US20080314758A1 - Process for converting hydrocarbon feedstocks with electrolytic recovery of halogen - Google Patents

Process for converting hydrocarbon feedstocks with electrolytic recovery of halogen Download PDF

Info

Publication number
US20080314758A1
US20080314758A1 US12/152,515 US15251508A US2008314758A1 US 20080314758 A1 US20080314758 A1 US 20080314758A1 US 15251508 A US15251508 A US 15251508A US 2008314758 A1 US2008314758 A1 US 2008314758A1
Authority
US
United States
Prior art keywords
halide
hydrogen
halogen
alkyl halides
alkaline
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US12/152,515
Other languages
English (en)
Inventor
Philip Grosso
Eric W. McFarland
Jeffrey H. Sherman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Reaction 35 LLC
Original Assignee
GRT Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by GRT Inc filed Critical GRT Inc
Priority to US12/152,515 priority Critical patent/US20080314758A1/en
Publication of US20080314758A1 publication Critical patent/US20080314758A1/en
Assigned to HOOK, THOMAS W. reassignment HOOK, THOMAS W. SECURITY AGREEMENT Assignors: GRT, INC.
Assigned to REACTION 35, LLC reassignment REACTION 35, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GRT, INC.
Assigned to REACTION 35, LLC reassignment REACTION 35, LLC RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: HOOK, THOMAS W.
Abandoned legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/24Halogens or compounds thereof
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00Electrolytic production of organic compounds
    • C25B3/20Processes
    • C25B3/27Halogenation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/26Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/26Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
    • C07C1/30Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms by splitting-off the elements of hydrogen halide from a single molecule
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00Aliphatic unsaturated hydrocarbons
    • C07C11/02Alkenes
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00Preparation of halogenated hydrocarbons
    • C07C17/013Preparation of halogenated hydrocarbons by addition of halogens
    • C07C17/06Preparation of halogenated hydrocarbons by addition of halogens combined with replacement of hydrogen atoms by halogens
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/06Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
    • C07C209/08Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/12Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
    • C07C29/124Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids of halides
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/04Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of powdered coal
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
    • C10B57/06Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G29/00Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/02Non-metals
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/02Hydrogen or oxygen
    • C25B1/04Hydrogen or oxygen by electrolysis of water
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1011Biomass
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1025Natural gas
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30Aromatics
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/013Alloys
    • H01L2924/014Solder alloys
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/141Feedstock
    • Y02P20/145Feedstock the feedstock being materials of biological origin

Definitions

  • the present invention is directed to a process for converting natural gas and other hydrocarbon feedstocks into higher-value products, such as fuel-grade hydrocarbons, methanol, and aromatic compounds.
  • the process includes the steps of alkane halogenation, “reproportionation” of polyhalogenated compounds to increase the amount of monohalides that are formed, oligomerization (C—C coupling) of alkyl halides to form higher carbon number products, separation of products from hydrogen halide, continuous regeneration of halogen, and recovery of molecular halogen from water.
  • Hydrohalic acid e.g., HBr
  • molecular halogen e.g., bromine
  • the '358 application represents a significant advance in the art of C—H bond activation and industrial processes for converting a hydrocarbon feedstock into higher value products.
  • the present invention builds on the '358 application by employing electrolysis to regenerate molecular halogen (e.g., Br 2 , Cl 2 ) from hydrohalic acid (e.g., HBr, HCl).
  • molecular halogen e.g., Br 2 , Cl 2
  • hydrohalic acid e.g., HBr, HCl
  • Electrolysis of aqueous solutions to produce hydrogen and oxygen is a known way of producing hydrogen with electrical energy.
  • halogens have been produced by electrolysis of halide brines or metal halide vapor.
  • Conventional hydrogen production relies on reforming of hydrocarbons with water (steam) to produce carbon monoxide and molecular hydrogen:
  • the energetically unfavorable reforming reaction can be compared to the exothermic complete oxidation of hydrocarbons in oxygen to produce the low-energy products water and carbon dioxide:
  • the reforming process is coupled with complete oxidation to provide energy to drive the otherwise endothermic reaction.
  • the resulting overall reaction produces both carbon oxides and hydrogen and can be operated nearly isoergically:
  • hydrogen can be produced by dissociation of water:
  • the reaction can be driven by electrolysis using 2 ⁇ 10 5 Coulombs per gram-mole H 2 .
  • Water is the source of both the hydrogen and the oxygen, and the high activation energy for oxygen production requires over potentials of approximately 1.6 Volts and a stoichiometric current. In practice, the electrical energy required is approximately 300 kJ/mol H 2 .
  • halogen Cl 2
  • alkali base NaOH
  • bromine can be produced from bromine salts (NaBr).
  • the production of molecular halogen from the haloanion is energetically and kinetically advantageous compared to oxygen production, requiring a lower over potential (1.1 V versus 1.6V):
  • hydrocarbons can be directly oxidized electrochemically using oxygen (as in a solid oxide fuel cell) and/or water to produce hydrogen; however this typically leads to complex, difficult to separate intermediates and is not economically useful.
  • Another means of removing hydrogen from hydrocarbons is by stepwise partial oxidation with a halogen, (preferably bromine).
  • a halogen preferably bromine
  • this process requires that bromine produced in electrolysis be converted back to HBr, and this conversion step is a major disadvantage of the HBr electrolysis route to hydrogen.
  • the present invention uses the bromine generated in electrolysis to produce valuable products, rather than simply converting it back to HBr.
  • the present invention combines the thermal (non-electrochemical) reactivity of halogens (preferably bromine) with hydrocarbons to produce hydrogen halide (preferably HBr) and reactive alkyl halides or other carbon-containing intermediates that may be converted to subsequent products, more readily than the original hydrocarbon, with the facile electrolysis of hydrogen halides or halide salts to create an overall process with significantly higher efficiency.
  • halogens preferably bromine
  • hydrocarbons preferably HBr
  • reactive alkyl halides or other carbon-containing intermediates that may be converted to subsequent products, more readily than the original hydrocarbon
  • the use of halogens prevents the total oxidation of the hydrocarbon to carbon dioxide and allows subsequent production of partial oxidation products.
  • a continuous process for converting a hydrocarbon feedstock into one or more higher hydrocarbons comprises: (a) forming alkyl halides by reacting molecular halogen with a hydrocarbon feedstock under process conditions sufficient to form alkyl halides and hydrogen halide, preferably with substantially complete consumption of the molecular halogen; (b) forming higher hydrocarbons and hydrogen halide by contacting the alkyl halides with a first catalyst under process conditions sufficient to form higher hydrocarbons and hydrogen halide; (c) separating the higher hydrocarbons from hydrogen halide; (d) converting the hydrogen halide into hydrogen and molecular halogen electrolytically, thereby allowing the halogen to be reused; and (e) repeating steps (a) through (d) a desired number of times.
  • Electrolysis is carried out in aqueous media, or in the gas phase.
  • the alkyl halides are “reproportionated” by reacting some or all of the alkyl halides with an alkane feed, whereby the fraction of monohalogenated hydrocarbons present is increased.
  • hydrogen produced in the process is used for power generation.
  • a continuous process for converting a hydrocarbon feedstock into methanol comprises: (a) forming alkyl halides by reacting molecular halogen with a hydrocarbon feedstock under process conditions sufficient to form alkyl halides and hydrogen halide, preferably with substantially complete consumption of the molecular halogen; (b) forming methanol and alkaline halide by contacting the alkyl halides with aqueous alkali under process conditions sufficient to form methanol and alkaline halide; (c) separating the methanol from the alkaline halide; (d) converting the alkaline halide into hydrogen, or molecular halogen, and aqueous alkali electrolytically, thereby allowing the halogen and the alkali to be reused; and (e) repeating steps (a) through (d) a desired number of times.
  • the polyhalogenated hydrocarbons are “reproportionated” by reacting some or all of the alkyl halides with an alkane feed, whereby the fraction of monohalogenated hydrocarbons present is increased.
  • the production of methanol by this process requires that the reaction of alkyl halides with aqueous alkali be carried out under alkaline conditions.
  • the electrolysis process yields alkali and acid in stoichiometrically equivalent amounts.
  • simply recombining all of the alkali with all of the acid would result in a neutral solution.
  • the process described herein provides for disproportionation of the acid and base such that more than sufficient alkali is available to react with the alkyl bromides to achieve alkaline conditions.
  • the acid removed in the disproportionation step is later recombined with the excess alkali after methanol and other products have been formed and separated.
  • anolyte in acidic condition, which may require a small amount of acid to be added.
  • the separation of a portion of the acid can be accomplished by a liquid phase process or, alternatively, by the use of a regenerable solid reactant or adsorbent.
  • Acid can also be provided from an external source, either from on-site or off-site generation. Alternatively, an overall excess of acid can be achieved by removal of a small amount of alkali from the system.
  • a continuous process for converting a hydrocarbon feedstock into an alkyl amine comprises: (a) forming alkyl halides by reacting molecular halogen with a hydrocarbon feedstock under process conditions sufficient to form alkyl halides (e.g., ethyl bromide) and hydrogen halide, preferably with substantially complete consumption of the molecular halogen; (b) forming alkyl amines and alkaline halide by contacting the alkyl halides with ammonia or aqueous ammonia under process conditions sufficient to form alkyl amines and alkaline halide; (c) separating the alkyl amines from the alkaline halide; (d) converting the alkaline halide into hydrogen and molecular halogen electrolytically, thereby allowing the halogen to be reused; and (e) repeating steps (a) through (d) a desired number of times.
  • alkyl halides e.g., eth
  • the alkyl halides are “reproportionated” by reacting some or all of the alkyl halides with an alkane feed, whereby the fraction of monohalogenated hydrocarbons present is increased.
  • a continuous process for converting coal into coke and hydrogen comprises the steps of (a) forming brominated coal intermediates and hydrogen halide by reacting crushed coal with molecular halogen under process conditions sufficient to brominate and dissociate significant elements of the coal skeleton, thereby forming a mixture of brominated coal intermediates (e.g., polybrominated hydrocarbons); (b) forming coke and hydrogen halide by reacting the brominated coal intermediates over a catalyst under process conditions sufficient to from coke and hydrogen halide; (c) separating the coke from the hydrogen halide; (d) converting hydrogen halide formed in step (a) and/or step (b) into hydrogen and molecular halogen electrolytically, thereby allowing the halogen to be reused; and (e) repeating steps (a) through (d) a desired number of times. These steps can be carried out in the order presented or, alternatively, in a different order.
  • a continuous process for converting coal or biomass-derived hydrocarbons into polyols and hydrogen comprises: (a) forming alkyl halides by reacting molecular halogen with coal or a biomass-derived hydrocarbon feedstock under process conditions sufficient to form alkyl halides and hydrogen halide, preferably with substantially complete consumption of the molecular halogen; (b) forming polyols and alkaline halide by contacting the alkyl halides with aqueous alkali under process conditions sufficient to form polyols and alkaline halide; (c) separating the polyols from the alkaline halide; (d) converting the alkaline halide into hydrogen and molecular halogen electrolytically, thereby allowing the halogen to be reused; and (e) repeating steps (a) through (d) a desired number of times.
  • the alkyl halides are “reproportionated” by reacting some or all of the alkyl halides with an alkane feed, whereby the fraction of monohalogenated hydrocarbons present is increased.
  • an oxygen-depolarized electrode is used in the electrolyzer, and electrolysis of hydrogen halide yields molecular halogen and water, and electrolysis of alkaline halide yields molecular halogen and alkaline hydroxide, rather than hydrogen.
  • This variation has the advantage of greatly reducing the power requirements of the electrolytic cell(s).
  • An improved electrolytic cell, having an oxygen-depolarized electrode is also provided as yet another aspect of the invention.
  • a number of elements are common to various aspects of the invention, including: (1) halogenation of a hydrocarbon feedstock in the presence of molecular halogen to produce hydrogen halide and an oxidized carbon-containing product; (2) further reaction of the oxidized carbon products to produce final products; (3) separation of carbon-containing products from bromine-containing components; (4) electrolysis of the remaining halogen-containing components (e.g., HBr, NaBr) to form halogen and hydrogen in an electrolytic cell (or, alternatively, use of an oxygen-depolarized electrode to yield halogen and water, or halogen and alkaline hydroxide, instead of hydrogen). Hydrogen that is produced can be used to power one or more process components, or compressed and sold.
  • syngas CO+H 2
  • the present conventional commercial process for utilizing methane, coal, and other hydrocarbons yields syngas (CO+H 2 ), which can be converted to higher value products, such as methanol and linear alkanes.
  • the intermediate syngas is extremely expensive to form, and the nearly fully oxidized carbon must be reduced to form useful products.
  • the present invention is superior in many respects and has at least the following advantages:
  • molecular halogen used to form alkyl halides is recovered as hydrogen halide and recycled to the electrolytic cell, and the alkyl halides are converted to higher value products.
  • examples include the conversion of methyl bromide over a zeolite catalyst to aromatic chemicals and HBr, and conversion of mono alkyl bromides (e.g. ethyl bromide) over a catalyst to olefins (e.g. ethylene) and HBr.
  • the alkyl halides are readily converted to oxygenates, such as alcohols, ethers, and aldehydes.
  • Examples include the conversion of methyl bromide in an aqueous solution of NaOH to methanol and NaBr, and the conversion of dibromomethane in NaOH to ethylene glycol and NaBr.
  • the alkyl halides are readily converted to amines. Examples include the conversion of bromobenzene in an aqueous solution of ammonia to phenol and aniline, and the conversion of ethyl bromide in ammonia to ethylamine and NaBr.
  • the invention finds particular utility when it is used on-site at an oil or gas production facility, such as an offshore oil or gas rig, or at a wellhead located on land.
  • the continuous processes described herein can be utilized in conjunction with the production of oil and/or gas, using electricity generated on-site to power the electrolytic cell(s).
  • FIG. 1 is a schematic diagram of a continuous process for converting a hydrocarbon feedstock into higher hydrocarbons according to one embodiment of the invention
  • FIG. 2 is a schematic diagram of a continuous process for converting a hydrocarbon feedstock into higher hydrocarbons according to another embodiment of the invention
  • FIG. 3 is a schematic diagram of a continuous process for converting a hydrocarbon feedstock into methanol according to one embodiment of the invention, in which a membrane-type electrolytic cell is used to regenerate molecular bromine;
  • FIG. 4 is a schematic diagram of a continuous process for converting a hydrocarbon feedstock into methanol according to another embodiment of the invention, in which a diaphragm-type electrolytic cell is used to generate molecular bromine;
  • FIG. 5 is a schematic diagram of a continuous process for converting a hydrocarbon feedstock into higher hydrocarbons in which an oxygen-depolarized cathode is provided, according to one embodiment of the invention
  • FIG. 6 is a schematic illustration of an electrolytic cell according to one embodiment of the invention.
  • FIG. 7 is a schematic illustration of a continuous process for converting coal into coke and hydrogen, according to one embodiment of the invention.
  • FIG. 8 is a schematic illustration of a process for converting coal or biomass into polyols and hydrogen, according to one embodiment of the invention.
  • FIG. 9 is a chart illustrating product selectivity for bromination of methane according to one embodiment of the invention.
  • FIG. 10 is a chart illustrating product selectivity for coupling of methyl bromide according to one embodiment of the invention.
  • FIG. 11 is a chart illustrating product selectivity for coupling of methyl bromide according to another embodiment of the invention.
  • the present invention provides a chemical process for converting hydrocarbon feedstocks into higher value products, such as fuel-grade hydrocarbons, methanol, aromatics, amines, coke, and polyols, using molecular halogen to activate C—H bonds in the feedstock and electrolysis to convert hydrohalic acid (hydrogen halide) or halide salts (e.g., sodium bromide) formed in the process back into molecular halogen.
  • hydrohalic acid hydrogen halide
  • halide salts e.g., sodium bromide
  • hydrocarbon feedstocks appropriate for use in the present invention include alkanes, e.g., methane, ethane, propane, and even larger alkanes; olefins; natural gas and other mixtures of hydrocarbons; biomass-derived hydrocarbons; and coal.
  • light-ends typically a mixture of C 1 -C 3 hydrocarbons, which can be used with or without added methane as the hydrocarbon feedstock.
  • feedstock With the exception of coal, in most cases the feedstock will be primarily aliphatic in nature.
  • the hydrocarbon feedstock is converted into higher products by reaction with molecular halogen, as described below.
  • Bromine (Br 2 ) and chlorine (Cl 2 ) are preferred, with bromine being most preferred, in part because the over potential required to convert Br ⁇ to Br 2 is significantly lower than that required to convert Cl ⁇ to Cl 2 (1.09V for Br ⁇ vs. 1.36V for Cl ⁇ ).
  • fluorine and iodine can be used, though not necessarily with equivalent results.
  • higher hydrocarbons refers to hydrocarbons having a greater number of carbon atoms than one or more components of the hydrocarbon feedstock, as well as olefinic hydrocarbons having the same or a greater number of carbon atoms as one or more components of the hydrocarbon feedstock.
  • the feedstock is natural gas—typically a mixture of light hydrocarbons, predominantly methane, with lesser amounts of ethane, propane and butane, and even smaller amounts of longer chain hydrocarbon such as pentane, hexane, etc.—the “higher hydrocarbon(s)” produced according to the invention can include a C 2 or higher hydrocarbon, such as ethane, propane, butane, C 5 + hydrocarbons, aromatic hydrocarbons, etc., and optionally ethylene, propylene and/or longer olefins.
  • natural gas typically a mixture of light hydrocarbons, predominantly methane, with lesser amounts of ethane, propane and butane, and even smaller amounts of longer chain hydrocarbon such as pentane, hexane, etc.
  • the “higher hydrocarbon(s)” produced according to the invention can include a C 2 or higher hydrocarbon, such as ethane, propane, butane, C 5 + hydrocarbons, aromatic hydrocarbons, etc., and optionally
  • LHCs light hydrocarbons
  • Fuel grade hydrocarbons typically have 5 or more carbons and are liquids at room temperature.
  • alkyl halides includes one or more alkyl halides, which can be the same (e.g., 100% methyl bromide) or different (e.g., methyl bromide and dibromomethane); “higher hydrocarbons” includes one or more higher hydrocarbons, which can be the same (e.g., 100% octane) or different (e.g., hexane, pentane, and octane).
  • FIGS. 1-5 are schematic flow diagrams generally depicting different embodiments of the invention, in which a hydrocarbon feedstock is allowed to react with molecular halogen (e.g., bromine) and converted into one or more higher value products.
  • molecular halogen e.g., bromine
  • FIG. 1 one embodiment of a process for making higher hydrocarbons from natural gas, methane, or other light hydrocarbons is depicted.
  • the feedstock (e.g., natural gas) and molecular bromine are carried by separate lines 1 , 2 into a bromination reactor 3 and allowed to react.
  • Products HBr, alkyl bromides, optionally olefins
  • unreacted hydrocarbons exit the reactor and are carried by a line 4 into a carbon-carbon coupling reactor 5 .
  • the alkyl bromides are first routed to a separation unit (not shown), where monobrominated hydrocarbons and HBr are separated from polybrominated hydrocarbons, with the latter being carried back to the bromination reactor to undergo “reproportionation” with methane and/or other light hydrocarbons, as described in the '358 application.
  • HBr, higher hydrocarbons, and (possibly) unreacted hydrocarbons and alkyl bromides exit the coupling reactor and are carried by a line 6 to a hydrogen bromide absorption unit 7 , where hydrocarbon products are separated from HBr via absorption, distillation, and/or some other suitable separation technique.
  • Hydrocarbon products are carried away by a line 8 to a product recovery unit 9 , which separates the higher hydrocarbon products from any residual natural gas or other gaseous species, which can be vented through a line 10 or, in the case of natural gas or lower alkanes, recycled and carried back to the bromination reactor.
  • combustible species can be routed to a power generation unit and used to generate heat and/or electricity for the system.
  • Aqueous sodium hydroxide or other alkali is carried by a line 11 into the HBr absorption unit, where it neutralizes the HBr, and forms aqueous sodium bromide.
  • the aqueous sodium bromide and minor amounts of hydrocarbon products and other organic species are carried by a line 12 to a separation unit 13 , which operates via distillation, liquid-liquid extraction, flash vaporization, or some other suitable method to separate the organic components from the sodium bromide.
  • the organics are either routed away from the system to a separate product cleanup unit or, in the embodiment shown, returned to the HBr absorption unit 7 through a line 14 and ultimately exit the system via line 8 .
  • Aqueous sodium bromide is carried from the NaBr-organics separation unit 13 by a line 15 to an electrolytic cell 16 , having an anode 17 , and a cathode 18 .
  • An inlet line 19 is provided for the addition of water, additional electrolyte, and/or acid or alkali for pH control.
  • a series of electrolytic cells rather than a single cell, is used as an electrolyzer.
  • several series of cells can be connected in parallel.
  • Nonlimiting examples of electrolytic cells include diaphragm, membrane, and mercury cell, which can be mono-polar or di-polar. The exact material flows with respect to make-up water, electrolyte, and other process features will vary with the type of cell used.
  • Aqueous sodium bromide is electrolyzed in the electrolytic cell(s), with bromide ion being oxidized at the anode (2Br ⁇ ⁇ Br 2 +2e ⁇ ) and water being reduced at the cathode (2H 2 O+2e ⁇ ⁇ H 2 +2OH ⁇ ).
  • Aqueous sodium hydroxide is removed from the electrolyzer and routed to the HBr absorption unit via line 11 .
  • Bromine and hydrogen produced in the electrolyzer are recovered, with bromine being recycled and used again in the process. Specifically, wet bromine is carried by a line 20 to a dryer 21 , and dry bromine is carried by a line 22 to a heater 23 , and then by line 2 back into the bromination reactor 3 . In instances where the amount of water associated with the bromine is tolerable in bromination and coupling, the dryer may be eliminated.
  • Hydrogen produced at the anode of the electrolytic cell can be off-gassed or, more preferably, collected, compressed, and routed through a line 24 to a power generation unit, such as a fuel cell or hydrogen turbine. Alternatively, hydrogen produced can be recovered for sale or other use.
  • the electrical power that is generated can be used to power various pieces of equipment employed in the continuous process, including the electrolytic cells.
  • Exemplary and preferred conditions for bromination, C—C coupling, reproportionation, product separation, HBr clean-up, and corrosion-resistant materials are provided in the '358 application at ⁇ 39-42 (bromination), 43-50 (reproportionation), 61-65 (C—C coupling), 66-75 (product separation), 82-86 (HBr clean-up and halogen recovery), and 87-90 (corrosion-resistant materials), which paragraphs are incorporated herein in their entirety.
  • Anodes, cathodes, electrolytes, and other features of the electrolytic cell(s) are selected based on a number of factors understood by the skilled person, such as throughput, current power levels, and the chemistry of the electrolysis reaction(s).
  • Nonlimiting examples are found in U.S. Pat. Nos. 4,110,180 (Nidola et al.) and 6,368,490 (Gestermann); Y. Shimizu, N. Miura, N. Yamazoe, Gas - Phase Electrolysis of Hydrocarbonic Acid Using PTFE - Bonded Electrode , Int. J. Hydrogen Energy, Vol. 13, No. 6, 345-349 (1988); D. van Velzen, H. Langenkamp, A. Moryoussef, P.
  • methane is introduced into a plug flow reactor made of the alloy ALCOR, at a rate of 1 mole/second, and molecular bromine is introduced at a rate of 0.50 moles/second with a total residence time of a 60 seconds at 425° C.
  • the major hydrocarbon products include methyl bromide (85%) and dibromomethane (14%), and 0.50 moles/s of HBr is produced.
  • the methane conversion is 46%.
  • the products are carried by a line 4 into a coupling reactor 5 , which is a packed bed reactor containing a transition metal (e.g., Mn) ion-exchanged alumina-supported ZSM5 zeolite coupling catalyst at 425° C.
  • a coupling reactor 5 a packed bed reactor containing a transition metal (e.g., Mn) ion-exchanged alumina-supported ZSM5 zeolite coupling catalyst at 425° C.
  • a distribution of higher hydrocarbons is formed, as determined by the space time of the reactor. In this example, 10 seconds is preferred to produce products that are in the gasoline range.
  • HBr, higher hydrocarbons, and (trace) unreacted alkyl bromides exit the coupling reactor and are carried by a line 6 to a hydrogen bromide separation unit 7 , where HBr is partially separated by distillation.
  • Aqueous sodium hydroxide is introduced and allowed to react at 150° C., forming sodium bromide and alcohols from the HBr and unreacted alkyl bromides.
  • the aqueous and organic species are carried by a line 12 to a separation unit 13 , which operates via distillation to separate the organic components from the sodium bromide.
  • Aqueous sodium bromide is carried from the NaBr-organics separation unit 13 by line 15 to an electrolytic cell 16 , having an anode 17 , and a cathode 18 .
  • An inlet line 19 is provided for the addition of water, additional electrolyte, and the pH adjusted to be less then 2 by addition of acid. Electrolysis is performed in a membrane cell type.
  • Aqueous sodium bromide is electrolyzed in the electrolytic cell, with bromide ion being oxidized at the anode (2Br ⁇ ⁇ Br 2 +2e ⁇ ) and water being reduced at the cathode (2H 2 O+2e ⁇ ⁇ H 2 +2OH ⁇ ).
  • Aqueous sodium hydroxide is removed from the electrolyzer and routed to the HBr absorption unit via line 11 . Bromine and hydrogen are produced in the electrolyzer.
  • FIG. 2 an alternate embodiment for converting natural gas, methane, or other hydrocarbon feedstocks into higher hydrocarbons, such as fuel grade hydrocarbons and aromatic compounds, is depicted.
  • electrolysis takes place in a non-alkaline medium.
  • Products from the coupling reactor i.e., higher hydrocarbons and HBr
  • HBr absorption unit 7 where hydrocarbon products are separated from HBr.
  • rich aqueous HBr is carried by a line 15 to the electrolytic cell 16 .
  • Make-up water, electrolyte, or acid/base for pH control, if needed, is provided by a line 19 .
  • the aqueous HBr is electrolyzed, forming molecular bromine and hydrogen. As Br 2 is evolved and removed from the electrolyzer, the concentration of HBr in the electrolyzer drops.
  • the resulting lean aqueous HBr, along with some bromine (Br 2 ) entrained or dissolved therein, is carried by a line 25 to a bromine stripper 26 , which separates bromine (Br 2 ) from lean aqueous HBr via distillation or some other suitable separation operation.
  • the lean aqueous HBr is carried back to the HBr absorption unit by a line 27 .
  • Wet bromine is carried by a line 28 to the dryer 21 , where it is dried.
  • natural gas, methane, or another hydrocarbon feedstock is converted into higher hydrocarbons, and halogen (e.g., Br 2 ) is recovered by gas phase electrolysis of hydrogen halide (e.g., HBr).
  • halogen e.g., Br 2
  • gases from the coupling reactor i.e., higher hydrocarbons and HBr
  • HBr absorption unit where hydrocarbon products are separated from HBr.
  • gaseous HBr is carried by a line to the electrolytic cell.
  • the gaseous HBr is electrolyzed, forming molecular bromine and hydrogen. Wet bromine is carried by a line to the dryer, where it is dried.
  • the dryer can be eliminated.
  • FIG. 3 depicts one embodiment of another aspect of the invention, in which natural gas, methane, or another hydrocarbon feedstock is converted into methanol via the intermediate, methyl bromide.
  • Natural gas and gaseous bromine are carried by separate lines 201 and 202 into a bromination reactor 203 and allowed to react.
  • the products e.g., methyl bromide and HBr
  • the products are carried by a line 204 through a heat exchanger 205 , which lowers their temperature.
  • the gasses are further cooled by passing through a cooler 206 .
  • a portion of the gasses 206 are carried by a line 207 to an HBr absorber 208 .
  • the split proportions are determined by the acid/base disproportionation needed to achieve the proper pH in the reactor absorber.
  • Water optionally pre-treated in, e.g., a reverse osmosis unit 211 to minimize salt content, is provided to the methanol reactor 210 via line 212 .
  • a separate line 213 carries water to the HBr absorber 208 .
  • HBr solution formed in the HBr absorber 208 is sent via a line 214 to a stripper 215 (where organics are separated by stripping or other means) and then sent to the reactor/absorber 210 via a line 216 .
  • Gasses from the HBr absorber join the by-passed stream from the cooler 206 and are carried by a line 209 to the reactor/absorber 210 .
  • HBr solution from the stripper 215 is carried by a line 217 to an HBr holding tank 218 .
  • Aqueous sodium hydroxide (e.g., 5-30 wt %) is provided to the methanol reactor 210 by a line 219 .
  • a weak NaBr/water solution is also delivered to the methanol reactor 210 by a line 220 .
  • methyl bromide reacts with water in the presence of strong base (sodium hydroxide), and methanol is formed, along with possible byproducts such as formaldehyde or formic acid.
  • a liquid stream containing methanol, by-products, aqueous sodium bromide, and aqueous sodium hydroxide is carried away from the reactor via a line 221 , to a stripper 222 .
  • a portion of the bottom liquid from the reactor/absorber 210 is circulated via a line 223 through a cooler 224 to control temperature in the reactor/absorber 210 .
  • the stripper 222 is equipped with a reboiler 225 and, optionally, a partial reflux. Aqueous sodium bromide and sodium hydroxide are removed with most of the water as the “bottoms” stream of the stripper. The vapor exiting the top of the stripper is carried by a line 226 to another distillation unit 227 equipped with a reboiler 228 and a condenser 229 . In the distillation unit 227 , by-products are separated from methanol, and the methanol is removed from the distillation unit 227 via a line 230 , through a cooler 231 , to a storage tank 232 .
  • the vapor from the distillation unit 227 (which contains by-products) is carried via a line 233 through the condenser 229 and then through a line 234 to a by-product storage tank 235 .
  • methanol may be taken as a distillate while by-products are recovered as bottoms.
  • the effluent stream removed from the distillation unit 222 and reboiler 225 contains water and aqueous sodium bromide and sodium hydroxide. This is carried away from the distillation unit via a line 236 and cooled by passing through a cooler 237 before being delivered to a sodium bromide holding tank 238 . It is desirable to lower the pH of this salt solution. This is accomplished by metering the delivery of aqueous HBr from the hydrogen bromide holding tank 218 via a line 239 to a pH control device 240 coupled to the sodium bromide holding tank 238 .
  • aqueous sodium bromide is removed from the tank and carried via a line 241 through a filter 242 , and delivered to an electrolytic cell 243 , having an anode 244 and a cathode 245 .
  • the filter is provided to protect the membranes in the electrolytic cells.
  • a series of electrolytic cells rather than a single cell, is used as an electrolyzer.
  • Aqueous sodium bromide is electrolyzed in the electrolytic cell(s), with bromide ion being oxidized at the anode (2Br ⁇ ⁇ Br 2 +2e ⁇ ) and water being reduced at the cathode (2H 2 O+2e ⁇ ⁇ H 2 +2OH ⁇ ).
  • This results in the formation of sodium hydroxide which is carried away from the electrolyzer as an aqueous solution via line 246 to a holding tank 247 .
  • the sodium hydroxide solution is then routed to the methanol reactor 210 via a line 219 .
  • Molecular bromine is removed from the electrolyzer via a line 248 to a compressor 249 , and then to a dryer 250 .
  • the bromine is returned to the bromination reactor 203 by passing it through a heat exchanger 205 and, if necessary, a heater 251 .
  • Molecular bromine that is dissolved in the anolyte is also removed from the electrolytic cell(s) 243 by carrying the anolyte from the cell(s) via a line 252 to a stripper 253 , where bromine is removed by stripping with natural gas (supplied via a line 254 ) or by other means.
  • the molecular bromine is carried by a line 255 to the compressor 249 , dryer 250 , etc., before being returned to the bromination reactor as described above.
  • Hydrogen generated in the electrolyzer is removed by a line 256 , compressed in a compressor 257 and, optionally, routed to a power generation unit 258 .
  • Residual methane or other inert gasses can be removed from the methanol formation reactor via a line 259 .
  • the methane or natural gas can be routed to the power generation unit 258 to augment power generation. Additional natural gas or methane can be supplied to the unit via a line 260 if needed.
  • methane is reacted with gaseous bromine at 450° C. in a glass tube bromination reactor, with a space time is a 60 seconds.
  • the products are methyl bromide, HBr, and dibromomethane with a methane conversion of 75%.
  • the methyl bromide, HBr, and dibromomethane react with water in the presence of sodium hydroxide to form methanol and formaldehyde (from the dibromomethane). It is further demonstrated that the formaldehyde is disproportionated to methanol and formic acid. Hence, overall, the products are methanol and formic acid.
  • FIG. 3 employs membrane-type electrolytic cells, rather than diaphragm-type cells.
  • a membrane cell sodium ions with only a small amount of water flow to the cathode compartment.
  • both sodium ions and water proceed into the cathode compartment.
  • diaphragm cells are used, resulting in continuous depletion of the anolyte with respect to NaBr.
  • depleted anolyte is taken through a line 252 to a bromine stripper 253 where bromine is removed and carried to a compressor 249 and then a dryer 250 .
  • NaBr solution from the stripper 253 is carried by a line 270 to the NaBr holding tank 238 , where it combines with a richer NaBr solution.
  • Other features of the process are similar to those in FIG. 3 .
  • molecular halogen is recovered by electrolysis using a non-hydrogen producing cathode, i.e., an oxygen depolarized cathode, which significantly reduces the power consumption by producing water instead of hydrogen.
  • FIG. 5 depicts one embodiment of this aspect of the invention, in this case involving the production of higher hydrocarbons. The flow diagram is similar to that shown in FIG. 1 , with the differences noted below.
  • Bromine and natural gas, methane, or another light hydrocarbon are caused to react in a bromination reactor 303 , and followed by a coupling reactor 305 .
  • the organics and HBr are separated in an HBr absorption unit 307 .
  • Aqueous sodium bromide is carried via line 315 to an electrolytic cell 316 equipped with an anode 317 , oxygen depolarized cathode 318 , and an oxygen inlet manifold or line 324 .
  • additional water or electrolyte or pH control chemicals are carried into the cell via a line 319 .
  • Molecular bromine is generated at the anode (2Br ⁇ ⁇ Br 2 +2e ⁇ ), and the wet bromine is carried via a line 320 to a dryer 321 , through a heater 323 , and then routed back to the bromination reactor 303 .
  • oxygen is electrolytically reduced in the presence of water (1 ⁇ 2O 2 +H 2 O+2e ⁇ ⁇ 2OH ⁇ ), and hydroxyl ions are carried away as aqueous sodium hydroxide, via line 311 , to the HBr absorption unit 307 .
  • the invention also provides an improved electrolytic cell for converting halides into molecular halogen, one embodiment of which is shown in FIG. 6 .
  • the cell 400 includes a gas supply manifold 401 , through which oxygen gas, air, or oxygen-enriched air can be introduced; a gas diffusion cathode 402 , which is permeable to oxygen (or an oxygen-containing gas); a cation exchange membrane 403 ; a cathode electrolyte chamber 404 disposed between the cation exchange membrane and the gas diffusion cathode; an anode electrolyte chamber 405 ; and an anode 406 , extending into the anode electrolyte chamber.
  • anode and cathode can be connected to an electrical power supply (not shown), which may include equipment for converting AC to DC current (e.g. mechanical rectifier, motor-generator set, semiconductor rectifier, synchronous converter, etc.) and other components.
  • water is introduced into the cathode electrolyte chamber through the water inlet port 407 , and aqueous sodium bromide is introduced into the anode electrolyte chamber 405 through port 409 .
  • Oxygen flow through the gas supply manifold 401 is commenced and the power to the cell is turned on.
  • Sodium bromide is reduced at the anode, bromine gas is evolved and carried away by line 410 , and sodium ions are carried through the cation exchange membrane into the cathode electrolyte chamber.
  • oxygen is electrolytically reduced to hydroxyl ion in the presence of water.
  • Aqueous sodium hydroxide exits the cathode electrolyte chamber through port 408 .
  • the electrolytic cell described herein can be used in conjunction with various processes, including the embodiments presented above. It is particularly advantageous when power consumption is an issue, and where it is desirable not to form hydrogen (for example, where the risk of fire warrants extra precautions, such as on an offshore drilling rig).
  • a continuous process as described herein for making, e.g., higher hydrocarbons or methanol is carried out at an offshore oil rig or drilling platform, or at a facility located onshore in a remote location.
  • Part of the utility lies in the conversion of a difficult to transport material (e.g., natural gas) into a more easily transported liquid material, such as higher hydrocarbons or methanol.
  • Another utility resides in the use of the production facility's existing electrical generation capacity, such as an electrical generator or other power supply.
  • an improved production facility where oil or gas is pumped from a well and thereby extracted from the earth
  • the facility having an electrical generator or other electrical power supply
  • the improvement comprising: (a) forming alkyl halides by reacting molecular halogen with oil or gas pumped from the well, under process conditions sufficient to form alkyl halides and hydrogen halide; optionally with substantially complete consumption of the molecular halogen; (b) forming higher hydrocarbons and hydrogen halide by contacting the alkyl halides with a first catalyst under process conditions sufficient to form higher hydrocarbons and hydrogen halide; (c) separating the higher hydrocarbons from hydrogen halide; and (d) converting the hydrogen halide into hydrogen and molecular halogen electrolytically, using electricity provided by the electrical generator or electrical power supply, thereby allowing the halogen to be reused.
  • an improved production facility where oil or gas is pumped from a well and thereby extracted from the earth
  • the facility having an electrical generator or other electrical power supply
  • the improvement comprising: (a) forming alkyl halides by reacting molecular halogen with a hydrocarbon feedstock under process conditions sufficient to form alkyl halides and hydrogen halide, optionally with substantially complete consumption of the molecular halogen; (b) forming methanol and alkaline halide by contacting the alkyl halides with aqueous alkali under process conditions sufficient to form methanol and alkaline halide; (c) separating the methanol from the alkaline halide; (d) converting the alkaline halide into hydrogen, molecular halogen, and aqueous alkali electrolytically, using electricity provided by the electrical generator or electrical power supply, thereby allowing the halogen and the alkali to be reused.
  • the general approach described above including the steps of halogenation, product formation, product separation, and electrolytic regeneration of halogen is used to make alkyl amines.
  • natural gas, methane, or another aliphatic hydrocarbon feedstock is converted into alkyl amines via intermediate alkyl bromides.
  • the feedstock and gaseous bromine are carried by separate lines into a bromination reactor and allowed to react.
  • the bromination products e.g., methyl bromide and HBr
  • the alkyl bromides are then carried by a line to an amination reactor.
  • Ammonia or aqueous ammonia is also provided to the amination reactor by a separate line.
  • the alkyl bromide and ammonia are allowed to react under process conditions sufficient to form alkyl amines (e.g., RN 2 ) and sodium bromide, which are then separated in a manner analogous to that described above with respect to the production of methanol.
  • Aqueous sodium bromide is carried by a line to an electrolytic cell or cells, where it is converted into hydrogen and molecular bromine electrolytically, thereby allowing the bromine to be reused in the next cycle.
  • coal is converted to higher value coke, or coal or biomass is converted into higher value polyols (poly-alcohols), and the halogen used in the process is regenerated electrolytically.
  • crushed coal is allowed to react with molecular bromine at elevated temperature, forming coke, HBr, and brominated coal intermediates (“C x Br n ”).
  • the brominated coal intermediates are converted into coke by allowing them to contact a catalyst, thereby forming additional hydrogen bromide.
  • the coke and hydrogen bromide are then separated, and the hydrogen bromide is then carried by a line to an electrolytic cell or cells, similar to that described above, thereby allowing molecular bromine to be regenerated and reused.
  • FIG. 8 depicts a similar process in which coal or biomass-derived hydrocarbons are brominated, thereby forming alkyl bromines or alkyl bromides and HBr, which are then processed in a manner analogous to that described above, e.g., the alkyl bromides and HBr are at least partially separated and the alkyl bromides are allowed to react with alkali, (e.g., sodium hydroxide), thereby forming sodium bromide, water, and poly-alcohols (“C x H y-q (OH) q ”).
  • alkali e.g., sodium hydroxide
  • C x H y-q (OH) q poly-alcohols
  • Methane (11 sccm, 1.0 atm) was combined with nitrogen (15 sccm, 1.0 atm) at room temperature via a mixing tee and passed through an 18° C. bubbler full of bromine.
  • the CH 4 /N 2 /Br 2 mixture was passed into a preheated glass tube (inside diameter 2.29 cm, length, 30.48 cm, filled with glass beads) at 500° C., where bromination of methane took place with a residence time of 60 seconds, producing primarily bromomethane, dibromomethane and HBr:
  • Pellets of Mn ion exchanged ZSM-5 zeolite (CBV3024, 6 cm in length) were loaded in a tubular quartz reactor (ID, 1.0 cm), which was preheated to 425° C. before the reaction.
  • CH 3 Br diluted by N 2 , was pumped into the reactor at a flow rate of 18 ⁇ l/min for CH 3 Br, controlled by a micro liquid pump, and 7.8 ml/min for N 2 .
  • the CH 3 Br coupling reaction took place over the catalyst bed with a residence time of 5.0 sec and a CH 3 Br partial pressure of 0.5 based on this flow rate setting.
  • the reactor was placed in an ice-water bath for a start time to cool the products inside. After opening the reactor, the reaction liquid was transferred to a vessel and diluted by cold water. The vessel was connected with a gas bag used to collect the un-reacted bromomethane, if any. The reaction liquid was weighed and the product concentrations were analyzed with a GC-FID, in which an aqueous injection applicable capillary column was installed.
  • Examples 4 and 5 demonstrate that bromomethane can be completely hydrolyzed to methanol, and dibromomethane can be completely hydrolyzed to methanol and formic acid, under mild caustic conditions.
  • the results are summarized in Table 1.
  • molecular bromine can also be removed from the electrolytic cell(s) using a concurrent extraction technique, wherein an inert organic solvent, such as chloroform, carbon tetrachloride, ether, etc. is used.
  • an inert organic solvent such as chloroform, carbon tetrachloride, ether, etc.
  • the solvent is introduced on one side of a cell; bromine partitions between the aqueous and organic phases; and bromine-laden solvent is withdrawn from another side of the cell.
  • Bromine can then be separated from the solvent by distillation or another suitable technique and then returned to the system for reuse. Partitioning is favored by bromine's significantly enhanced solubility in solvents such as chloroform and carbon tetrachloride, as compared to water.
  • Extraction in this way serves a dual purpose: it separates Br 2 from other forms of bromine that may be present (e.g., Br ⁇ , OBr ⁇ , which are insoluble in the organic phase); and it allows bromine to be concentrated and easily separated from the organic phase (e.g., by distillation).
  • An optimal pH for extraction (as well as for separation of bromine by heating bromine-containing aqueous solutions in a gas flow) is pH 3.5—the pH at which the concentration of molecular bromine (Br 2 ) is at its highest, as compared to other bromine species.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US12/152,515 2007-05-14 2008-05-14 Process for converting hydrocarbon feedstocks with electrolytic recovery of halogen Abandoned US20080314758A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US12/152,515 US20080314758A1 (en) 2007-05-14 2008-05-14 Process for converting hydrocarbon feedstocks with electrolytic recovery of halogen

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US93022007P 2007-05-14 2007-05-14
US12/152,515 US20080314758A1 (en) 2007-05-14 2008-05-14 Process for converting hydrocarbon feedstocks with electrolytic recovery of halogen

Publications (1)

Publication Number Publication Date
US20080314758A1 true US20080314758A1 (en) 2008-12-25

Family

ID=40122241

Family Applications (1)

Application Number Title Priority Date Filing Date
US12/152,515 Abandoned US20080314758A1 (en) 2007-05-14 2008-05-14 Process for converting hydrocarbon feedstocks with electrolytic recovery of halogen

Country Status (19)

Country Link
US (1) US20080314758A1 (zh)
EP (1) EP2148942A4 (zh)
JP (1) JP2010527358A (zh)
KR (1) KR20100027135A (zh)
CN (1) CN101687725A (zh)
AP (1) AP2009005040A0 (zh)
AU (1) AU2008254937C1 (zh)
BR (1) BRPI0811606A2 (zh)
CA (1) CA2684765A1 (zh)
CO (1) CO6241174A2 (zh)
EA (2) EA017229B1 (zh)
EC (1) ECSP099732A (zh)
IN (1) IN2009DN07232A (zh)
MX (1) MX2009012353A (zh)
NO (1) NO20093337L (zh)
NZ (1) NZ580996A (zh)
TN (1) TN2009000480A1 (zh)
WO (1) WO2008143940A2 (zh)
ZA (1) ZA200907775B (zh)

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090069606A1 (en) * 2005-04-11 2009-03-12 Grt, Inc. Method of making alkoxylates
US20090308759A1 (en) * 2008-06-13 2009-12-17 Marathon Gtf Technology, Ltd. Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery
US20100087688A1 (en) * 2008-10-01 2010-04-08 Jorge Miller Process and catalyst for converting alkanes
WO2010124041A1 (en) * 2009-04-22 2010-10-28 Grt, Inc. Process for converting hydrocarbon feedstocks with electrolytic and photoelectrocatalytic recovery of halogens
WO2010132325A1 (en) * 2009-05-12 2010-11-18 Shell Oil Company An integrated process to produce hydrocarbons from natural gas containing carbon dioxide
US7838708B2 (en) 2001-06-20 2010-11-23 Grt, Inc. Hydrocarbon conversion process improvements
US7847139B2 (en) 2003-07-15 2010-12-07 Grt, Inc. Hydrocarbon synthesis
US7964764B2 (en) 2003-07-15 2011-06-21 Grt, Inc. Hydrocarbon synthesis
US7998438B2 (en) 2007-05-24 2011-08-16 Grt, Inc. Zone reactor incorporating reversible hydrogen halide capture and release
US8053616B2 (en) 2006-02-03 2011-11-08 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US8273929B2 (en) 2008-07-18 2012-09-25 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US20120313034A1 (en) * 2011-06-10 2012-12-13 Marathon Gtf Technology, Ltd. Processes and Systems for Demethanization of Brominated Hydrocarbons
US8444844B1 (en) 2012-07-26 2013-05-21 Liquid Light, Inc. Electrochemical co-production of a glycol and an alkene employing recycled halide
US8641885B2 (en) 2012-07-26 2014-02-04 Liquid Light, Inc. Multiphase electrochemical reduction of CO2
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
US8815050B2 (en) 2011-03-22 2014-08-26 Marathon Gtf Technology, Ltd. Processes and systems for drying liquid bromine
US8829256B2 (en) 2011-06-30 2014-09-09 Gtc Technology Us, Llc Processes and systems for fractionation of brominated hydrocarbons in the conversion of natural gas to liquid hydrocarbons
US8858777B2 (en) 2012-07-26 2014-10-14 Liquid Light, Inc. Process and high surface area electrodes for the electrochemical reduction of carbon dioxide
WO2014193957A1 (en) * 2013-05-30 2014-12-04 Reaction 35, Llc Recovery of halogens by partial condensation
US9085827B2 (en) 2012-07-26 2015-07-21 Liquid Light, Inc. Integrated process for producing carboxylic acids from carbon dioxide
US9133078B2 (en) 2010-03-02 2015-09-15 Gtc Technology Us, Llc Processes and systems for the staged synthesis of alkyl bromides
US9193641B2 (en) 2011-12-16 2015-11-24 Gtc Technology Us, Llc Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems
US9206093B2 (en) 2004-04-16 2015-12-08 Gtc Technology Us, Llc Process for converting gaseous alkanes to liquid hydrocarbons
WO2015195149A1 (en) * 2014-06-19 2015-12-23 Liquid Light, Inc Integrated process for co-production of carboxylic acids and halogen products from carbon dioxide
US9267212B2 (en) 2012-07-26 2016-02-23 Liquid Light, Inc. Method and system for production of oxalic acid and oxalic acid reduction products
US9702049B1 (en) * 2012-05-14 2017-07-11 Melahn L. Parker Biowaste treatment and recovery system
US9873951B2 (en) 2012-09-14 2018-01-23 Avantium Knowledge Centre B.V. High pressure electrochemical cell and process for the electrochemical reduction of carbon dioxide
US10329676B2 (en) 2012-07-26 2019-06-25 Avantium Knowledge Centre B.V. Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode
US11167242B1 (en) 2012-05-14 2021-11-09 Chemergy, Inc. Process for desulpherization and hydrogen recovery
CN115491697A (zh) * 2022-10-21 2022-12-20 上海科技大学 一种烃类原料高效转化的方法及其装置

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7696390B2 (en) * 2008-06-10 2010-04-13 Stauffer John E Methanol synthesis
WO2014138252A1 (en) * 2013-03-06 2014-09-12 Ceramatec, Inc. Method of producing coupled radical products via desulfoxylation
CN103556173B (zh) * 2013-10-21 2015-12-02 夏五湖 一种煤电化液化电解装置
CN103952717A (zh) * 2014-05-07 2014-07-30 北京化工大学 一种光电化学分解水与有机合成相互耦合的串联反应设计方法
KR102291922B1 (ko) 2015-04-28 2021-08-20 대우조선해양 주식회사 천연가스를 이용하여 중질탄화수소를 생산하는 flng 및 flng에서 천연가스를 이용하여 중질탄화수소를 생산하는 방법
CN109608329A (zh) * 2018-12-12 2019-04-12 浙江大学 一种低溴排放的对苯二甲酸生产方法
EP4126798A1 (en) 2020-03-30 2023-02-08 Totalenergies Onetech Gas to olefins processes with coproduction of hydrogen
WO2021198166A1 (en) 2020-03-30 2021-10-07 Total Se Gas to olefins process with coproduction of hydrogen together with heat integration process
CN115697947B (zh) * 2020-03-30 2023-11-21 道达尔能源一技术 联产碳的气体制氢工艺
WO2021198175A1 (en) 2020-03-30 2021-10-07 Total Se Gas to olefins process with coproduction of hydrogen together with electrified reactional section
CN111607442A (zh) * 2020-05-15 2020-09-01 重庆燃气集团股份有限公司 一种天然气储气调峰的综合能源利用体系及储气调峰方法
WO2021239811A1 (en) 2020-05-29 2021-12-02 Total Se Gas to methanol with coproduction of hydrogen
DE102020212022A1 (de) 2020-07-09 2022-01-13 Siemens Aktiengesellschaft Verfahren und Vorrichtung zur Herstellung von Kohlenmonoxid aus Kohlendioxid
WO2024023018A1 (en) * 2022-07-25 2024-02-01 Totalenergies Onetech Process for the production of dimethyl ether and hydrogen from methane using a solid metal oxide reagent

Citations (98)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2824891A (en) * 1955-11-07 1958-02-25 Universal Oil Prod Co Surface active agents derived from aromatic aldehyde intermediates
US3076784A (en) * 1957-01-25 1963-02-05 Bayer Ag Polyethers from aryl halides and organic diols
US3496242A (en) * 1967-08-30 1970-02-17 Fmc Corp Oxychlorination of mixed hydrocarbons
US3562321A (en) * 1961-10-10 1971-02-09 Sun Oil Co Preparation of oxygenated hydrocarbons
US3865886A (en) * 1973-06-20 1975-02-11 Lummus Co Production of allyl chloride
US4006169A (en) * 1976-02-26 1977-02-01 Smithkline Corporation Epoxidation of α,β-ethylenic ketones
US4071753A (en) * 1975-03-31 1978-01-31 Gte Laboratories Incorporated Transducer for converting acoustic energy directly into optical energy
US4072733A (en) * 1976-04-02 1978-02-07 Ethyl Corporation Conversion of methanol and dimethyl ether
US4133966A (en) * 1977-12-23 1979-01-09 Gulf Research & Development Company Selective formation of ethanol from methanol, hydrogen and carbon monoxide
US4133838A (en) * 1975-05-15 1979-01-09 Pearson Research Corp. Process for preparing hydrocarbons from methanol and phosphorus pentoxide
US4138440A (en) * 1974-08-14 1979-02-06 Mobil Oil Corporation Conversion of liquid alcohols and ethers with a fluid mass of ZSM-5 type catalyst
US4187255A (en) * 1978-08-21 1980-02-05 Conoco, Inc. Process for methylating naphthalene
US4191618A (en) * 1977-12-23 1980-03-04 General Electric Company Production of halogens in an electrolysis cell with catalytic electrodes bonded to an ion transporting membrane and an oxygen depolarized cathode
US4249031A (en) * 1979-04-12 1981-02-03 Shell Oil Company Process for the preparation of a hydrocarbon mixture
US4311865A (en) * 1979-04-04 1982-01-19 Mobil Oil Corporation Manufacture of hydrocarbons from oxygenates
US4371716A (en) * 1979-09-04 1983-02-01 Shell Oil Company β-(Sec-alkoxy) ethanol process
US4373109A (en) * 1981-08-05 1983-02-08 Olah George A Bifunctional acid-base catalyzed conversion of hetero-substituted methanes into olefins
US4431856A (en) * 1980-09-29 1984-02-14 Mobil Oil Corporation Fluid zeolite catalyst conversion of alcohols and oxygenated derivatives to hydrocarbons
US4433192A (en) * 1981-09-01 1984-02-21 Olah George A Condensation of natural gas or methane into gasoline range hydrocarbons
US4433189A (en) * 1982-03-18 1984-02-21 Mobil Oil Corporation Catalytic conversion of methanol to light olefins
US4492657A (en) * 1982-05-05 1985-01-08 Hoechst Aktiengesellschaft Imines of alkyl 4-halomethylbenzoates
US4496752A (en) * 1979-05-03 1985-01-29 The Lummus Company Production of epoxy compounds from olefinic compounds
US4497967A (en) * 1984-06-15 1985-02-05 The Halcon Sd Group, Inc. Process for the preparation of ethanol from methanol, carbon monoxide _and hydrogen
US4499314A (en) * 1982-03-31 1985-02-12 Imperial Chemical Industries Plc Methanol conversion to hydrocarbons with zeolites and cocatalysts
US4568660A (en) * 1982-01-25 1986-02-04 Hercules Incorporated Cycloolefin polymerization catalyst composition
US4634800A (en) * 1984-04-16 1987-01-06 Atlantic Richfield Company Methane conversion process
US4642403A (en) * 1984-11-16 1987-02-10 The British Petroleum Company P.L.C. Production of aromatics from ethane and/or ethylene
US4642404A (en) * 1984-01-23 1987-02-10 Mobil Oil Corporation Conversion of olefins and paraffins to higher hydrocarbons
US4720600A (en) * 1983-06-29 1988-01-19 Mobil Oil Corporation Production of middle distillate range hydrocarbons by light olefin upgrading
US4720602A (en) * 1986-09-08 1988-01-19 Mobil Oil Corporation Process for converting C2 to C12 aliphatics to aromatics over a zinc-activated zeolite
US4724275A (en) * 1985-07-01 1988-02-09 National Distillers And Chemical Corporation Crystalline aluminosilicates and their use in the conversion of methanol to low molecular weight hydrocarbons
US4795848A (en) * 1986-08-28 1989-01-03 The Standard Oil Company Method for upgrading a low molecular weight alkane with a lead-zirconate catalyst
US4795843A (en) * 1985-08-26 1989-01-03 Uop Inc. Conversion of methane into larger organic hydrocarbons
US4795732A (en) * 1985-07-25 1989-01-03 The British Petroleum Company P.L.C. Sulphided platinum group metal-silicalite dehydrogenation catalysts
US4795737A (en) * 1987-03-25 1989-01-03 Eastman Kodak Company Process for the iodination of aromatic compounds over solid catalysts
US4804797A (en) * 1987-08-24 1989-02-14 Gas Research Institute Production of commodity chemicals from natural gas by methane chlorination
US4804800A (en) * 1984-12-21 1989-02-14 Exxon Research & Engineering Co. Process for synthesizing a zeolite catalyst on a pH controlled basis to improve catalyst life
US4808763A (en) * 1987-08-05 1989-02-28 Amoco Corporation Process for upgrading light paraffins
US4891463A (en) * 1986-07-07 1990-01-02 Mobil Oil Corporation Aromatization of aliphatics over a zeolite containing framework gallium
US4895995A (en) * 1988-12-02 1990-01-23 Uop Process for the simultaneous hydroconversion of a first feedstock comprising unsaturated, halogenated organic compounds and a second feedstock comprising saturated, halogenated organic compounds
US4899001A (en) * 1988-11-21 1990-02-06 Uop Process for the simultaneous hydroconversion of a first feedstock comprising unsaturated, halogenated organic compounds and a second feedstock comprising saturated, halogenated organic compounds
US4899000A (en) * 1989-01-27 1990-02-06 Stauffer John E Production of allyl chloride
US4899002A (en) * 1988-07-25 1990-02-06 Mobil Oil Corp. Integrated staged conversion of methanol to gasoline and distillate
US4982041A (en) * 1990-01-10 1991-01-01 Union Carbide Chemicals And Plastics Company Inc. Double perovskite catalysts for oxidative coupling
US4982024A (en) * 1989-12-26 1991-01-01 Ethyl Corporation Process for the selective dehydrohalogenation of an admixture of alkylhalides
US4988660A (en) * 1990-06-25 1991-01-29 Union Carbide Chemicals And Plastics Company Inc. Double perovskite catalysts for oxidative coupling
US4990696A (en) * 1988-12-29 1991-02-05 Stauffer John E Methyl alcohol process
US4990711A (en) * 1988-06-23 1991-02-05 Mobil Oil Corporation Synthetic polyolefin lubricant blends having high viscosity indices
US5082816A (en) * 1986-08-28 1992-01-21 The Standard Oil Company Lead-zirconate catalysts
US5082473A (en) * 1990-07-23 1992-01-21 Keefer Bowie Extraction and concentration of a gas component
US5085674A (en) * 1990-10-25 1992-02-04 Union Carbide Industrial Gases Technology Corporation Duplex adsorption process
US5087786A (en) * 1990-04-25 1992-02-11 Amoco Corporation Halogen-assisted conversion of lower alkanes
US5087787A (en) * 1986-12-29 1992-02-11 Phillips Petroleum Company Method of oxidative conversion
US5087779A (en) * 1990-04-25 1992-02-11 Amoco Corporation Hydrocarbon halogenation
US5178748A (en) * 1988-12-22 1993-01-12 Imperial Chemical Industries Catalytic reactions using zeolites
US5185479A (en) * 1992-04-21 1993-02-09 Stauffer John E Process for methyl alcohol
US5188725A (en) * 1991-03-15 1993-02-23 Mobil Oil Corporation Fluidized catalyst process for production and etherification of olefins
US5276226A (en) * 1992-10-05 1994-01-04 Exxon Research & Engineering Company Low temperature halogenation of alkanes
US5276242A (en) * 1992-08-26 1994-01-04 Phillips Petroleum Company Alkylation process
US5276240A (en) * 1991-10-18 1994-01-04 Board Of Regents, The University Of Texas System Catalytic hydrodehalogenation of polyhalogenated hydrocarbons
US5284990A (en) * 1992-07-16 1994-02-08 Stratco, Inc. Method for converting a hydrogen fluoride alkylation unit to a sulfuric acid alkylation unit
US5382704A (en) * 1993-06-30 1995-01-17 E. I. Du Pont De Nemours And Company Fluorinated methyl ethers
US5382743A (en) * 1993-04-26 1995-01-17 Mobil Oil Corporation Skeletal isomerization of n-pentenes using ZSM-35 in the presence of hydrogen
US5382744A (en) * 1993-07-12 1995-01-17 Phillips Petroleum Company Control of synthetic isopentane production during alkylation of amylenes
US5385718A (en) * 1990-06-21 1995-01-31 Imperial Chemical Industries Plc Zeolites
US5385650A (en) * 1991-11-12 1995-01-31 Great Lakes Chemical Corporation Recovery of bromine and preparation of hypobromous acid from bromide solution
US5480629A (en) * 1993-08-09 1996-01-02 The Trustees Of Princeton University Catalytic production of hydrogen peroxide
US5486627A (en) * 1994-12-02 1996-01-23 The Dow Chemical Company Method for producing epoxides
US5489727A (en) * 1994-10-28 1996-02-06 Phillips Petroleum Company Isopentane disproportionation
US5489719A (en) * 1992-06-02 1996-02-06 Mobil Oil Corporation Process for the production of tertiary alkyl ether rich FCC gasoline
US5600043A (en) * 1995-03-27 1997-02-04 The Geon Company Oxychlorination process
US5600045A (en) * 1993-12-02 1997-02-04 The Dow Chemical Company Process for conversion of crude hydrocarbon mixtures
US5599381A (en) * 1993-03-08 1997-02-04 Whitlock; David R. Separation of solutes in gaseous solvents
US5705728A (en) * 1990-12-06 1998-01-06 Occidental Chemical Corporation Process for the production of ethylene and mixture containing ethylene
US5705712A (en) * 1995-10-05 1998-01-06 Uop Integrated process for producing diisopropyl ether, an isopropyl tertiary alkyl ether and isopropyl alcohol
US5705729A (en) * 1995-11-22 1998-01-06 Mobil Oil Corporation Isoparaffin-olefin alkylation process
US5708246A (en) * 1996-08-28 1998-01-13 Battelle Memorial Institute Method of photocatalytic conversion of C-H organics
US5720858A (en) * 1996-07-17 1998-02-24 The United States Of America As Represented By The United States Department Of Energy Method for the photocatalytic conversion of methane
US5866735A (en) * 1996-02-01 1999-02-02 Phillips Petroleum Company Hydrocarbon hydrogenation process
US6015867A (en) * 1994-09-28 2000-01-18 Showa Denko K.K. 3-alkoxypropionic ester derivative, olefin polymerization catalyst, and process for preparation of polyolefin
US6018088A (en) * 1997-05-07 2000-01-25 Olah; George A. Superacid catalyzed formylation-rearrangement of saturated hydrocarbons
US6022929A (en) * 1992-12-17 2000-02-08 Exxon Chemical Patents Inc. Amorphous olefin polymers, copolymers, methods of preparation and derivatives thereof
US6169218B1 (en) * 1992-02-10 2001-01-02 Catalytic Distillation Technologies Selective hydrogenation of highly unsaturated compounds in hydrocarbon streams
US6180841B1 (en) * 1994-10-20 2001-01-30 Evc Technology Ag Single stage fixed bed oxychlorination of ethylene
US6337063B1 (en) * 1998-11-02 2002-01-08 Institut Francais Du Petrole Process for preparing a zeolite with structure type EUO using structuring agent precursors and its use as an AC8 isomerisation catalyst
US6342200B1 (en) * 1998-11-02 2002-01-29 Institut Francais Du Petrole Process for preparing a zeolite with structure type EUO
US20030004380A1 (en) * 2000-11-29 2003-01-02 Helmut Grumann Method for producing 1,2-dichloroethane
US6509485B2 (en) * 2001-02-22 2003-01-21 Sri International Preparation of epoxides from alkanes using lanthanide-promoted silver catalysts
US6511526B2 (en) * 2001-01-12 2003-01-28 Vbox, Incorporated Pressure swing adsorption gas separation method and apparatus
US6672572B2 (en) * 2000-09-11 2004-01-06 L'air Liquide - Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude Packed column for exchanging heat and/or mass
US20040006246A1 (en) * 2001-06-20 2004-01-08 Sherman Jeffrey H. Method and apparatus for synthesizing olefins, alcohols, ethers, and aldehydes
US6680415B1 (en) * 1999-11-22 2004-01-20 Dow Global Technologies Inc. Oxyhalogenation process using catalyst having porous rare earth halide support
US6679986B1 (en) * 1999-05-18 2004-01-20 Total Raffinage Distribution S.A. Catalytic support with an oxide base from a metal belonging to the SVI group of the periodic table, its preparation and its uses
US6838576B1 (en) * 2003-10-23 2005-01-04 3M Innovative Properties Company Process for preparing functional group-containing olefinic compounds
US6841063B2 (en) * 2000-05-31 2005-01-11 Chevron U.S.A. Inc. Hydrocarbon conversion using zeolite SSZ-53
US6984763B2 (en) * 2001-05-23 2006-01-10 Dow Global Technologies Inc. Oxidative halogenation and optional dehydrogenation of c3+hydrocarbons
US20070004955A1 (en) * 2003-09-03 2007-01-04 Richard Kay Process for preparing branched chain hydrocarbons
US7169730B2 (en) * 1999-01-12 2007-01-30 Hyperion Catalysis International, Inc. Modified carbide and oxycarbide containing catalysts and methods of making and using thereof

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4333805A (en) * 1980-05-02 1982-06-08 General Electric Company Halogen evolution with improved anode catalyst
US4732660A (en) * 1985-09-09 1988-03-22 The Dow Chemical Company Membrane electrolyzer
US5068478A (en) * 1990-05-25 1991-11-26 Energia Andina, Ltd. Producing alkenes and alkynes from alkanes and alkenes
CA2219922A1 (en) * 1995-05-01 1996-11-07 E. I. Du Pont De Nemours And Company Electrochemical conversion of anhydrous hydrogen halide to halogen gas using a cation-transporting membrane
JPH0977707A (ja) * 1995-09-13 1997-03-25 Hironori Ishikawa 水熱法によるメタノール等の燃料用アルコール類の合成法
IN192223B (zh) * 1995-12-28 2004-03-20 Du Pont
DE19755636A1 (de) * 1997-12-15 1999-06-17 Bayer Ag Verfahren zur elektrochemischen Aufarbeitung von HCl-Gas zu hochreinem Chlor
US5998679A (en) * 1998-05-20 1999-12-07 Jlm Technology, Ltd. Methods for converting lower alkanes and alkanes to alcohols and diols
IT1317753B1 (it) * 2000-02-02 2003-07-15 Nora S P A Ora De Nora Impiant Cella di elettrolisi con elettrodo a diffusione di gas.
US6685821B2 (en) * 2001-08-29 2004-02-03 Giner Electrochemical Systems, Llc Method and system for producing high-pressure hydrogen
JP2007525477A (ja) * 2003-07-15 2007-09-06 ジーアールティー インコーポレイテッド 炭化水素の合成
US7244867B2 (en) * 2004-04-16 2007-07-17 Marathon Oil Company Process for converting gaseous alkanes to liquid hydrocarbons
US20060100469A1 (en) * 2004-04-16 2006-05-11 Waycuilis John J Process for converting gaseous alkanes to olefins and liquid hydrocarbons
AU2005237458B2 (en) * 2004-04-16 2011-10-13 Gtc Technology Us, Llc Process for converting gaseous alkanes to liquid hydrocarbons
CN101817720A (zh) * 2006-02-03 2010-09-01 Grt公司 天然气转化为液体烃的连续方法

Patent Citations (100)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2824891A (en) * 1955-11-07 1958-02-25 Universal Oil Prod Co Surface active agents derived from aromatic aldehyde intermediates
US3076784A (en) * 1957-01-25 1963-02-05 Bayer Ag Polyethers from aryl halides and organic diols
US3562321A (en) * 1961-10-10 1971-02-09 Sun Oil Co Preparation of oxygenated hydrocarbons
US3496242A (en) * 1967-08-30 1970-02-17 Fmc Corp Oxychlorination of mixed hydrocarbons
US3865886A (en) * 1973-06-20 1975-02-11 Lummus Co Production of allyl chloride
US4138440A (en) * 1974-08-14 1979-02-06 Mobil Oil Corporation Conversion of liquid alcohols and ethers with a fluid mass of ZSM-5 type catalyst
US4071753A (en) * 1975-03-31 1978-01-31 Gte Laboratories Incorporated Transducer for converting acoustic energy directly into optical energy
US4133838A (en) * 1975-05-15 1979-01-09 Pearson Research Corp. Process for preparing hydrocarbons from methanol and phosphorus pentoxide
US4006169A (en) * 1976-02-26 1977-02-01 Smithkline Corporation Epoxidation of α,β-ethylenic ketones
US4072733A (en) * 1976-04-02 1978-02-07 Ethyl Corporation Conversion of methanol and dimethyl ether
US4133966A (en) * 1977-12-23 1979-01-09 Gulf Research & Development Company Selective formation of ethanol from methanol, hydrogen and carbon monoxide
US4191618A (en) * 1977-12-23 1980-03-04 General Electric Company Production of halogens in an electrolysis cell with catalytic electrodes bonded to an ion transporting membrane and an oxygen depolarized cathode
US4187255A (en) * 1978-08-21 1980-02-05 Conoco, Inc. Process for methylating naphthalene
US4311865A (en) * 1979-04-04 1982-01-19 Mobil Oil Corporation Manufacture of hydrocarbons from oxygenates
US4249031A (en) * 1979-04-12 1981-02-03 Shell Oil Company Process for the preparation of a hydrocarbon mixture
US4496752A (en) * 1979-05-03 1985-01-29 The Lummus Company Production of epoxy compounds from olefinic compounds
US4371716A (en) * 1979-09-04 1983-02-01 Shell Oil Company β-(Sec-alkoxy) ethanol process
US4431856A (en) * 1980-09-29 1984-02-14 Mobil Oil Corporation Fluid zeolite catalyst conversion of alcohols and oxygenated derivatives to hydrocarbons
US4373109A (en) * 1981-08-05 1983-02-08 Olah George A Bifunctional acid-base catalyzed conversion of hetero-substituted methanes into olefins
US4433192A (en) * 1981-09-01 1984-02-21 Olah George A Condensation of natural gas or methane into gasoline range hydrocarbons
US4568660A (en) * 1982-01-25 1986-02-04 Hercules Incorporated Cycloolefin polymerization catalyst composition
US4433189A (en) * 1982-03-18 1984-02-21 Mobil Oil Corporation Catalytic conversion of methanol to light olefins
US4499314A (en) * 1982-03-31 1985-02-12 Imperial Chemical Industries Plc Methanol conversion to hydrocarbons with zeolites and cocatalysts
US4492657A (en) * 1982-05-05 1985-01-08 Hoechst Aktiengesellschaft Imines of alkyl 4-halomethylbenzoates
US4720600A (en) * 1983-06-29 1988-01-19 Mobil Oil Corporation Production of middle distillate range hydrocarbons by light olefin upgrading
US4642404A (en) * 1984-01-23 1987-02-10 Mobil Oil Corporation Conversion of olefins and paraffins to higher hydrocarbons
US4634800A (en) * 1984-04-16 1987-01-06 Atlantic Richfield Company Methane conversion process
US4497967A (en) * 1984-06-15 1985-02-05 The Halcon Sd Group, Inc. Process for the preparation of ethanol from methanol, carbon monoxide _and hydrogen
US4642403A (en) * 1984-11-16 1987-02-10 The British Petroleum Company P.L.C. Production of aromatics from ethane and/or ethylene
US4804800A (en) * 1984-12-21 1989-02-14 Exxon Research & Engineering Co. Process for synthesizing a zeolite catalyst on a pH controlled basis to improve catalyst life
US4724275A (en) * 1985-07-01 1988-02-09 National Distillers And Chemical Corporation Crystalline aluminosilicates and their use in the conversion of methanol to low molecular weight hydrocarbons
US4795732A (en) * 1985-07-25 1989-01-03 The British Petroleum Company P.L.C. Sulphided platinum group metal-silicalite dehydrogenation catalysts
US4795843A (en) * 1985-08-26 1989-01-03 Uop Inc. Conversion of methane into larger organic hydrocarbons
US4891463A (en) * 1986-07-07 1990-01-02 Mobil Oil Corporation Aromatization of aliphatics over a zeolite containing framework gallium
US4795848A (en) * 1986-08-28 1989-01-03 The Standard Oil Company Method for upgrading a low molecular weight alkane with a lead-zirconate catalyst
US5082816A (en) * 1986-08-28 1992-01-21 The Standard Oil Company Lead-zirconate catalysts
US4720602A (en) * 1986-09-08 1988-01-19 Mobil Oil Corporation Process for converting C2 to C12 aliphatics to aromatics over a zinc-activated zeolite
US5087787A (en) * 1986-12-29 1992-02-11 Phillips Petroleum Company Method of oxidative conversion
US4795737A (en) * 1987-03-25 1989-01-03 Eastman Kodak Company Process for the iodination of aromatic compounds over solid catalysts
US4808763A (en) * 1987-08-05 1989-02-28 Amoco Corporation Process for upgrading light paraffins
US4804797A (en) * 1987-08-24 1989-02-14 Gas Research Institute Production of commodity chemicals from natural gas by methane chlorination
US4990711A (en) * 1988-06-23 1991-02-05 Mobil Oil Corporation Synthetic polyolefin lubricant blends having high viscosity indices
US4899002A (en) * 1988-07-25 1990-02-06 Mobil Oil Corp. Integrated staged conversion of methanol to gasoline and distillate
US4899001A (en) * 1988-11-21 1990-02-06 Uop Process for the simultaneous hydroconversion of a first feedstock comprising unsaturated, halogenated organic compounds and a second feedstock comprising saturated, halogenated organic compounds
US4902842A (en) * 1988-12-02 1990-02-20 Uop Process for the simultaneous hydroconversion of a first feedstock comprising unsaturated, halogenated organic compounds and a second feedstock comprising saturated, halogenated organic compounds
US4895995A (en) * 1988-12-02 1990-01-23 Uop Process for the simultaneous hydroconversion of a first feedstock comprising unsaturated, halogenated organic compounds and a second feedstock comprising saturated, halogenated organic compounds
US5178748A (en) * 1988-12-22 1993-01-12 Imperial Chemical Industries Catalytic reactions using zeolites
US4990696A (en) * 1988-12-29 1991-02-05 Stauffer John E Methyl alcohol process
US4899000A (en) * 1989-01-27 1990-02-06 Stauffer John E Production of allyl chloride
US4982024A (en) * 1989-12-26 1991-01-01 Ethyl Corporation Process for the selective dehydrohalogenation of an admixture of alkylhalides
US4982041A (en) * 1990-01-10 1991-01-01 Union Carbide Chemicals And Plastics Company Inc. Double perovskite catalysts for oxidative coupling
US5087786A (en) * 1990-04-25 1992-02-11 Amoco Corporation Halogen-assisted conversion of lower alkanes
US5087779A (en) * 1990-04-25 1992-02-11 Amoco Corporation Hydrocarbon halogenation
US5385718A (en) * 1990-06-21 1995-01-31 Imperial Chemical Industries Plc Zeolites
US4988660A (en) * 1990-06-25 1991-01-29 Union Carbide Chemicals And Plastics Company Inc. Double perovskite catalysts for oxidative coupling
US5082473A (en) * 1990-07-23 1992-01-21 Keefer Bowie Extraction and concentration of a gas component
US5085674A (en) * 1990-10-25 1992-02-04 Union Carbide Industrial Gases Technology Corporation Duplex adsorption process
US5705728A (en) * 1990-12-06 1998-01-06 Occidental Chemical Corporation Process for the production of ethylene and mixture containing ethylene
US5188725A (en) * 1991-03-15 1993-02-23 Mobil Oil Corporation Fluidized catalyst process for production and etherification of olefins
US5276240A (en) * 1991-10-18 1994-01-04 Board Of Regents, The University Of Texas System Catalytic hydrodehalogenation of polyhalogenated hydrocarbons
US5385650A (en) * 1991-11-12 1995-01-31 Great Lakes Chemical Corporation Recovery of bromine and preparation of hypobromous acid from bromide solution
US6169218B1 (en) * 1992-02-10 2001-01-02 Catalytic Distillation Technologies Selective hydrogenation of highly unsaturated compounds in hydrocarbon streams
US5185479A (en) * 1992-04-21 1993-02-09 Stauffer John E Process for methyl alcohol
US5489719A (en) * 1992-06-02 1996-02-06 Mobil Oil Corporation Process for the production of tertiary alkyl ether rich FCC gasoline
US5284990A (en) * 1992-07-16 1994-02-08 Stratco, Inc. Method for converting a hydrogen fluoride alkylation unit to a sulfuric acid alkylation unit
US5276242A (en) * 1992-08-26 1994-01-04 Phillips Petroleum Company Alkylation process
US5276226A (en) * 1992-10-05 1994-01-04 Exxon Research & Engineering Company Low temperature halogenation of alkanes
US6022929A (en) * 1992-12-17 2000-02-08 Exxon Chemical Patents Inc. Amorphous olefin polymers, copolymers, methods of preparation and derivatives thereof
US5599381A (en) * 1993-03-08 1997-02-04 Whitlock; David R. Separation of solutes in gaseous solvents
US5382743A (en) * 1993-04-26 1995-01-17 Mobil Oil Corporation Skeletal isomerization of n-pentenes using ZSM-35 in the presence of hydrogen
US5382704A (en) * 1993-06-30 1995-01-17 E. I. Du Pont De Nemours And Company Fluorinated methyl ethers
US5382744A (en) * 1993-07-12 1995-01-17 Phillips Petroleum Company Control of synthetic isopentane production during alkylation of amylenes
US5480629A (en) * 1993-08-09 1996-01-02 The Trustees Of Princeton University Catalytic production of hydrogen peroxide
US5600045A (en) * 1993-12-02 1997-02-04 The Dow Chemical Company Process for conversion of crude hydrocarbon mixtures
US6015867A (en) * 1994-09-28 2000-01-18 Showa Denko K.K. 3-alkoxypropionic ester derivative, olefin polymerization catalyst, and process for preparation of polyolefin
US6180841B1 (en) * 1994-10-20 2001-01-30 Evc Technology Ag Single stage fixed bed oxychlorination of ethylene
US5489727A (en) * 1994-10-28 1996-02-06 Phillips Petroleum Company Isopentane disproportionation
US5486627A (en) * 1994-12-02 1996-01-23 The Dow Chemical Company Method for producing epoxides
US5600043A (en) * 1995-03-27 1997-02-04 The Geon Company Oxychlorination process
US5705712A (en) * 1995-10-05 1998-01-06 Uop Integrated process for producing diisopropyl ether, an isopropyl tertiary alkyl ether and isopropyl alcohol
US5705729A (en) * 1995-11-22 1998-01-06 Mobil Oil Corporation Isoparaffin-olefin alkylation process
US5866735A (en) * 1996-02-01 1999-02-02 Phillips Petroleum Company Hydrocarbon hydrogenation process
US5720858A (en) * 1996-07-17 1998-02-24 The United States Of America As Represented By The United States Department Of Energy Method for the photocatalytic conversion of methane
US5708246A (en) * 1996-08-28 1998-01-13 Battelle Memorial Institute Method of photocatalytic conversion of C-H organics
US6018088A (en) * 1997-05-07 2000-01-25 Olah; George A. Superacid catalyzed formylation-rearrangement of saturated hydrocarbons
US6337063B1 (en) * 1998-11-02 2002-01-08 Institut Francais Du Petrole Process for preparing a zeolite with structure type EUO using structuring agent precursors and its use as an AC8 isomerisation catalyst
US6342200B1 (en) * 1998-11-02 2002-01-29 Institut Francais Du Petrole Process for preparing a zeolite with structure type EUO
US7169730B2 (en) * 1999-01-12 2007-01-30 Hyperion Catalysis International, Inc. Modified carbide and oxycarbide containing catalysts and methods of making and using thereof
US6679986B1 (en) * 1999-05-18 2004-01-20 Total Raffinage Distribution S.A. Catalytic support with an oxide base from a metal belonging to the SVI group of the periodic table, its preparation and its uses
US6680415B1 (en) * 1999-11-22 2004-01-20 Dow Global Technologies Inc. Oxyhalogenation process using catalyst having porous rare earth halide support
US6841063B2 (en) * 2000-05-31 2005-01-11 Chevron U.S.A. Inc. Hydrocarbon conversion using zeolite SSZ-53
US6672572B2 (en) * 2000-09-11 2004-01-06 L'air Liquide - Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude Packed column for exchanging heat and/or mass
US20030004380A1 (en) * 2000-11-29 2003-01-02 Helmut Grumann Method for producing 1,2-dichloroethane
US6511526B2 (en) * 2001-01-12 2003-01-28 Vbox, Incorporated Pressure swing adsorption gas separation method and apparatus
US6509485B2 (en) * 2001-02-22 2003-01-21 Sri International Preparation of epoxides from alkanes using lanthanide-promoted silver catalysts
US6984763B2 (en) * 2001-05-23 2006-01-10 Dow Global Technologies Inc. Oxidative halogenation and optional dehydrogenation of c3+hydrocarbons
US20040006246A1 (en) * 2001-06-20 2004-01-08 Sherman Jeffrey H. Method and apparatus for synthesizing olefins, alcohols, ethers, and aldehydes
US7161050B2 (en) * 2001-06-20 2007-01-09 Grt, Inc. Method and apparatus for synthesizing olefins, alcohols, ethers, and aldehydes
US20070004955A1 (en) * 2003-09-03 2007-01-04 Richard Kay Process for preparing branched chain hydrocarbons
US6838576B1 (en) * 2003-10-23 2005-01-04 3M Innovative Properties Company Process for preparing functional group-containing olefinic compounds

Cited By (56)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7838708B2 (en) 2001-06-20 2010-11-23 Grt, Inc. Hydrocarbon conversion process improvements
US8415512B2 (en) 2001-06-20 2013-04-09 Grt, Inc. Hydrocarbon conversion process improvements
US7964764B2 (en) 2003-07-15 2011-06-21 Grt, Inc. Hydrocarbon synthesis
US7847139B2 (en) 2003-07-15 2010-12-07 Grt, Inc. Hydrocarbon synthesis
US8642822B2 (en) 2004-04-16 2014-02-04 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor
US9206093B2 (en) 2004-04-16 2015-12-08 Gtc Technology Us, Llc Process for converting gaseous alkanes to liquid hydrocarbons
US20090069606A1 (en) * 2005-04-11 2009-03-12 Grt, Inc. Method of making alkoxylates
US8053616B2 (en) 2006-02-03 2011-11-08 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US8449849B2 (en) 2006-02-03 2013-05-28 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US8921625B2 (en) 2007-02-05 2014-12-30 Reaction35, LLC Continuous process for converting natural gas to liquid hydrocarbons
US7998438B2 (en) 2007-05-24 2011-08-16 Grt, Inc. Zone reactor incorporating reversible hydrogen halide capture and release
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
US20090308759A1 (en) * 2008-06-13 2009-12-17 Marathon Gtf Technology, Ltd. Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery
US8273929B2 (en) 2008-07-18 2012-09-25 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US8415517B2 (en) 2008-07-18 2013-04-09 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US7968755B2 (en) 2008-10-01 2011-06-28 Sajet Development Llc Process and catalyst for converting alkanes
US20100087688A1 (en) * 2008-10-01 2010-04-08 Jorge Miller Process and catalyst for converting alkanes
US7812201B2 (en) 2008-10-01 2010-10-12 Targa Resources, Inc. Process and catalyst for converting alkanes
US20120215034A1 (en) * 2009-04-22 2012-08-23 Mcfarland Eric Process for converting hydrocarbon feedstocks with electrolytic and photoelectrocatalytic recovery of halogens
WO2010124041A1 (en) * 2009-04-22 2010-10-28 Grt, Inc. Process for converting hydrocarbon feedstocks with electrolytic and photoelectrocatalytic recovery of halogens
WO2010132325A1 (en) * 2009-05-12 2010-11-18 Shell Oil Company An integrated process to produce hydrocarbons from natural gas containing carbon dioxide
US9133078B2 (en) 2010-03-02 2015-09-15 Gtc Technology Us, Llc Processes and systems for the staged synthesis of alkyl bromides
US8815050B2 (en) 2011-03-22 2014-08-26 Marathon Gtf Technology, Ltd. Processes and systems for drying liquid bromine
US8436220B2 (en) * 2011-06-10 2013-05-07 Marathon Gtf Technology, Ltd. Processes and systems for demethanization of brominated hydrocarbons
US20120313034A1 (en) * 2011-06-10 2012-12-13 Marathon Gtf Technology, Ltd. Processes and Systems for Demethanization of Brominated Hydrocarbons
US8829256B2 (en) 2011-06-30 2014-09-09 Gtc Technology Us, Llc Processes and systems for fractionation of brominated hydrocarbons in the conversion of natural gas to liquid hydrocarbons
US8802908B2 (en) 2011-10-21 2014-08-12 Marathon Gtf Technology, Ltd. Processes and systems for separate, parallel methane and higher alkanes' bromination
US9193641B2 (en) 2011-12-16 2015-11-24 Gtc Technology Us, Llc Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems
US11167242B1 (en) 2012-05-14 2021-11-09 Chemergy, Inc. Process for desulpherization and hydrogen recovery
US10472721B1 (en) * 2012-05-14 2019-11-12 Chemergy, Inc. Biowaste treatment and recovery system
US9702049B1 (en) * 2012-05-14 2017-07-11 Melahn L. Parker Biowaste treatment and recovery system
US9175409B2 (en) 2012-07-26 2015-11-03 Liquid Light, Inc. Multiphase electrochemical reduction of CO2
US8845876B2 (en) 2012-07-26 2014-09-30 Liquid Light, Inc. Electrochemical co-production of products with carbon-based reactant feed to anode
US8845875B2 (en) 2012-07-26 2014-09-30 Liquid Light, Inc. Electrochemical reduction of CO2 with co-oxidation of an alcohol
US8647493B2 (en) 2012-07-26 2014-02-11 Liquid Light, Inc. Electrochemical co-production of chemicals employing the recycling of a hydrogen halide
US9080240B2 (en) 2012-07-26 2015-07-14 Liquid Light, Inc. Electrochemical co-production of a glycol and an alkene employing recycled halide
US9085827B2 (en) 2012-07-26 2015-07-21 Liquid Light, Inc. Integrated process for producing carboxylic acids from carbon dioxide
US8641885B2 (en) 2012-07-26 2014-02-04 Liquid Light, Inc. Multiphase electrochemical reduction of CO2
US10329676B2 (en) 2012-07-26 2019-06-25 Avantium Knowledge Centre B.V. Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode
US9175407B2 (en) 2012-07-26 2015-11-03 Liquid Light, Inc. Integrated process for producing carboxylic acids from carbon dioxide
US8858777B2 (en) 2012-07-26 2014-10-14 Liquid Light, Inc. Process and high surface area electrodes for the electrochemical reduction of carbon dioxide
US8444844B1 (en) 2012-07-26 2013-05-21 Liquid Light, Inc. Electrochemical co-production of a glycol and an alkene employing recycled halide
US11131028B2 (en) 2012-07-26 2021-09-28 Avantium Knowledge Centre B.V. Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode
US9267212B2 (en) 2012-07-26 2016-02-23 Liquid Light, Inc. Method and system for production of oxalic acid and oxalic acid reduction products
US9303324B2 (en) 2012-07-26 2016-04-05 Liquid Light, Inc. Electrochemical co-production of chemicals with sulfur-based reactant feeds to anode
US8692019B2 (en) 2012-07-26 2014-04-08 Liquid Light, Inc. Electrochemical co-production of chemicals utilizing a halide salt
US9708722B2 (en) 2012-07-26 2017-07-18 Avantium Knowledge Centre B.V. Electrochemical co-production of products with carbon-based reactant feed to anode
US8821709B2 (en) 2012-07-26 2014-09-02 Liquid Light, Inc. System and method for oxidizing organic compounds while reducing carbon dioxide
US8691069B2 (en) 2012-07-26 2014-04-08 Liquid Light, Inc. Method and system for the electrochemical co-production of halogen and carbon monoxide for carbonylated products
US10287696B2 (en) 2012-07-26 2019-05-14 Avantium Knowledge Centre B.V. Process and high surface area electrodes for the electrochemical reduction of carbon dioxide
US9873951B2 (en) 2012-09-14 2018-01-23 Avantium Knowledge Centre B.V. High pressure electrochemical cell and process for the electrochemical reduction of carbon dioxide
US10016701B2 (en) 2013-05-30 2018-07-10 Reaction 35, Llc Recovery of halogens by partial condensation
WO2014193957A1 (en) * 2013-05-30 2014-12-04 Reaction 35, Llc Recovery of halogens by partial condensation
WO2015195149A1 (en) * 2014-06-19 2015-12-23 Liquid Light, Inc Integrated process for co-production of carboxylic acids and halogen products from carbon dioxide
CN115491697A (zh) * 2022-10-21 2022-12-20 上海科技大学 一种烃类原料高效转化的方法及其装置
WO2024082393A1 (zh) * 2022-10-21 2024-04-25 上海科技大学 一种烃类原料高效转化的方法及其装置

Also Published As

Publication number Publication date
IN2009DN07232A (zh) 2015-07-24
MX2009012353A (es) 2010-02-17
CN101687725A (zh) 2010-03-31
ZA200907775B (en) 2010-07-28
BRPI0811606A2 (pt) 2019-09-24
EA201200888A1 (ru) 2013-02-28
AU2008254937A1 (en) 2008-11-27
WO2008143940A3 (en) 2009-12-30
ECSP099732A (es) 2010-02-26
EP2148942A4 (en) 2011-11-09
AU2008254937C1 (en) 2013-05-30
CO6241174A2 (es) 2011-01-20
JP2010527358A (ja) 2010-08-12
WO2008143940A2 (en) 2008-11-27
EA017229B1 (ru) 2012-10-30
NZ580996A (en) 2011-09-30
CA2684765A1 (en) 2008-11-27
KR20100027135A (ko) 2010-03-10
EP2148942A2 (en) 2010-02-03
EA200970960A1 (ru) 2010-04-30
AU2008254937B2 (en) 2013-01-17
TN2009000480A1 (en) 2011-03-31
NO20093337L (no) 2010-02-12
AP2009005040A0 (en) 2009-12-31

Similar Documents

Publication Publication Date Title
US20080314758A1 (en) Process for converting hydrocarbon feedstocks with electrolytic recovery of halogen
US20100270167A1 (en) Process for converting hydrocarbon feedstocks with electrolytic and photoelectrocatalytic recovery of halogens
CA2727545C (en) Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery
AU2017209876B2 (en) Electrolysis system and method for electrochemical ethylene oxide production
KR101433781B1 (ko) 탄화수소를 형성하기 위한 시스템 및 방법
CA2727544C (en) Hydrogenation of multi-brominated alkanes
US20120141356A1 (en) Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor
CN104271538A (zh) 用于将硫化氢转化为二硫化碳的方法
CN101646640B (zh) 含氯含氟化合物的制造方法
KR101356630B1 (ko) 원자력 수소 생산용 하이브리드형 요오드화수소 분해장치 및 이를 이용한 연속 수소 분해 방법
AU2020369070B2 (en) Electrolyser device and method for carbon dioxide reduction
CN115697947B (zh) 联产碳的气体制氢工艺
WO2023220731A2 (en) Halogen mediated production of hydrogen and carbon from hydrocarbons
WO2024023016A1 (en) Process for the production of methanol and hydrogen from methane using a solid metal hydroxide reagent
Nora US 9,085,827 Β2

Legal Events

Date Code Title Description
AS Assignment

Owner name: HOOK, THOMAS W., TEXAS

Free format text: SECURITY AGREEMENT;ASSIGNOR:GRT, INC.;REEL/FRAME:028498/0541

Effective date: 20120703

AS Assignment

Owner name: REACTION 35, LLC, TEXAS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:GRT, INC.;REEL/FRAME:031778/0327

Effective date: 20131209

Owner name: REACTION 35, LLC, TEXAS

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:HOOK, THOMAS W.;REEL/FRAME:031784/0696

Effective date: 20131209

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO PAY ISSUE FEE