Classifications

• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
  • C25B1/00—Electrolytic production of inorganic compounds or non-metals
  • C25B1/01—Products
  • C25B1/24—Halogens or compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
  • C25B3/00—Electrolytic production of organic compounds
  • C25B3/20—Processes
  • C25B3/27—Halogenation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
  • C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
  • C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
  • C07C1/30—Preparation 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C11/00—Aliphatic unsaturated hydrocarbons
  • C07C11/02—Alkenes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
  • C07C17/06—Preparation of halogenated hydrocarbons by addition of halogens combined with replacement of hydrogen atoms by halogens
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
  • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
  • C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
  • C07C209/08—Preparation 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
  • C07C29/12—Preparation 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
  • C07C29/124—Preparation 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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
  • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
  • C10B53/04—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of powdered coal
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
  • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
  • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
  • C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
  • C10G29/02—Non-metals
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
  • C10K3/00—Modifying 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
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
  • C25B1/00—Electrolytic production of inorganic compounds or non-metals
  • C25B1/01—Products
  • C25B1/02—Hydrogen or oxygen
  • C25B1/04—Hydrogen or oxygen by electrolysis of water
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1011—Biomass
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1025—Natural gas
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/30—Aromatics
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
  • H01L2924/013—Alloys
  • H01L2924/014—Solder alloys
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/30—Hydrogen technology
  • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/141—Feedstock
  • Y02P20/145—Feedstock 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:
• Combustion of these final products in an oxygen atmosphere containing trace water may be used to produce heat and carbon oxides and to convert the residual bromine 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. 62178P/G506
• 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. Hence, 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 62178P/G506
• 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
• 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
• 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., 62178P/G506
• Hydrogen that is produced can be used to power one or more process components, or compressed and sold.
• syngas CO + H 2
• 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:
• Lower peak operating temperature e.g., ⁇ 50°C vs. -I 5 OOO 0 C.
• 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 62178P/G506
• 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; 62178P/G506
• 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
• 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.
• alkanes e.g., methane, ethane, propane, and even larger alkanes
• olefins natural gas and other mixtures of hydrocarbons
• biomass- derived hydrocarbons and coal.
• Certain oil refinery processes yield light hydrocarbon streams (so- called "light-ends"), typically a mixture Of Ci-C 3 hydrocarbons, which can be used with or without added methane as the hydrocarbon 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 " ). It is contemplated that fluorine and iodine can be used, though not necessarily with equivalent results. Some of the problems associated with fluorine can likely be addressed by using dilute streams of fluorine (e.g., fluorine gas carried by helium nitrogen, or other diluent). It is expected, however, that more vigorous reaction conditions will be required for alkyl fluorides to couple and form higher hydrocarbons, due to the strength of the fluorine-carbon bond.
• fluorine and iodine can be used, though not necessarily with equivalent results.
• the term "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 62178P/G506
• hydrocarbon such as ethane, propane, butane, C 5 + hydrocarbons, aromatic hydrocarbons, etc., and optionally ethylene, propylene and/or longer olefins.
• light hydrocarbons (sometimes abbreviated “LHCs”) refers to Ci-C 4 hydrocarbons, e.g., methane, ethane, propane, ethylene, propylene, butanes, and butenes, all of which are normally gasses at room temperature and atmospheric pressure.
• 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).
• FIG. 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. 62178P/G506
• 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. More preferably, a series of electrolytic cells, rather than a single cell, is used as an electrolyzer. As an alternative, 62178P/G506
• 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 e.g., catalysts, pressure, temperature, residence time, etc.
• bromination, C-C coupling, reproportionation, product separation, HBr clean-up, and corrosion-resistant materials are provided in the '358 application at ffl ⁇ 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 62178P/G506
• 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 0 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 0 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 62178P/G506
• 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 phase electrolysis of hydrogen halide e.g., HBr.
• Products 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.
• 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
• 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
• 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
• 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.
• 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
• 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.
• 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 62178P/G506
• 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. [0064] In a laboratory implementation of elements of the process depicted in FIG. 3, methane is reacted with gaseous bromine at 45O 0 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 62178P/G506
• FIG. 3 The process shown in 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.
• a diaphragm-type cell 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. 62178P/G506
• 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 ('/2O 2 +
• 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 62178P/G506
• 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).
• the invention can be used in a variety of industrial settings, particular value is realized where 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.
• a difficult to transport material e.g., natural gas
• 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.
• FIGS. 7 and 8 two other aspects of the invention are presented, in which 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
• the poly- alcohols are separated from sodium bromide, and the aqueous sodium bromide is carried by a line to an electrolytic cell or cells, where molecular bromine is regenerated and subsequently separated and reused.
• the following nonlimiting examples illustrate various embodiments or features of the invention, including methane bromination, C-C coupling to form higher hydrocarbons, e.g., light olefins and aromatics (benzene, toluene, xylenes ("BTX”)), hydrolysis of methyl bromide to methanol, hydrolysis of dibromomethane to methanol and formaldehyde, and subsequent disproportionation to formic acid.
• Example 1 Bromination of Methane
• Methane (11 seem, l.Oatm) was combined with nitrogen (15 seem, l.Oatm) at room temperature via a mixing tee and passed through an 18 0 C bubbler full of bromine.
• Pellets of Mn ion exchanged ZSM-5 zeolite (CBV3024, 6 cm in length) were loaded in a tubular quartz reactor (ID, 1.0cm), which was preheated to 425 0 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 7.8ml/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 62178P/G506
• 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.

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