CN101687725A - Process for converting hydrocarbon feedstocks with electrolytic recovery of halogen - Google Patents

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

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CN101687725A
CN101687725A CN200880016076A CN200880016076A CN101687725A CN 101687725 A CN101687725 A CN 101687725A CN 200880016076 A CN200880016076 A CN 200880016076A CN 200880016076 A CN200880016076 A CN 200880016076A CN 101687725 A CN101687725 A CN 101687725A
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haloalkane
alkali
halide
halogen
hydrocarbon
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菲利普·罗索
埃里克·W.·麦克法兰
杰弗里·H.·谢尔曼
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GRT Inc
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    • 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
    • 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
    • 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

Abstract

An improved continuous process for converting methane, natural gas, and other hydrocarbon feedstocks into one or more higher hydrocarbons, methanol, amines, or other products comprises continuously cycling through hydrocarbon halogenation, product formation, product separation, and electrolytic regeneration of halogen, optionally using an improved electrolytic cell equipped with an oxygen depolarized cathode.

Description

Make hydrocarbon raw material transform the method for electrolytic recovery halogen simultaneously
Technical field
The present invention relates to Sweet natural gas and other hydrocarbon raw material are changed into more high value products, for example the method for fuel-grade hydrocarbon, methyl alcohol and aromatic substance.
Background technology
The U.S. Patent application US 11/703 that on February 5th, 2007 submitted to, 358 (being called for short " ' 358 application "), name is called " the continuous production method that conversion of natural gas is liquid hydrocarbon ", the U.S. Provisional Application US 60/765 that it was submitted to based on February 3rd, 2006,115, described making molecular halogen and hydrocarbon raw material reaction to produce the continuous processing of higher hydrocarbon.In one embodiment, this technology may further comprise the steps: the alkane halogenation, multi-halogenated compounds " contrary disproportionation (reproportionation) reaction " is to increase the halid amount of formed list, haloalkane oligomeric (C-C coupling) is to form the product of higher carbon number, separated product from hydrogen halide, halogen cyclic regeneration and from water, reclaim molecular halogen.The separation of hydrogen hydracid (for example, HBr), changes into molecular halogen (for example, bromine) by reacting with oxygen source then in the presence of metal oxide catalyst from liquid hydrocarbon in the liquid-liquid phase separation device.The full content of ' 358 applications is incorporated this paper by reference into.
' 358 applications have been represented the c h bond activation method and have been made hydrocarbon feed change into the more significant improvement of the industrial production method of high value products.The present invention builds on ' 358 applications on, (HBr for example, HCl) regeneration obtains molecular halogen (Br for example from haloid acid to use electrolytic process 2, Cl 2).
Electrolytic aqueous solution is the known way that produces hydrogen with electric energy to produce hydrogen and oxygen.Similarly, produce halogen by electrolysis halogenide salt solution or metal halide steam.Traditional hydrogen production depends on water (steam) makes hydrocarbon reforming to produce carbon monoxide and molecular hydrogen:
CH 4+H 2O→CO+3H 2 ΔH＝+206kJ/mol
C xH y+xH 2O→xCO+(x+y/2)H 2 ΔH＞＞0kJ/mol
The reforming reaction of this power consumption can compare with the reaction that produces low energy product water and carbonic acid gas by complete oxidation with make the hydro carbons heat release in oxygen:
CH 4+2O 2→CO 2+2H 2O ΔH＝-882kJ/mol
C xH y+(x+y/2)O 2→XCO 2+y/2H 2O ΔH＜＜0kJ/mol
Like this, usually this reforming process and this complete oxidation are united and carry out, provide energy to drive the opposing party's thermo-negative reaction with a side.Resulting entire reaction produces oxycarbide and hydrogen, and can almost wait and can operate on ground:
C nH m+xO 2+yH 2O→(n-m)CO+mCO 2+(m/2+y)H 2
Perhaps, can produce hydrogen by water of decomposition:
H 2O→1/2O 2+H 2 ΔH＝286kJ/mol?H 2
Because be disadvantageous on the energy, this reaction can be by using 2 * 10 5Enclosed pasture/Gram-mole H 2Carrying out electrolysis drives.Water is the source of hydrogen and oxygen, and the overactivity that is used for oxygen production can about 1.6 volts overvoltage and the stoichiometric electric current of needs.In fact, the about 300kJ/mol H of needed electric energy 2
By the electrolysis halide salts for example alkali metal chloride technology produce in the halogen process halogen (Cl 2) and halide anion and the water of alkali metal base (NaOH) from the aqueous solution of salt (NaCl) make.Water is again the source of hydrogen.Similarly, bromine can make from bromine salt (NaBr).Under the back kind situation, compare with oxygen production, from halide anion production molecular halogen on energy and kinetics be favourable, only need lower overvoltage (1.1V is with respect to 1.6V):
H 2O+NaBr→Br 2+H 2+NaOH
This reacts every Gram-mole H 2Need electric weight 2 * 10 5The enclosed pasture and its required electric energy obviously reduce (with use H separately 2O compares) to about 200kJ/g mol H 2
A lot of hydrogen production technique of attempting the exploiting economy practicality had been carried out.In principle, hydrocarbon can directly be used oxygen (as in Solid Oxide Fuel Cell) and/or aqueous electrochemical oxidation to produce hydrogen; But this causes the complicated isolating intermediate that is difficult to usually, and not economical and practical.The another way of removing dehydrogenation from hydrocarbon is by using halogen (preferred bromine) substep partial oxidation.Major advantage is that hydrocarbon can not take place is completely oxidized to carbonic acid gas, and hydrogen is transformed into HBr (the Δ H of less stable Form=-36kJ/mol), rather than water (Δ H Form=-286kJ/mol):
C nH m+p/2Br 2→C nH m-pBr p+pHBr
C nH zBr z+x/2Br 2→C nH zBr p+xHBr
The final product of removing behind the HBr depends on reaction conditions, can be made up of the mixture of coke and bromination and full brominated hydrocarbon: C x+ C yH zBr t+ C rBr qThese final products of burning can be used to produce heat and oxycarbide in containing the oxygen atmosphere of trace water, and residual bromine is converted into HBr:
C x+C yH zBr t+C rBr q+n/2O 2+(t+q)/2H 2O→(x+y+r＝n)CO 2+(t+q)HBr
It is reported that the another kind of method of making hydrogen based on the HBr electrolysis is brought about 25% energy saving with respect to water electrolysis.But, the bromine that produces in this processing requirement electrolysis is transformed back HBr, and this step of converting is the main drawback that HBr is electrolyzed to produce the route of hydrogen.On the contrary, the bromine that utilization of the present invention produces in electrolysis is produced valuable product, rather than its simple conversion is returned HBr.
Summary of the invention
The invention reside in and make halogen (preferred bromine) and hydrocarbon carry out heat (non-electrochemical) reaction, produce hydrogen halide (preferred HBr) and generation than easier active haloalkane or other the carbonaceous intermediate that is converted into after product of original hydrocarbon, hydrogen halide or also more advantageously electrolysis of halide salts simultaneously, these technologies combine, and have just founded obviously higher a whole set of production method of efficient.The use of halogen can prevent that hydrocarbon all is oxidized to carbonic acid gas, and produces partial oxidation products subsequently.
One aspect of the present invention is to make hydrocarbon feed be converted into one or more more continuous production methods of higher hydrocarbon, comprise: (a) make molecular halogen and hydrocarbon feed be enough to form under the processing condition of haloalkane and hydrogen halide, also preferably under the molecular halogen condition that completely consumed is fallen substantially, react simultaneously, the formation haloalkane; (b) haloalkane and first catalyzer are contacted being enough to form under the processing condition of higher hydrocarbon and hydrogen halide, generate more high-grade hydrocarbon and hydrogen halide; (c) from hydrogen halide, separate higher hydrocarbon; (d) electrolysis conversion hydrogen halide is hydrogen and molecular halogen, makes that thus halogen utilizes again; (e) press desirable number of times repeating step (a) to (d).These steps can be carried out with described order, perhaps carry out with different order.Electrolysis is carried out in aqueous medium, perhaps carries out in gas phase.With some or all haloalkanes and paraffinic feedstock reaction, make haloalkane " contrary disproportionation " as required, single halon deal is increased.Simultaneously, in some embodiments, the hydrogen that produces in this technology is used for generating.
Second aspect of the present invention is that the convert hydrocarbons raw material is the continuous production method of methyl alcohol, comprise: (a) make molecular halogen and hydrocarbon feed be enough to form under the processing condition of haloalkane and hydrogen halide, preferably under the molecular halogen condition that completely consumed is fallen substantially, react simultaneously, the formation haloalkane; (b) haloalkane and alkali aqueous solution are contacted being enough to form under the processing condition of methyl alcohol and alkali halide, form methyl alcohol and alkali halide; (c) separation of methanol from alkali halide; (d) electrolysis conversion alkali halide is hydrogen or molecular halogen, and alkali aqueous solution, makes halogen and alkali utilize thus again; (e) press desirable number of times repeating step (a) to (d).These steps can be carried out with described order, perhaps carry out with different order.As required, make the reaction of some or all haloalkanes and paraffinic feedstock, make many halons " contrary disproportionation ", single halon deal is increased.
Requiring haloalkane and alkali aqueous solution to be reflected under the alkaline condition by this explained hereafter methyl alcohol carries out.Yet electrolysis process can produce alkali and acid with the stoichiometry equivalent.Therefore, the simple reorganization of all alkali and all acid can produce neutral solution.The method of the invention provides the disproportionation of bronsted lowry acids and bases bronsted lowry, and alkali makes it to realize alkaline condition with the bromoalkane reaction thereby can obtain more fully.After methyl alcohol formed with other product and separates, the acid of removing in the disproportionation step was recombinated with excessive alkali after a while.
In some embodiments, be necessary that holding anode electrolytic solution is in acidic conditions, this may need to add small amount of acid.The separation of part acid can be passed through liquid phase method, perhaps uses renewable solid reactant or absorption agent to finish.Can also provide acid from external source, perhaps provide from on-the-spot (on-site) or (off-site) generation outside the venue.In addition, make excessive acid on the whole, can also reach by removing small amount of alkali from system.
The 3rd aspect of the present invention is that the convert hydrocarbons raw material is the continuous production method of alkylamine, comprise: (a) make molecular halogen and hydrocarbon feed be enough to (for example to form haloalkane, monobromethane) and under the processing condition of hydrogen halide react, preferably under the molecular halogen condition that completely consumed is fallen substantially, react simultaneously, form haloalkane; (b) make haloalkane and ammonia or ammoniacal liquor form alkylamine and alkali halide being enough to form contact under the condition of alkylamine and alkali halide; (c) from alkali halide, separate alkylamine; (d) electrolysis conversion alkali halide is hydrogen and molecular halogen, makes that thus halogen utilizes again; (e) press desired number of times repeating step (a) to (d).These steps can be carried out with described order, perhaps carry out with different order.Make the reaction of some or all haloalkanes and paraffinic feedstock as required, make haloalkane " contrary disproportionation ", single halon deal is increased.
The 4th aspect of the present invention provides and transform coal is the continuous production method of coke and hydrogen, it may further comprise the steps: broken coal and molecular halogen are reacted under the processing condition that are enough to bromination and decomposition coal skeleton principal element, form bromination coal intermediate and hydrogen halide, form the mixture of bromination coal intermediate (for example, many brominations hydro carbons) thus; (b) bromizate the coal intermediate on the catalyzer, be enough to form that reaction forms coke and hydrogen halide under the processing condition of coke and hydrogen halide; (c) separate coke from hydrogen halide; (d) the hydrogen halide electrolysis that will form in step (a) and/or step (b) is converted into hydrogen and molecular halogen, makes halogen utilize thus again; (e) press desirable number of times repeating step (a) to (d).These steps can be carried out with described order, perhaps carry out with different order.The coke that produces can be used in and produces the used electric power of this technology (through burning, generation steam and generating), or collects and sell.
The 5th aspect of the present invention provides the conversion coal or biogenic hydro carbons is the continuous production method of polyvalent alcohol and hydrogen, it comprises: (a) make molecular halogen and coal or biogenic hydrocarbon raw material be enough to form under the processing condition of haloalkane and hydrogen halide, preferably react under the molecular halogen condition that completely consumed is fallen substantially simultaneously, the formation haloalkane; (b) make haloalkane and alkali aqueous solution form polyvalent alcohol and alkali halide being enough to form contact under the processing condition of polyvalent alcohol and alkali halide; (c) separating multicomponent alcohol from alkali halide; (d) electrolysis conversion alkali halide is hydrogen and molecular halogen, makes that thus halogen utilizes again; (e) press desired number of times repeating step (a) to (d).These steps can be carried out with described order, perhaps carry out with different order.Make the reaction of part or all of haloalkane and paraffinic feedstock as required, make haloalkane " contrary disproportionation ", single halon deal is increased.
In an important change scheme of the present invention, the oxygen depolarization electrode is used for electrolyzer, the hydrogen halide electrolysis produces molecular halogen and water, and the alkali halide electrolysis produces molecular halogen and alkaline hydrated oxide, rather than hydrogen.This change scheme has the advantage that significantly reduces the electrolyzer energy requirement.Like this, the improvement electrolyzer with oxygen depolarization electrode is an another aspect of the present invention.
All respects of the present invention have a lot of shared key elements, comprising: (1) in the presence of molecular halogen, the hydrocarbon feed halogenation produces the carbonaceous products of hydrogen halide and oxidation; (2) carbon product of oxidation further reacts the generation final product; (3) from brominated composition, separate carbonaceous products; (4) in electrolyzer the residual halogen-containing composition (for example, HBr, NaBr) of electrolysis to form halogen and hydrogen (perhaps use the oxygen depolarization electrode producing halogen and water, or halogen and alkaline hydrated oxide rather than hydrogen).The hydrogen that produces can be as the energy of one or more technology compositions, perhaps compresses and sells.
Utilize the conventional suitability for industrialized production method of methane, coal and other hydrocarbon, produce synthetic gas (CO+H 2), it can be converted into more high value products, for example methyl alcohol and straight-chain paraffin.The formation of intermediate synthetic gas is extremely expensive, is necessary to reduce almost all carbon of oxidation, to form useful products.When comparing with conventional synthesis gas process, the present invention has superiority aspect a lot, and has the following advantages at least:
-use the haloalkane intermediate to produce more high value products, comprise fuel and high value chemical more.
-reduction working pressure (for example ,～the 1-5atm replacement～80atm).
-reduction peak service temperature (for example ,～50 ℃ replacement is～1000 ℃).
-need not pure oxygen
-the reformer of not lighting a fire, therefore safer when being used for offshore platform.
-simple reactor design replaces complicated synthetic gas to be converted into the conversion system of methyl alcohol.
-catalyst-free demand replaces reforming and synthetic gas transforms required catalyzer.
-seldom by product and therefore simple methanol purification process more.
-reforming need not the steam supply.
-on separate mesh electrode, produce hydrogen as pure relatively product.
-in final step, finish by from reaction vessel, removing the product driving a reaction.
According to the present invention, the molecular halogen that is used to form haloalkane is recovered as hydrogen halide, and is recycled to electrolyzer, and haloalkane then is converted into more high value products.Embodiment comprises with zeolites as catalysts makes methyl bromide be converted into aromatic substance and HBr, makes single bromoalkane (for example monobromethane) be converted into alkene (for example ethene) and HBr at catalyzer.In addition, haloalkane is easy to be converted into oxygenate product (oxygenate) for example alcohol, ether and aldehyde.Example comprises that the methyl bromide in the NaOH aqueous solution is converted into methyl alcohol and NaBr, and the methylene bromide among the NaOH is converted into ethylene glycol and NaBr.In the embodiment, haloalkane easily is converted into amine again.Example comprises that the bromobenzene in the ammonia soln is converted into phenol and aniline, and the monobromethane in the ammonia is converted into ethamine and NaBr.
When at oil or gas production equipment for example offshore oil or Sweet natural gas drilling rigs, or in the well head set-up on land during on-the-spot the use, find that the present invention is practical especially.Continuous processing described herein can combine utilization with the production of oil and/or Sweet natural gas, adopts on-site generated power to provide power to electrolyzer.
Description of drawings
When the consideration detailed description, and pass through with reference to the accompanying drawings, a plurality of features of the present invention, embodiment and advantage will better be understood, wherein:
Fig. 1 is according to one embodiment of the present invention, is used for hydrocarbon feed is converted into the synoptic diagram of the continuous processing of higher hydrocarbon;
Fig. 2 is another embodiment according to the present invention, is used for hydrocarbon feed is converted into the synoptic diagram of the continuous processing of higher hydrocarbon;
Fig. 3 is according to one embodiment of the present invention, is used for hydrocarbon feed is converted into the synoptic diagram of the continuous processing of methyl alcohol, and wherein, membrane-type electrolytic cell is used to the molecular bromine of regenerating;
Fig. 4 is another embodiment according to the present invention, is used for hydrocarbon feed is converted into the synoptic diagram of the continuous processing of methyl alcohol, and wherein, the diaphragm type electrolyzer is used to produce molecular bromine;
Fig. 5 is according to one embodiment of the present invention, is used for hydrocarbon feed is converted into the synoptic diagram of the continuous processing of higher hydrocarbon, and the negative electrode of oxygen depolarization wherein is provided;
Fig. 6 is the synoptic diagram according to the electrolyzer of one embodiment of the present invention;
Fig. 7 is according to one embodiment of the present invention, coal is converted into the synoptic diagram of the continuous processing of coke and hydrogen;
Fig. 8 is according to one embodiment of the present invention, is used for coal or biological substance are converted into the synoptic diagram of the method for polyvalent alcohol and hydrogen;
Fig. 9 is according to one embodiment of the present invention, and the figure of the selectivity of product of methane bromination is described;
Figure 10 is according to one embodiment of the present invention, and the figure of the selectivity of product of coupling methyl bromide is described; With
Figure 11 is another embodiment according to the present invention, and the figure of the selectivity of product of coupling methyl bromide is described.
Embodiment
The invention provides and be used for the convert hydrocarbons raw material and be high value products more, the chemical technology of fuel-grade hydrocarbon, methyl alcohol, aromatic substance, amine, coke and polyvalent alcohol for example, it uses molecular halogen with the c h bond in the activation raw material, and to carry out electrolysis be molecular halogen with haloid acid (hydrogen halide) or the halide salts (for example, Sodium Bromide) that forms in the conversion process.
The non-limiting example that is applicable to raw material hydrocarbon of the present invention comprises alkane, for example methane, ethane, propane and more high-grade alkane; Alkene; The mixture of Sweet natural gas and other hydrocarbon; Biological substance deutero-hydrocarbon; And coal.The lightweight hydrocarbon stream that produces in some petroleum refining processes (so-called " lightweight tail gas ") is generally C 1-C 3The mixture of hydrocarbon, it can be used as hydrocarbon feed under the situation that adds or do not add methane.Except coal, in most cases raw material properties will mainly be aliphatic.
Hydrocarbon feed is by reacting the method that is converted into senior product with molecular halogen, and is as described below.Bromine (Br 2) and chlorine (Cl 2) be preferred, bromine is most preferred, in part because Br -Be converted into Br 2Required overvoltage is starkly lower than Cl -Be converted into Cl 2Required overvoltage (Br -Required voltage 1.09V and Cl -Required voltage is 1.36V).Certainly expection fluorine and iodine also can use, although may not have identical result.Some problems of relevant use fluorine probably can be overcome by the diluent stream (for example, the fluorine gas that is carried by helium nitrogen or other thinners) of using fluorine.Yet because the intensity of fluoro-carbon bond, expection fluoroalkane coupling also forms higher hydrocarbon and can need more violent reaction conditions.Similarly, the relevant problem (for example heat absorptivity of some Iod R) of using iodine probably can be by carrying out halogenation and/or linked reaction is overcome under high temperature and/or pressure.Generally speaking, preferably use bromine or chlorine, most preferably bromine.
The term of Shi Yonging " higher hydrocarbon " (perhaps being called for short " the higher hydrocarbon ") meaning is meant the hydrocarbon that has more carbonatoms than one or more compositions of raw material hydrocarbon, and has alkene identical with one or more compositions of hydrocarbon feed or more carbonatomss herein.For example, if raw material is a Sweet natural gas, the mixture of typical light hydrocarbon, it is mainly methane, has more a spot of ethane, propane and butane, and even the more long chain hydrocarbon of less amount for example pentane, hexane etc." higher hydrocarbon " that produce according to the present invention can comprise C 2Or more higher hydrocarbon, for example ethane, propane, butane, C 5 +Hydrocarbon, aromatic hydrocarbon etc. and optional ethene, propylene and/or longer alkene.Term " light hydrocarbon " (being abbreviated as " LHCs " sometimes) meaning is meant C 1-C 4Hydrocarbon, for example methane, ethane, propane, ethene, propylene, butane and butylene, their all i.e. gasifications under room temperature and normal atmosphere usually.The fuel-grade hydrocarbon typically has the carbon more than 5, at room temperature liquefaction.
In this specification sheets and claims, when chemical substance during, also comprise the odd number object with complex representation, vice versa, unless context clearly shows not like this.For example, " haloalkane " comprises one or more haloalkanes, and it can identical (for example, 100% methyl bromide) or different (for example, methyl bromide and methylene bromide); " higher hydrocarbon " comprises one or more higher hydrocarbons, and it can identical (for example, 100% octane) or difference (for example, hexane, pentane and octane).
Fig. 1-5 is for describing the illustrative flow of the different embodiments of the present invention, wherein makes hydrocarbon feed and molecular halogen (for example, bromine) react and is converted into one or more more high value products.With reference to figure 1, a kind of embodiment for preparing the technology of higher hydrocarbon from Sweet natural gas, methane or other light hydrocarbon is described.Raw material (for example, Sweet natural gas) is sent to bromination reactor 3 and makes it reaction by separating pipeline 1,2 with molecular bromine.Product (HBr, bromoalkane, optional alkene) and the unreacted hydrocarbon of possibility leave reactor, are sent to carbon-to-carbon coupler reactor 5 by pipeline 4.Randomly, bromoalkane at first passes to the separating unit (not shown), and wherein single brominated hydrocarbon separates from many brominated hydrocarbons with HBr, and the latter transmits and is back to bromination reactor to carry out " contrary disproportionation " with methane and/or other light hydrocarbon, described in ' 358 applications.
In coupler reactor 5, single bromide and possible other bromoalkane and alkene react in the presence of coupling catalyst to form higher hydrocarbon.The non-limiting example of coupling catalyst is provided in ' 358 applications
Figure A20088001607600151
Among the 61-65.Doping type prepare zeolite and be described in US patent publication No. 2005/0171393 A1 as the purposes of carbon-to-carbon coupling catalyst in the 4-5 page or leaf, is introduced it with for referencial use in full at this.
HBr, higher hydrocarbon and (possible) unreacted hydrocarbon and bromoalkane leave coupler reactor, are sent to hydrogen bromide absorptive unit 7 by pipeline 6, and wherein hydrocarbon product separates through absorption, distillation and/or some other isolation technique from HBr.Hydrocarbon product is sent to product by pipeline 8 and reclaims unit 9, reclaim unit 9 and from any residual Sweet natural gas or other gaseous matter, isolate higher hydrocarbon products, it can be discharged by pipeline 10, or recirculation and transmit and be back to bromination reactor under the situation of Sweet natural gas or lower paraffin hydrocarbons.On the other hand, combustible material can feed generator unit and is used for producing heat and/or electricity to be used for this system.
Aqueous sodium hydroxide solution or other alkali are sent to the HBr absorptive unit by pipeline 11, and form aqueous sodium bromide with HBr therein.The low amounts of product of aqueous sodium bromide and hydrocarbon and other organic substance is sent to separating unit 13 by pipeline 12, and this separating unit 13 is operated to separate organic composition from Sodium Bromide through distillation, liquid-liquid extraction, flash distillation or some other appropriate means.This organism can pass to separated product clearing cell (cleanup unit) at once from system, perhaps passes to HBr absorptive unit 7 and finally leaves system through pipeline 8 by pipeline 14 in illustrated embodiment.
Aqueous sodium bromide is sent to the electrolyzer 16 with anode 17 and negative electrode 18 by pipeline 15 from NaBr-separating organic matters unit 13.Be provided with and inject pipeline 19 to add water, additional electrolytic solution (electrolyte)/and/or be used for the acid or the alkali of pH control.More preferably, be used as electrolyzer with series connection electrolyzer rather than single pond.In addition, also available several series connection pond parallel connection.The non-limiting example of electrolyzer comprises barrier film, film and mercury pool, and it can be one pole or two utmost points.Accurate logistics about preparation water, electrolytic solution and other specific raw materials for production will change along with used electrolyzer type.Aqueous sodium bromide is electrolysis in electrolyzer, and bromide anion is at anodic oxidation (2Br -→ Br 2+ 2e -), water is at cathodic reduction (2H 2O+2e -→ H 2+ 2OH -).Aqueous sodium hydroxide solution is removed and is passed to the HBr absorptive unit through pipeline 11 from electrolyzer.
Reclaim the bromine and the hydrogen that produce in the electrolyzer, bromine recirculation also is used for this technology once more.Particularly, wet bromine is sent to moisture eliminator 21 by pipeline 20, and dried bromine is sent to well heater 23 by pipeline 22, is back to bromination reactor 3 by pipeline 2 then.If bromine institute water content is in allowable range in bromination and coupling, can be without moisture eliminator.The hydrogen that produces at cathode of electrolytic tank can give off, or more preferably passes to the production capacity unit with its collection, compression and through pipeline 24, for example fuel cell or hydrogen turbine (turbine).Perhaps, the hydrogen of recyclable generation is used for selling or other purposes.The electric power that produces can be given the equipment that uses in various these continuous processings, comprises that electrolyzer etc. provides power.
Be used for that bromination, C-C coupling, contrary disproportionation, product separate, HBr removes, the exemplary and preferred condition (for example, catalyzer, pressure, temperature, the residence time etc.) of corrosion resistant material is provided in ' 358 applications
Figure A20088001607600161
Among 39-42 (bromination), 43-50 (contrary disproportionation), 61-65 (C-C coupling), 66-75 (product separations), 82-86 (HBr removes and the halogen recovery) and the 87-90 (corrosion resistant material), be incorporated herein whole these paragraphs with as a reference.The anode of electrolyzer, negative electrode, electrolytic solution and further feature are basic as selecting with the several factors that those skilled in the art understand, for example the throughput of electrolytic reaction, current power level and chemical factor etc.Non-limiting example is seen United States Patent (USP) 4,110,180 (people such as Nidola) and 6,368,490 (Gestermann); Y.Shimizu, N.Miura, N.Yamazoe, Gas-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.Millington, HBr Electrolysis in the Ispara Mark 13A Flue GasDesulphurization Process:Electrolysis in a DEM Cell, J.Applied Electrochemistry, Vol.20,60-68 (1990); And S.Motupally, D.Mak, F.reire, J.Weidner, RecyclingChlorine from Hydrogen Chloride, The Electrochemical Society Interface, Fall 1998,32-36, at this full text of introducing them respectively with for referencial use.
In an embodiment of the invention, as shown in Figure 1, methane is introduced into the choked flow reactor of being made by alloy A LCOR with the speed of 1mol/ second, molecular bromine is introduced with the speed of 0.50mol/ second, the total residence time under 425 ℃ is 60 seconds.Main hydrocarbon product comprises methyl bromide (85%) and two bromo methane (14%), and produces the 0.50mol/ HBr of second.Methane conversion is 46%.Product is sent to coupler reactor 5 by pipeline 4, and coupler reactor 5 is packed bed reactors, and it is filled with transition metal (for example, Mn) the ZSM5 zeolite coupling catalyst that carries aluminum oxide of ion-exchange of 425 ℃ of uses.In coupler reactor 5, the distribution of the higher hydrocarbon of formation was determined by the period of reactor internal reaction.In this example, 10 seconds is the preferred period that produces product in the gas and oil scope.HBr, higher hydrocarbon and (trace) unreacted bromoalkane leave coupler reactor, are sent to hydrogen bromide separating unit 7 by pipeline 6, and HBr separates by distillation fraction therein.The introducing aqueous sodium hydroxide solution also makes it to react under 150 ℃, forms Sodium Bromide and alcohol from HBr and unreacted bromoalkane.The aqueous solution and organic substance are sent to separating unit 13 by 12, separating unit 13 via distillation procedure to isolate organic composition from Sodium Bromide.Aqueous sodium bromide is sent to the electrolyzer 16 with anode 17 negative electrodes 18 from NaBr-organic substance separating unit 13 through pipeline 15.Be provided with and inject line 19 with interpolation water, additional electrolytic solution and sour to regulate pH extremely less than 2 by adding.Electrolysis is carried out in the membranous type pond.Aqueous sodium bromide is electrolysis in electrolyzer, and bromide anion is at anodic oxidation (2Br -→ Br 2+ 2e -) and water at cathodic reduction (2H 2O+2e -→ H 2+ 2OH -).Aqueous sodium hydroxide solution is removed and is passed to the HBr absorptive unit through pipeline 11 from electrolyzer.In electrolyzer, produce bromine and hydrogen.
With reference to figure 2, describe that to be used to transform Sweet natural gas, methane or other hydrocarbon feed be for example another embodiment of fuel-grade hydrocarbon and aromatic substance of higher hydrocarbon.In the present embodiment, electrolysis is carried out in non-alkaline medium.Product (that is, higher hydrocarbon and HBr) from coupler reactor is sent to HBr absorptive unit 7 by pipeline 6, therein separate hydrocarbons product from HBr.In separating unit 13, after residual organic composition was removed from HBr, dense HBr solution was sent to electrolyzer 16 by pipeline 15.As required, provide preparation water, electrolytic solution or pH control acid/alkali by pipeline 19.The HBr aqueous electrolysis forms molecular bromine and hydrogen.Along with Br 2Separate out and remove from electrolyzer, the HBr concentration in the electrolyzer reduces.The rare HBr aqueous solution of gained with wherein carry or dissolved bromine (Br 2) being sent to bromine stripping tower 26 by pipeline 25, bromine stripping tower 26 is isolated bromine (Br from rare HBr aqueous solution through distillation or some other suitable lock out operation 2).Rare HBr aqueous solution transmits by pipeline 27 and is back to the HBr absorptive unit.Wet bromine is sent to moisture eliminator by pipeline 28, carries out drying therein.
(not shown) in the present invention's another embodiment aspect this, Sweet natural gas, methane or other hydrocarbon feeds are converted into higher hydrocarbon, halogen (for example, Br 2) by hydrogen halide (for example, gas phase electrolytic recovery HBr).(that is, higher hydrocarbon and HBr) product is sent to the HBr absorptive unit by pipeline, and hydrocarbon product separates from HBr therein from coupler reactor.In separating unit, after residual organic composition separated from HBr, gas HBr was sent to electrolyzer by circuit.Gas HBr electrolysis forms molecular bromine and hydrogen.Wet bromine is sent to moisture eliminator by pipeline, and is dry therein.Randomly, if that the supply electrolyzer is the HBr that does, just without moisture eliminator.
Fig. 3 describes the present invention's embodiment on the other hand, and wherein Sweet natural gas, methane or other hydrocarbon feeds are converted into methyl alcohol through the intermediate methyl bromide.Sweet natural gas and gas bromine are sent to bromination reactor 203 by pipeline 201 and 202 respectively and make it reaction.Product (for example, methyl bromide and HBr) and possible unreacting hydrocarbon transmit through reducing the heat exchanger 205 of their temperature by pipeline 204.As required, gas further cools off through supercooler 206.Gas part 206 is sent to HBr resorber 208 by pipeline 207.Residue passes through from the bypass of HBr resorber, and directly is sent to reactor/resorber 210 by pipeline 209.The decomposition ratio by greatly in reactor/resorber suitably the required acid/alkali disproportionation of pH determine.
Supply water to methanol reactor 210 through pipeline 212, optionally this water can be to carry out pretreatedly, for example handles through reverse osmosis unit 211 that its saltiness was minimized.In addition, another pipeline 213 transmits water to HBr resorber 208.
The HBr solution that forms in HBr resorber 208 is sent to stripping tower 215 (organism separates by stripping or other modes therein) through pipeline 214, is sent to reactor/resorber 210 through pipeline 216 then.Merge from the gas of HBr resorber and byproduct stream, and be sent to reactor/resorber 210 by pipeline 209 from water cooler 206.Be sent to HBr receiving tank 218 from the HBr solution of stripping tower 215 through pipeline 217.
Provide aqueous sodium hydroxide solution (for example, 5-30wt%) to methanol reactor 210 through pipeline 219.And pass through pipeline 220 and transmit rare NaBr/ aqueous solution to methanol reactor 210.
In the reactor that forms methyl alcohol, methyl bromide and water react in the presence of highly basic (sodium hydroxide), form methyl alcohol and possible by product, for example formaldehyde or formic acid.The liquid stream that contains methyl alcohol, by product, aqueous sodium bromide and aqueous sodium hydroxide solution is sent to stripping tower 222 from reactor through pipeline 221.Come the end liquid part of autoreactor/resorber 210 to flow through the water cooler 224 of controlled temperature in reactor/resorber 210 through pipeline 223.
Stripping tower 222 is equipped with reboiler 225 and optional partial reflux device (reflux).Sodium Bromide and aqueous sodium hydroxide solution are removed most of water and are flowed as stripping tower " end " liquid.The steam that leaves the stripping tower top is sent to another distillation unit 227 that is equipped with reboiler 228 and condenser 229 through 226.In distillation unit 227, from methyl alcohol, isolate by product, distillation unit 227 passes through water cooler 231 to storagetank 232 through pipeline output methyl alcohol.Steam (it contains by product) from distillation unit 227 transmits process condenser 229 and passes through pipeline 234 then to by product storagetank 235 through pipeline 233.Randomly, according to the concrete by product and the boiling point thereof that produce, methyl alcohol can be used as overhead product and takes out, and by product reclaims as substrate.
The discharging current of removing from distillation unit 222 and reboiler 225 comprises water and Sodium Bromide and aqueous sodium hydroxide solution.It is sent out through pipeline 236 from the distillation unit, and before being sent to Sodium Bromide receiving tank 238, cool off by water cooler 237.Expectation reduces the pH of this salts solution.This can be by from hydrogen bromide receiving tank 218, through pipeline 239, up to the pH control device 240 that is connected to Sodium Bromide receiving tank 238, the HBr aqueous solution that it transmitted is measured realize.
Make when Sodium Bromide pH transfers to aspiration level (for example, omiting subacidity) in the receiving tank 238, aqueous sodium bromide is put from this groove and is removed, and transmits by strainer 242 through pipeline 241, is sent to the electrolyzer 243 with anode 244 and negative electrode 245.Strainer is set with the film in the protection electrolyzer.The electrolyzer of preferred polyphone rather than single pond are as electrolyzer.
Aqueous sodium bromide is electrolysis in electrolyzer, and bromide anion is at anodic oxidation (2Br -→ Br 2+ 2e -), water is at cathodic reduction (2H 2O+2e -→ H 2+ 2OH -).This causes forming sodium hydroxide, and it is sent to receiving tank 247 as the aqueous solution through pipeline 246 from electrolyzer.Sodium hydroxide solution passes to methanol reactor 210 through pipeline 219 then.
Molecular bromine is sent to compressor (compressor) 249 from electrolyzer through pipeline 248, is sent to moisture eliminator 250 then.Make bromine through over-heat-exchanger 205, return bromination reactor 203 then through well heater 251 more if necessary simultaneously.Dissociate and also remove from electrolyzer 243 in the molecular bromine of anolyte, transmit anolyte to stripping tower 253 from this pond through pipeline 252, in stripping tower 253, bromine is by isolating with Sweet natural gas stripping (supplying with through pipeline 254) or by alternate manner.Before being back to bromination reactor as mentioned above, molecular bromine is sent to compressor 249, moisture eliminator 250 etc. by pipeline 255.
The hydrogen that produces in the electrolyzer is by pipeline 256 output, compression and randomly pass to generator unit 258 in compressor 257.Residual methane or other rare gas element can form reactor from methyl alcohol and remove through pipeline 259.Methane or Sweet natural gas can pass to generator unit 258 to strengthen generating.If desired, Sweet natural gas that adds or methane can be supplied to this unit through pipeline 260.
Describe the laboratory implementation key element of this method among Fig. 3, methane and gas bromine are reacting in the Glass tubing bromination reactor under 450 ℃, and the period is 60 seconds.Product is methyl bromide, HBr and methylene bromide, and methane conversion is 75%.Form in the reactor at methyl alcohol, methyl bromide, HBr and methylene bromide and water react in the presence of sodium hydroxide to form methyl alcohol and formaldehyde (forming from methylene bromide).Confirm that further the formaldehyde disproportionation is methyl alcohol and formic acid.Therefore, generally speaking, product is methyl alcohol and formic acid.
The membrane-type electrolytic cell of process using shown in Fig. 3, rather than diaphragm type pond.In membrane cisterna, sodium ion flow to cathode compartment with water gaging seldom.On the contrary, in the diaphragm type pond, sodium ion and water all enter cathode compartment.In another embodiment of the present invention shown in Fig. 4, be to use the barrier film pond, cause the anolyte relevant constantly to consume with NaBr.For the NaBr restock, the anolyte that consumes is transported to bromine stripping tower 253 through pipeline 252, in stripping tower 253, remove bromine and be sent to compressor 249 and moisture eliminator then 250.NaBr solution is sent to NaBr receiving tank 238 from stripping tower 253 through pipeline 270, and it mixes with denseer NaBr solution in receiving tank 238.The further feature of this technology and among Fig. 3 those are similar.
In the present invention on the other hand, molecular halogen is used the negative electrode that does not produce hydrogen, and promptly the oxygen depolarization negative electrode is by electrolytic recovery, and this negative electrode that does not produce hydrogen obviously reduces power consumption by producing water to replace hydrogen.Fig. 5 describes an embodiment of this aspect of the present invention, relates to the production higher hydrocarbon in this case.Schema is similar to shown in Fig. 1, note is arranged below to show difference.
In bromination reactor 303, bromine and Sweet natural gas, methane or other light hydrocarbons react, then reaction in coupling reactor 305.Organism separates in HBr absorptive unit 307 with HBr.Aqueous sodium bromide is sent to the electrolyzer 316 that is equipped with anode 317, oxygen depolarization negative electrode 318 and oxygen intake manifold or pipeline 324 through pipeline 315.Water that adds or electrolytic solution or pH control compound is sent to this pond through pipeline 319 as required.
Produce molecular bromine (2Br at anode -→ Br 2+ 2e -), wet bromine is sent to moisture eliminator 321 through pipeline 320, by well heater 323, and the logical then bromination reactor 303 that is back to.At negative electrode, oxygen is electrolytic reduction (2H in the presence of water 2O+2e -→ H 2+ 2OH -), hydroxide ion leaves as aqueous sodium hydroxide solution, is sent to HBr absorptive unit 307 through 311.
The present invention also provides the improved electrolyzer that halogenide is molecular halogen that is used to transform, and an one embodiment is shown among Fig. 6.Pond 400 comprises gas supply manifold 401, can supply with manifold 401 by gas and introduce oxygen, air or oxygen-rich air; Gas diffusion cathode 402, its oxygen permeable (or oxygen-containing gas); Cationic exchange membrane 403; Be arranged at the catholyte liquid chamber 404 between cationic exchange membrane and the gas diffusion cathode; Anolyte chamber 405; With anode 406, it extends to anolyte chamber.When operating under alkaline condition, to the negative electrode electrolyte liquor chamber, aqueous sodium hydroxide solution is removed from this chamber through another outlet 408 by the 407 introducing water that enter the mouth.Similarly, to the anode electrolyte liquor chamber, molecular bromine sends away through pipeline 410 from anolyte chamber by the 409 introducing aqueous sodium bromides that enter the mouth.Anode and negative electrode can be connected to the power supply (not shown), and it can comprise the equipment that is used to transform AC to DC electric current (for example commutator rectifier, motor generator, semiconductor rectifier, convertor or the like synchronously) and other assembly.
In operation, introduce water to the negative electrode electrolyte liquor chamber, 409 introduce aqueous sodium bromides to anode electrolyte liquor chamber 405 by entering the mouth by water inlet 407.Oxygen Flow is supplied with manifold 401 by gas and is fed, and opens the power supply that feeds the pond.Sodium Bromide reduces at anode, and bromine gas is emitted and sent away through pipeline 410, and sodium ion is sent to the catholyte liquid chamber by cationic exchange membrane.At negative electrode, in the presence of water, the oxygen electrolytic reduction is a hydroxide ion.Aqueous sodium hydroxide solution leaves the catholyte liquid chamber by exporting 408.
Electrolyzer described herein can be used for cooperating various production technique to use, and comprises being used for the respective embodiments described above.When power consumption became the essential problem of considering, just this method shows his superiority especially, and it was also advantageous for the place of not wishing to produce hydrogen (for example, need pay special attention to the fire part, as offshore drilling assembly etc.).
Although the present invention can be used for various full scale plants, but at sea oil-well rig or production platform or be positioned at the equipment of land, side area adopt the continuous processing of preparation higher hydrocarbon described herein or methyl alcohol etc., can embody its special value.The part practicality is to transform and is difficult to fluent material for example higher hydrocarbon or the methyl alcohol that transporting material (for example, Sweet natural gas) is easier transportation.Other practicality are to apply to have on the production unit of power generation capacity, for example generator or other power-supply units.
This aspect embodiment according to the present invention, improved production unit is provided, wherein oilyly gentlely go out from well pump, and extract from underground thus, this equipment has generator or other power-supply unit, improvement comprises: (a) reaction forms haloalkane, the optional basic completely consumed of molecular halogen under the processing condition of haloalkane and hydrogen halide being enough to form by molecular halogen and the oil that pumps from well or gas; (b) by making haloalkane and first catalyzer form higher hydrocarbon and hydrogen halide being enough to form contact under the processing condition of higher hydrocarbon and hydrogen halide; (c) separate higher hydrocarbon from hydrogen halide; (d) use the electricity that provides by generator or power supply to come electrolysis to transform hydrogen halide and be hydrogen and molecular halogen, make that thus halogen utilizes again.
In another embodiment, improved production unit is provided, wherein oil or gas pump from well, and extract from underground thus, this equipment has generator or other power supply, improvement comprises: (a) reaction forms haloalkane, the optional basic completely consumed of molecular halogen under the processing condition of haloalkane and hydrogen halide being enough to form by molecular halogen and hydrocarbon feed; (b) by making haloalkane and alkali aqueous solution form methyl alcohol and alkali halide being enough to form contact under the processing condition of methyl alcohol and alkali halide; (c) from the alkaline halide separation of methanol; (d) use the electricity that provides by generator or power supply to come electrolysis to transform alkali halide and be hydrogen, molecular halogen and alkali aqueous solution, make halogen and alkali utilize again thus.
In another aspect of this invention, the above-mentioned general fashion of halogenation, product formation, product separation and electrolytic regeneration halogen step that comprises is used to make alkylamine.Therefore, in one embodiment, Sweet natural gas, methane or other aliphatic hydrocrbon raw materials are converted into alkylamine through the intermediate bromoalkane.Raw material and gas bromine are sent to bromination reactor by the pipeline that separates and make it reaction.Brominated product (for example, methyl bromide and HBr) and possible unreacting hydrocarbon are sent to heat exchanger through pipeline, and heat exchanger reduces their temperature.Bromoalkane is sent to the amination reaction device through pipeline then.Ammonia or ammoniacal liquor also provide to the amination reaction device by the pipeline that separates.Make bromoalkane and ammonia be enough to form alkylamine (for example, RN 2) and the processing condition of Sodium Bromide under react, then it is separated in the above-mentioned relevant similar mode of methyl alcohol of producing.Aqueous sodium bromide is sent to electrolyzer through pipeline, and its electrolysis in electrolyzer is converted into hydrogen and molecular bromine, makes bromine be used in next circulation thus again.
With reference now to Fig. 7 and 8,, other two aspects of the present invention are described, wherein coal is converted into the more coke of high value, and perhaps coal or biological substance are converted into the more polyvalent alcohol of high value (polyvalent alcohol), and the halogen that uses in this technology passes through electrolytic regeneration.In embodiment shown in Figure 7, broken coal and molecular bromine are reacted at low temperatures, form coke, HBr and bromination coal intermediate (" C xBr n").Bromination coal intermediate is converted into coke by contact catalyst, forms other hydrogen bromide thus.Coke is with after hydrogen bromide separates, and hydrogen bromide is sent to electrolyzer through pipeline, and is similar to the above, makes molecular bromine regeneration and utilizing again thus.
Fig. 8 describes similar technology, wherein coal or biological substance derived hydrocarbon bromination, form bromoalkane or bromoalkane and HBr thus, in above-mentioned similar mode handle thereafter, for example, bromoalkane and HBr separate and make to small part and bromoalkane and alkali (for example, sodium hydroxide) reaction form Sodium Bromide, water and polyvalent alcohol (" C thus xH Y-q(OH) q").From Sodium Bromide separating multicomponent alcohol, aqueous sodium bromide is sent to electrolyzer through pipeline, and molecular bromine regeneration therein also separates and utilization more subsequently.
Following indefiniteness embodiment illustrates various embodiment of the present invention or feature, comprise that methane bromination, C-C coupling form higher hydrocarbon, as light olefin and aromatic substance (benzene,toluene,xylene (" BTX ")), methyl bromide be hydrolyzed to that methyl alcohol, methylene bromide are hydrolyzed to methyl alcohol and formaldehyde and subsequently disproportionation be formic acid.
Embodiment 1 methane bromination
Methane (11sccm, 1.0atm) with nitrogen (15sccm 1.0atm) at room temperature mixes by T type pipe, in 18 ℃ by being full of the bubbler of bromine.CH 4/ N 2/ Br 2Mixture passes to 500 ℃ of Glass tubings (internal diameter 2.29cm, long 30.48cm is full of granulated glass sphere) of preheating, and the methane bromination reaction takes place therein, and the residence time is 60 seconds, mainly produces monobromethane, methylene bromide and HBr:
CH 4+Br 2→CH 3Br+CH 2Br 2+HBr
Along with product leaves reactor, they are collected by polyphone trap (trap), the 4MNaOH that uses with HBr in wherein containing, and contain the n-Hexadecane of dissolved hydrocarbon product (containing octadecane) as much as possible as internal standard.Volatile constituent (as methane) is collected in the HBr/ hydrocarbon trap airbag afterwards.
After the bromination reaction, coke or carbonaceous sediment burnt 4 hours in 500 ℃ of hot blasts (5sccm), absorbed CO with saturated barium hydroxide solution 2As barium carbonate.All products are quantitative by GC.The CO that emits when amount of coke can be according to decoking 2Amount is determined.The result is summarized in Fig. 9.
Embodiment 2 CH 3The Br coupling is a light olefin
2.27g 5%Mg doping ZSM-5 (CBV8014) zeolite is put into tubular type quartz reactor (1.0cm ID), this reactor is preheated to 400 ℃ before reaction.To pass through N 2The CH of dilution 3Br is pumped to reactor, with miniature liquid pump (micro liquid pump) control CH 3Br flow velocity 24 μ l/min, N 2Flow velocity 93.3ml/min.CH 3The Br linked reaction is carried out on catalyst bed, and the residence time is 0.5sec, CH 3The Br dividing potential drop is 0.1, sets according to this flow velocity.
React after 1 hour, product leaves reactor, and collects by the polyphone trap, wherein contains in being useful on and the 4M NaOH of HBr, and contains the n-Hexadecane of dissolved hydrocarbon product (containing octadecane as internal standard) as much as possible.Volatile constituent such as methane and light olefin are collected in the HBr/ hydrocarbon trap airbag afterwards.
After the linked reaction, coke or carbonaceous sediment burnt 4 hours in 500 ℃ of hot blasts (5sccm), and saturated barium hydroxide solution absorbs CO 2As barium carbonate.All products are quantitative by GC.The CO that amount of coke is emitted during according to decoking 2Amount is determined.The result is summarized in Figure 10.
Even under the so short residence time, CH 3The Br transformation efficiency also reaches 97.7%.In the coupled product, C 3H 6And C 2H 4Be primary product, their total amount accounts for 50% of carbon yield.BTX, other hydrocarbon, hydrobromic ether and micro-coke account for all the other shares that transform carbon.
Embodiment 3 CH 3Br is coupled to BTX
Mn ion-exchange ZSM-5 zeolite (CBV3024, long 6cm) grain pack into the quartz tubular reactor (ID, 1.0cm) in, this reactor is preheated to 425 ℃ before reaction.N 2The CH of dilution 3The Br pump is to reactor, by miniature liquid pump control CH 3Br flow velocity 18 μ l/min, N 2Flow velocity 7.8ml/min.CH 3The Br linked reaction is carried out on catalyst bed, and the residence time is 5.0sec, CH 3The Br dividing potential drop is 0.5, sets according to flow velocity.
React after 1 hour, product leaves reactor, and collects by the polyphone trap, and the 4M NaOH that uses with HBr in wherein containing also contains the n-Hexadecane of dissolved hydrocarbon product (containing octadecane as internal standard) as much as possible.Volatile constituent such as methane and light olefin are collected in the HBr/ hydrocarbon trap airbag afterwards.
After the linked reaction, coke or carbonaceous sediment burnt 4 hours in 500 ℃ of hot blasts (5sccm), absorbed CO with saturated barium hydroxide solution 2As barium carbonate.All products are by the GC quantification.The CO that amount of coke is emitted during according to decoking 2Amount is determined.The result is summarized in Fig. 8.
Adopt this BTX maximum operation pattern, CH 3Br can transform fully.The BTX productive rate reaches 35.9%.Other hydrocarbon, aromatic substance, hydrobromic ether and coke account for 51.4%, 4.8%, 1.0% and 6.9% of carbon recovery respectively.Propane is the main ingredient of " other hydrocarbon ", and it is sent back to be used for contrary disproportionation, follows further coupling to promote the BTX overall yield higher.
Embodiment 4 monobromethane causticities are hydrolyzed to methyl alcohol
CH 3Br+NaOH→CH 3OH+NaBr
In being equipped with the 30ml stainless steel VCR reactor of stirring rod, add 13.2g 1M aqueous sodium hydroxide solution (13.2mmol) and 1.3g monobromethane (12.6mmol) successively.Reactor purges to remove upper air before closing cover cap gently with nitrogen.Closed reactor places and is preheated to 150 ℃ aluminum heater, reaction beginning simultaneously.Be reflected at and stir operation 2 hours under this temperature.
Behind the stopped reaction, reactor places ice-water bath cooled interior product at the beginning.After opening reactor, reaction solution is sent in the container dilutes with cold water.Container is connected in the airbag (if airbag is arranged) of collecting the unreacted monobromethane.Reaction solution is weighed, and production concentration is analyzed with the GC-FID instrument, and the capillary column of suitable water-based injection wherein is installed.
The gaseous product analysis shows does not have monobromethane residual, shows that monobromethane transforms fully.According to product liquid concentration is measured, by calculating, the productive rate of methyl alcohol (comprising micro-methyl ether) is 96%.
Embodiment 5 methylene bromide causticities are hydrolyzed to formaldehyde, and then disproportionation is methyl alcohol and formic acid
CH 2Br 2+2NaOH→HCHO+2NaBr+H 2O
HCHO+1/2H 2O→1/2CH 3OH+1/2HCOOH
Except adopting higher NaOH/CH 2Br 2Ratio (2.26) adopts the mode identical with embodiment 5 to carry out the causticity hydrolysis of methylene bromide in addition.Collect after the reaction solution, the dense hydrogen chloride solution that adds q.s with in and excessive sodium hydrate and acidifying sodium formate.Observing methyl alcohol and formic acid is only product, shows to be hydrolyzed to behind methyl alcohol and the formaldehyde then that the complete disproportionation of formaldehyde is (other) methyl alcohol and formic acid.GC analyzes and shows that the methylene bromide transformation efficiency reaches 99.9%; And methyl alcohol and formic acid productive rate reach 48.5% and 47.4% respectively.
Embodiment 4 and 5 confirms: under the causticity condition of appropriateness, monobromethane can complete hydrolysis be a methyl alcohol, and methylene bromide can complete hydrolysis be methyl alcohol and formic acid.The result is summarized in table 1.
Table 1
CH 3Br and CH 2Br 2Causticity hydrolysis and HCHO disproportionation subsequently
Figure A20088001607600251
The present invention describes with reference to various representativenesses and preferred implementation, but the invention is not restricted to this.When considering the disclosure content, conspicuous for those skilled in the art other improves and equivalent is also included within the scope of the invention.
As an example, molecular bromine also can adopt the abstraction technique that carries out simultaneously to remove from electrolyzer, wherein uses inert organic solvents for example chloroform, tetracol phenixin, ether etc.The introducing solvent is one side to the pond; Bromine distributes between water and organic phase; Carrying the bromine solvent exports from the pond opposite side.Bromine can separate from solvent by distillation or other suitable technology then, and the system that is back to is then utilized again.With the water ratio, bromine more helps being distributed in to be had in the solvent of obvious more high resolution, in chloroform and tetracol phenixin it.Extract in this mode and to play dual purpose: it makes Br 2With other bromine form (for example, Br that may exist -, OBr -, they dissolve in organic phase) separate; Separate (for example, by distillation) with bromine being concentrated and being easy to from organic phase.The best pH that is used for extracting (and be used for containing bromine solutions in the air-flow heating separate bromine) is pH 3.5, under this pH, compares molecular bromine (Br with other bromine kind 2) concentration is the highest.
Improved another example as to open technology in the literary composition can utilize other various pumps, valve, well heater, water cooler, heat exchanger, control unit, power supply, equipment etc., it is added or replacement figure shown in those, with optimization process.In addition, further feature and embodiment for example be described in ' 358 the application in other examples all can be used for practice of the present invention.The present invention only limits by appended claims and equivalents thereof.

Claims (27)

1. hydrocarbon feed is converted into the continuous production method of higher hydrocarbon, this method comprises:
(a) make molecular halogen and hydrocarbon feed be enough to form haloalkane and and the working system condition of hydrogen halide under, can also be chosen under the molecular halogen condition that completely consumed is fallen substantially simultaneously and react, the formation haloalkane;
(b) haloalkane and first catalyzer are contacted being enough to form under the working system condition of higher hydrocarbon and hydrogen halide, form higher hydrocarbon and hydrogen halide;
(c) isolate higher hydrocarbon from hydrogen halide;
(d) electrolysis conversion hydrogen halide is hydrogen and molecular halogen, makes that thus halogen utilizes again; With
(e) press desirable number of times repeating step (a) to (d).
2. continuous production method as claimed in claim 1, wherein said hydrocarbon feed comprises Sweet natural gas.
3. continuous production method as claimed in claim 1, wherein said hydrocarbon feed comprises methane.
4. continuous production method as claimed in claim 1, wherein electrolysis is carried out in aqueous medium.
5. continuous production method as claimed in claim 1, wherein electrolysis is carried out in gas phase.
6. continuous production method as claimed in claim 1, wherein said higher hydrocarbon comprises fuel-grade hydrocarbon and/or aromatic hydrocarbon.
7. continuous production method as claimed in claim 6, wherein said aromatic hydrocarbon comprises benzene, toluene and dimethylbenzene.
8. hydrocarbon feed is converted into the continuous production method of methyl alcohol, this method comprises:
(a) make molecular halogen and hydrocarbon feed be enough to form under the processing condition of haloalkane and hydrogen halide, can also be chosen under the molecular halogen condition that completely consumed is fallen substantially simultaneously and react, the formation haloalkane;
(b) make haloalkane and alkaline solution form methyl alcohol and alkali halide being enough to form contact under the processing condition of methyl alcohol and alkali halide;
(c) from the alkali halide separation of methanol;
(d) electrolytic alkali halogenide is converted into hydrogen, molecular halogen and alkaline solution, makes halogen and alkali utilize thus again; With
(e) press desirable number of times repeating step (a) to (d).
9. continuous production method as claimed in claim 8, wherein said hydrocarbon feed comprises Sweet natural gas.
10. continuous production method as claimed in claim 8, wherein said hydrocarbon feed comprises methane.
11. continuous production method as claimed in claim 8, wherein electrolysis is carried out in aqueous medium.
12. continuous production method as claimed in claim 8, wherein electrolysis is carried out in gas phase.
13. hydrocarbon feed is converted into the continuous production method of alkylamine, and this method comprises:
(a) make molecular halogen and hydrocarbon feed be enough to form under the processing condition of haloalkane and hydrogen halide, can also be chosen under the molecular halogen condition that completely consumed is fallen substantially simultaneously and react, form haloalkane;
(b) make haloalkane and the basic amine aqueous solution form alkylamine and alkali halide being enough to form contact under the processing condition of alkylamine and alkali halide;
(c) from alkali halide, separate alkylamine;
(d) electrolysis conversion alkali halide is hydrogen and molecular halogen, makes that thus halogen utilizes again; With
(e) press desirable number of times repeating step (a) to (d).
14. continuous production method as claimed in claim 12, wherein, described basic amine comprises NaNH 2
15. continuous production method as claimed in claim 12, wherein said haloalkane comprises monobromethane, and described basic amine comprises NaNH 2, described haloalkane comprises monobromethane.
16. for a cover oil or gas are pumped from well, and thus from the underground production unit that obtains oil or gas, this equipment has generator or other power supply, its improvements are to introduce following technology in this equipment:
(a) make molecular halogen and the oil that from well, pumps or gas be enough to form under the processing condition of haloalkane and hydrogen halide, can also be chosen under the molecular halogen condition that completely consumed is fallen substantially simultaneously and react, the formation haloalkane;
(b) by making haloalkane and first catalyzer form higher hydrocarbon and hydrogen halide being enough to form contact under the processing condition of higher hydrocarbon and hydrogen halide;
(c) from hydrogen halide, separate higher hydrocarbon;
(d) electricity that uses generator or power supply to provide comes electrolysis conversion hydrogen halide to be hydrogen and molecular halogen, makes that thus halogen utilizes again.
17. improve technology described in claim 16, wherein said oil or gas production unit are positioned at the sea.
18. for a cover oil or gas are pumped from well, and thus from the underground production unit that obtains oil or gas, this equipment has generator or other power supply, its improvements are to introduce following technology in this equipment:
(a) make molecular halogen and hydrocarbon feed be enough to form under the processing condition of haloalkane and hydrogen halide, can also be chosen under the molecular halogen condition that completely consumed is fallen substantially simultaneously and react, the formation haloalkane;
(b) by making haloalkane and alkali aqueous solution form methyl alcohol and alkali halide being enough to form contact under the processing condition of methyl alcohol and alkali halide;
(c) separation of methanol from alkali halide;
(d) electricity that uses generator or power supply to provide comes electrolysis conversion alkali halide to be hydrogen, molecular halogen and alkali aqueous solution, makes halogen and alkali utilize thus again.
19. improve technology described in claim 18, wherein said oil or gas production unit are positioned at the sea.
20. coal is converted into the continuous production method of coke and hydrogen, and this method comprises:
(a) reaction forms bromination coal intermediate and hydrogen halide under the processing condition of bromination coal intermediate and hydrogen halide being enough to form to make broken coal and molecular halogen;
(b) reaction forms coke and hydrogen halide under the processing condition of coke and hydrogen halide being enough on the catalyzer to form by bromizating the coal intermediate;
(c) separate coke from hydrogen halide;
(d) the hydrogen halide electrolysis that will form in step (a) and/or step (b) is converted into hydrogen and molecular halogen, makes halogen utilize thus again; With
(e) press desirable number of times repeating step (a) to (d).
21. the hydrocarbon that coal or biological substance are produced is converted into the continuous production method of polyvalent alcohol, this method comprises:
(a) make hydrocarbon feed that molecular halogen and coal or biological substance produce be enough to form under the processing condition of haloalkane and hydrogen halide, can also be chosen under the molecular halogen condition that completely consumed is fallen substantially simultaneously and react, the formation haloalkane;
(b) by making haloalkane and alkali aqueous solution form polyvalent alcohol and alkali halide being enough to form contact under the processing condition of polyvalent alcohol and alkali halide;
(c) separating multicomponent alcohol from alkali halide;
(d) electrolysis conversion alkali halide is hydrogen and molecular halogen, makes that thus halogen utilizes again; With
(e) press desirable number of times repeating step (a) to (d).
22. hydrocarbon feed is converted into the continuous production method of higher hydrocarbon, and this method comprises:
(a) make molecular halogen and hydrocarbon feed be enough to form under the processing condition of haloalkane and hydrogen halide, can also be chosen under the molecular halogen condition that completely consumed is fallen substantially simultaneously and react, the formation haloalkane;
(b) make haloalkane and first catalyzer form higher hydrocarbon and hydrogen halide being enough to form contact under the processing condition of higher hydrocarbon and hydrogen halide;
(c) from hydrogen halide, separate higher hydrocarbon;
(d) electrolysis conversion hydrogen halide is water and molecular halogen in electrolyzer, perhaps carries out this conversion in the electrolyzer that is equipped with the oxygen depolarization negative electrode, makes that thus halogen utilizes again; With
(e) press desirable number of times repeating step (a) to (d).
23. hydrocarbon feed is converted into the continuous production method of methyl alcohol, and this method comprises:
(a) reaction forms haloalkane under the processing condition of haloalkane and hydrogen halide being enough to form to make molecular halogen and hydrocarbon feed, and molecular halogen might basic completely consumed;
(b) make haloalkane and alkali aqueous solution form methyl alcohol and alkali halide being enough to form contact under the processing condition of methyl alcohol and alkali halide;
(c) separation of methanol from alkali halide;
(d) electrolysis conversion alkali halide is molecular halogen and alkali aqueous solution in electrolyzer, perhaps carries out this conversion in the electrolyzer that is equipped with the oxygen depolarization negative electrode, makes halogen and alkali utilize thus again; With
(e) press desirable number of times repeating step (a) to (d).
24. be used for halogenide is converted into the electrolyzer of molecular halogen, this electrolyzer comprises:
Gas is supplied with manifold, can supply with manifold by described gas and introduce oxygen, air or oxygen-rich air;
Gas diffusion cathode, its oxygen permeable or oxygen-containing gas;
Cationic exchange membrane;
Be arranged at the catholyte liquid chamber between cationic exchange membrane and the described gas diffusion cathode;
Anolyte chamber; With
Anode, it extends to described anolyte chamber.
25. one kind is used to transform the method that halogenide is molecular halogen, it comprises:
The electrolyzer that comprises with lower member is provided: gas is supplied with manifold, the gas diffusion cathode of oxygen permeable or oxygen-containing gas, and cationic exchange membrane is arranged at the catholyte liquid chamber between cationic exchange membrane and the described gas diffusion cathode; Anolyte chamber; With the anode that extends to described anolyte chamber;
Introduce water to described catholyte liquid chamber;
Introduce oxygen or oxygen-containing gas to described gas and supply with manifold;
Introduce the alkali halide aqueous solution to described anolyte chamber;
Supply electric power is to described electrolyzer;
Alkali bromide forms the gas bromine in the anode reduction;
Oxygen forms alkali hydroxide in cathodic reduction;
Remove alkali hydroxide soln from described catholyte liquid chamber; With
Remove molecular bromine from described anolyte chamber.
26. method as claimed in claim 25, wherein said alkali halide comprises Sodium Bromide.
27. method as claimed in claim 25, wherein said alkali hydroxide comprises sodium hydroxide.
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