. Gaseous fluid in conduit 625 is vented via vent 623; samples of gaseous fluid in conduit 625 can be taken through valve 645.

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Abstract

L'invention concerne des procédés pour produire de l'hydrogène, au moins un halogénure métallisé et une source d'alimentation en hydrocarbures et/ou un flux gazeux comprenant du méthane étant combinés.
PCT/US2008/065839 2007-06-14 2008-06-05 Procédés pour produire de l'hydrogène à partir de sources d'alimentation en hydrocarbures WO2008157047A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US94403607P 2007-06-14 2007-06-14
US60/944,036 2007-06-14
US98934307P 2007-11-20 2007-11-20
US60/989,343 2007-11-20
US5727408P 2008-05-30 2008-05-30
US61/057,274 2008-05-30

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US8282810B2 (en) 2008-06-13 2012-10-09 Marathon Gtf Technology, Ltd. Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery
US8367884B2 (en) 2010-03-02 2013-02-05 Marathon Gtf Technology, Ltd. Processes and systems for the staged synthesis of alkyl bromides
US8436220B2 (en) 2011-06-10 2013-05-07 Marathon Gtf Technology, Ltd. Processes and systems for demethanization of brominated hydrocarbons
US8642822B2 (en) 2004-04-16 2014-02-04 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor
US8802908B2 (en) 2011-10-21 2014-08-12 Marathon Gtf Technology, Ltd. Processes and systems for separate, parallel methane and higher alkanes' bromination
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