CN107254689A

CN107254689A - The electrochemical hydrogen oxide system and method aoxidized using metal

Info

Publication number: CN107254689A
Application number: CN201710352177.1A
Authority: CN
Inventors: R·J·吉利亚姆; B·博格斯; K·塞尔夫; 马格里特·K·莱克勒克; A·戈里尔; 迈克尔·约瑟夫·韦斯; 约翰·亨特·米勒; 萨马雷什·莫汗塔
Original assignee: Calera Corp
Current assignee: Arelac Inc
Priority date: 2012-03-29
Filing date: 2013-03-13
Publication date: 2017-10-17
Also published as: EP2831313A4; EP2831313B1; EP3219829A1; JP6039054B2; CN104271810B; JP2017075398A; EP2831313A1; JP2015522706A; CN104271810A; WO2013148216A1

Abstract

The invention provides the method and system to contain anode and the electrochemical cell of negative electrode, wherein the anode is contacted with metal ion, metal ion is converted into higher oxidation state from low oxidation state.Metal ion and hydrogen, unsaturated hydrocarbons and/or saturation hydrocarbon reaction formation product in higher oxidation state.

Description

The electrochemical hydrogen oxide system and method aoxidized using metal

The application be submit within 03 13rd, 2013 it is entitled " using metal aoxidize electrochemical hydrogen oxide system and The divisional application of No. 201380024643.3 Chinese patent application (international application no PCT/US2013/031064) of method ".

The cross reference of related application

The application is that Shen is continued in the part for the U.S. Patent Application Serial 13/474,598 submitted on May 17th, 2012 Please, the U.S. Patent Application Serial 13/474,598 requires the U.S. Provisional Patent Application 61/ submitted on May 19th, 2011 488,079th, the U.S. that on June 21st, 2011 submits U.S. Provisional Patent Application 61/499,499, August in 2011 are submitted on the 5th U.S. Provisional Patent Application 61/546,461 that temporary patent application 61/515,474, on October 12nd, 2011 submit, 2011 U.S. Provisional Patent Application 61/552,701 that October 28 submitted, the U.S. Provisional Patent Application submitted for 10th for 2 months for 2012 The priority for the U.S. Provisional Patent Application 61/617,390 that on March 29th, 61/597,404 and 2012 submits, above-mentioned all Shens It please be incorporated herein by reference in their entirety in this disclosure.

Background technology

In many chemical processes, it may be necessary to which caustic soda completes chemical reaction, for example, to neutralize acid, or buffer molten The pH of liquid, or precipitate from solution insoluble hydroxide.A kind of method that can be used to produce caustic soda is via electrochemistry system System.When electrochemically for example producing caustic soda by chlor-alkali, substantial amounts of energy, Yan Heshui can be used.

Polyvinyl chloride is generally known as PVC, and it is probably the third-largest most widely produced plastics, is only second to polyethylene and poly- Propylene.PVC is widely used in building because its is durable, cheap and ease of use.PVC can be made by the polymerization of VCM Make, and VCM can be manufactured by ethylene dichloride.Ethylene dichloride can be direct by using the chlorine manufactured by chlor-alkali Ethene is carried out chlorination to manufacture.

It is to need one of the electrochemical process of high energy consumption by electrolytic sodium chloride aqueous solution or brine production chlorine and caustic soda. To maintain this process of chlorine industry, overall energy requirement is, for example, about 2% (U.S.) and the about 1% (day of the total electricity of generation This).High energy consumption may to due to caused by combustion of fossil fuels high carbon dioxide discharge it is related.Accordingly, it would be desirable to meet electric power The reduction of demand is to reduce environmental pollution and slowing global warming.

The content of the invention

On the one hand there is provided a kind of method, it includes：Anode is set to be contacted with anodolyte,

Wherein the anodolyte includes metal ion；Metal ion is oxidized to higher oxygen from low oxidation state at anode State；Negative electrode is set to be contacted with catholyte；And make unsaturated hydrocarbons or saturated hydrocarbons with comprising the metal in higher oxidation state from The anodolyte of son reacts in an aqueous medium, is organised with forming the one or more comprising halogenated hydrocarbons in an aqueous medium Compound and the metal ion in low oxidation state；And by one or more organic compounds from comprising in low oxidation state Metal ion aqueous medium separation.

In the foregoing aspects of the embodiments, this method further comprises forming alkali, water or hydrogen at negative electrode. In some foregoing aspects of embodiments, this method further comprises forming alkali at negative electrode.In some foregoing aspects of implementations In scheme, this method further comprises forming hydrogen at negative electrode.In the foregoing aspects of the embodiments, this method enters one Step is included in formation water at negative electrode.In the foregoing aspects of the embodiments, negative electrode be by oxygen and water be reduced into hydroxyl from The oxygen depolarization negative electrode of son.In the foregoing aspects of the embodiments, negative electrode is that water is reduced into hydrogen and hydroxide ion Hydrogen generation negative electrode.In the foregoing aspects of the embodiments, negative electrode is that the hydrogen that hydrochloric acid is reduced into hydrogen generates the moon Pole.In the foregoing aspects of the embodiments, negative electrode is to make the oxygen depolarization negative electrode of hydrochloric acid and oxygen reaction formation water.

In some of the foregoing aspects and embodiments, methods described further comprises comprising in relatively low The aqueous medium of the metal ion of oxidation state is recycled back into anodolyte.In foregoing aspect and some realities of embodiment Apply in scheme, the aqueous medium being recycled back into anodolyte, which is included, is less than 100ppm or less than 50ppm or less than 10ppm Or less than 1ppm organic compound.

In some of the foregoing aspects and embodiments, aqueous medium includes 5-95wt% water or 5- 90wt% water or 5-99wt% water.

In some of the foregoing aspects and embodiments, metal ion include but is not limited to iron, chromium, copper, tin, Silver, cobalt, uranium, lead, mercury, vanadium, bismuth, titanium, ruthenium, osmium, europium, zinc, cadmium, gold, nickel, palladium, platinum, rhodium, iridium, manganese, technetium, rhenium, molybdenum, tungsten, niobium, Tantalum, zirconium, hafnium and combinations thereof.In some embodiments, metal ion includes but is not limited to iron, chromium, copper and tin.In some implementations In scheme, metal ion is copper.In some embodiments, the low oxidation state of metal ion is 1+, 2+, 3+, 4+ or 5+. In some embodiments, the higher oxidation state of metal ion is 2+, 3+, 4+, 5+ or 6+.In some embodiments, metal from Son is from Cu⁺It is converted into Cu²⁺Copper, metal ion is from Fe²⁺It is converted into Fe³⁺Iron, metal ion is from Sn²⁺It is converted into Sn⁴⁺ Tin, metal ion is from Cr²⁺It is converted into Cr³⁺Chromium, metal ion is from Pt²⁺It is converted into Pt⁴⁺Platinum, or its combination.

In some of the foregoing aspects and embodiments, at anode without using or do not form gas.

In some of the foregoing aspects and embodiments, this method further comprises adding into anodolyte Enter part, wherein the part interacts with the metal ion.

In some of the foregoing aspects and embodiments, this method further comprises making unsaturated hydrocarbons or saturation Hydrocarbon and the anode electrolysis qualitative response comprising the metal ion in higher oxidation state and part, the wherein reaction are in an aqueous medium Carry out.

In some of the foregoing aspects and embodiments, unsaturated hydrocarbons or saturated hydrocarbons with comprising in higher oxygen The reaction for changing the anodolyte of the metal ion of state is the metal halide or metal sulfate for being used in higher oxidation state Produce respectively halogenated hydrocarbons or sulfo group and metal halide or the halogenation of metal sulfate in low oxidation state or Sulfonating reaction.In some embodiments, metal halide or metal sulfate in low oxidation state are recycled back into sun In the electrolyte of pole.

In some of the foregoing aspects and embodiments, the sun of the metal ion in higher oxidation state is included Pole electrolyte further includes the metal ion in low oxidation state.

In some of the foregoing aspects and embodiments, unsaturated hydrocarbons is compound of formula I, and it is produced after halogenation Raw Formula II compound：

Wherein, n is 2-10；M is 0-5；And q is 1-5；

R is independently selected from hydrogen, halogen ,-COOR ' ,-OH and-NR ' (R "), and wherein R ' and R " is independently selected from hydrogen, alkyl and substitution Alkyl；And

X is the halogen selected from chlorine, bromine and iodine.

In some embodiments, m is 0；N is 2；Q is 2；And X is chlorine.In some embodiments, compound of formula I is Ethene, propylene or butylene, and Formula II compound is then ethylene dichloride, propylene dichloride or Isosorbide-5-Nitrae-dichloroetane respectively.One In a little embodiments, this method further comprises forming VCM by ethylene dichloride and forms poly- by VCM (vinyl chloride).

In some of the foregoing aspects and embodiments, saturated hydrocarbons is formula III compound, and it is produced after halogenation Raw formula IV compound：

Wherein, n is 2-10；K is 0-5；And s is 1-5；

X is the halogen selected from chlorine, bromine and iodine.

In some embodiments, formula III compound is methane, ethane or propane.

In some of the foregoing aspects and embodiments, one or more organic compounds are further wrapped Include chlorethanol, dichloro acetaldehyde, trichloroacetaldehyde or its combination.

In some of the foregoing aspects and embodiments, by one or more organic compounds from comprising in The step of aqueous medium of the metal ion of low oxidation state is separated is including the use of adsorbent.

In some of the foregoing aspects and embodiments, adsorbent be selected from activated carbon, alumina (alumina), Active silica, polymer and combinations thereof.In some of the foregoing aspects and embodiments, adsorbent is to be selected from Polyethylene, polypropylene, polystyrene, polymethylpentene, PB Polybutene-1, polyolefin elastomer, polyisobutene, ethylene, propylene rubber The polyolefin of glue, PMA, poly- (methyl methacrylate), poly- (Isobutyl methacrylate) and combinations thereof.Preceding In some embodiments for stating aspect and embodiment, adsorbent is activated carbon.In foregoing aspect and some realities of embodiment Apply in scheme, adsorbent is polystyrene.

In some of the foregoing aspects and embodiments, adsorbent absorption organising more than 95%w/w Compound.

In some of the foregoing aspects and embodiments, methods described, which further comprises using, is selected from inertia stream Body purging, the skill for changing electrochemical conditions, improving temperature, reduction partial pressure, reduction concentration, inert gas or steam blowing and combinations thereof Art reproducing adsorbent.In some of the foregoing aspects and embodiments, methods described further comprises by inertia Fluid purging carrys out reproducing adsorbent.In some of the foregoing aspects and embodiments, methods described further comprises At high temperature by inert gas or steam blowing come reproducing adsorbent.

In some of the foregoing aspects and embodiments, methods described further comprises in anodolyte Turbulent flow is provided to improve the mass transfer at anode.Description has been carried out in the method for providing turbulent flow herein.

In some of the foregoing aspects and embodiments, methods described further comprises making such as, but not limited to The diffusion-enhanced anode of porous anode is contacted with anodolyte.The diffusion-enhanced anode, such as, but not limited to porous anode, Description has been carried out herein.

On the one hand there is provided a kind of system, it is included：The anode contacted with the anodolyte comprising metal ion, its In the anode be configured as metal ion being oxidized to higher oxidation state from low oxidation state；The moon contacted with catholyte Pole；Reactor, the reactor is operably coupled to anode chamber, and is configured as making comprising the metal in higher oxidation state The anodolyte of ion reacts to be formed in an aqueous medium comprising halo in an aqueous medium with unsaturated hydrocarbons or saturated hydrocarbons One or more organic compounds of hydrocarbon and the metal ion in low oxidation state；And separator, the separator is operable Ground is connected to reactor and anode, and is configured as one or more organic compounds from comprising in low oxidation state The aqueous medium separation of metal ion.

In some of the foregoing aspects and embodiments, the separator further comprises recirculating system, The recirculating system is operably coupled to anode to recycle the aqueous medium comprising the metal ion in low-oxidation-state To anodolyte.

In some of the foregoing aspects and embodiments, anode is diffusion-enhanced anode, such as, but not limited to Porous anode.As described herein, the porous anode can be flat or undulatory.

In some of the foregoing aspects and embodiments, separator is included selected from activated carbon, alumina, activity two The adsorbent of silica, polymer and combinations thereof.

In some of the foregoing aspects and embodiments, the system is further included in anodolyte and matched somebody with somebody Body, the wherein part are configured as interacting with metal ion.

In some embodiments of the foregoing aspects and embodiments of the system, negative electrode is arranged to react oxygen and water Form the gas diffusion cathode of hydroxide ion.In some embodiments of the foregoing aspects and embodiments of the system, negative electrode It is arranged to generate negative electrode by the hydrogen of reductive water formation hydrogen and hydroxide ion.In terms of aforementioned system and embodiment party In some embodiments of case, negative electrode is arranged to the hydrogen that acid such as hydrochloric acid is reduced into hydrogen generating negative electrode.In aforementioned system Aspect and embodiment some embodiments in, negative electrode be arranged to make hydrochloric acid and oxygen react to be formed water gas diffusion it is cloudy Pole.

In some embodiments of the foregoing aspects and embodiments of the system, anode is configured as not forming gas.

In some of the foregoing aspects and embodiments, the system further includes and is configured to make catholyte Matter contacts to form the settling vessel of carbonate and/or bicarbonate product with bivalent cation.

In some of the foregoing aspects and embodiments, metal ion is copper.In foregoing aspect and embodiment party In some embodiments of case, unsaturated hydrocarbons is ethene.In some of the foregoing aspects and embodiments, described one Plant or a variety of organic compounds are selected from ethylene dichloride, chlorethanol, dichloro acetaldehyde, trichloroacetaldehyde and combinations thereof.

In some of the foregoing aspects and embodiments, separator is one or more comprising polystyrene Fill column.

In some embodiments, with unsaturated hydrocarbons to the processing of the metal ion in higher oxidation state in anode chamber Carry out.In some embodiments, the processing of the metal ion in higher oxidation state is entered outside anode room with unsaturated hydrocarbons OK.In some embodiments, chlorohydrocarbon is produced to the processing of the metal ion in higher oxidation state with unsaturated hydrocarbons.One In a little embodiments, the chlorohydrocarbon is ethylene dichloride.In some embodiments, this method further comprises being handled with ethene Cu²⁺Ion is to form ethylene dichloride.In some embodiments, this method further comprises processing ethylene dichloride to be formed VCM.In some embodiments, this method further comprises processing VCM to be formed poly- (vinyl chloride).

Brief description of the drawings

The new feature of the present invention is specifically described in the appended claims.By reference to below to former using the present invention Detailed description and its accompanying drawing that the illustrative embodiment of reason is illustrated by, are better understood the features and advantages of the present invention, In the drawings：

Figure 1A is the diagram of one embodiment of the invention.

Figure 1B is the diagram of one embodiment of the invention.

Fig. 2 is the diagram of one embodiment of the invention.

Fig. 3 A are the diagrams of one embodiment of the invention.

Fig. 3 B are the diagrams of one embodiment of the invention.

Fig. 4 A are the diagrams of one embodiment of the invention.

Fig. 4 B are the diagrams of one embodiment of the invention.

Fig. 5 A are the diagrams of one embodiment of the invention.

Fig. 5 B are the diagrams of one embodiment of the invention.

Fig. 5 C are the diagrams of one embodiment of the invention.

Fig. 6 is the diagram of one embodiment of the invention.

Fig. 7 A are the diagrams of one embodiment of the invention.

Fig. 7 B are the diagrams of one embodiment of the invention.

Fig. 7 C are the diagrams of one embodiment of the invention.

Fig. 8 A are the diagrams of one embodiment of the invention.

Fig. 8 B are the diagrams of one embodiment of the invention.

Fig. 8 C are the diagrams of one embodiment of the invention.

Fig. 9 is the diagram of one embodiment of the invention.

Figure 10 A are the diagrams of one embodiment of the invention.

Figure 10 B are the diagrams of one embodiment of the invention.

Figure 11 is the diagram of one embodiment of the invention.

Figure 12 is the diagram of one embodiment of the invention.

Figure 13 is the diagram of one embodiment of the invention.

Figure 14 is the illustrative graph as described in embodiment hereof 2.

Figure 15 is the illustrative graph as described in embodiment hereof 3.

Figure 16 shows that diffusion-enhanced anode as described herein is such as, but not limited to several examples of porous anode.

Figure 17 be the different adsorbents as described in embodiment hereof 5 it is illustrative shown in.

Figure 18 is the illustrative graph of absorption as described in embodiment hereof 5 and regeneration.

Figure 19 is the exemplary dynamic adsorption column as described in embodiment hereof 5.

Figure 20 is the illustrative graph as described in embodiment hereof 5.

Detailed description of the invention

Disclosed herein is the system and method being related in the anode compartment by anodized metallization ion, the metal ion is in sun In pole room higher oxidation state is oxidized to from low oxidation state.

As one of ordinary skill understandable, electro-chemical systems of the invention and method may be configured with replacement, Salting liquid of equal value, such as Klorvess Liquid or sodium chloride solution or magnesium chloride solution or metabisulfite solution or ammonium chloride solution, To generate the aqueous slkali of equivalence, such as potassium hydroxide and/or potassium carbonate and/or saleratus or hydroxide in catholyte Sodium and/or sodium carbonate and/or sodium acid carbonate or magnesium hydroxide and/or magnesium carbonate.Therefore, with regard to such equivalent based on the present invention's System and method or by the present invention system and method propose for, these equivalents are within the scope of application.

Before the present invention is more fully described, it will be appreciated that the invention is not restricted to described specific embodiment, its Itself is it is of course possible to changing.It will also be understood that terms used herein is only used for describing the purpose of particular, rather than purport In limitation, because the scope of the invention is only defined by the appended claims.

When the scope of offer value, it will be appreciated that each value between two parties between the upper and lower bound of this scope (is accurate to Pointed by any other 1/10th of lower limit unit, unless the context clearly indicates otherwise) and in the scope Or value between two parties be included in the present invention.These small range of upper and lower bounds can be independently include the smaller range In, and be also contained in the present invention, except any limit value specifically excluded in the scope.When the scope is included in limit value One or two when, the scope for excluding any one or two in these contained limit values is also included in the present invention.

The some scopes proposed herein with numerical value can be interpreted the numerical value of " about "." about " it is used herein to after it Precise number and provide literal support with the numeral numeral nearly or approximately after the term.It is determined that a numeral is It is no nearly or approximately when the numeral specifically enumerated, close to or approximate unrequited (unrequited) numerical value can be at it The numerical value of the offer value of substantially equal with the numerical value specifically enumerated in the context occurred.

Unless otherwise defined, otherwise all technologies used herein and scientific terminology have with it is of the art general The identical implication that logical technical staff is commonly understood by.Will now be described representational illustrative method and material, but with herein The similar or equivalent any method of these methods and material and material of description can also be used in the practice or inspection of the present invention.

Cited all publications and patents are all incorporated herein by reference in this specification, just as especially and individually Ground points out that each single publication or patent are incorporated by reference into, and is incorporated herein by reference with disclosure and description and institute The relevant method of the publication of reference and/or material.Quoting for any publication should be for it in the disclosure before the applying date Hold, and should not be construed as recognizing the present invention due to first invention without qualification earlier than this publication.In addition, the public affairs provided Opening the date may be different from actual publication date, and actual publication date may need independent confirmation.

It should be pointed out that unless the context clearly indicates otherwise, the odd number shape otherwise used herein and in appended claims Formula " one ", " one kind " and "the" include the plural form of referring to thing.It should further be noted that claim can be written as excluding Any optional key element.Therefore, this statement is intended to enumerate relevant exclusiveness term as " solely as using with claim elements From ground ", " only " etc. or the first basis for using " negative " limitation.

Those skilled in the art should be understood that each single reality described and illustrated herein upon reading the present disclosure The scheme of applying has single component and feature, the spy that the component and feature can easily with any of other several embodiments Levy and separate or combine, without departing from the scope of the present invention or spirit.Any method enumerated can by cited event order Or carried out by any other possible order in logic.

Composition, method and system

On the one hand there is provided be related to metal ion in the anode chamber of electrochemical cell from low oxidation state be oxidized to compared with The method and system of high oxidation state.The metal ion with higher oxidation state formed can be used or for commercial use as former state, Such as, but not limited to chemosynthesis reaction, reduction reaction etc..On the one hand, electrochemical cell described herein provide efficiently and The system of low-voltage, wherein metallic compound such as metal halide, the metal with higher oxidation state for example generated by anode Chloride or metal sulfate, available for other purposes, such as, but not limited to generate hydrogen chloride, hydrochloric acid, hydrogen bromide, hydrogen by hydrogen Bromic acid, hydrogen iodide, hydroiodic acid or sulfuric acid, and/or halogenated hydrocarbons or sulfo group (sulfohydrocarbons) are generated by hydrocarbon.

" halogenated hydrocarbons " or " halogenated hydrocarbon " includes the hydrocarbon that halogen replaces as used herein, and wherein halogen can be based on The chemical valence allowed and be connected to any number of halogen on hydrocarbon.Halogen includes fluorine, chlorine, bromine and iodine.The example bag of halogenated hydrocarbons Include chlorohydrocarbon, bromo-hydrocarbons and idohydrocarbon.Chlorohydrocarbon includes but is not limited to single chlorohydrocarbon, dichloromethane, three chlorohydrocarbons etc..For gold Belong to halide, such as, but not limited to metal bromide and metal iodide, the gold with higher oxidation state generated by anode chamber Belong to bromide or metal iodide can be used for other purposes, such as, but not limited to generate hydrogen bromide or hydrogen iodide and/or generation bromine For hydrocarbon or idohydrocarbon, such as, but not limited to single bromo-hydrocarbons, two bromo-hydrocarbons, three bromo-hydrocarbons, single idohydrocarbon, two idohydrocarbons, three iodos Hydrocarbon etc..In some embodiments, the metal ion in higher oxidation state can as former state be sold on commercial market.

" sulfo group " is included based on the chemical valence allowed by one or more-SO as used herein₃H or-OSO₂OH replaces Hydrocarbon.

The electrochemical cell of the present invention can be any electrochemical cell, wherein the metal ion in low oxidation state exists The metal ion in higher oxidation state is converted into anode chamber.In such electrochemical cell, cathode reaction can be Any reaction of alkali is formed with or without in cathode chamber.Such cathode consumption electronics simultaneously carries out any reaction, including but do not limit In the reaction of the reaction of water formation hydroxide ion and hydrogen, or oxygen and water formation hydroxide ion, or from acid such as hydrochloric acid Proton reduction to form hydrogen, or the proton from hydrochloric acid and oxygen formation water reaction.

In some embodiments, electrochemical cell may include to generate alkali in the cathode chamber of battery.Give birth in the cathodic compartment Into alkali can be used for commercial use as former state, or can be handled form carbonate/carbonic acid containing bivalent cation with bivalent cation Hydrogen salt.In some embodiments, the alkali generated in the cathodic compartment can be used for sequestering or capture carbon dioxide.Carbon dioxide can be deposited It is in the flue gas discharged by a variety of industrial plants.Carbon dioxide can be in the form of carbonate and/or bicarbonate product Sequestering.In some embodiments, the metallic compound containing the metal in higher oxidation state can be taken out from anode chamber, and Use it for any commercial process well known by persons skilled in the art.Therefore, anodolyte and catholyte two Person can be used in product of the production available for commercial use, so as to provide the technique of more economical efficient and low energy consumption.

In some embodiments, the metallic compound generated by anode chamber can be used as former state, or can with hydrogen, no Saturated hydrocarbons or saturation hydrocarbon reaction generate respectively hydrogen chloride, hydrochloric acid, hydrogen bromide, hydrobromic acid, hydrogen iodide or hydroiodic acid, sulfuric acid and/or Purified before halogenated hydrocarbons or sulfo group.In some embodiments, metallic compound can be in the place of generation hydrogen on the spot Use, and/or in some embodiments, the metallic compound taken out from anode chamber can be transferred to the position of generation hydrogen, And hydrogen chloride, hydrochloric acid, hydrogen bromide, hydrobromic acid, hydrogen iodide or hydroiodic acid are formed by it.In some embodiments, metal compound Thing can be formed and used on the spot in electro-chemical systems, and such as, but not limited to the unsaturated hydrocarbons of ethylene gas is generated or turned here Move on to herein, and/or in some embodiments, the metallic compound taken out from anode chamber can be transferred to such as, but not limited to second The position that the unsaturated hydrocarbons of alkene gas is generated or is transferred to, and halogenated hydrocarbons such as chlorohydrocarbon is formed by it.In some embodiment party In case, ethylene gas generates facility and the electro-chemical systems of the present invention are integrated, to produce the metal in higher oxidation state simultaneously Compound and ethylene gas, and make their mutual phase processors to form product, such as ethylene dichloride (EDC).Ethylene dichloride 1,2- dichloroethanes, dichloroethanes, 1,2- ethylene dichlorides, glycol dichloride, freon 150, borer can be referred to as Sol, brocide, destruxol borer-sol, dichlor-mulsion, Holland's oil or granosan.In some embodiment party In case, electro-chemical systems and VCM (VCM) production facility or polyvinyl chloride (PVC) production facility of the invention are integrated, So that the EDC for the system and method formation for passing through the present invention is used for VCM and/or PVC and produced.

Electro-chemical systems described herein and method provide one or more better than Conventional electrochemical known in the art The advantage of system, including but not limited to undesirable gas diffusion anodes；Higher battery efficiency；Lower voltage；Without platinum anode； The sequestering of carbon dioxide；Green and environment-friendly chemicals；And/or the formation of a variety of viable commercial products.

The system and method for the present invention provide the electrochemical cell for producing multi-products, and the product such as, but not limited to exists Anode formation metal salt, for forming the metal salt of various other chemicals, negative electrode formation alkali, for formed it is a variety of its The alkali of his product, and/or in the hydrogen of negative electrode formation.All such products have all been defined herein, and are referred to alternatively as " green Colour chemistry product ", are formed because such chemicals is used under low-voltage or low energy with the electrochemical cell of high-efficiency operation 's.Low-voltage described herein or low energy consumption process will cause less compared with the conventional method for manufacturing similar chemicals or product CO2 emission.In some embodiments, carbon dioxide is captured from flue gas by the alkali by being generated in negative electrode To form chemicals or product, such as, but not limited to carbonate and bicarbonate product.Such carbonate and bicarbonate product It is " green chemical ", because they, which are reduced, pollutes and provide cleaner environment.

Metal

" metal ion " or " metal " includes that higher oxidation state can be converted into from low oxidation state as used herein Any metal ion.The example of metal ion include but is not limited to iron, chromium, copper, tin, silver, cobalt, uranium, lead, mercury, vanadium, bismuth, titanium, Ruthenium, osmium, europium, zinc, cadmium, gold, nickel, palladium, platinum, rhodium, iridium, manganese, technetium, rhenium, molybdenum, tungsten, niobium, tantalum, zirconium, hafnium and combinations thereof.In some realities Apply in scheme, metal ion includes but is not limited to iron, copper, tin, chromium or its combination.In some embodiments, metal ion is Copper.In some embodiments, metal ion is tin.In some embodiments, metal ion is iron.In some embodiments In, metal ion is chromium.In some embodiments, metal ion is platinum." oxidation state " is included in material as used herein The oxidizability of atom.For example, in some embodiments, oxidation state is the net charge on ion.Metal ion is at anode Some examples of reaction are as shown in following table I (SHE is standard hydrogen electrode).It is also shown for the theoretical value of anode potential.Should Understand, some changes can occur based on condition, pH, electrolyte concentration etc. for these voltages, and these changes are completely in the present invention In the range of.

Table I

Metal ion can exist as metallic compound or metal alloy or its combination.In some embodiments, connect It is identical in the anion of metal and the anion of electrolyte.For example, when sodium chloride or potassium chloride are used as electrolyte, such as but not limiting It is used as metallic compound in metal chlorides such as iron chloride, copper chloride, stannic chloride, chromium chlorides.For example, sodium sulphate or potassium sulfate are used When making electrolyte, such as, but not limited to the metal sulfate such as ferric sulfate, copper sulphate, STANNOUS SULPHATE CRYSTALLINE, chromium sulfate is used as metallic compound. For example, when sodium bromide or KBr are used as electrolyte, the such as, but not limited to metal bromide such as ferric bromide, copper bromide, stannic bromide As metallic compound.

In some embodiments, the anion of electrolyte can be partially or completely different from the anion of metal.For example, In some embodiments, the anion of electrolyte can be sulfate radical, and the anion of metal can be chlorion.In such reality Apply in scheme, the chlorion with low concentration may be needed in an electrochemical cell.For example, in some embodiments, by Relatively high Cl- concentration in anodolyte caused by the chlorion of electrolyte and the chlorion of metal, can cause anode Undesired ionic species in electrolyte.This can be avoided by using the electrolyte containing the ion beyond removing chloride. In some embodiments, anodolyte can be the ion similar from anionic metal and it is different with metal ion it is cloudy from The combination of son.For example, when anionic metal is chlorion, anodolyte can be the mixing of sulfate ion and chlorion Thing.In such embodiment, it may be needed with sufficient concentrations of chlorion with dissolved metal salt in electrolyte, but can not be high Attend the meeting and cause undesired ionic species to be formed.

In some embodiments, based on required final product selection electrolyte and/or metallic compound.For example, such as Fruit wants that the reaction between hydrogen and metallic compound obtains HCl, then metal chloride is used as into metallic compound, and by chlorination Sodium is used as electrolyte.For example, if it is desired to the reaction between metallic compound and hydrocarbon obtains brominated hydrocarbon, then metal bromide is used Make metallic compound, and sodium bromide or KBr are used as electrolyte.

In some embodiments, can be based on solubility of the metal in anodolyte and/or metal from compared with suboxides State is oxidized to the cell voltage needed for higher oxidation state to select the metal ion used in electro-chemical systems described herein. For example, by Cr²⁺It is oxidized to Cr³⁺Required voltage is likely lower than Sn²⁺To Sn⁴⁺Required voltage, still, hydrogen and Cr³⁺Reaction The HCl of formation amount is likely lower than and Sn⁴⁺The HCl of formation, because obtaining two chlorine atoms from each tin molecule.Therefore, one In a little embodiments, when that may need relatively low cell voltage, can be used causes the metal ion oxygen of relatively low cell voltage Change, such as, but not limited to Cr²⁺.For example, the reaction captured for wherein carbon dioxide by the alkali generated by catholyte, can Relatively low voltage can be needed.In some embodiments, when the product such as hydrochloric acid of higher amount may be needed, even if voltage phase To higher, it is possible to use cause the metal ion of the product of higher amount, such as, but not limited to Sn²⁺.For example, the battery electricity of tin system Pressure may be higher than chromium system, but uses Sn⁴⁺The sour concentration of formation may offset the high voltage of the system.It should be appreciated that The product formed by system and method described herein, such as acid, halogenated hydrocarbons, sulfo group, carbonate, bicarbonate still It is " green " chemicals, because compared with the energy input needed for manufacturing the conventionally known method of same products, they are to pass through The technique manufacture of more low energy consumption.

In some embodiments, in anodolyte simultaneously exist in low oxidation state metal ion and in compared with The metal ion of high oxidation state.In some embodiments, it may need simultaneously to have in compared with suboxides in anodolyte The metal ion of state and higher oxidation state.The proper ratio of metal ion in relatively low and higher oxidation state in anodolyte It has been described herein.The metal ion in low oxidation state of mixing may have with the metal ion in higher oxidation state Help the voltage in relatively low electro-chemical systems, and to the high yield in the corresponding catalytic reaction of hydrogen or hydrocarbon and selection Property.

In some embodiments, the metal ion in anodolyte is the metal ion of mixing.For example, comprising in The anodolyte of the copper ion of low oxidation state and copper ion in higher oxidation state can also include another metal ion species, Such as, but not limited to iron.In some embodiments, in anodolyte the presence of the second metal ion can advantageously reduce with The gross energy for the electrochemical reaction that catalytic reaction is combined.

Some examples including but not limited to copper sulphate for the metallic compound that can be used in the system and method for the present invention (II), copper nitrate (II), stannous chloride (I), cuprous bromide (I), cuprous iodide (I), ferric sulfate (III), ferric nitrate (III), Frerrous chloride (II), ferrous bromide (II), iron iodide (II), stannous sulfate (II), nitric acid stannous (II), stannous chloride (II), stannous bromide (II), stannous iodide (II), chromium sulfate (III), chromic nitrate (III), chromous chloride (II), chromous bromide (II), chromous iodide (II), zinc chloride (II), zinc bromide (II) etc..

Part

In some embodiments, additive such as part is used together with metal ion, to improve anode indoor metal The efficiency of ionic oxide formation and/or improve catalytic reaction of the metal ion in anode chamber's inside/outside, such as, but not limited to hydrogen, with Unsaturated hydrocarbons and/or the reaction with saturated hydrocarbons.In some embodiments, part and metal are added into anodolyte together In.In some embodiments, part is connected with metal ion.In some embodiments, part passes through covalent bond, ionic bond And/or coordinate bond is connected with metal ion.In some embodiments, part is connected by Van der Waals'attractive force and metal ion Connect.

Therefore, there is provided the method comprised the following steps in some embodiments：Anode is set to be connect with anodolyte Touch；Metal ion is oxidized to higher oxidation state from low oxidation state at anode；Part is added into anodolyte, wherein The part interacts with metal ion；With negative electrode is contacted with catholyte.In some embodiments there is provided including The method of following steps：Anode is set to be contacted with anodolyte；At anode by metal ion from low oxidation state be oxidized to compared with High oxidation state；Part is added into anodolyte, wherein the part interacts with metal ion；Negative electrode and negative electrode are electric with making Solve matter contact, wherein negative electrode generation hydroxide ion, water and/or hydrogen.There is provided including following in some embodiments The method of step：Anode is set to be contacted with anodolyte；Metal ion is oxidized to higher oxygen from low oxidation state at anode Change state；Part is added into anodolyte, wherein the part interacts with metal ion；Negative electrode is set to be connect with catholyte Touch, wherein negative electrode generation hydroxide ion, water and/or hydrogen；With make metal containing part and in higher oxidation state from Anodolyte and the unsaturated hydrocarbons of son, hydrogen, saturated hydrocarbons or its combine and contact.

There is provided the method comprised the following steps in some embodiments：Anode is set to be contacted with anodolyte；In sun Metal halide is oxidized to higher oxidation state from low oxidation state at pole；Part is added into metal halide, wherein this is matched somebody with somebody Body interacts with metal ion；Negative electrode is contacted with catholyte, wherein the negative electrode generation hydroxide ion, water and/or Hydrogen；Halogenation is carried out to unsaturated hydrocarbons and/or saturated hydrocarbons with the metal halide in higher oxidation state.In some embodiment party In case, metal halide is metal chloride, and halogenation is chlorination reaction.In some embodiments, such method contains There is hydrogen to generate negative electrode.In some embodiments, such method contains oxygen depolarization negative electrode.In some embodiments, this Unsaturated hydrocarbons in class method is substituted or unsubstituted alkene, such as C_nH_2n, wherein n is 2-20 (or alkynes, or as entered one herein Walk the Formulas I of description), such as ethene, propylene, butylene.In some embodiments, the saturated hydrocarbons in such method be substitution or Unsubstituted alkane, such as C_nH_2n+2, wherein n is 2-20 (or formula III as further described herein), such as methane, ethane, third Alkane etc..In some embodiments, the metal in such method is metal chloride, such as copper chloride.In some embodiments In, such method causes more than 100kJ/mol or more than 150kJ/mol or more than 200kJ/mol or be 100-250kJ/mol's Net energy is saved, or this method causes the voltage more than 1V to save (below with described in Fig. 8 C).In some embodiments, Unsaturated hydrocarbons in such method is C₂-C₅Alkene, such as, but not limited to ethene, propylene, isobutene, 2- butylene (it is cis and/or It is trans), amylene etc., or C₂-C₄Alkene, such as, but not limited to ethene, propylene, isobutene, 2- butylene (cis and/or trans) etc.. In some embodiments, the unsaturated hydrocarbons in such method is that the metal ion in ethene, and such method is metal chlorine Compound, such as copper chloride.In such method, the halogenation of ethene forms EDC.In some embodiments, in such method Saturated hydrocarbons is that the metal ion in ethane, and such method is metal chloride, such as platinum chloride or copper chloride.In such side In method, the halogenation of ethane forms chloroethanes or EDC.

There is provided the system for including following component in some embodiments：The anode contacted with anodolyte, wherein The anode is configured as metal ion being oxidized to higher oxidation state from low oxidation state；Part in anodolyte, Wherein the part is configured as interacting with metal ion；With the negative electrode contacted with catholyte.In some embodiments In there is provided the system for including following component：The anode contacted with anodolyte, the wherein anode be configured as by metal from Son is oxidized to higher oxidation state from low oxidation state；Part in anodolyte, the wherein part are configured as and gold Belong to ionic interaction；With the negative electrode contacted with catholyte, the wherein negative electrode is configurable to generate hydroxide ion, water And/or hydrogen.There is provided the system for including following component in some embodiments：The anode contacted with anodolyte, its In the anode be configured as metal ion being oxidized to higher oxidation state from low oxidation state；Matching somebody with somebody in anodolyte Body, the wherein part are configured as interacting with metal ion；With the negative electrode contacted with catholyte, wherein the negative electrode quilt It is configured to form hydroxide ion, water and/or hydrogen；And reactor, it is configured as making comprising part and in higher oxygen The anodolyte of the metal ion of state and unsaturated hydrocarbons, hydrogen, saturated hydrocarbons or its composite reaction.In some embodiments, Such system includes oxygen depolarization negative electrode.In some embodiments, such system generates negative electrode comprising hydrogen.In some implementations In scheme, such system causes more than 100kJ/mol or more than 150kJ/mol or more than 200kJ/mol or be 100-250kJ/ Mol net energy is saved, or the system causes the voltage more than 1V to save (below with described in Fig. 8 C).In some embodiment party In case, the unsaturated hydrocarbons in such system is C₂-C₅Alkene, such as, but not limited to ethene, propylene, isobutene, 2- butylene are (cis And/or it is trans), amylene etc., or C₂-C₄Alkene, such as, but not limited to ethene, propylene, isobutene, 2- butylene are (cis and/or anti- Formula) etc..In some embodiments, the unsaturated hydrocarbons in such system is ethene.In some embodiments, in such system Metal be metal chloride, such as copper chloride.In some embodiments, the unsaturated hydrocarbons in such system is ethene, and Metal ion in such system is metal chloride, for example copper chloride.In such systems, the halogenation of ethene forms EDC. In some embodiments, the saturated hydrocarbons in such system is that the metal ion in ethane, and such system is metal chloride, example Such as platinum chloride, copper chloride.In such systems, the halogenation of ethane forms chloroethanes and/or EDC.

In some embodiments, part causes one or more of characteristic：Metal ion is directed to unsaturated hydrocarbons, saturation The reactivity enhancing of hydrocarbon or hydrogen, metal ion is for unsaturated hydrocarbons or the Selective long-range DEPT of saturated hydrocarbons halogenation, and halogen is from metal Ion strengthens to the transfer of unsaturated hydrocarbons, saturated hydrocarbons or hydrogen, and the redox potential reduction of electrochemical cell, metal ion exists The solubility of aqueous medium is improved, and the film of catholyte of the metal ion into electrochemical cell, which is crossed over, to be reduced, electrochemistry The corrosion of battery and/or reactor is reduced, the separation (such as size exclusion film) of metal ion and acid solution after being reacted with hydrogen Enhancing, separation (such as size exclusion film) enhancing of metal ion and halohydrocarbon solution, and combinations thereof.

In some embodiments, the connection of part and metal ion adds greatly the size of metal ion enough, obtains To prevent it from passing through the amberplex migration in battery.In some embodiments, anion-exchange membrane in electrochemical cell It can be used together with size exclusion film so that the metal ion being connected with part moving from anodolyte to catholyte Shifting is prevented.Such film is described below.In some embodiments, the connection of part and metal ion adds metal The solubility of ion in an aqueous medium.In some embodiments, the connection of part and metal ion reduces electrochemistry electricity Corrosion of metal in pond and reactor.In some embodiments, the connection of part and metal ion is added greatly enough The size of metal ion, is able to promote metal ion and acid or the separation with halogenated hydrocarbons after reaction.In some embodiments, match somebody with somebody The presence of body and/or can be prevented with the connection of metal ion metal ion in solution a variety of halogenation species formation, and only have Beneficial to the formation of required species.For example, the presence of part can limit a variety of halogenation species of copper ion for example in copper ion solution But it is not limited to [CuCl₃]^2-Or CuCl₂ ⁰Formation, and be conducive to Cu²⁺/Cu⁺The formation of ion.In some embodiments, part Presence in metal ion solution and/or connect through the total voltage that one or more above-mentioned advantages reduce battery is provided.

" part " includes the part of any characteristic that can strengthen metal ion as used herein.In some embodiments In, the part includes but is not limited to substituted or unsubstituted aliphatic phosphine, substituted or unsubstituted aromatic series phosphine, substitution or not taken The amino phosphine in generation, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen compound, substituted or unsubstituted ring Shape nitrogen-containing compound, substituted or unsubstituted aliphatic sulfur-containing compound, substituted or unsubstituted cyclic compounds containing sulfur, substitution Or unsubstituted heterocyclic compound and substituted or unsubstituted heteroaromatics.

Substituted or unsubstituted aliphatic nitrogen compound

In some embodiments, part is formula A substituted or unsubstituted aliphatic nitrogen compound：

Wherein n and m independently are 0-2, and R and R¹It is independently H, alkyl or substituted alkyl.In some embodiments, alkane Base is methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group or amyl group.In some embodiments, substituted alkyl is by one The alkyl that individual or multiple groups (including alkenyl, halogen, amine, the amine of substitution and combinations thereof) are replaced.In some embodiments, Substituted amine is selected from hydrogen and/or the group of alkyl is replaced.

In some embodiments, part is formula B substituted or unsubstituted aliphatic nitrogen compound：

Wherein R and R¹It is independently H, alkyl or substituted alkyl.In some embodiments, alkyl is methyl, ethyl, third Base, isopropyl, butyl, isobutyl group or amyl group.In some embodiments, substituted alkyl is by one or more groups (bag Include alkenyl, halogen, amine, amine and combinations thereof of substitution) alkyl that is replaced.In some embodiments, substituted amine is selected from The group of hydrogen and/or alkyl is replaced.

In some embodiments, part is formula B substituted or unsubstituted aliphatic nitrogen donor, wherein R and R¹It is independent Ground is H, C₁-C₄Alkyl or substituted C₁-C₄Alkyl.In some embodiments, C₁-C₄Alkyl is methyl, ethyl, propyl group, different Propyl group, butyl or isobutyl group.In some embodiments, substituted C₁-C₄Alkyl be by one or more groups (including alkenyl, Halogen, amine, amine and combinations thereof of substitution) C that is replaced₁-C₄Alkyl.In some embodiments, substituted amine is selected from hydrogen And/or C₁-C₃The group of alkyl is replaced.

The concentration of part can be selected based on many kinds of parameters, including but not limited to concentration of metal ions, part solubility etc..

Containing the heteroatomic substituted or unsubstituted crown ether of O, S, P or N

In some embodiments, part is formula C substituted or unsubstituted crown ether：

Wherein R is independently O, S, P or N；And n is 0 or 1.

In some embodiments, part is formula C substituted or unsubstituted crown ether, and wherein R is O, and n is 0 or 1. In some embodiments, part is formula C substituted or unsubstituted crown ether, and wherein R is S, and n is 0 or 1.In some embodiment party In case, part is formula C substituted or unsubstituted crown ether, and wherein R is N, and n is 0 or 1.In some embodiments, part is Formula C substituted or unsubstituted crown ether, wherein R is P, and n is 0 or 1.In some embodiments, part be formula C substitution or Unsubstituted crown ether, wherein R are O or S, and n is 0 or 1.In some embodiments, part is the substituted or unsubstituted of formula C Crown ether, wherein R are O or N, and n is 0 or 1.In some embodiments, part is formula C substituted or unsubstituted crown ether, its Middle R is N or S, and n is 0 or 1.In some embodiments, part is formula C substituted or unsubstituted crown ether, wherein R be N or P, and n is 0 or 1.

Substituted or unsubstituted phosphine

In some embodiments, part is formula D substituted or unsubstituted phosphine, or its oxide：

Wherein R¹、R²And R³It is independently H, alkyl, the alkyl of substitution, alkoxy, the alkoxy of substitution, aryl, the virtue of substitution Base, heteroaryl, the heteroaryl of substitution, amine, the amine of substitution, cycloalkyl, cycloalkyl, Heterocyclylalkyl and the substituted heterocycle alkane of substitution Base.

The example of formula D oxide is：

In formula D compounds or some embodiments of its oxide, R¹、R²And R³It is independently the alkane of alkyl and substitution Base.In formula D compounds or some embodiments of its oxide, R¹、R²And R³It is independently the alkyl of alkyl and substitution, its The group that middle substituted alkyl is selected from alkoxy, the alkoxy of substitution, amine and substituted amine is replaced.In formula D compounds or In some embodiments of its oxide, R¹、R²And R³It is independently the alkyl of alkyl and substitution, wherein the alkyl replaced is selected Replaced from the group of alkoxy and amine.

In formula D compounds or some embodiments of its oxide, R¹、R²And R³It is independently alkoxy and substitution Alkoxy.In formula D compounds or some embodiments of its oxide, R¹、R²And R³It is independently the alkane of alkoxy and substitution Epoxide, wherein the group that the alkoxy replaced is selected from alkyl, the alkyl of substitution, amine and substituted amine is replaced.In formula D chemical combination In some embodiments of thing or its oxide, R¹、R²And R³It is independently the alkoxy of alkoxy and substitution, wherein replace Alkoxy is selected from alkyl and the group of amine is replaced.

In formula D compounds or some embodiments of its oxide, R¹、R²And R³It is independently the virtue of aryl and substitution Base.In formula D compounds or some embodiments of its oxide, R¹、R²And R³It is independently the aryl of aryl and substitution, its The group that middle substituted aryl is selected from alkyl, the alkyl of substitution, alkoxy, the alkoxy of substitution, amine and substituted amine is taken Generation.In formula D compounds or some embodiments of its oxide, R¹、R²And R³It is independently the aryl of aryl and substitution, its The group that middle substituted aryl is selected from alkyl, alkoxy and amine is replaced.In some implementations of formula D compounds or its oxide In scheme, R¹、R²And R³It is independently the aryl of aryl and substitution, wherein the aryl replaced is selected from the base of alkyl and alkoxy Group is replaced.

In formula D compounds or some embodiments of its oxide, R¹、R²And R³It is independently heteroaryl and substitution Heteroaryl.In formula D compounds or some embodiments of its oxide, R¹、R²And R³Be independently heteroaryl and substitution it is miscellaneous Aryl, wherein the heteroaryl replaced is selected from alkyl, the alkyl of substitution, alkoxy, the alkoxy of substitution, amine and substituted amine Group is replaced.In formula D compounds or some embodiments of its oxide, R¹、R²And R³It is independently heteroaryl and substitution Heteroaryl, wherein the group that the heteroaryl replaced is selected from alkyl, alkoxy and amine is replaced.

In formula D compounds or some embodiments of its oxide, R¹、R²And R³It is independently cycloalkyl and substitution Cycloalkyl.In formula D compounds or some embodiments of its oxide, R¹、R²And R³It is independently the ring of cycloalkyl and substitution Alkyl, wherein the cycloalkyl replaced is selected from alkyl, the alkyl of substitution, alkoxy, the alkoxy of substitution, amine and substituted amine Group is replaced.In formula D compounds or some embodiments of its oxide, R¹、R²And R³It is independently cycloalkyl and substitution Cycloalkyl, wherein the group that the cycloalkyl replaced is selected from alkyl, alkoxy and amine is replaced.

In formula D compounds or some embodiments of its oxide, R¹、R²And R³It is independently Heterocyclylalkyl and substitution Heterocyclylalkyl.In formula D compounds or some embodiments of its oxide, R¹、R²And R³It is independently Heterocyclylalkyl and to take The Heterocyclylalkyl in generation, wherein the Heterocyclylalkyl replaced be selected from alkyl, substitution alkyl, alkoxy, substitution alkoxy, amine and The group of substituted amine is replaced.In formula D compounds or some embodiments of its oxide, R¹、R²And R³It is independently miscellaneous Cycloalkyl and the Heterocyclylalkyl of substitution, wherein the group that the Heterocyclylalkyl replaced is selected from alkyl, alkoxy and amine is replaced.

In formula D compounds or some embodiments of its oxide, R¹、R²And R³It is independently the amine of amine and substitution. In formula D compounds or some embodiments of its oxide, R¹、R²And R³It is independently the amine of amine and substitution, wherein the amine replaced The group for being selected from alkyl, the alkyl of substitution, alkoxy and substituted alkoxy is replaced.In formula D compounds or its oxide Some embodiments in, R¹、R²And R³It is independently the amine of amine and substitution, wherein the amine replaced is selected from alkyl and alkoxy Group replaced.In formula D compounds or some embodiments of its oxide, R¹、R²And R³It is independently amine and substitution Amine, wherein the amine replaced is replaced by alkyl.

Wherein R¹、R²And R³It is independently H；Alkyl；It is selected from the group institute of alkoxy, the alkoxy of substitution, amine and substituted amine Substituted substitution alkyl；Aryl；It is selected from alkyl, the alkyl of substitution, alkoxy, the alkoxy of substitution, amine and substituted amine The substituted aryl that group is replaced；Heteroaryl；It is selected from alkyl, the alkyl of substitution, alkoxy, the alkoxy of substitution, amine and takes The substituted heteroaryl that the group of the amine in generation is replaced；Amine；It is selected from alkyl, alkyl, alkoxy and the substituted alkoxy of substitution The substitution amine that is replaced of group；Cycloalkyl；It is selected from alkyl, the alkyl of substitution, alkoxy, the alkoxy of substitution, amine and takes The substituted cycloalkyl that the group of the amine in generation is replaced；Heterocyclylalkyl；Be selected from alkyl, substitution alkyl, alkoxy, substitution The substituted heterocycle alkyl that the group of alkoxy, amine and substituted amine is replaced.

Wherein R¹、R²And R³It is independently H；Alkyl；It is selected from the substitution alkyl that the group of alkoxy and amine is replaced；Aryl；Quilt The substituted aryl that group selected from alkyl, alkoxy and amine is replaced；Heteroaryl；It is selected from the group of alkyl, alkoxy and amine The substituted heteroaryl replaced；Amine；It is selected from the substitution amine that the group of alkyl and alkoxy is replaced；Cycloalkyl；It is selected from alkane The substituted cycloalkyl that the group of base, alkoxy and amine is replaced；Heterocyclylalkyl；With the group for being selected from alkyl, alkoxy and amine The substituted heterocycle alkyl replaced.

Substituted or unsubstituted pyridine

In some embodiments, part is formula E substituted or unsubstituted pyridine：

Wherein R¹And R²Be independently H, alkyl, substitution alkyl, aryl, substitution aryl, heteroaryl, substitution heteroaryl, Amine, the amine of substitution, cycloalkyl, cycloalkyl, Heterocyclylalkyl and the substituted Heterocyclylalkyl of substitution.

In some embodiments, part is formula E substituted or unsubstituted pyridine：

Wherein R¹And R²It is independently H, alkyl, the alkyl of substitution, heteroaryl, heteroaryl, amine and the substituted amine of substitution.

In some embodiments, part is formula E substituted or unsubstituted pyridine, wherein R¹And R²It is independently H, alkane Base and the alkyl of substitution, wherein the group that the alkyl replaced is selected from alkoxy, the alkoxy of substitution, amine and substituted amine is taken Generation.In some embodiments, part is formula E substituted or unsubstituted pyridine, wherein R¹And R²It is independently H, alkyl and takes The alkyl in generation, wherein the alkyl replaced is selected from amine and the group of the amine of substitution is replaced, wherein the amine replaced is by alkyl, heteroaryl Base or substituted heteroaryl are replaced.

In some embodiments, part is formula E substituted or unsubstituted pyridine, wherein R¹And R²It is independently heteroaryl Base and the heteroaryl of substitution.In some embodiments, part is formula E substituted or unsubstituted pyridine, wherein R¹And R²It is independent Ground is heteroaryl and the substituted heteroaryl replaced by alkyl, alkoxy or amine.

In some embodiments, part is formula E substituted or unsubstituted pyridine, wherein R¹And R²Be independently amine and Substituted amine.In some embodiments, part is formula E substituted or unsubstituted pyridine, wherein R¹And R²Be independently amine and Substituted amine, wherein the amine replaced is replaced by alkyl, heteroaryl or substituted heteroaryl.

In some embodiments, part is formula E substituted or unsubstituted pyridine：

Wherein R¹And R²It is independently H；Alkyl；It is selected from the substitution alkyl that is replaced of group of amine and the amine of substitution；Heteroaryl； The substituted heteroaryl replaced by alkyl, alkoxy or amine；Amine；With replaced by alkyl, heteroaryl or substituted heteroaryl Replace amine.

Substituted or unsubstituted dintrile

In some embodiments, part is formula F substituted or unsubstituted dintrile：

Wherein R is hydrogen, alkyl or substituted alkyl；N is 0-2；M is 0-3；And k is 1-3.

In some embodiments, part is formula F substituted or unsubstituted dintrile, and wherein R is hydrogen, alkyl or by alcoxyl Base or the substitution alkyl of amine substitution；N is 0-1；M is 0-3；And k is 1-3.

In some embodiments, part is formula F substituted or unsubstituted dintrile, and wherein R is hydrogen or alkyl；N is 0- 1；M is 0-3；And k is 1-3.

On the one hand there is provided the composition comprising aqueous medium, the aqueous medium is included selected from substituted or unsubstituted Phosphine, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen compound, substituted or unsubstituted pyridine, substitution Or the part of unsubstituted dintrile and combinations thereof；And metal ion.

On the one hand there is provided the composition comprising aqueous medium, the aqueous medium is included selected from substituted or unsubstituted Phosphine, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen compound, substituted or unsubstituted pyridine, substitution Or the part of unsubstituted dintrile and combinations thereof；With selected from iron, chromium, copper, tin, silver, cobalt, uranium, lead, mercury, vanadium, bismuth, titanium, ruthenium, osmium, The metal ion of europium, zinc, cadmium, gold, nickel, palladium, platinum, rhodium, iridium, manganese, technetium, rhenium, molybdenum, tungsten, niobium, tantalum, zirconium, hafnium and combinations thereof.

On the one hand there is provided the composition comprising aqueous medium, the aqueous medium is included selected from substituted or unsubstituted Phosphine, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen compound, substituted or unsubstituted pyridine, substitution Or the part of unsubstituted dintrile and combinations thereof；Metal ion；And salt.

On the one hand there is provided the composition comprising aqueous medium, the aqueous medium is included selected from substituted or unsubstituted Phosphine, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen compound, substituted or unsubstituted pyridine, substitution Or the part of unsubstituted dintrile and combinations thereof；Selected from iron, chromium, copper, tin, silver, cobalt, uranium, lead, mercury, vanadium, bismuth, titanium, ruthenium, osmium, The metal ion of europium, zinc, cadmium, gold, nickel, palladium, platinum, rhodium, iridium, manganese, technetium, rhenium, molybdenum, tungsten, niobium, tantalum, zirconium, hafnium and combinations thereof；And salt.

On the one hand there is provided the composition comprising aqueous medium, the aqueous medium is included selected from substituted or unsubstituted Phosphine, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen compound, substituted or unsubstituted pyridine, substitution Or the part of unsubstituted dintrile and combinations thereof；Selected from iron, chromium, copper, tin, silver, cobalt, uranium, lead, mercury, vanadium, bismuth, titanium, ruthenium, osmium, The metal ion of europium, zinc, cadmium, gold, nickel, palladium, platinum, rhodium, iridium, manganese, technetium, rhenium, molybdenum, tungsten, niobium, tantalum, zirconium, hafnium and combinations thereof；And bag Include sodium chloride, ammonium chloride, sodium sulphate, ammonium sulfate, calcium chloride or the salt of its combination.

On the one hand there is provided the composition comprising aqueous medium, the aqueous medium is included selected from substituted or unsubstituted Phosphine, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen compound, substituted or unsubstituted pyridine, substitution Or the part of unsubstituted dintrile and combinations thereof；Metal ion；With including sodium chloride, ammonium chloride, sodium sulphate, ammonium sulfate, chlorination The salt of calcium or its combination.

On the one hand there is provided the composition comprising aqueous medium, the aqueous medium is included selected from substituted or unsubstituted Phosphine, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen compound, substituted or unsubstituted pyridine, substitution Or the part of unsubstituted dintrile and combinations thereof；Metal ion；Salt；With unsaturated hydrocarbons or saturated hydrocarbons.

On the one hand there is provided the composition comprising aqueous medium, the aqueous medium is included selected from substituted or unsubstituted Phosphine, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen compound, substituted or unsubstituted pyridine, substitution Or the part of unsubstituted dintrile and combinations thereof；Selected from iron, chromium, copper, tin, silver, cobalt, uranium, lead, mercury, vanadium, bismuth, titanium, ruthenium, osmium, The metal ion of europium, zinc, cadmium, gold, nickel, palladium, platinum, rhodium, iridium, manganese, technetium, rhenium, molybdenum, tungsten, niobium, tantalum, zirconium, hafnium and combinations thereof；Salt；With Unsaturated hydrocarbons or saturated hydrocarbons.

On the one hand there is provided the composition comprising aqueous medium, the aqueous medium is included selected from substituted or unsubstituted Phosphine, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen compound, substituted or unsubstituted pyridine, substitution Or the part of unsubstituted dintrile and combinations thereof；Selected from iron, chromium, copper, tin, silver, cobalt, uranium, lead, mercury, vanadium, bismuth, titanium, ruthenium, osmium, The metal ion of europium, zinc, cadmium, gold, nickel, palladium, platinum, rhodium, iridium, manganese, technetium, rhenium, molybdenum, tungsten, niobium, tantalum, zirconium, hafnium and combinations thereof；Including Sodium chloride, ammonium chloride, sodium sulphate, ammonium sulfate, calcium chloride or the salt of its combination；With unsaturated hydrocarbons or saturated hydrocarbons.

On the one hand there is provided the composition comprising aqueous medium, the aqueous medium is included selected from substituted or unsubstituted Phosphine, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen compound, substituted or unsubstituted pyridine, substitution Or the part of unsubstituted dintrile and combinations thereof；Metal ion；Including sodium chloride, ammonium chloride, sodium sulphate, ammonium sulfate, calcium chloride Or the salt of its combination；With unsaturated hydrocarbons or saturated hydrocarbons.

On the one hand there is provided the composition comprising aqueous medium, the aqueous medium is included selected from substituted or unsubstituted Phosphine, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen compound, substituted or unsubstituted pyridine, substitution Or the part of unsubstituted dintrile and combinations thereof；Metal ion；Including sodium chloride, ammonium chloride, sodium sulphate, ammonium sulfate, calcium chloride Or the salt of its combination；With unsaturated hydrocarbons or saturated hydrocarbons selected from ethene, propylene, butylene, ethane, propane, butane and combinations thereof.

On the one hand there is provided the composition comprising aqueous medium, the aqueous medium is included selected from substituted or unsubstituted Phosphine, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen compound, substituted or unsubstituted pyridine, substitution Or the part of unsubstituted dintrile and combinations thereof；Selected from iron, chromium, copper, tin, silver, cobalt, uranium, lead, mercury, vanadium, bismuth, titanium, ruthenium, osmium, The metal ion of europium, zinc, cadmium, gold, nickel, palladium, platinum, rhodium, iridium, manganese, technetium, rhenium, molybdenum, tungsten, niobium, tantalum, zirconium, hafnium and combinations thereof；Including Sodium chloride, ammonium chloride, sodium sulphate, ammonium sulfate, calcium chloride or the salt of its combination；With selected from ethene, propylene, butylene, ethane, third The unsaturated hydrocarbons or saturated hydrocarbons of alkane, butane and combinations thereof.

Provided herein is method and system some embodiments in, part is：

The bathocuproine (bathocuprine) of sulfonation；

Pyridine；

Three (2- pyridylmethyls) amine；

Glutaronitrile；

Iminodiacetonitrile；

Malononitrile；

Succinonitrile；

Three (diethylamino) phosphines；

Three (dimethylamino) phosphines；

Three (2- furyls) phosphines；

Three (4- methoxyphenyls) phosphines；

Double (diethylamino) Phenylphosphines；

Three (N, N- tetramethylene) phosphoric triamides；

N, N- diisopropylphosphoramidite di tert butyl carbonate；

Phosphoramidic acid diethylester (diethylphosphoramidate)；

Hexamethyl phosphoramide；

Diethylenetriamines；

Three (2- amino-ethyls) amine；

N, N, N ', N ', N "-five methyl diethylentriamine；

15- crown-s 5；

The thia ring tetradecanes of 1,4,8,11- tetra-；With

Its salt or stereoisomer.

In some embodiments there is provided the method using part, including it is electric to the anode comprising metal ion solution Xie Zhizhong adds part, so as to cause one or more characteristics, includes but is not limited to：Metal ion is directed to unsaturated hydrocarbons, saturation The reactivity enhancing of hydrocarbon or hydrogen, metal ion is for unsaturated hydrocarbons or the Selective long-range DEPT of saturated hydrocarbons halogenation, and halogen is from metal Ion strengthens to the transfer of unsaturated hydrocarbons, saturated hydrocarbons or hydrogen, and the redox potential reduction of electrochemical cell, metal ion exists The solubility of aqueous medium is improved, and the film of catholyte of the metal ion into electrochemical cell, which is crossed over, to be reduced, electrochemistry The corrosion of battery and/or reactor is reduced, and the separation of metal ion and acid solution strengthens after being reacted with hydrogen, metal ion and halogen For the separation enhancing of hydrocarbon solution, and combinations thereof.

In some embodiments there is provided the method for the efficiency including improving electrochemical cell, the wherein electrochemistry is electric Pond includes the anode that is contacted with the anodolyte comprising metal ion, wherein the anode by metal ion from low oxidation state oxygen Turn to higher oxidation state.In some embodiments, efficiency is related to the voltage for putting on electrochemical cell.

" alkenyl " refers to straight or branched alkyl as used herein, and it has 2-10 carbon atom, and in some implementations In scheme, with 2-6 carbon atom or 2-4 carbon atom, and with the unsaturated position of at least one vinyl (>C=C<). Such as vinyl, acrylic, 1,3- butadienyls.

" alkoxy " refers to-O- alkyl as used herein, and wherein alkyl is defined herein.For example, alcoxyl Base includes methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, tert-butoxy, sec-butoxy and n-pentyloxy.

" alkyl " refers to monovalence saturated aliphatic hydrocarbons as used herein, and it has 1-10 carbon atom, and at some In embodiment, with 1-6 carbon atom.“C_x-C_yAlkyl " refers to the alkyl with x to y carbon atom.For example, the art Language includes straight chain and branched hydrocarbyl, such as methyl (CH₃-), ethyl (CH₃CH₂-), n-propyl (CH₃CH₂CH₂-), isopropyl ((CH₃)₂CH-), normal-butyl (CH₃CH₂CH₂CH₂-), isobutyl group ((CH₃)₂CHCH₂-), sec-butyl ((CH₃)(CH₃CH₂)CH-)、 The tert-butyl group ((CH₃)₃C-), n-pentyl (CH₃CH₂CH₂CH₂CH₂-) and neopentyl ((CH₃)₃CCH₂-)。

" amino " or " amine " refers to-NH as used herein₂Group.

" aryl " refers to the aromatic group with 6-14 carbon atom and without ring hetero atom as used herein, and it has There are monocyclic (such as phenyl) or multiple condensation (fusion) rings (such as naphthyl or anthryl).

" cycloalkyl " refers to the saturation or partly full with 3-14 carbon atom and without ring hetero atom as used herein The cyclic group of sum, it has monocyclic or including the polycyclic of condensed ring, bridged ring and spiro ring system.The example of cycloalkyl includes such as ring Propyl group, cyclobutyl, cyclopenta, cyclooctyl and cyclohexenyl group.

" halo " or " halogen " refers to fluorine, chlorine, bromine and iodine group as used herein.

" heteroaryl " refers to the 1-6 heteroatomic aromatic groups for being selected from oxygen, nitrogen and sulphur as used herein, and Including monocyclic (such as furyl) and polycyclic system (such as benzimidazolyl-2 radicals-base and benzimidazole -6- bases).Heteroaryl include but It is not limited to pyridine radicals, furyl, thienyl, thiazolyl, isothiazolyl, triazolyl, imidazole radicals, isoxazolyls, pyrrole radicals, pyrazoles Base, pyridazinyl, pyrimidine radicals, benzofuranyl, tetrahydrochysene benzfuran base, isobenzofuran-base, benzothiazolyl, benzisothiazole Base, BTA base, indyl, isoindolyl, benzoxazolyl, quinolyl, tetrahydric quinoline group, isoquinolyl, quinazolinone Base, benzimidazolyl, benzoisoxazole base or benzothienyl.

" Heterocyclylalkyl " refers to 1-5 selected from nitrogen, sulphur or the heteroatomic saturation of oxygen or part as used herein The cyclic group of saturation, and including monocyclic and polycyclic system, including condensed ring, bridged ring and spiro ring system.Heterocyclic radical includes but not limited In THP trtrahydropyranyl, piperidyl, N- methyl piperidine -3- bases, piperazinyl, N- methylpyrrolidin- 3- bases, 3- pyrrolidinyls, 2- pyrroles Pyrrolidone -1- bases, morpholinyl and pyrrolidinyl.

" substituted alkoxy " refers to the alkyl of-O- substitutions as used herein, wherein the alkyl replaced as determined herein Justice.

" substituted alkyl " refers to 1-5 substituent as used herein, and has 1-3 in some embodiments Individual or 1-2 substituent alkyl, the substituent is selected from alkenyl, halogen ,-OH ,-COOH, amino, the wherein amino of substitution, institute State substituent as defined herein.

" substituted amino " or " substituted amine " refers to-NR as used herein¹⁰R¹¹Group, wherein R¹⁰And R¹¹Independently Selected from hydrogen, alkyl, the alkyl of substitution, aryl, aryl, heteroaryl and the substituted heteroaryl replaced.

" substituted aryl " refers to by 1-8 substituent as used herein, and in some embodiments by 1-5, 1-3 or the aryl of 1-2 substituent substitution, the substituent be selected from alkyl, the alkyl of substitution, alkoxy, the alkoxy replaced, Amine, amine, alkenyl, halogen ,-OH and the-COOH of substitution, wherein the substituent is as defined herein.

" substituted cycloalkyl " refers to 1-8 or 1-5 substituent, or in some embodiments as used herein In there is the cycloalkyl as herein defined of 1-3 substituent, the substituent is selected from alkyl, the alkyl replaced, alkoxy, taken Alkoxy, amine, amine, alkenyl, halogen ,-OH and the-COOH of substitution in generation, wherein the substituent is as defined herein.

" substituted heteroaryl " refers to the heteroaryl replaced by 1-5 or 1-3 or 1-2 substituent as used herein Base, the substituent is selected from for substituent defined in the aryl of substitution.

" substituted Heterocyclylalkyl " refers to by 1-5 substituent, or in some embodiments by 1-3 as used herein The heterocyclic group as herein defined of individual substituent substitution, the substituent is as defined in the cycloalkyl for substitution.

It should be appreciated that in all substituted groups defined above, by being further substituted with base with what its own had Polymer obtained from defining substituent is (for example, with substituted aryl of the substituted aryl as substituent, its own is substituted Aryl replace, etc.) be not intended to be incorporated herein.In the case, such substituted maximum number is 3.Similarly, should Work as understanding, the substitute mode (for example, the methyl replaced with 5 cl radicals) defined above for being not intended to include being impermissible for.It is such not The substitute mode allowed is known to those of skill in the art.

In some embodiments, the ligand concentration in electrochemical cell depends on being in relatively low and/or higher oxidation state Metal ion concentration.In some embodiments, ligand concentration is 0.25M-5M；Or 0.25M-4M；Or 0.25M-3M；Or 0.5M-5M；Or 0.5M-4M；Or 0.5M-3M；Or 0.5M-2.5M；Or 0.5M-2M；Or 0.5M-1.5M；Or 0.5M-1M；Or 1M- 2M；Or 1.5M-2.5M；Or 1.5M-2M.

In some embodiments, the ratio between ligand concentration and Cu (I) ion concentration are 1:1 to 4:1；Or 1:1 to 3:1；Or 1:1 to 2:1；Or be 1:1, or 2:1, or 3:1, or 4:1.

In some embodiments, catalytic reaction (metal ion and unsaturated hydrocarbons or saturation i.e. in higher oxidation state The reaction of hydrocarbon) in the solution that uses, and the solution used in electrochemical reaction is in higher oxygen comprising concentration for 4.5M-7M Change metal ion such as the Cu (II) of state, concentration for 0.25M-1.5M such as Cu of the metal ion in low oxidation state (I), it is and dense Spend the part for 0.25M-6M.In some embodiments, the sodium chloride concentration in solution can influence part and/or metal ion Solubility；The yield and selectivity of catalytic reaction；And/or the efficiency of electrochemical cell.Therefore, in some embodiments, The concentration of Chlorine in Solution sodium is 1M-3M.In some embodiments, catalytic reaction (i.e. the metal in higher oxidation state from The reaction of son and unsaturated hydrocarbons or saturated hydrocarbons) in the solution that uses, and the solution used in electrochemical reaction is comprising concentration The 4.5M-7M such as Cu of the metal ion in higher oxidation state (II), concentration is 0.25M-1.5M in low oxidation state Metal ion such as Cu (I), concentration is 0.25M-6M part, and the sodium chloride that concentration is 1M-3M.

Electrochemical method and system

There is provided the method comprised the following steps on the one hand：Make anode and the gold in anodolyte in the anode compartment Belong to contacted with ions；Metal ion is converted into higher oxidation state from low oxidation state in the anode compartment；Make the moon in the cathodic compartment Pole is contacted with catholyte.There is provided the method comprised the following steps on the one hand：Make anode and anode electricity in the anode compartment Solve the metal ion contact in matter；Metal ion is converted into higher oxidation state from low oxidation state in the anode compartment；In negative electrode Negative electrode is set to be contacted with catholyte in room；Alkali, water and/or hydrogen are formed in the cathodic compartment.On the one hand there is provided including The method of following steps：Anode is set to be contacted with the metal ion in anodolyte in the anode compartment；In the anode compartment by metal Ion is converted into higher oxidation state from low oxidation state；With the metal in higher oxidation state with unsaturated hydrocarbons or saturated hydrocarbons processing Ion.In some embodiments, the processing with unsaturated hydrocarbons or saturated hydrocarbons to the metal ion in higher oxidation state causes Form halogenated hydrocarbons.In some embodiments, with the place of unsaturated hydrocarbons or saturated hydrocarbons to the metal ion in higher oxidation state Reason is carried out in anode chamber.In some embodiments, with unsaturated hydrocarbons or saturated hydrocarbons to the metal in higher oxidation state from The processing of son is carried out outside anode room.In some embodiments, negative electrode is oxygen depolarization negative electrode.

Some embodiments of electrochemical cell as shown in drawings and are described herein.It should be appreciated that accompanying drawing is only used for Illustration purpose, and reagent and set change entirely within the ambit of the present invention.All electrochemical methods described herein and System all generates chlorine unlike as seen in chlor-alkali system.All halogenations or sulfonation phase with unsaturated hydrocarbons or saturated hydrocarbons The system and method for pass are in catalytic reactor all without using oxygen.

There is provided the method comprised the following steps in some embodiments：Make anode and anode electrolysis in the anode compartment Metal ion contact in matter；Metal ion is converted into or is oxidized at anode higher oxidation state from low oxidation state；With Negative electrode is set to be contacted with catholyte in the cathodic compartment；With formation alkali, water and/or hydrogen at negative electrode.In some embodiments In there is provided the method comprised the following steps：Anode is set to be contacted with the metal ion in anodolyte in the anode compartment；In sun Metal ion is oxidized to higher oxidation state from low oxidation state at pole；Negative electrode is set to be contacted with catholyte in the cathodic compartment； Alkali, water and/or hydrogen are formed at negative electrode；With the anodolyte and insatiable hunger for making the metal ion comprising higher oxidation state is in With hydrocarbon and/or saturated hydrocarbons contact to form halogenated hydrocarbons, or make the anodolyte that includes the metal ion in higher oxidation state Contact to form acid, or combination with hydrogen.

There is provided the system for including following component in some embodiments：Anode chamber, its include with anodolyte Metal ion contact anode, the wherein anode chamber is configured as metal ion being converted into higher oxygen from low oxidation state State；And cathode chamber, it includes the negative electrode contacted with catholyte.On the other hand there is provided the system for including following component：Sun Pole room, it includes the anode contacted with the metal ion in anodolyte, and the wherein anode chamber is configured as metal ion Higher oxidation state is converted into from low oxidation state；And cathode chamber, it includes the negative electrode contacted with catholyte, the wherein negative electrode Room is configurable to generate alkali, water and/or hydrogen.There is provided the system for including following component in some embodiments：Anode Room, it includes the anode that is contacted with the metal ion in anodolyte, wherein the anode be configured as by metal ion from compared with Low-oxidation-state is converted into higher oxidation state；And cathode chamber, it includes the negative electrode that is contacted with catholyte, wherein the negative electrode by with It is set in catholyte and forms alkali, water and/or hydrogen；And reactor, it is operably coupled to anode chamber, and by with Being set to makes the anodolyte comprising the metal ion in higher oxidation state and unsaturated hydrocarbons and/or saturated hydrocarbons and/or hydrogen Contact, to form halogenated hydrocarbons or acid respectively.On the other hand there is provided the system for including following component：Anode chamber, it is included and sun The anode of metal ion contact in the electrolyte of pole, the wherein anode chamber are configured as converting metal ion from low oxidation state For higher oxidation state；With the unsaturated hydrocarbons and/or saturated hydrocarbons for being configured as unsaturated hydrocarbons and/or saturated hydrocarbons being delivered to anode chamber Delivery system, the wherein anode chamber are also arranged to unsaturated hydrocarbons and/or saturated hydrocarbons being converted into halogenated hydrocarbons.

As shown in Figure 1A, electro-chemical systems 100A includes the anode chamber with the anode contacted with anodolyte, wherein The anodolyte contains the metal ion in low oxidation state and (is expressed as M^L+), the metal ion by anodic conversion be in The metal ion of higher oxidation state (is expressed as M^H+).Metal ion can be sulfate, chloride, bromide or form of iodide.

As used herein, with M^L+In L+ " low oxidation state " that represents include the low oxidation state of metal.For example, golden The low oxidation state for belonging to ion can be 1+, 2+, 3+, 4+ or 5+.As used herein, with M^H+In " the higher oxygens that represent of H+ Change state " include the higher oxidation state of metal.For example, the higher oxidation state of metal ion can be 2+, 3+, 4+, 5+ or 6+.

The electronics produced at anode is used for driving the reaction at negative electrode.Cathode reaction can be known in the art What reacts.Anode chamber and cathode chamber can be separated with amberplex (IEM), the amberplex can allow ion by, for example, But it is not limited to, in some embodiments, if anodolyte is sodium chloride or sodium sulphate containing metal halide etc. Words, it allows sodium ion to enter catholyte by it.Some reactions that can occur in negative electrode include but is not limited to water and formed The reaction of hydroxide ion and hydrogen, oxygen and water formation hydroxide ion reaction, HCl formation hydrogen reduction, or HCl and The reaction of oxygen formation water.

As shown in Figure 1B, electro-chemical systems 100B includes the cathode chamber with the negative electrode contacted with catholyte, the moon Pole forms hydroxide ion in catholyte.Electro-chemical systems 100B is also included with the anode contacted with anodolyte Anode chamber, the wherein anodolyte contains the metal ion in low oxidation state and (is expressed as M^L+), the metal ion quilt Anodic conversion is that the metal ion in higher oxidation state (is expressed as M^H+).The electronics produced at anode is used for driving in negative electrode The reaction at place.Anode chamber and cathode chamber are ion exchanged film (IEM) and separated, if anodolyte is sodium chloride, sodium bromide, iodine Change sodium, sodium sulphate, ammonium chloride etc. or the solution of equal value containing the metal halide, then the amberplex allows sodium ion to pass through It enters catholyte.In some embodiments, if catholyte be for example sodium chloride, sodium bromide, sodium iodide or Sodium sulphate or solution of equal value, then amberplex allow anion to be such as, but not limited to chlorion, bromide ion, iodide ion or sulfuric acid Radical ion enters anodolyte by it.Sodium ion combines to form sodium hydroxide with the hydroxide ion in catholyte. Anion combines to form metal halide or metal sulfate with metal ion.It should be appreciated that hydroxyl shape as shown in Figure 1B It is for illustration purposes only into negative electrode, other negative electrodes, for example, reduces the negative electrode of HCl formation hydrogen or form HCl and oxygen reaction The negative electrode of water, is equally applicable to the system.Such negative electrode has been described herein.

In some embodiments, electro-chemical systems of the invention include one or more amberplexes.Therefore, one There is provided the method comprised the following steps in a little embodiments：Make in the anode compartment metal in anode and anodolyte from Son contact；Metal ion is oxidized to higher oxidation state from low oxidation state at anode；Make negative electrode and negative electrode in the cathodic compartment Electrolyte is contacted；Alkali, water and/or hydrogen are formed at negative electrode；Isolate negative electrode and anode with least one amberplex. There is provided the method comprised the following steps in some embodiments：Make anode and the metal in anodolyte in the anode compartment Contacted with ions；Metal ion is oxidized to higher oxidation state from low oxidation state at anode；Make negative electrode and the moon in the cathodic compartment Pole electrolyte contact；Alkali, water and/or hydrogen are formed at negative electrode；Isolate negative electrode and anode with least one amberplex；With The anodolyte comprising the metal ion in higher oxidation state is set to contact to form halo with unsaturated hydrocarbons and/or saturated hydrocarbons Hydrocarbon, or make the anodolyte comprising the metal ion in higher oxidation state contact to form acid, or the group of the two with hydrogen Close.In some embodiments, amberplex is cation-exchange membrane (CEM), anion-exchange membrane (AEM) or its combination.

There is provided the system for including following component in some embodiments：Anode chamber, its include with anodolyte Metal ion contact anode, the wherein anode is configured as metal ion being converted into higher oxygen from low oxidation state State；Cathode chamber, it includes the negative electrode contacted with catholyte, and the wherein negative electrode is configurable to generate alkali, water and/or hydrogen； With isolation negative electrode and at least one amberplex of anode.There is provided be including following component in some embodiments System：Anode chamber, it includes the anode that is contacted with the metal ion in anodolyte, wherein the anode be configured as by metal from Son is converted into higher oxidation state from low oxidation state；Cathode chamber, it includes the negative electrode contacted with catholyte, the wherein negative electrode It is configurable to generate alkali, water and/or hydrogen；Isolate at least one amberplex of negative electrode and anode；And reactor, it can be grasped It is connected to anode chamber with making, and is configured as making the anodolyte comprising the metal ion in higher oxidation state and insatiable hunger Contacted with hydrocarbon and/or saturated hydrocarbons and/or hydrogen, to form halogenated hydrocarbons and acid respectively.In some embodiments, amberplex It is cation-exchange membrane (CEM), anion-exchange membrane (AEM) or its combination.

As shown in Fig. 2 electro-chemical systems 200 include the negative electrode that is contacted with catholyte and contacted with anodolyte Anode.Negative electrode forms hydroxide ion in catholyte, and anode by metal ion from low oxidation state (M^L+) be converted into Higher oxidation state (M^H+).Anode and negative electrode are isolated with anion-exchange membrane (AEM) and cation-exchange membrane (CEM).By the 3rd electricity Solution matter (such as sodium chloride, sodium bromide, sodium iodide, sodium sulphate, ammonium chloride or its combination or solution of equal value) is placed on AEM and CEM Between.Sodium ion from the 3rd electrolyte is through CEM and forms sodium hydroxide in the cathodic compartment, and from the 3rd electrolyte Halide anion such as chlorine, bromine or iodine ion or sulfate anion pass through AEM and form metal halide or gold in the anode compartment Belong to sulfate liquor.The metal halide or metal sulfate that are formed in anodolyte then be delivered in reactor with Hydrogen or unsaturated hydrocarbons or saturation hydrocarbon reaction, to generate hydrogen chloride, hydrochloric acid, hydrogen bromide, hydrobromic acid, hydrogen iodide or hydroiodic acid respectively And/or halogenated hydrocarbons.After ion-transfer, the 3rd electrolyte can take as (depleted) solion of consumption from medial compartment Go out.For example, in some embodiments, when the 3rd electrolyte is sodium chloride solution, being then transferred to catholyte in sodium ion Matter and chlorion are transferred to after anodolyte, and the sodium chloride solution of consumption can be taken out from medial compartment.The salting liquid of consumption Available for commercial use, or anode chamber and/or cathode chamber are can be transferred to as electrolyte, or it is concentrated to be re-used as the 3rd electricity Xie Zhi.In some embodiments, the salting liquid of consumption can be used for preparing desalted water.It should be appreciated that hydroxyl as shown in Figure 2 Form negative electrode to be for illustration purposes only, other negative electrodes, for example, reduce the negative electrode of HCl formation hydrogen or make HCl and oxygen reaction shape Cheng Shui negative electrode, is equally applicable to the system and has been described further herein.

In some embodiments, two amberplexes as shown in Figure 2 can be replaced with as shown in figures 1A or ib An amberplex.In some embodiments, amberplex is anion-exchange membrane as shown in Figure 3A.So Embodiment in, catholyte can be sodium halide, sodium sulphate or solution of equal value, and AEM allows anion to pass through it Into anodolyte, but metal ion is prevented to enter catholyte by it from anodolyte.In some embodiments In, amberplex is cation-exchange membrane as shown in Figure 3 B.In such embodiments, anodolyte can be halogen Change sodium, sodium sulphate or the solution of equal value comprising metal halide solution or solution of equal value, and CEM allows sodium cation to enter by it Enter catholyte, but prevent metal ion from entering catholyte by it from anodolyte.In some embodiments, The resistance that multiple IEM is brought can be reduced using an amberplex rather than using two amberplexes, and can be had Help the voltage that reduction is used to run electrochemical reaction.Some examples of suitable anion-exchange membrane are provided herein.

In some embodiments, the negative electrode used in the electro-chemical systems of the present invention is hydrogen generation negative electrode.Therefore, There is provided the method comprised the following steps in some embodiments：Make anode and the gold in anodolyte in the anode compartment Belong to contacted with ions；Metal ion is oxidized to higher oxidation state from low oxidation state at anode；Make in the cathodic compartment negative electrode with Catholyte is contacted；Alkali and hydrogen are formed at negative electrode.There is provided the side comprised the following steps in some embodiments Method：Anode is set to be contacted with the metal ion in anodolyte in the anode compartment；By metal ion from compared with suboxides at anode State is oxidized to higher oxidation state；Negative electrode is set to be contacted with catholyte in the cathodic compartment；Alkali and hydrogen are formed at negative electrode；With make Anodolyte comprising the metal ion in higher oxidation state contacts to form halogenated hydrocarbons with unsaturated hydrocarbons or saturated hydrocarbons, or The anodolyte comprising the metal ion in higher oxidation state is set to contact to form acid, or combination with hydrogen. In some embodiments, this method further comprises isolating negative electrode and anode with least one amberplex.In some implementations In scheme, amberplex is cation-exchange membrane (CEM), anion-exchange membrane (AEM) or its combination.In some embodiments In, above-named method includes not forming the anode of gas.In some embodiments, this method is included without using gas Anode.

There is provided the system for including following component in some embodiments：Anode chamber, its include with anodolyte Metal ion contact anode, the wherein anode is configured as metal ion being converted into higher oxygen from low oxidation state State；And cathode chamber, it includes the negative electrode contacted with catholyte, and the wherein negative electrode is configurable to generate alkali and hydrogen.One There is provided the system for including following component in a little embodiments：Anode chamber, it includes and connect with the metal ion in anodolyte Tactile anode, the wherein anode are configured as metal ion being converted into higher oxidation state from low oxidation state；And cathode chamber, its Comprising the negative electrode contacted with catholyte, the wherein negative electrode is configurable to generate alkali and hydrogen；And reactor, it is operationally Anode chamber is connected to, and is configured as making including the anodolyte and unsaturated hydrocarbons of the metal ion in higher oxidation state Or saturated hydrocarbons and/or hydrogen contact, to form halogenated hydrocarbons and acid respectively.In some embodiments, the system is configured as Gas is not generated at anode.In some embodiments, the system is configured as at anode without using gas.In some implementations In scheme, the system further comprises at least one amberplex for isolating negative electrode and anode.In some embodiments, from Proton exchange is cation-exchange membrane (CEM), anion-exchange membrane (AEM) or its combination.

For example, as shown in Figure 4 A, electro-chemical systems 400 include the negative electrode contacted with catholyte 401, wherein in the moon Hydroxyl is formed in the electrolyte of pole.System 400 also includes the anode contacted with anodolyte 402, and the anode will be in relatively low Metal ion (the M of oxidation state^L+) it is converted into the metal ion (M in higher oxidation state^H+).The following is at negative electrode and anode The reaction of generation：

H₂O+e^-→1/2H₂+OH^-(negative electrode)

M^L+→M^H++xe^-(anode, wherein x=1-3)

For example, Fe²⁺→Fe³⁺+e^-(anode)

Cr²⁺→Cr³⁺+e^-(anode)

Sn²⁺→Sn⁴⁺+2e^-(anode)

Cu⁺→Cu²⁺+e^-(anode)

As shown in Figure 4 A, electro-chemical systems 400 include negative electrode, and hydroxide ion and hydrogen are formed at the negative electrode.Hydrogen It can be discharged or capture and store for commercial use.In some embodiments, the hydrogen discharged at negative electrode can be used in The metal halide or metal sulfate formed in anodolyte carries out halogenation or sulfonation (including sulphation), to form chlorination Hydrogen, hydrochloric acid, hydrogen bromide, hydrobromic acid, hydrogen iodide, hydroiodic acid or sulfuric acid.The reaction is described in detail herein.Formed at anode M^H+With metal chloride of the chloride binding formation in higher oxidation state, such as, but not limited to FeCl₃、CrCl₃、SnCl₄Or CuCl₂Deng.The hydroxide ion formed at negative electrode combines to form sodium hydroxide with sodium ion.

It should be appreciated that the chlorion in the application is for illustration purposes only, other equivalent ions are such as, but not limited to sulfuric acid Root, bromide ion or iodide ion are also entirely within the ambit of the present invention, and corresponding metal halide will be produced in anodolyte Thing or metal sulfate.It is also understood that the MCl shown in accompanying drawing shown in this article_nBe in low oxidation state metal from The mixture of metal ion and in higher oxidation state.MCl_nIn Integer n only represent metal ion be in it is relatively low and compared with High oxidation state, can be 1-5 or bigger, this depends on metal ion.For example, in some embodiments, when copper be metal from The period of the day from 11 p.m. to 1 a.m, MCl_nCan be CuCl and CuCl₂Mixture.In anodolyte copper ion this mixture then can with hydrogen, Unsaturated hydrocarbons and/or saturated hydrocarbons contact to form respective product.

In some embodiments, the negative electrode used in the electro-chemical systems of the present invention is the hydrogen generation for not forming alkali Negative electrode.Therefore, there is provided the method comprised the following steps in some embodiments：Make anode and anode electricity in the anode compartment Solve the metal ion contact in matter；Metal ion is oxidized to higher oxidation state from low oxidation state at anode；In cathode chamber In negative electrode is contacted with catholyte；Hydrogen is formed at negative electrode.There is provided comprise the following steps in some embodiments Method：Anode is set to be contacted with the metal ion in anodolyte in the anode compartment；By metal ion from relatively low at anode Oxidation state is oxidized to higher oxidation state；Negative electrode is set to be contacted with catholyte in the cathodic compartment；Hydrogen is formed at negative electrode；With make Anodolyte comprising the metal ion in higher oxidation state contacts to form halogenated hydrocarbons with unsaturated hydrocarbons or saturated hydrocarbons, or The anodolyte comprising the metal ion in higher oxidation state is set to contact to form acid, or combination with hydrogen. In some embodiments, this method further comprises isolating negative electrode and anode with least one amberplex.In some implementations In scheme, amberplex is cation-exchange membrane (CEM), anion-exchange membrane (AEM) or its combination.In some embodiments In, above-named method includes not forming the anode of gas.In some embodiments, methods described is included without using gas Anode.

There is provided the system for including following component in some embodiments：Anode chamber, its include with anodolyte Metal ion contact anode, the wherein anode is configured as metal ion being converted into higher oxygen from low oxidation state State；And cathode chamber, it includes the negative electrode contacted with catholyte, and the wherein negative electrode is configurable to generate hydrogen.In some realities Apply in scheme that there is provided the system for including following component：Anode chamber, it includes what is contacted with the metal ion in anodolyte Anode, the wherein anode are configured as metal ion being converted into higher oxidation state from low oxidation state；And cathode chamber, it is included The negative electrode contacted with catholyte, the wherein negative electrode are configurable to generate hydrogen；And reactor, it is operably coupled to sun Pole room, and be configured as making the anodolyte comprising the metal ion in higher oxidation state and unsaturated hydrocarbons or saturated hydrocarbons And/or hydrogen contact, to form halogenated hydrocarbons and acid respectively.In some embodiments, the system is configured as at anode not Generate gas.In some embodiments, the system is configured as at anode without using gas.In some embodiments, The system further comprises at least one amberplex for isolating negative electrode and anode.In some embodiments, ion exchange Film is cation-exchange membrane (CEM), anion-exchange membrane (AEM) or its combination.

For example, as shown in Figure 4 B, electro-chemical systems 400 include the negative electrode contacted with catholyte 401, wherein being delivered to The hydrochloric acid of the catholyte is converted into hydrogen in the catholyte.System 400 also includes contacting with anodolyte 402 Anode, the anode is by the metal ion (M in low oxidation state^L+) it is converted into the metal ion (M in higher oxidation state^H ⁺).The following is the reaction occurred at negative electrode and anode：

2H⁺+2e^-→H₂(negative electrode)

M^L+→M^H++xe^-(anode, wherein x=1-3)

For example, Fe²⁺→Fe³⁺+e^-(anode)

Cr²⁺→Cr³⁺+e^-(anode)

Sn²⁺→Sn⁴⁺+2e^-(anode)

Cu⁺→Cu²⁺+e^-(anode)

As shown in Figure 4 B, electro-chemical systems 400 include negative electrode, and hydrogen is formed at the negative electrode.Hydrogen can be discharged or catch Obtain and store for commercial use.In some embodiments, the hydrogen discharged at negative electrode can be used in shape in anodolyte Into metal halide or metal sulfate carry out halogenation or sulfonation (including sulphation), to form hydrogen chloride, hydrochloric acid, bromination Hydrogen, hydrobromic acid, hydrogen iodide, hydroiodic acid or sulfuric acid.The reaction is described in detail herein.The M formed at anode^H+With chlorion Combine to form the metal chloride in higher oxidation state, such as, but not limited to FeCl₃、CrCl₃、SnCl₄Or CuCl₂Deng.In the moon The hydroxide ion formed at pole combines to form sodium hydroxide with sodium ion.

It should be appreciated that an AEM in Fig. 4 B is for illustration purposes only, the system is designed to, with CEM, make HCl It is delivered in anodolyte and hydrogen ion enters catholyte through CEM.In some embodiments, shown in Fig. 4 B System can include AEM and CEM simultaneously, and medial compartment contains villaumite.It is also understood that the MCl shown in accompanying drawing shown in this article_n It is the mixture of the metal ion in low oxidation state and the metal ion in higher oxidation state.MCl_nIn Integer n only Represent that metal ion is in relatively low and higher oxidation state, can be 1-5 or bigger, this depends on metal ion.For example, at some In embodiment, when copper is metal ion, MCl_nCan be CuCl and CuCl₂Mixture.Copper ion in anodolyte Then this mixture can contact to form respective product with hydrogen, unsaturated hydrocarbons and/or saturated hydrocarbons.

In some embodiments, the negative electrode in electro-chemical systems of the invention can be gas diffusion cathode.At some In embodiment, the negative electrode in electro-chemical systems of the invention can be the gas diffusion cathode that alkali is formed at negative electrode.One There is provided the method comprised the following steps in a little embodiments：Anode is set to be contacted with the metal ion in anodolyte；In sun Metal ion is oxidized to higher oxidation state from low oxidation state at pole；With gas diffusion cathode is contacted with catholyte. In some embodiments, gas diffusion cathode is oxygen depolarization negative electrode (ODC).In some embodiments, this method includes Alkali is formed at ODC.There is provided the method comprised the following steps in some embodiments：Anode is set to be connect with anodolyte Touch；Metal ion is oxidized to higher oxidation state from low oxidation state at anode；With negative electrode is contacted with catholyte, its In the negative electrode be the oxygen depolarization negative electrode that oxygen and water are reduced into hydroxide ion.In some embodiments there is provided including The method of following steps：Anode is set to be contacted with the metal ion in anodolyte in the anode compartment；At anode by metal from Son is oxidized to higher oxidation state from low oxidation state；Gas diffusion cathode is set to be contacted with catholyte in the cathodic compartment；In the moon Alkali is formed at pole；With the anodolyte and unsaturated hydrocarbons and/or saturated hydrocarbons for making to include the metal ion in higher oxidation state Contact to form halogenated hydrocarbons, or make the anodolyte comprising the metal ion in higher oxidation state contact to be formed with hydrogen Acid, or combination.In some embodiments, the gas diffusion cathode does not form gas.In some embodiments, should Method includes not forming the anode of gas.In some embodiments, this method includes the anode without using gas.In some realities Apply in scheme, this method further comprises isolating negative electrode and anode with least one amberplex.In some embodiments, Amberplex is cation-exchange membrane (CEM), anion-exchange membrane (AEM) or its combination.

There is provided the system for including following component in some embodiments：Anode chamber, its include with anodolyte Metal ion contact anode, wherein the anode be configured as metal ion is converted into or is oxidized to from low oxidation state compared with High oxidation state；And cathode chamber, it includes the gas diffusion cathode contacted with catholyte, and the wherein negative electrode is configurable to generate Alkali.In some embodiments, gas diffusion cathode is oxygen depolarization negative electrode (ODC).There is provided bag in some embodiments The system for including following component：Anode chamber, it includes the anode contacted with the metal ion in anodolyte, wherein the anode quilt It is configured to metal ion being converted into higher oxidation state from low oxidation state；And cathode chamber, it includes and contacted with catholyte Gas diffusion cathode, the wherein negative electrode is configurable to generate alkali；And reactor, it is operably coupled to anode chamber, and Be configured as making the anodolyte comprising the metal ion in higher oxidation state and unsaturated hydrocarbons and/or saturated hydrocarbons and/or Hydrogen is contacted, to form halogenated hydrocarbons and acid respectively.In some embodiments, the system is configured as at gas diffusion cathode Do not generate gas.In some embodiments, the system is configured as at anode not generating gas.In some embodiments In, the system is configured as at anode without using gas.In some embodiments, the system further comprises isolating negative electrode With at least one amberplex of anode.In some embodiments, amberplex is cation-exchange membrane (CEM), the moon Amberplex (AEM) or its combination.

" gas diffusion cathode " or " gas-diffusion electrode " or its other equivalents include any energy as used herein Gas reaction is enough set to form the electrode of ionic species.In some embodiments, gas diffusion cathode as used herein is oxygen Depolarized cathode (ODC).The gas diffusion cathode is referred to alternatively as gas-diffusion electrode, oxygen-consuming cathodes, oxygen reduction cathode, oxygen uptake the moon Pole, oxygen depolarization negative electrode etc..

In some embodiments, as shown in Figure 5A, gas diffusion cathode (such as ODC) and anode in electrochemical cell Combination can cause to generate alkali in the cathodic compartment.In some embodiments, electro-chemical systems 500 include and catholyte 501 The gas diffusion cathode of contact and the anode contacted with anodolyte 502.With anion-exchange membrane (AEM) and cation exchange Film (CEM) isolates anode and negative electrode.3rd electrolyte (such as sodium halide or sodium sulphate) is positioned between AEM and CEM.Below It is the reaction that can occur at anode and negative electrode.

H₂O+1/2O₂+2e^-→2OH^-(negative electrode)

M^L+→M^H++xe^-(anode, wherein x=1-3)

For example, 2Fe²⁺→2Fe³⁺+2e^-(anode)

2Cr²⁺→2Cr³⁺+2e^-(anode)

Sn²⁺→Sn⁴⁺+2e^-(anode)

2Cu⁺→2Cu²⁺+2e^-(anode)

The M formed at anode^H+With chloride binding formation metal chloride MCl_n, such as, but not limited to FeCl₃、 CrCl₃、SnCl₄Or CuCl₂Deng.The hydroxide ion formed at negative electrode reacts to form sodium hydroxide with sodium ion.At negative electrode Oxygen can be air or it is any can be with commercially available oxygen source.

The method and system containing gas diffusion cathode or ODC as shown in being described herein with Fig. 5 A, with being given birth to including hydrogen Method and system (as shown in Figure 4 A) into negative electrode is compared, and voltage can be caused to save.Voltage is saved then can cause relatively low consumption The electric and less CO2 emission caused by generating.This can produce more green chemicals such as sodium hydroxide, halo The generation of hydrocarbon and/or acid, they are formed by the method and system of the efficient of the present invention and energy-conservation.In some embodiments, Compared with the electrochemical cell without ODC or compared with the electrochemical cell of negative electrode is generated containing hydrogen, the electrochemistry containing ODC Battery has more than 0.5V or saved more than 1V or more than 1.5V or for 0.5-1.5V theoretical voltage.In some embodiments In, the voltage, which is saved, to be realized with 7-15 or 7-14 or 6-12 or 7-12 or 7-10 catholyte pH.

Total cell voltage potential can be determined by the combination of the Nernst equation for each half-cell reaction：

E=E^o–RT ln(Q)/n F

Wherein, E^oIt is normal reduction potential, R is universal gas constant (8.314J/mol K), and T is absolute temperature, and n is half-cell The electron number being related in reaction, F is Faraday constant (96485J/V mol), and Q is reaction business, so：

E_Always=E_Anode-E_{Negative electrode}

When the metal in low oxidation state is oxidized to the metal in higher oxidation state at anode：

Cu⁺→Cu²⁺+2e^-

The E of varied concentration based on II valency copper species_AnodeCan be 0.159-0.75V.

When water is reduced into hydroxide ion and hydrogen (as shown in Figure 4 A) as follows at negative electrode：

2H₂O+2e^-=H₂+2OH^-,

E_{Negative electrode}=-0.059pH_c, wherein pH_cIt is the pH=14 of catholyte

E_{Negative electrode}=-0.83

So E_AlwaysFor 0.989 to 1.53, this copper ion concentration depended in anodolyte.

When water is reduced into hydroxide ion (as shown in Figure 5A) as follows at ODC：

2H₂O+O₂+4e^-→4OH^-

E_{Negative electrode}=1.224-0.059pH_c, wherein pH_c=14

E_{Negative electrode}=0.4V

So E_AlwaysFor -0.241 to 0.3V, this copper ion concentration depended in anodolyte.

Therefore, compared with the electrochemical cell without ODC or compared with the electrochemical cell of negative electrode is generated containing hydrogen, The theoretical voltage brought in cathode chamber using ODC in about 1.5V or 0.5-2V or 0.5-1.5V or 1-1.5V cathode chamber is saved Or the theoretical voltage in battery is saved.

Therefore, there is provided the method comprised the following steps in some embodiments：Make in anode and anodolyte Metal ion is contacted；Oxygen depolarization negative electrode is set to be contacted with catholyte；Voltage is applied to anode and negative electrode；Formed at negative electrode Alkali；Metal ion is converted into higher oxidation state from low oxidation state at anode；With with hydrogen generation negative electrode compared with or with not Battery containing ODC more than 0.5V or is 0.5-1.5V voltage compared to saving.There is provided including following in some embodiments The system of component：Anode chamber, it includes the anode contacted with the metal ion in anodolyte, and the wherein anode is configured as Metal ion is converted into higher oxidation state from low oxidation state；And cathode chamber, it includes the oxygen contacted with catholyte and gone Polarize negative electrode, and the wherein negative electrode is configurable to generate alkali, wherein compared with the system of negative electrode is generated containing hydrogen or with without ODC System compare, this system provides more than 0.5V or for 0.5-1.5V voltage saving.In some embodiments, voltage section Province is Ohmic resistance that can be in battery and the theoretical voltage that changes is saved.

Although the method and system containing gas diffusion cathode or ODC and the method and system phase that negative electrode is generated containing hydrogen Than causing voltage to be saved, but both systems, the i.e. system containing ODC of the invention and the system containing hydrogen generation negative electrode, All show that significant voltage is saved compared with conventionally known in the art chlor-alkali system.Voltage is saved then can cause less consumption The electric and less CO2 emission caused by generating.This can cause more green chemicals such as sodium hydroxide, The generation of halogenated hydrocarbons and/or acid, they are formed by the method and system of the efficient of the present invention and energy-conservation.For example, voltage is saved It is beneficial, chlorine of the EDC typically by producing chlor-alkali of the ethene with being consumed by high voltage in halogenated hydrocarbons such as EDC production Solid/liquid/gas reactions and formed.In some embodiments, electro-chemical systems of the invention (there is hydrogen to generate negative electrode or the 2 of ODC or 3 Room battery) have compared with chlor-alkali more than 0.5V or saved more than 1V or more than 1.5V or for 0.5-3V theoretical voltage. In some embodiments, the voltage, which is saved, to be realized with 7-15 or 7-14 or 6-12 or 7-12 or 7-10 catholyte pH 's.

For example, the theoretical E in chlor-alkali_AnodeIt is about 1.36V, the following reaction of experience：

2Cl^-→Cl₂+2e^-

Theoretical E in chlor-alkali_{Negative electrode}It is about -0.83V (in pH>When 14), the following reaction of experience：

2H₂O+2e^-=H₂+2OH^-

The theoretical E of chlor-alkali_AlwaysIt is then 2.19V.In present system hydrogen generation negative electrode theoretical E for 0.989 to 1.53V, and the E of the ODC in present system_AlwaysIt is then -0.241 to 0.3V, the copper ion that this is depended in anodolyte is dense Degree.Therefore, compared with chlor-alkali system, electro-chemical systems of the invention are brought more than 3V or more than 2V or be 0.5-2.5V or 0.5- Theoretical voltage in 2.0V or 0.5-1.5V or 0.5-1.0V or 1-1.5V or 1-2V or 1-2.5V or 1.5-2.5V cathode chamber Theoretical voltage in saving or battery is saved.

In some embodiments, the electrochemical cell can be adjusted with the first electrolyte, and can use the second electrolysis Matter is run.For example, in some embodiments, electrochemical cell and AEM, CEM or its combination are come using sodium sulphate as electrolyte Regulation, and after voltage stabilization is made with sodium sulphate, battery can be run with sodium chloride as electrolyte.Embodiment hereof 13 In describe this stabilized illustrative example of electrochemical cell.Therefore, in some embodiments there is provided including with The method of lower step：Anode is set to be contacted with the first anode electrolyte in anode chamber；Make negative electrode and the catholyte in cathode chamber Matter is contacted；Isolate negative electrode and anode with least one amberplex；Should be from the first anode electrolyte regulation in anode chamber Proton exchange；Anode is set to be contacted with the second plate electrolyte comprising metal ion；By metal ion from compared with hypoxemia at anode Change state and be oxidized to higher oxidation state；With formation alkali, water and/or hydrogen at negative electrode.In some embodiments, first anode electricity Solution matter is sodium sulphate and second plate electrolyte is sodium chloride.In some embodiments, this method further comprises making to include The second plate electrolyte of metal ion in higher oxidation state contacts to form halo with unsaturated hydrocarbons and/or saturated hydrocarbons Hydrocarbon, or make the second plate electrolyte comprising the metal ion in higher oxidation state contact to form acid, or two with hydrogen The combination of person.In some embodiments, the amberplex is cation-exchange membrane (CEM), anion-exchange membrane or its group Close.

In some embodiments, the negative electrode in electro-chemical systems of the invention can HCl is formed with oxygen reaction The gas diffusion cathode of water.There is provided the method comprised the following steps in some embodiments：Make anode and anodolyte In metal ion contact；Metal ion is oxidized to higher oxidation state from low oxidation state at anode；With make gas diffusion Negative electrode is contacted with catholyte.In some embodiments, the gas diffusion cathode is oxygen depolarization negative electrode (ODC).One In a little embodiments, this method, which is included at ODC, makes HCl and oxygen reaction formation water.There is provided bag in some embodiments The method for including following steps：Anode is contacted with anodolyte, be oxidized to metal ion from low oxidation state at anode Higher oxidation state；With negative electrode is contacted with catholyte, wherein negative electrode is oxygen and HCl is reacted the oxygen depolarization to form water Negative electrode.There is provided the method comprised the following steps in some embodiments：Make in the anode compartment in anode and anodolyte Metal ion contact；Metal ion is oxidized to higher oxidation state from low oxidation state at anode；Make gas in the cathodic compartment Body dispenser cathode is contacted with catholyte；Water is formed by HCl and oxygen at negative electrode；Higher oxidation state is in making to include The anodolyte of metal ion contacts to form halogenated hydrocarbons with unsaturated hydrocarbons and/or saturated hydrocarbons, or makes to include in higher The anodolyte of the metal ion of oxidation state contacts to form acid, or combination with hydrogen.In some embodiments, The gas diffusion cathode does not form gas.In some embodiments, this method includes not forming the anode of gas.In some realities Apply in scheme, this method includes the anode without using gas.In some embodiments, this method further comprises using at least one Individual amberplex isolation negative electrode and anode.In some embodiments, the amberplex be cation-exchange membrane (CEM), Anion-exchange membrane (AEM) or its combination.

There is provided the system for including following component in some embodiments：Anode chamber, the anode chamber is included and anode electricity The anode of the metal ion contact in matter is solved, the wherein anode is configured as making metal ion be converted into from low oxidation state or oxygen Turn to higher oxidation state；And cathode chamber, the cathode chamber includes the gas diffusion cathode that is contacted with catholyte, the wherein negative electrode It is configured as producing water by HCl.In some embodiments, the gas diffusion cathode is oxygen depolarization negative electrode (ODC).At some There is provided the system for including following component in embodiment：Anode chamber, the anode chamber include with the metal in anodolyte from The anode of son contact, wherein anode is configured as making metal ion be converted into higher oxidation state from low oxidation state；And negative electrode Room, the cathode chamber includes the gas diffusion cathode contacted with catholyte, and the wherein negative electrode is configured as producing water by HCl； And reative cell, it is operably coupled to anode chamber, and is configured as making comprising the metal ion in higher oxidation state Anodolyte is contacted with unsaturated hydrocarbons and/or saturated hydrocarbons and/or hydrogen, to form halogenated hydrocarbons and acid respectively.In some implementations In scheme, the system is configured as at gas diffusion cathode not producing gas.In some embodiments, the system is configured Not produce gas at anode.In some embodiments, the system is configured as at anode without using gas.At some In embodiment, the system further comprises at least one amberplex for isolating negative electrode and anode.In some embodiments In, the amberplex is cation-exchange membrane (CEM), anion-exchange membrane (AEM) or its combination.

In some embodiments, as shown in Figure 5 B, gas diffusion cathode (such as ODC) and anode in electrochemical cell Combination can cause to generate water in the cathodic compartment.In some embodiments, electro-chemical systems 500 include and catholyte The gas diffusion cathode of 501 contacts and the anode contacted with anodolyte 502.The following is what can be occurred at anode and negative electrode Reaction.

2H⁺+1/2O₂+2e^-→H₂O (negative electrode)

M^L+→M^H++xe^-(anode, wherein x=1-3)

For example, 2Fe²⁺→2Fe³⁺+2e^-(anode)

2Cr²⁺→2Cr³⁺+2e^-(anode)

Sn²⁺→Sn⁴⁺+2e^-(anode)

2Cu⁺→2Cu²⁺+2e^-(anode)

The M formed at anode^H+With chloride binding to form metal chloride MCl_n, such as, but not limited to FeCl₃、 CrCl₃、SnCl₄Or CuCl₂Deng.Oxygen at negative electrode can be air or any commercially available oxygen source.It should be appreciated that Fig. 5 B In an AEM be for illustration purposes only, the system is designed to CEM, HCl be delivered in anodolyte and Hydrogen ion enters catholyte through CEM.In some embodiments, the system shown in Fig. 5 B can contain AEM and CEM, in Compartment contains villaumite.

In some embodiments, electro-chemical systems of the invention can be combined with other electrochemical cells with formed efficiently and The system of low energy consumption.For example, in some embodiments, as shown in Figure 5 C, Fig. 4 B electro-chemical systems 400 can be with another electrification Learn battery to combine, so that the hydrochloric acid formed in another electrochemical cell is provided to the catholyte of system 400. Electro-chemical systems 400 can be by system 100A (Figure 1A), 100B (Figure 1B), 200 (Fig. 2), 400 (Fig. 4 A), 500 (Fig. 5 A and Fig. 5 B) Substitute, difference is that cathodic compartment is modified to receive the HCl from another electrochemical cell and be oxidized with shape Into hydrogen.Chlorion moves to anodolyte from catholyte through AEM.This can cause the overall improvement of system voltage, For example, the theoretical cell voltage of system can be 0.1-0.7V.In some embodiments, when negative electrode is ODC, theoretical cell electricity Pressure can be -0.5 to -1V.The U.S. that HCl electrochemical cell has been submitted on July 15th, 2009 is produced in anodolyte Patent application 12/503, described in 557, this application is incorporated herein by reference in their entirety.Other HCl sources are known in the art 's.Following Fig. 8 B show the example in the HCl sources from VCM production technologies and its into the electro-chemical systems of the present invention It is integrated.

In some embodiments of method described herein and system, size exclusion film (SEM) is together with anion exchange Film (AEM) is used together or used instead of AEM.In some embodiments, AEM Surface coatings have one layer of SEM.In some implementations In scheme, SEM is bonded in or is pressed together on AEM., will because the size of metal ion that is single or being connected to part is larger SEM is used together with AEM or can prevent metal ion or the metal ion of linking ligand from anolyte instead of AEM uses Move to catholyte.This can further prevent that CEM is contaminated by the metal ions or catholyte is contaminated by the metal ions.Should Work as understanding, SEM is used in combination with AEM or instead of AEM uses chlorion will be promoted electric from the 3rd electrolyte to anode Solve in liquid.There is provided the method comprised the following steps in some embodiments：Anode is set to be contacted with anodolyte, in sun Metal ion is oxidized to higher oxidation state from low oxidation state at pole；Negative electrode is set to be contacted with catholyte；With by using Size exclusion film prevents migration of the metal ion from anodolyte to catholyte.In some embodiments, this method Further comprise the negative electrode that alkali is produced in catholyte, or the oxygen depolarization negative electrode of alkali is produced in catholyte, or The oxygen depolarization negative electrode of water, or hydrogen generation negative electrode are produced in catholyte.In some embodiments, this method enters one Step includes making the anodolyte comprising the metal ion in higher oxidation state contact to be formed with unsaturated hydrocarbons or saturated hydrocarbons Halogenated hydrocarbons, or make the anodolyte comprising the metal ion in higher oxidation state contact to form acid, or the two with hydrogen Combination.In some embodiments, the unsaturated hydrocarbons in such method is ethene.In some embodiments, such method In metal ion be copper chloride.In some embodiments, the unsaturated hydrocarbons in such method is ethene and metal ion is Copper chloride.The example for the halogenated hydrocarbons that can be formed by ethene is ethylene dichloride, EDC.

There is provided the system for including following component in some embodiments：Contact and be configured as with anodolyte Metal ion is oxidized to the anode of higher oxidation state from low oxidation state；The negative electrode contacted with catholyte；Be arranged on Between anode and negative electrode and it is configured as preventing size exclusion film from anodolyte to catholyte that migrate from of metal ion. In some embodiments, the system further comprises being configured as producing alkali in catholyte or in catholyte Produce water or generate the negative electrode of hydrogen.In some embodiments, the system further comprises being configured as in catholyte The middle oxygen depolarization negative electrode for producing alkali and/or water.In some embodiments, the system further comprises that hydrogen generates negative electrode. In some embodiments, the system further comprises reactor, and it is operably connected to anode chamber, and is configured as making Anodolyte comprising the metal ion in higher oxidation state contacts to form halogenated hydrocarbons with unsaturated hydrocarbons or saturated hydrocarbons, or The anodolyte comprising the metal ion in higher oxidation state is set to contact to form acid, or combination with hydrogen. In some embodiments, the unsaturated hydrocarbons in such system is ethene.In some embodiments, the metal in such system Ion is copper chloride.In some embodiments, the unsaturated hydrocarbons in such system is ethene and metal ion is copper chloride.Can The example of the halogenated hydrocarbons formed by ethene is EDC.

In some embodiments, as above and defined herein size exclusion film prevents metal ion to cathode chamber completely Or the medial compartment migration with the 3rd electrolyte, or migration is reduced 100%；Or 99%；Or 95% or 75%；Or 50%；Or 25%；Or 25%-50%；Or 50%-75%；Or 50%-95%.

In some embodiments, AEM resistance organic compound (such as parts used in the inventive method and system Or hydrocarbon), so that AEM does not interact with organic matter, and/or AEM does not react or adsorbing metal ions with metal ion.Only For example, this can be by using without polymerizeing available for the free radical or anion reacted with organic matter or with metal ion Thing is realized.Only for example, the polymer of the amine comprising complete quaternary (quarternized) can be used as AEM.Retouch herein AEM other examples are stated.

In some embodiments of method described herein and system, in the anode compartment using turbulence promoter (turbulence promoter) is to improve the mass transfer at anode.For example, as the current density in electrochemical cell increases Plus, realize the mass transfer of the controlled reaction speed at anode.The laminar flow of anolyte can cause resistance and diffusion problem. In order to improve the mass transfer at anode so as to reduce the voltage of battery, turbulence promoter can be used in the anode compartment.Herein " turbulence promoter " used is included in the component that turbulent flow is provided in the anodal compartment of electrochemical cell.In some embodiments In, turbulence promoter can be arranged on the back side of anode, i.e., between anode and the wall of electrochemical cell, and/or one In a little embodiments, turbulence promoter can be arranged between anode and anion-exchange membrane.Only for example, in Figure 1A, figure Electro-chemical systems shown in 1B, Fig. 2, Fig. 4 A, Fig. 4 B, Fig. 5 A, 5B, Fig. 5 C, Fig. 6, Fig. 8 A, Fig. 9 and Figure 12 can anode with There is turbulence promoter between amberplex such as anion-exchange membrane, and/or with turbulent flow between anode and battery outer wall Promoters.

One example of turbulence promoter is the bubbling of the gas in anodal compartment.The gas can be not with anode electrolysis Any inert gas that the composition of liquid reacts.For example, the gas includes but is not limited to air, nitrogen, argon gas etc..In anode The gas sparging at place can stir anodolyte and improve the mass transfer at anode.Improved mass transfer can cause battery Voltage reduction.Other examples of turbulence promoter include but is not limited to：Against anode add carbon cloth, against anode add carbon/ Graphite felt, against anode add foamed plastic, fishing net, foregoing combination etc. are added by the anode.

In some embodiments, there is provided herein the method comprised the following steps：Anode is set to be contacted with anodolyte； Metal ion is oxidized to higher oxidation state from low oxidation state at anode；Negative electrode is set to be contacted with catholyte；And it is logical Cross and turbulent flow is provided in anodolyte using turbulence promoter.In some embodiments, preceding method further comprises leading to Crossing offer turbulent flow makes cell voltage reduce 50-200mV or 100-200mV.In some embodiments, there is provided herein including with The method of lower step：Anode is set to be contacted with anodolyte；Metal ion is oxidized to from low oxidation state at anode higher Oxidation state；Negative electrode is set to be contacted with catholyte；And provided by being passed through bubble at anode in anodolyte rapid Stream.The example of gas includes but is not limited to air, nitrogen, argon gas etc..In some embodiments, preceding method further comprises Cell voltage is reduced 50-200mV or 100-200mV by providing turbulent flow (see embodiment 3).

In some embodiments, preceding method further comprises the negative electrode that alkali is produced in catholyte, or in the moon In the electrolyte of pole produce alkali oxygen depolarization negative electrode, or in catholyte produce water oxygen depolarization negative electrode, or produce hydrogen The negative electrode of gas.In some embodiments, preceding method further comprises：Make comprising the metal ion in higher oxidation state Anodolyte contacts to form halogenated hydrocarbons with unsaturated hydrocarbons or saturated hydrocarbons, or makes comprising the metal ion in higher oxidation state Anodolyte contact to form acid, or combination with hydrogen.In some embodiments, in such method not Saturated hydrocarbons is ethene.In some embodiments, the metal ion in such method is copper chloride.In some embodiments, Unsaturated hydrocarbons in such method is ethene and metal ion is copper chloride.The example for the halogenated hydrocarbons that can be formed by ethene is dichloro Change ethene, EDC.In some embodiments, part as described herein can be used in preceding method.

In some embodiments, there is provided herein the system for including following component：Contact and configure with anodolyte For metal ion to be oxidized to the anode of higher oxidation state from low oxidation state；The negative electrode contacted with catholyte；And cloth Put near anode and be configured to provide in anodolyte the turbulence promoter of turbulent flow.In some embodiments, herein There is provided the system for including following component：Contacted with anodolyte and be configured to metal ion being oxidized to from low oxidation state The anode of higher oxidation state；The negative electrode contacted with catholyte；And be arranged in anode nearby and be configured to gas sparging And the gas sparger of turbulent flow is provided in anodolyte.The example of gas includes but is not limited to air, nitrogen, argon gas etc.. Gas sparger can be any device as known in the art by gas sparging into anodal compartment.

In some embodiments, aforementioned system, which is further included, is configured to produce alkali in catholyte or in negative electrode Water is produced in electrolyte or produces the negative electrode of hydrogen.In some embodiments, aforementioned system is further included and is configured in the moon The oxygen depolarization negative electrode of alkali and/or water is produced in the electrolyte of pole.In some embodiments, aforementioned system further includes hydrogen Produce negative electrode.In some embodiments, aforementioned system further comprises reactor, and the reactor is operably coupled to anode Room simultaneously is configured as making the anodolyte comprising the metal ion in higher oxidation state contact with unsaturated hydrocarbons or saturated hydrocarbons To form halogenated hydrocarbons, or the anodolyte comprising the metal ion in higher oxidation state is set to be contacted with hydrogen to form acid, Or combination.In some embodiments, the unsaturated hydrocarbons in such system is ethene.In some embodiments, Metal ion in such system is copper chloride.In some embodiments, the unsaturated hydrocarbons in such system is ethene and gold It is copper chloride to belong to ion.One example of the halogenated hydrocarbons that can be formed by ethene is EDC.

In some embodiments, the experience of the metal with higher oxidation state formed in anodolyte can produce phase The reaction of the oxidation product (halogenated hydrocarbons and/or acid) and the metal of the low oxidation state in reduction answered.In compared with suboxides The metal ion of state and then the recyclable electro-chemical systems that return to are for metal ion of the generation in higher oxidation state.By Include but is not limited in such reaction of metal ion of the metal ion regeneration in low oxidation state of higher oxidation state such as this The reaction with hydrogen or hydrocarbon described in text.

With the reaction of hydrogen, unsaturated hydrocarbons and saturated hydrocarbons

There is provided the method comprised the following steps in some embodiments：Make anode and anode electrolysis in the anode compartment Metal ion contact in matter；Make metal ion that higher oxidation state is converted into or be oxidized to from low oxidation state at anode；With The metal ion of higher oxidation state is in hydrogen treat.In some embodiments of this method, this method includes making negative electrode Contacted with catholyte and alkali is formed in catholyte.In some embodiments of this method, this method includes making Negative electrode contacts and formed at negative electrode alkali and/or hydrogen with catholyte.In some embodiments of this method, this method Including making negative electrode be contacted with catholyte and alkali, water and/or hydrogen being formed at negative electrode.In some embodiments of this method In, this method includes making gas diffusion cathode that alkali is contacted and formed at negative electrode with catholyte.In some embodiments, There is provided the method comprised the following steps：Anode is set to be contacted with the metal ion in anodolyte in the anode compartment；In anode Place makes metal ion be converted into higher oxidation state from low oxidation state；Negative electrode is set to be contacted with catholyte；Formed at negative electrode Alkali, water or hydrogen；With with the metal ion in higher oxidation state in the hydrogen treat anodolyte from negative electrode.One There is provided the method comprised the following steps in a little embodiments：Make in the anode compartment metal in anode and anodolyte from Son contact；Metal ion is set to be converted into higher oxidation state from low oxidation state at anode；Make oxygen depolarization negative electrode and negative electrode electricity Solve matter contact；Alkali or water are formed at negative electrode；With with the metal in higher oxidation state in hydrogen treat anodolyte from Son.There is provided the method comprised the following steps in some embodiments：Make in the anode compartment in anode and anodolyte Metal ion is contacted；Metal ion is set to be converted into higher oxidation state from low oxidation state at anode；Make negative electrode and catholyte Matter is contacted；Water or hydrogen are formed at negative electrode；With with the metal in higher oxidation state in hydrogen treat anodolyte from Son.In some embodiments, can be in cathode chamber or cloudy to the processing of hydrogen with the metal ion in higher oxidation state Carried out outside pole room.In some embodiments, method listed above includes being in higher oxidation state by using hydrogen treat Metal ion is to form hydrogen chloride, hydrochloric acid, hydrogen bromide, hydrobromic acid, hydrogen iodide, hydroiodic acid and/or sulfuric acid.In some embodiments In, hydrogen chloride, hydrochloric acid, hydrogen bromide, hydrobromic acid, iodine are resulted in the processing of the metal ion in higher oxidation state with hydrogen Change hydrogen, hydroiodic acid and/or sulfuric acid and the metal ion in low oxidation state.In some embodiments, in compared with suboxides The metal ion of state is recycled back into anode chamber.In some embodiments, the metal ion in low oxidation state and acid Mixture experience acid retardance (acid retardation) technology, to be recycled back into the metal ion in low oxidation state The metal ion in low oxidation state is separated with acid before anode chamber.

In some embodiments of method listed above, this method does not produce chlorine at anode.

There is provided the system for including following component in some embodiments：Anode chamber, its include with anodolyte Metal ion contact anode, the wherein anode is configured as metal ion being converted into higher oxygen from low oxidation state State；And reactor, it is operably connected to anode chamber, and is configured as making comprising the metal ion in higher oxidation state Anodolyte and hydrogen react.In some embodiments of the system, the system includes cathode chamber, and the cathode chamber is included Negative electrode and catholyte, the wherein negative electrode are configured as in catholyte forming alkali.In some embodiment party of the system In case, the system includes cathode chamber, and the cathode chamber includes negative electrode and catholyte, and the wherein negative electrode is configured as in negative electrode electricity Xie Zhizhong formation hydrogen.In some embodiments of the system, the system includes cathode chamber, and the cathode chamber includes negative electrode and the moon Pole electrolyte, the wherein negative electrode are configured as in catholyte forming alkali and hydrogen.In some embodiments of the system In, the system includes gas diffusion cathode and catholyte, and the wherein negative electrode is configured as in catholyte forming alkali. In some embodiments of the system, the system includes gas diffusion cathode and catholyte, and the wherein negative electrode is configured To form water in catholyte.There is provided the system for including following component in some embodiments：Anode chamber, it is wrapped Containing the metal ion in anode and anodolyte, the wherein anode is configured as in the anode compartment by metal ion from compared with hypoxemia Change state and be converted into higher oxidation state；Cathode chamber comprising negative electrode and catholyte, the wherein negative electrode are configured as in negative electrode electricity Xie Zhizhong formation alkali and/or hydrogen；And reactor, it is operably connected to anode chamber, and is configured as making to include being in The anodolyte of the metal ion of higher oxidation state reacts with the hydrogen from negative electrode.In some embodiments, the reaction Device is operably connected to anode chamber, and is configured as making including the anodolyte of the metal ion in higher oxidation state Reacted with the hydrogen of the negative electrode from same electrochemical cell or with the hydrogen of external source.In some embodiments, use It can be carried out in processing of the metal ion to hydrogen of higher oxidation state in cathode chamber or outside negative electrode room.In some embodiments In, system listed above is included by making the metal ion in higher oxidation state react or be in hydrogen treat with hydrogen The metal ion of higher oxidation state, to form hydrogen chloride, hydrochloric acid, hydrogen bromide, hydrobromic acid, hydrogen iodide, hydroiodic acid and/or sulfuric acid. In some embodiments, hydrogen chloride, hydrochloric acid, bromine are resulted in the processing of the metal ion in higher oxidation state with hydrogen Change hydrogen, hydrobromic acid, hydrogen iodide, hydroiodic acid and/or sulfuric acid and the metal ion in low oxidation state.In some embodiments In, the system be configured as with hydrogen make in higher oxidation state metal ion formation in low oxidation state metal from Son, and the metal ion in low oxidation state is recycled back into anode chamber.In some embodiments, the system is configured To use acid block technique, such as, but not limited to ion exchange resin, size exclusion film and acid dialysis etc. will be in compared with suboxides The metal ion of state is separated with acid.

In some embodiments of system listed above, the anode in the system is configured as not producing chlorine.

In some embodiments, in Figure 1A, Figure 1B, Fig. 2, Fig. 3 A, Fig. 3 B, Fig. 4 A, Fig. 4 B, Fig. 5 A and Fig. 5 B electrification The metal with higher oxidation state formed in the anodolyte of system can react with hydrogen, with based on investing on metal Anion forms corresponding product.For example, after hydrogen and metal halide or metal sulfate reactant salt, by metal chlorination Thing, metal bromide, metal iodide or metal sulfate can generate corresponding hydrogen chloride, hydrochloric acid, hydrogen bromide, hydrogen bromine respectively Acid, hydrogen iodide, hydroiodic acid or sulfuric acid.In some embodiments, hydrogen comes from external source.In some embodiments, such as Shown in Fig. 4 A or Fig. 4 B, the hydrogen with metal halide or metal sulfate reactant salt is the hydrogen formed at negative electrode.At some In embodiment, hydrogen is that the combination of the hydrogen formed from external source and at negative electrode is obtained.In some embodiments, The reaction of metal halide or metal sulfate and hydrogen causes to generate above-mentioned product and the metal halogen in low oxidation state Compound or metal sulfate.Metal ion in low oxidation state is then recyclable to return to electro-chemical systems, for life Into the metal ion in higher oxidation state.

One example of Fig. 5 A electro-chemical systems is as shown in Figure 6.It should be appreciated that Fig. 6 system 600 is merely to illustrate mesh , other metal ions (for example, chromium, tin etc.) with different oxidation state and product in addition to alkali is formed in the cathodic compartment such as Other electro-chemical systems of water (such as in Fig. 5 B) or hydrogen (such as in Fig. 4 A or 4B) are equally applicable to the system.In some embodiment party In case, as shown in fig. 6, electro-chemical systems 600 include producing the oxygen depolarization negative electrode of hydroxide ion by water and oxygen.System 600 Also the sun for making metal ion be converted into 3+ oxidation state (or from 2+ oxidation state to 4+ oxidation state, such as Sn) from 2+ oxidation state is included Pole.M³⁺Ion and chloride binding formation MCl₃.Metal chloride MCl₃Then reacted with hydrogen, experience metal ion is to relatively low The reduction of oxidation state is to form MCl₂。MCl₂Then anode chamber is recycled back into be converted into MCl₃.Hydrochloric acid is generated during being somebody's turn to do, It can be used for commercial use or can use as described herein during other.In some embodiments, the method is passed through The HCl of generation can be used for dissolved mineral can be used with generating in carbonate precipitation process as described herein divalence sun from Son.In some embodiments, metal halide or metal sulfate in (being not shown) as described herein, Fig. 6 can With unsaturated hydrocarbons or saturation hydrocarbon reaction to form halogenated hydrocarbons or sulfo group.In some embodiments, the negative electrode is not that gas expands Scattered negative electrode, but the negative electrode as shown in Fig. 4 A or Fig. 4 B.In some embodiments, system 600 can be applied to any generation The electro-chemical systems of alkali.

There is provided herein some examples of the reactor for the reaction for carrying out metallic compound and hydrogen.As an example, Fig. 7 A show a kind of reactor, such as anti-for metal ion (being formed as shown in the figure) and hydrogen in higher oxidation state The reaction tower answered.In some embodiments, as shown in Figure 7 A, anolyte passes through reaction tower.The gas of hydrogen also by It is delivered to reaction tower.Excessive hydrogen can be discharged from reaction tower, and it can be collected and branch back to reaction tower.In reaction tower, Containing the metal ion in higher oxidation state (with FeCl₃Show) anolyte can be reacted with hydrogen, with formed HCl and In low oxidation state, i.e. reduced form metal ion, with FeCl₂Show.Reaction tower optionally contains activated carbon or carbon, or Alternatively, activated carbon may be present in outside reaction tower person.The reaction of metal ion and hydrogen can occur on the activated carbon, by activity The anolyte of the renewable reduction of charcoal, or activated carbon only may act as filter to remove impurity from gas. Use isolation technics known in the art or acid block technique, including but not limited to ion exchange resin, size exclusion film and acid Dialysis etc., acid recovery can be undergone by making the anolyte of the reduction of the metal ion containing HCl and in low oxidation state, so that HCl is separated from anolyte.In some embodiments, because the size for the part being connected with metal ion is larger, institute Metal ion can be promoted to be separated with acid solution with part described herein.Anode containing the metal ion in low oxidation state Electrolyte is recyclable to return to electrochemical cell, and collects HCl.

As another example of reactor, the metal ion in higher oxidation state is also shown in Fig. 7 B (such as figure institute Show what is formed) with the reaction of hydrogen.As shown in Figure 7 B, from anode chamber and comprising the metal ion in higher oxidation state for example But it is not limited to Fe³⁺、Sn⁴⁺、Cr³⁺Deng anolyte can be used for reacting to form HCl with hydrogen, or contain available for washing SO₂Gas to form clean gas or sulfuric acid.In some embodiments, it is contemplated that NOx gases can with higher oxidation state Metal ion react to form nitric acid.In some embodiments, as shown in Figure 7 B, anolyte passes through reaction tower.Contain Hydrogen, SO₂And/or NOx gas is also delivered to reaction tower.Excessive hydrogen can be discharged from reaction tower, and it can be collected simultaneously It is transferred back to reaction tower.Excessive SO₂Washer is may pass through, the gas of relatively cleaning is discharged into the atmosphere afterwards.In reaction tower, contain The anolyte for having the metal ion in higher oxidation state can be with hydrogen and/or SO₂Reaction, to form HCl and/or H₂SO₄ With in low oxidation state, i.e. reduced form metal ion.Reaction tower optionally contains activated carbon or carbon, or alternatively, Activated carbon may be present in outside reaction tower.Metal ion and hydrogen or SO₂The reaction of gas can occur on the activated carbon, by activity The anolyte of the renewable reduction of charcoal, or activated carbon only may act as filter to remove impurity from gas. Using isolation technics known in the art, including but not limited to ion exchange resin, size exclusion film and acid dialysis etc. contain HCl and/or H₂SO₄Acid recovery can be undergone with the reproducibility anolyte of the metal ion in low oxidation state, so that from sun HCl and/or H is separated in the electrolyte of pole₂SO₄.In some embodiments, due to the size of part that is connected with metal ion compared with Greatly, so part described herein can promote the separation of metal ion and acid solution.Containing the metal in low oxidation state from The anolyte of son is recyclable to return to electrochemical cell, and collects HCl and/or H₂SO₄.In some embodiments, Reaction in reaction tower can occur 1-10 hours at a temperature of 50 DEG C -100 DEG C.

For an example such as Fig. 7 C institutes for the ion exchange resin that HCl is isolated from the anolyte containing metal Show.As seen in figure 7 c, separation process may include inorganic acid selective absorption/be adsorbed onto on anion exchange resin.In the first step In, containing HCl and/or H₂SO₄Anolyte pass through ion exchange resin, the ion exchange resin absorption HCl and/or H₂SO₄, anolyte is then demultiplex out.HCl and/or H can be made by the way that resin is washed with water₂SO₄Regeneration is returned from resin. Diffusion dialysis can be another method for the separating acid from anolyte.In some embodiments, due to gold The size for belonging to the part of ion connection is larger, so part described herein can promote the separation of metal ion and acid solution.

In some embodiments, the hydrochloric acid generated in this process is partially or even wholly used to dissolve iron filings to be formed FeCl₂And hydrogen.The FeCl generated in this process₂It is recyclable to return to anode chamber to be converted into FeCl₃.In some embodiment party In case, hydrogen can be used in hydrogen fuel cell.Fuel cell can be used for generating electricity powering to electrochemical process as described herein again. In some embodiments, hydrogen is transferred to U.S. Provisional Application 61/477, in the electro-chemical systems described in 097, this application It is incorporated herein by reference in its entirety.

In some embodiments, another electrification is undergone with or without the hydrochloric acid of the metal ion in low oxidation state Process is to generate hydrogen and metal ion in higher oxidation state.Such system is as shown in Figure 11.

In some embodiments, as follows, the hydrochloric acid generated in this process is used to generate ethylene dichloride：

2CuCl (aqueous solution)+2HCl (aqueous solution)+1/2O₂(gas) → 2CuCl₂(aqueous solution)+H₂O (liquid)

C₂H₄(gas)+2CuCl₂(aqueous solution) → 2CuCl (aqueous solution)+C₂H₄Cl₂(liquid)

In some embodiments, in Figure 1A, Figure 1B, Fig. 2, Fig. 3 A, Fig. 3 B, Fig. 4 A, Fig. 4 B, Fig. 5 A, Fig. 5 B and Fig. 5 C Electro-chemical systems anodolyte in the metal with higher oxidation state that is formed can be reacted with unsaturated hydrocarbons, with based on attached Corresponding halogenated hydrocarbons or sulfo group are formed in the anion on metal.For example, in unsaturated hydrocarbons and metal halide or metal sulphur After hydrochlorate reaction, corresponding chloro can be generated by metal chloride, metal bromide, metal iodide or metal sulfate etc. Hydrocarbon, bromo-hydrocarbons, idohydrocarbon or sulfo group.In some embodiments, metal halide or metal sulfate and unsaturated hydrocarbons Reaction causes to generate above-mentioned product and metal halide or metal sulfate in low oxidation state.In low oxidation state Metal ion then it is recyclable return to electro-chemical systems for generate in higher oxidation state metal ion.

" unsaturated hydrocarbons " includes the hydrocarbon with unsaturated carbon or had at least between adjacent carbon atom as used herein The hydrocarbon of one double bond and/or at least one three key.Unsaturated hydrocarbons can be straight chain, side chain or ring-type (it is aromatic or Non-aromatic).For example, hydrocarbon can be olefin(e), alkyne series, non-aromatic hydrocarbon such as cyclohexene, aryl or substituted unsaturation Hydrocarbon, such as, but not limited to halo unsaturated hydrocarbons.Hydrocarbon with least one double bond is referred to alternatively as alkene or alkene, and can have not Replace the formula C of alkene_nH_2n, wherein n is 2-20 or 2-10 or 2-8 or 2-5.In some embodiments, on alkene one or many Individual hydrogen can further by other functional groups be such as, but not limited to halogen (including chlorine, bromine, iodine and fluorine), carboxylic acid (- COOH), hydroxyl (- OH), amine etc. replaces.Unsaturated hydrocarbons includes all isomeric forms of unsaturation, and such as, but not limited to cis and trans are different Structure body, E and Z isomers, position isomer etc..

In some embodiments, provided herein is method and system in unsaturated hydrocarbons be Formulas I unsaturated hydrocarbons, its Production II compounds after halogenation or sulfonation (including sulphation)：

Wherein, n is 2-10；M is 0-5；And q is 1-5；

X is the halogen selected from fluorine, chlorine, bromine and iodine；–SO₃H；Or-OSO₂OH。

It should be appreciated that R substituent can be on a carbon atom or on more than one carbon atom, this depends on R and carbon atom Number.Only for example, when n is 3 and m is 2, substituent R can be on same carbon atom or in two different carbon atoms On.

In some embodiments, provided herein is method and system in unsaturated hydrocarbons be Formulas I unsaturated hydrocarbons, its Production II compounds after halogenation, wherein, n is 2-10；M is 0-5；And q is 1-5；R independently selected from hydrogen, halogen ,- COOR ' ,-OH and-NR ' (R "), wherein R ' and R " is independently selected from hydrogen, alkyl and substituted alkyl；And X be selected from chlorine, bromine and The halogen of iodine.

In some embodiments, provided herein is method and system in unsaturated hydrocarbons be Formulas I unsaturated hydrocarbons, its Production II compounds after halogenation, wherein, n is 2-5；M is 0-3；And q is 1-4；R independently selected from hydrogen, halogen ,- COOR ' ,-OH and-NR ' (R "), wherein R ' and R " is independently selected from hydrogen and alkyl；And X is the halogen selected from chlorine and bromine.

In some embodiments, provided herein is method and system in unsaturated hydrocarbons be Formulas I unsaturated hydrocarbons, its Production II compounds after halogenation, wherein, n is 2-5；M is 0-3；And q is 1-4；R independently selected from hydrogen, halogen and-OH, and X is the halogen selected from chlorine and bromine.

It should be appreciated that when m is more than 1, substituent R can be on same carbon atom or on different carbon atoms.Similarly, should Work as understanding, when q is more than 1, substituent X can be on same carbon atom or on different carbon atoms.

In some embodiments of the embodiment above of Formulas I, m is 0 and q is 1-2.In such embodiments, X For chlorine.

The example of saturation or unsaturated olefin including Formulas I includes but is not limited to ethene, vinyl chloride, bromine ethene, iodine Ethene, propylene, chloropropene, hydroxy, 1- butylene, 2- butylene (cis or trans), isobutene, 1,3- butadiene, pentadiene, Hexene, cyclopropylene, cyclobutane, cyclohexene etc..Hydrocarbon with least one three key is referred to alternatively as alkynes, and can have unsaturation The formula C of alkynes_nH_2n-2, wherein n is 2-10 or 2-8 or 2-5.In some embodiments, one or more hydrogen on alkynes can Further by such as, but not limited to halogen, carboxylic acid, hydroxyl etc., other functional groups replace.

In some embodiments, provided herein is method and system in unsaturated hydrocarbons be Formulas I A unsaturated hydrocarbons, its The production IIA compounds after halogenation or sulfonation (including sulphation)：

Wherein, n is 2-10；M is 0-5；And q is 1-5；

The example of substituted or unsubstituted alkynes includes but is not limited to acetylene, propine, propargyl chloride, propargyl bromide, butine, penta Alkynes, hexin etc..

There is provided the method comprised the following steps in some embodiments：Make anode and anode electrolysis in the anode compartment Metal ion contact in matter；Metal ion is converted into or is oxidized at anode higher oxidation state from low oxidation state；With The anodolyte for including the metal ion in higher oxidation state is handled with unsaturated hydrocarbons.In some embodiments of this method In, this method includes making negative electrode contact with catholyte and forming alkali at negative electrode.In some embodiments of this method, This method includes making negative electrode contact with catholyte and forming alkali, water and/or hydrogen at negative electrode.In some realities of this method Apply in scheme, this method includes making gas diffusion cathode contact with catholyte and forming alkali or water at negative electrode.At some There is provided the method comprised the following steps in embodiment：Make anode and the metal ion in anodolyte in the anode compartment Contact；Metal ion is set to be converted into higher oxidation state from low oxidation state at anode；Negative electrode is set to be contacted with catholyte； Alkali, water and/or hydrogen are formed at negative electrode；It is electric with the anode comprising the metal ion in higher oxidation state is handled with unsaturated hydrocarbons Xie Zhi.There is provided the method comprised the following steps in some embodiments：Make in the anode compartment in anode and anodolyte Metal ion contact；Metal ion is set to be converted into higher oxidation state from low oxidation state at anode；Make gas diffusion cathode Contacted with catholyte；Alkali or water are formed at negative electrode；Handled with unsaturated hydrocarbons comprising the metal in higher oxidation state The anodolyte of ion.There is provided the method comprised the following steps in some embodiments：Make in the anode compartment anode with Metal ion contact in anodolyte；Metal ion is set to be converted into higher oxidation state from low oxidation state at anode；Make Gas diffusion cathode is contacted with catholyte；Alkali is formed at negative electrode；Higher oxygen is in handling to include with unsaturated hydrocarbons The anodolyte of the metal ion of state.In some embodiments, with the metal ion in higher oxidation state to unsaturation The processing of hydrocarbon can be carried out in cathode chamber or outside negative electrode room.In some embodiments, with unsaturated hydrocarbons in higher oxygen Change the metal ion of state processing produce chlorohydrocarbon, bromo-hydrocarbons, idohydrocarbon or sulfo group and metal in low oxidation state from Son.In some embodiments, the metal ion in low oxidation state is recycled back into anode chamber.

In some embodiments of the above method, anode does not produce chlorine.In some embodiments of the above method, Oxygen and/or chlorine are not needed to the processing of unsaturated hydrocarbons with the metal ion in higher oxidation state.The one of the above method In a little embodiments, anode does not produce chlorine, and with being in the metal ion of higher oxidation state to the processing of unsaturated hydrocarbons not Need oxygen and/or chlorine.

There is provided the system for including following component in some embodiments：Anode chamber, its include with anodolyte Metal ion contact anode, the wherein anode is configured as metal ion being converted into higher oxygen from low oxidation state State；And reactor, it is operably connected to anode chamber, and is configured as making comprising the metal ion in higher oxidation state Anodolyte and unsaturated hydrocarbons react.In some embodiments of the system, the system includes cathode chamber, and it includes the moon Pole and catholyte, the wherein negative electrode are configured as in catholyte forming alkali, water and/or hydrogen.In the system In some embodiments, the system includes cathode chamber, and it includes negative electrode and catholyte, and the wherein negative electrode is configured as in the moon Alkali and/or hydrogen are formed in the electrolyte of pole.In some embodiments of the system, the system includes gas diffusion cathode and the moon Pole electrolyte, the wherein negative electrode are configured as in catholyte forming alkali or water.There is provided bag in some embodiments The system for including following component：Anode chamber, it includes the metal ion in anode and anodolyte, and the wherein anode is configured as Metal ion is converted into higher oxidation state from low oxidation state in the anode compartment；Negative electrode comprising negative electrode and catholyte Room, the wherein negative electrode are configured as in catholyte forming alkali, water or hydrogen；And reactor, it is operably connected to Anode chamber, and be configured as making the anodolyte comprising the metal ion in higher oxidation state react with unsaturated hydrocarbons. There is provided the system for including following component in some embodiments：Anode chamber, it includes the gold in anode and anodolyte Belong to ion, the wherein anode is configured as that metal ion is converted into higher oxidation state from low oxidation state in the anode compartment；Bag Cathode chamber containing gas diffusion cathode and catholyte, the wherein negative electrode are configured as in catholyte forming alkali；With Reactor, it is operably connected to anode chamber, and is configured as making including the sun of the metal ion in higher oxidation state Pole electrolyte reacts with unsaturated hydrocarbons.In some embodiments, with the metal ion in higher oxidation state to unsaturated hydrocarbons Processing can be carried out in cathode chamber or outside negative electrode room.In some embodiments, with unsaturated hydrocarbons in higher oxygen The processing of the metal ion of state produces chlorohydrocarbon, bromo-hydrocarbons, idohydrocarbon or sulfo group and the metal ion in low oxidation state. In some embodiments, the system be configured as with unsaturated hydrocarbons by the metal ion in higher oxidation state is formed be in compared with The metal ion of low-oxidation-state, and the metal ion in low oxidation state is recycled back into anode chamber.

In some embodiments, in preceding method and system implementation plan and unsaturated hydrocarbons as described herein It is the unsaturated hydrocarbons of Formulas I, or C2-C10 alkene or C2-C5 alkene.In some embodiment party of method and system as described above In case, unsaturated hydrocarbons in foregoing embodiments and as described herein is ethene.The halogen formed by this class unsaturated hydrocarbons It is the halogenated hydrocarbons (as described herein) of Formula II for hydrocarbon, for example, ethylene dichloride, chlorethanol, butyl chloride, dichloroetane, methaform Deng.In some embodiments of method and system as described above, the metal ion is metal ion described herein, for example But it is not limited to copper, iron, tin or chromium.

In some embodiments of said system, anode is configured as not producing chlorine.In some realities of said system Apply in scheme, the reactor for being configured as making unsaturated hydrocarbons react with the metal ion in higher oxidation state is configured as being not required to Want oxygen and/or chlorine.In some embodiments of the above method, anode is configured as not producing chlorine, and reactor quilt It is configured to not need oxygen and/or chlorine.

One example of Fig. 5 A electro-chemical systems is as shown in Figure 8 A.It should be appreciated that Fig. 8 A system 800 is merely to illustrate Purpose, other metal ions, other unsaturated hydrocarbons with different oxidation state and forms the product in addition to alkali in cathode chamber Other electro-chemical systems such as water or hydrogen are equally applicable to the system.Fig. 4 A or Fig. 4 B negative electrode are also replaceable into Fig. 8 A. In some embodiments, as shown in Figure 8 A, electro-chemical systems 800 include the oxygen depolarization that hydroxide ion is generated by water and oxygen Negative electrode.System 800 also includes the anode for making metal ion be converted into 2+ oxidation state from 1+ oxidation state.Cu²⁺Ion and chlorion knot Conjunction forms CuCl₂.Metal chloride CuCl₂Then can be such as, but not limited to ethylene reaction with unsaturated hydrocarbons, experience metal ion to The reduction of low oxidation state is to form CuCl and dichloride hydrocarbon, such as, but not limited to ethylene dichloride.Then CuCl is recirculated back to To anode chamber to be converted into CuCl₂。

The ethylene dichloride formed by the inventive method and system can be used for any commercial use.In some embodiments In, the formation of process experience VCM (VCM) of the ethylene dichloride Jing Guo such as cracking/purifying.The VCM can Production for polyvinyl chloride.In some embodiments, the hydrochloric acid formed during EDC is converted to VCM can be separated and with Acetylene reaction is further to form VCM.

In some embodiments, the HCl generated in VCM forming processes can be recycled to one or more as described herein In electro-chemical systems, wherein using HCl with formation hydrogen or water at negative electrode in negative electrode or anodolyte.Such as Fig. 8 B institutes Show, integrated electro-chemical systems of the invention are synthesized with VCM/PVC to be shown in conjunction with.Any electro-chemical systems of the present invention are as schemed System shown in 1B, Fig. 2, Fig. 4 A or Fig. 5 A can be used for forming CuCl₂, work as CuCl₂EDC is produced during with ethylene reaction.EDC's splits Solution and VCM following process produce HCl, and HCl can be recycled in Fig. 4 B or Fig. 5 B any electro-chemical systems further to be formed CuCl₂.It should be appreciated that whole process can carry out (that is, Figure 1B, Fig. 2, Fig. 4 A not being incorporated to only in Fig. 4 B or Fig. 5 B system Or Fig. 5 A system).

In some embodiments, chlorine is carried out to ethene with the metal chloride in higher oxidation state in an aqueous medium Change obtains ethylene dichloride, chlorethanol or its combination.In some embodiments of method described herein and system, by ethene 10wt% is formed over, or more than 20wt%, or more than 30wt%, or more than 40wt%, or more than 50wt%, or exceed 60wt%, or more than 70wt%, or more than 80wt%, or more than 90wt%, or more than 95wt%, or about 99wt%, or about 10- 99wt%, or about 10-95wt%, or about 15-95wt%, or about 25-95wt%, or about 50-95wt%, or about 50-99wt% Ethylene dichloride, or about 50%-99.9wt% ethylene dichloride, or about 50%-99.99wt% ethylene dichloride. In some embodiments, remaining percentage by weight is the percentage by weight of chlorethanol.In some embodiments, nothing in reaction Chlorethanol is formed.In some embodiments, have in reaction less than 0.001wt% or less than 0.01wt% or less than 0.1wt% It is remaining or less than 0.5wt% or less than 1wt% or less than 5wt% or less than 10wt% or less than 20wt% chlorethanol is formed For EDC.In some embodiments, less than 0.001wt% or less than 0.01wt% or less than 0.1wt% or less than 0.5wt% or less than 1wt% or less than 5wt% metal ion is present in EDC products.In some embodiments, it is less than 0.001wt% or less than 0.01wt% or less than 0.1wt% chlorethanol and/or metal ion is present in EDC products.

In some embodiments, the EDC products containing metal ion can undergo washing step to remove metal ion, should Step may include to be rinsed with organic solvent or EDC products is passed through post.In some embodiments, EDC products can pass through distillation Purifying, any of which accessory substance such as trichloroacetaldehyde (CCl₃) and/or chloral hydrate (2,2,2- trichloroethanes -1,1- CHO Glycol) and (if formed if) can be separated.

In some embodiments, unsaturated hydrocarbons is propylene.In some embodiments, handled with propylene and be in higher oxygen Change the metal ion such as CuCl of state₂To obtain propane dichloride (C₃H₆Cl₂) or dichloropropane (DCP), the latter can be used for making Standby chloropropene (C₃H₅Cl).In some embodiments, unsaturated hydrocarbons is butane or butylene.In some embodiments, butylene is used Metal ion such as CuCl of the processing in higher oxidation state₂To obtain dichloroetane (C₄H₈Cl₂) or dichloro-butenes (C₄H₆Cl₂), the latter can be used for preparing chlorobutadiene (C₄H₅Cl).In some embodiments, unsaturated hydrocarbons is benzene.In some realities Apply in scheme, the metal ion such as CuCl in higher oxidation state is handled with benzene₂To obtain chlorobenzene.In some embodiments In, handle the metal ion such as CuCl in higher oxidation state with acetylene₂To obtain chloroacetylene, acetylene dichloride, vinyl chloride, two Vinyl chloride, tetrachloro-ethylene or its combination.In some embodiments, insatiable hunger is handled with the metal chloride in higher oxidation state With hydrocarbon to form product, including but not limited to ethylene dichloride, chlorethanol, chloropropene, propylene oxide (further dehydrochlorination), Allyl chloride, chloromethanes, trichloro ethylene, tetrachloro-ethylene, chlorobenzene, 1,2- dichloroethanes, 1,1,2- trichloroethanes, 1,1,2,2- tetra- Chloroethanes, pentachloroethane, 1,1- dichloroethylene, chlorophenol, chlorinated toluenes etc..

In some embodiments, the yield of halogenated hydrocarbons is generated by unsaturated hydrocarbons using metal ion, for example, is given birth to by ethene DCP yield is generated into EDC yield or by propylene, or the yield for generating dichloro-butenes by butylene is more than 90% or is more than 95% or for 90%-95% or 90%-99% or 90%-99.9% (weight).In some embodiments, using metal ion The selectivity of halogenated hydrocarbons is generated by unsaturated hydrocarbons, for example, DCP yield is generated by ethylene synthesis EDC yield or by propylene, or Person more than 80% or more than 90% or is 80%-99% (weight) by the yield of butylene generation dichloro-butenes.In some embodiment party In case, the STY (space-time yield) of halogenated hydrocarbons is generated by unsaturated hydrocarbons using metal ion, such as by ethylene synthesis EDC yield Or generate DCP yield by propylene, or the yield for generating dichloro-butenes by butylene is more than 3 or more than 4 or more than 5 or be 3-5 Or 3-6 or 3-8.

In some embodiments, in Figure 1A, Figure 1B, Fig. 2, Fig. 3 A, Fig. 3 B, Fig. 4 A, Fig. 4 B, Fig. 5 A and Fig. 5 B electrification The metal with higher oxidation state formed in the anodolyte of system can with saturation hydrocarbon reaction, with based on investing on metal Anion form corresponding halogenated hydrocarbons or sulfo group.For example, saturated hydrocarbons and metal halide or metal sulfate reactant salt it Afterwards, by metal chloride, metal bromide, metal iodide or metal sulfate etc. can produce corresponding chlorohydrocarbon, bromo-hydrocarbons, Idohydrocarbon or sulfo group.In some embodiments, the reaction of metal halide or metal sulfate and saturated hydrocarbons causes generation Above-mentioned product and metal halide or metal sulfate in low oxidation state.Metal ion in low oxidation state is right It is recyclable afterwards to return to electro-chemical systems to generate the metal ion in higher oxidation state.

" saturated hydrocarbons " includes the hydrocarbon without unsaturated carbon or hydrocarbon as used herein.The hydrocarbon can be straight chain, side chain Or ring-type.For example, the hydrocarbon can be substituted or unsubstituted alkane and/or substituted or unsubstituted cycloalkane.It is described Hydrocarbon can have the formula C of unsubstituted alkane_nH_2n+2, wherein n is 2-20 or 2-10 or 2-8 or 2-5.In some embodiments, One or more hydrogen on alkane or cycloalkane can be further by such as, but not limited to halogen (including chlorine, bromine, iodine and fluorine), carboxylic acid Other functional groups such as (- COOH), hydroxyl (- OH), amine are replaced.

In some embodiments, provided herein is method and system in saturated hydrocarbons be formula III saturated hydrocarbons, it is in halogen Production IV compounds after change or sulfonation (including sulphation)：

Wherein, n is 2-10；K is 0-5；And s is 1-5；

It should be appreciated that R substituent can be on a carbon atom or on more than one carbon atom, this depends on R and carbon atom Number.Only for example, when n is 3 and k is 2, substituent R can be on same carbon atom or in two different carbon atoms On.

In some embodiments, provided herein is method and system in saturated hydrocarbons be formula III saturated hydrocarbons, it is in halogen Production IV compounds after change：

Wherein, n is 2-10；K is 0-5；And s is 1-5；

X is the halogen selected from chlorine, bromine and iodine.

Wherein, n is 2-5；K is 0-3；And s is 1-4；

R is independently selected from hydrogen, halogen ,-COOR ' ,-OH and-NR ' (R "), and wherein R ' and R " is independently selected from hydrogen and alkyl；And

X is the halogen selected from chlorine and bromine.

Wherein, n is 2-5；K is 0-3；And s is 1-4；

R independently selected from hydrogen, halogen and-OH, and

X is the halogen selected from chlorine and bromine.

It should be appreciated that when k is more than 1, substituent R can be on same carbon atom or on different carbon atoms.Similarly, should Work as understanding, when s is more than 1, substituent X can be on same carbon atom or on different carbon atoms.

In some embodiments of the embodiment above of formula III, k is 0 and s is 1-2.In such embodiment In, X is chlorine.

The example of the alkane of substituted or unsubstituted alkane, such as formula III include but is not limited to methane, ethane, chloroethanes, Bromoethane, iodoethane, propane, chloropropane, hydroxypropyl alkane, butane, chlorobutane, hydroxyl butane, pentane, hexane, hexamethylene, pentamethylene, Chlorocyclopentane etc..

There is provided the method comprised the following steps in some embodiments：Make anode and anode electrolysis in the anode compartment Metal ion contact in matter；Metal ion is converted into or is oxidized at anode higher oxidation state from low oxidation state；With The anodolyte for including the metal ion in higher oxidation state is handled with saturated hydrocarbons.In some embodiments of this method In, this method includes making negative electrode that alkali is contacted and formed at negative electrode with catholyte.In some embodiments of this method In, this method includes making negative electrode that alkali and hydrogen are contacted and formed at negative electrode with catholyte.In some realities of this method Apply in scheme, this method includes making negative electrode that hydrogen is contacted and formed at negative electrode with catholyte.In some of this method In embodiment, this method includes making gas diffusion cathode that alkali is contacted and formed at negative electrode with catholyte.In the party In some embodiments of method, this method includes making gas diffusion cathode contact and be formed at negative electrode with catholyte Water.There is provided the method comprised the following steps in some embodiments：Make in the anode compartment in anode and anodolyte Metal ion is contacted；Metal ion is set to be converted into higher oxidation state from low oxidation state at anode；Make negative electrode and catholyte Matter is contacted；Alkali, water and/or hydrogen are formed at negative electrode；Handled with saturated hydrocarbons comprising the metal ion in higher oxidation state Anodolyte.There is provided the method comprised the following steps in some embodiments：Make anode and anode in the anode compartment Metal ion contact in electrolyte；Metal ion is set to be converted into higher oxidation state from low oxidation state at anode；Make gas Dispenser cathode is contacted with catholyte；Alkali or water are formed at negative electrode；Higher oxidation state is in handling to include with saturated hydrocarbons Metal ion anodolyte.In some embodiments, with the metal ion in higher oxidation state to saturated hydrocarbons Processing can be carried out in cathode chamber or outside negative electrode room.In some embodiments, with saturated hydrocarbons in higher oxidation state The processing of metal ion obtains halogenated hydrocarbons or sulfo group such as chlorohydrocarbon, bromo-hydrocarbons, idohydrocarbon or sulfo group and in compared with suboxides The metal ion of state.In some embodiments, the metal ion in low oxidation state is recycled back into anode chamber.At some In embodiment, saturated hydrocarbons in foregoing embodiments and described herein is the saturated hydrocarbons (as described herein) of formula III, or C2-C10 alkanes or C2-C5 alkanes.In some embodiments, in foregoing embodiments and saturated hydrocarbons described herein be first Alkane.In some embodiments, in foregoing embodiments and saturated hydrocarbons described herein be ethane.In some embodiments In, saturated hydrocarbons in foregoing embodiments and described herein is propane.The halogenated hydrocarbons formed by this class saturated hydrocarbons is formula IV Halogenated hydrocarbons (as described herein), for example, chloromethanes, dichloromethane, chloroethanes, dichloroethanes, chloropropane, dichloropropane etc..

In some embodiments of the above method, the metal ion used is platinum, palladium, copper, iron, tin and chromium.Above-mentioned In some embodiments of method, anode does not produce chlorine.In some embodiments of the above method, with higher oxygen Processing of the metal ion of state to saturated hydrocarbons does not need oxygen and/or chlorine.In some embodiments of the above method, anode Chlorine is not produced, and oxygen and/or chlorine are not needed to the processing of saturated hydrocarbons with the metal ion in higher oxidation state.

There is provided the system for including following component in some embodiments：Anode chamber, its include with anodolyte Metal ion contact anode, the wherein anode is configured as metal ion being converted into higher oxygen from low oxidation state State；And reactor, it is operably connected to anode chamber, and is configured as making comprising the metal ion in higher oxidation state Anodolyte and saturation hydrocarbon reaction.In some embodiments of the system, the system includes cathode chamber, the cathode chamber bag Containing negative electrode and catholyte, the wherein negative electrode is configured as at negative electrode forming alkali.In some embodiments of the system, The system includes cathode chamber, and the cathode chamber includes negative electrode and catholyte, and the wherein negative electrode is configured as being formed at negative electrode Hydrogen.In some embodiments of the system, the system includes cathode chamber, and the cathode chamber includes negative electrode and catholyte, Wherein the negative electrode is configured as at negative electrode forming alkali and hydrogen.In some embodiments of the system, the system includes gas Body dispenser cathode and catholyte, the wherein negative electrode are configured as at negative electrode forming alkali.In some embodiment party of the system In case, the system includes gas diffusion cathode and catholyte, and the wherein negative electrode is configured as at negative electrode forming water.One There is provided the system for including following component in a little embodiments：Anode chamber, its include anode and anodolyte in metal from Son, the wherein anode are configured as that metal ion is converted into higher oxidation state from low oxidation state in the anode compartment；Include the moon Pole and the cathode chamber of catholyte, the wherein negative electrode are configured as in catholyte forming alkali, water and hydrogen；And reaction Device, it is operably connected to anode chamber, and is configured as making the anode electricity comprising the metal ion in higher oxidation state Solve matter and saturation hydrocarbon reaction.There is provided the system for including following component in some embodiments：Anode chamber, it includes anode With the metal ion in anodolyte, the wherein anode is configured as in the anode compartment turning metal ion from low oxidation state Turn to higher oxidation state；Cathode chamber comprising gas diffusion cathode and catholyte, the wherein negative electrode are configured as in negative electrode Alkali or water are formed in electrolyte；And reactor, it is operably connected to anode chamber, and is configured as making to include in higher The anodolyte of the metal ion of oxidation state and saturation hydrocarbon reaction.In some embodiments, with higher oxidation state Processing of the metal ion to saturated hydrocarbons can be carried out in cathode chamber or outside negative electrode room.In some embodiments, saturated hydrocarbons is used Processing to the metal ion in higher oxidation state produces chlorohydrocarbon, bromo-hydrocarbons, idohydrocarbon or sulfo group and in compared with hypoxemia Change the metal ion of state.In some embodiments, the system is configured as with saturated hydrocarbons by the metal in higher oxidation state Metal ion of the ion formation in low oxidation state, and the metal ion in low oxidation state is recycled back into anode Room.

In some embodiments of method and system as described above, the metal ion be metal described herein from Son, such as, but not limited to platinum, palladium, copper, iron, tin or chromium.

In some embodiments of said system, anode is configured as not producing chlorine.In some realities of said system Apply in scheme, the reactor for being configured as making saturated hydrocarbons react with the metal ion in higher oxidation state is configured as not needing Oxygen and/or chlorine.In some embodiments of the above method, anode is configured as not producing chlorine, and reactor by with It is set to and does not need oxygen and/or chlorine.

It should be appreciated that the example of the electro-chemical systems shown in Fig. 8 A can replace unsaturated hydrocarbons and be configured by using saturated hydrocarbons For saturated hydrocarbons.Therefore, suitable metal ion can be used, such as platinum chloride, palladium bichloride, copper chloride.

In some embodiments, the ethane of aqueous medium is carried out with the metal chloride in higher oxidation state Chlorination obtains chloroethanes, dichloroethanes or its combination.In some embodiments of method described herein and system, by ethane 10wt% is formed over, or more than 20wt%, or more than 30wt%, or more than 40wt%, or more than 50wt%, or exceed 60wt%, or more than 70wt%, or more than 80wt%, or more than 90wt%, or more than 95wt%, or about 99wt%, or about 10%-99wt%, or about 10%-95wt%, or about 15%-95wt%, or about 25%-95wt%, or about 50%-95wt%, Or about 50%-99wt%, or about 50%-99.9wt%, or about 50%-99.99wt% chloroethanes.In some embodiments In, remaining percentage by weight is the percentage by weight of chlorethanol and/or ethylene dichloride.In some embodiments, react Middle chlorine-free ethanol is formed.In some embodiments, have in reaction less than 0.001wt% or less than 0.01wt% or less than 0.1wt% or less than 0.5wt% or less than 1wt% or less than 5wt% or less than 10wt% or less than 20wt% chlorethanol shape Into remaining is product.In some embodiments, less than 0.001wt% or less than 0.01wt% or less than 0.1wt% or less than 0.5wt% or less than 1wt% or less than 5wt% metal ion is present in product.In some embodiments, it is less than 0.001wt% or less than 0.01wt% or less than 0.1wt% chlorethanol and/or metal ion is present in product.

In some embodiments, the yield of halogenated hydrocarbons is generated by saturated hydrocarbons using metal ion, for example, is generated by ethane Chloroethanes or EDC yield are more than 90% or more than 95% or are 90%-95% or 90%-99% or 90%-99.9% (weights Amount).In some embodiments, the selectivity of halogenated hydrocarbons is generated by saturated hydrocarbons using metal ion, for example, chlorine is generated by ethane Ethane or EDC yield are more than 80% or more than 90% or are 80%-99% (weight).In some embodiments, by saturation The STY (space-time yield) of hydrocarbon generation halogenated hydrocarbons is more than 3 or more than 4 or more than 5 or is 3-5 or 3-6 or 3-8.

The product formed by the inventive method and system, such as, but not limited to halogenated hydrocarbons, acid, carbonate and/or bicarbonate Salt, the same products than being formed by conventionally known in the art method and system are more green.There is provided the green halo of preparation The method of hydrocarbon, it includes making anode contact with anodolyte；Metal chloride is oxidized to by low oxidation state at anode Higher oxidation state；Negative electrode is set to be contacted with catholyte；With with the metal chloride in higher oxidation state to unsaturated hydrocarbons or Saturated hydrocarbons carries out halogenation, to produce green halogenated hydrocarbons.There is provided formed by method described herein in some embodiments Green halogenated hydrocarbons.Also providing includes the system of following component：The anode contacted with anodolyte, the wherein anode are configured For metal ion is oxidized into higher oxidation state by low oxidation state；The negative electrode contacted with catholyte；And reactor, it can Anode chamber is operatively coupled to, and is configured as making metal ion and unsaturated hydrocarbons or saturated hydrocarbons in higher oxidation state anti- Should be to form green halogenated hydrocarbons.

Term " more green " as used herein or " green " or its grammatical equivalents are included by the method for the present invention Any chemicals or product formed with system, compared with the identical chemicals or product formed by methods known in the art, There is higher energy to save or voltage saving for it.For example, chlor-alkali is typically used for production chlorine and then utilizes the chlorine pair Ethene carries out technique of the chlorination to form EDC.It is higher than as the energy needed for chlor-alkali generates EDC and is aoxidized by the metal of the present invention Energy needed for method generation EDC.Therefore, the EDC produced by the method and system of the present invention is than the EDC that is produced by chlor-alkali It is more green.Such energy is saved and shown in Fig. 8 C, and Fig. 8 C show that the activation for implementing the inventive method is built The contrast that the activation of (activation barriers) and chlor-alkali is built.

As shown in Figure 8 C, to generating EDC institutes as the energy needed for chlor-alkali generation EDC and by the method and system of the present invention The energy needed is compared.Generation EDC process point two parts are shown.One is electrochemical part, wherein being in the present invention Copper oxidation occurs in system 1 and system 2, by comparison, chlorine generation occurs in chlor-alkali.One is catalysed partial, wherein being Copper chloride (II) (by being electrochemically generated) carries out chlorination to ethene in system 1 and 2, and (being generated by chlor-alkali) chlorine is to ethene Chlorination (conventionally known) is carried out to form EDC.In system 1, electrochemical reaction is carried out in the case of in the absence of part, and In system 2, electrochemical reaction is carried out in the case where there is part.In system 1, system 2 and chlor-alkali, negative electrode is hydrogen Negative electrode is generated, and the current density of electrochemical reaction is 300mA/cm².As shown in Figure 8 C, for electrochemical reaction, the phase of system 1 For chlor-alkali there is the energy more than 125kJ/mol to save, and system 2 has more than 225kJ/mol relative to chlor-alkali Energy is saved.Therefore, green halogenated hydrocarbons are produced by the method and system of the present invention and is such as, but not limited to EDC, with passing through routine Technique such as chlor-alkali is compared to produce EDC, can have up to 300kJ/mol, or up to 250kJ/mol, or 50-300kJ/ Mol, or 50-250kJ/mol, or 100-250kJ/mol, or 100-200kJ/mol energy are saved.For system 1 and 2, with Chlor-alkali is compared, and this is converted to the saving more than 1 megawatt hour/ton EDC or 1-21 megawatt hour/ton EDC.This also with compared to chlor-alkali Voltage of the method more than 1V or 1-2V (1Vx2 electronics is about 200kJ/mol) saves related.

Equally as shown in Figure 8 C, the catalysed partial of the reaction has theoretic low for each in system 1 and 2 Build, and there is theoretic Gao Lei for the two systems of system 1 and 2.Catalytic reaction in system 1 and system 2 can occur low Point or high base point or any point therebetween are built, this depends on the such as, but not limited to condition such as concentration, reactor size, flow velocity.I.e. The catalytic reaction in system 1 and 2 is set to there are some energy inputs, it will be saved by the obvious energy in electrochemical reaction and supports Disappear so that exist up to 100kJ/mol or more than 100kJ/mol or for 50-100kJ/mol or 0-100kJ/mol net energy Save.This is converted to compared with chlor-alkali up to or more than 1 megawatt hour/ton EDC, or 0-1V or more than 1V or be 1-2V electricity Pressure is saved.It should be appreciated that chlor-alkali, system 1 and system 2 are all carried out in an aqueous medium.With organic solvent (for example, passing through Azeotropic distillation removes some or all water from electrochemical cell) electrochemical cell of operation or catalysis system will be needed than conventional The higher energy of method, and green halogenated hydrocarbons will not be produced.

The energy section compared with the system 1 without using part using the system 2 of part is further illustrated in Fig. 8 C Save.

It thus provides preparing the method for green halogenated hydrocarbons, it includes making anode contact with anodolyte；At anode Metal chloride is oxidized to higher oxidation state from low oxidation state；Negative electrode is set to be contacted with catholyte；With with higher The metal chloride of oxidation state carries out halogenation to produce green halogenated hydrocarbons to unsaturated hydrocarbons or saturated hydrocarbons, and wherein this method causes to surpass Cross 100kJ/mol or more than 150kJ/mol or more than 200kJ/mol or for 100-250kJ/mol or 50-100kJ/mol or 0- 100kJ/mol net energy is saved, or this method causes to save more than 1V or for 0-1V or 1-2V or 0-2V voltage.Also carry Supply to include the system of following component：The anode contacted with anodolyte, the wherein anode be configured as by metal ion by Low oxidation state is oxidized to higher oxidation state；The negative electrode contacted with catholyte；And reactor, it is operably connected to sun Pole room, and it is configured as making metal ion and unsaturated hydrocarbons or saturation hydrocarbon reaction in higher oxidation state to form green halogen For hydrocarbon, wherein the system causes more than 100kJ/mol or more than 150kJ/mol or more than 200kJ/mol or be 100-250kJ/ Mol or 50-100kJ/mol or 0-100kJ/mol net energy is saved, or the system causes to exceed 1V or is 0-1V or 1-2V Or 0-2V voltage is saved.

All electro-chemical systems described herein and method are in the water more than 5wt% or the water more than 6wt% or aqueous Jie Carried out in matter.On the one hand, described method and system has carries out metal oxidation reaction and outside battery in an electrochemical cell Carry out the advantage of reduction reaction (all in an aqueous medium).Applicant is in surprise and it was unexpectedly observed that in unsaturated hydrocarbons or full Aqueous medium is used in halogenation or sulfonation with hydrocarbon or hydrogen, the high yield and selectivity (embodiment hereof of product are not only resulted in Middle display), and cause the generation of reducing metal ion of the aqueous medium in low oxidation state, the metal ion can be again It is circulated back to electro-chemical systems.In some embodiments, because electrochemical cell is efficiently run in an aqueous medium, so Water need not be removed from the anodolyte comprising the metal ion in higher oxidation state or only need minimally to remove Water (such as by azeotropic distillation), the metal ion reacts with unsaturated hydrocarbons or saturated hydrocarbons or hydrogen in an aqueous medium.Cause This, in electrochemical cell and catalysis system using aqueous medium provide the present invention efficient and low energy consumption integrated system and Method.

Therefore in some embodiments there is provided a kind of method, it includes：Anode is set to be contacted with anodolyte, its In the anodolyte include metal ion, metal ion is oxidized to higher oxidation state from low oxidation state at anode, made Negative electrode is contacted with catholyte, and make in aqueous medium unsaturated hydrocarbons or saturated hydrocarbons with comprising the gold in higher oxidation state Belong to the anode electrolysis qualitative response of ion, wherein the aqueous medium comprises more than 5wt% water, or more than 5.5wt% or exceedes 6wt% or 5-90wt% or 5-95wt% or 5-99wt% water, or 5.5-90wt% or 5.5-95wt% or 5.5-99wt% Water, or 6-90wt% or 6-95wt% or 6-99wt% water.In some embodiments there is provided a kind of method, it is wrapped Include：Anode is contacted with anodolyte, wherein the anodolyte includes metal ion, at anode by metal halide or Metal sulfate is oxidized to higher oxidation state from low oxidation state, negative electrode is contacted with catholyte, and in aqueous medium It is middle that halogenation or sulfonation are carried out to unsaturated hydrocarbons or saturated hydrocarbons with metal halide or metal sulfate in higher oxidation state, its In the aqueous medium comprise more than 5wt% or more than 5.5wt% or more than 6wt% or 5-90wt% or 5-95wt% or 5- 99wt% water, or 5.5-90wt% or 5.5-95wt% or 5.5-99wt% water, or 6-90wt% or 6-95wt% or 6- 99wt% water.The unsaturated hydrocarbons (such as Formulas I), saturated hydrocarbons (such as formula III), halogenated hydrocarbons (such as Formula II and IV), metal from Sons etc. are all described in detail herein.

In some embodiments there is provided a kind of method, it includes：Anode is set to be contacted with anodolyte, in anode Metal halide or metal sulfate are oxidized to higher oxidation state by place from low oxidation state, negative electrode is connect with catholyte Touch, and make metal halide or metal sulfate in higher oxidation state contact to form acid with hydrogen in an aqueous medium Such as hydrochloric acid or sulfuric acid, the wherein aqueous medium comprises more than 5wt% water, or more than 5.5wt% or more than 6wt% or 5- 90wt% or 5-95wt% or 5-99wt% water, or 5.5-90wt% or 5.5-95wt% or 5.5-99wt% water, or 6- 90wt% or 6-95wt% or 6-99wt% water.In some embodiments, negative electrode produces hydroxide ion.

In some embodiments of the above method, negative electrode produces water, alkali and/or hydrogen.In some realities of the above method Apply in scheme, negative electrode is the ODC for producing water.In some embodiments of the above method, negative electrode is the ODC for producing alkali.Upper In some embodiments for stating method, negative electrode produces hydrogen.In some embodiments of the above method, negative electrode is by oxygen and water It is reduced to the oxygen depolarization negative electrode of hydroxide ion；Negative electrode is that the hydrogen that water is reduced into hydrogen and hydroxide ion generates the moon Pole；Negative electrode is that the hydrogen that hydrochloric acid is reduced into hydrogen generates negative electrode；Or negative electrode is to make the oxygen of hydrochloric acid and oxygen reaction formation water Depolarized cathode.

In some embodiments of the above method, the metal ion is any metal ion described herein.Upper In some embodiments for stating method, metal ion be selected from iron, chromium, copper, tin, silver, cobalt, uranium, lead, mercury, vanadium, bismuth, titanium, ruthenium, osmium, Europium, zinc, cadmium, gold, nickel, palladium, platinum, rhodium, iridium, manganese, technetium, rhenium, molybdenum, tungsten, niobium, tantalum, zirconium, hafnium and combinations thereof.In some embodiments In, metal ion is selected from iron, chromium, copper and tin.In some embodiments, metal ion is copper.In some embodiments, it is golden The low oxidation state for belonging to ion is 1+, 2+, 3+, 4+ or 5+.In some embodiments, the higher oxidation state of metal ion is 2 +, 3+, 4+, 5+ or 6+.

In some embodiments, this method further comprises the metal ion for making at least a portion be in low oxidation state It is recycled back into electrochemical cell.In some embodiments, this method make the metal ion in higher oxidation state with not Without the azeotropic distillation of water before saturated hydrocarbons or saturation hydrocarbon reaction.In some embodiments, the above method at anode not Produce chlorine.In some embodiments, the above method does not need oxygen and/or chlorine by unsaturated hydrocarbons or saturated hydrocarbons chlorination For halogenated hydrocarbons.

In some embodiments there is provided a kind of system, it is included：Contacted with the anodolyte containing metal ion Anode, the wherein anode is configured as metal ion being oxidized to higher oxidation state by low oxidation state；With catholyte The negative electrode of contact；And reactor, it is operably connected to anode chamber, and is configured as making to include in higher oxidation state The anodolyte of metal ion in an aqueous medium with unsaturated hydrocarbons or saturation hydrocarbon reaction, the wherein aqueous medium comprises more than 5wt% water, or more than 5.5wt% or more than 6wt% or 5-90wt% or 5-95wt% or 5-99wt% water, or 5.5- 90wt% or 5.5-95wt% or 5.5-99wt% water, or 6-90wt% or 6-95wt% or 6-99wt% water.At some There is provided a kind of system in embodiment, it is included：Contact and be configured as metal halide at anode with anodolyte Thing or metal sulfate are oxidized to the anode of higher oxidation state from low oxidation state, the negative electrode contacted with catholyte, and instead Device is answered, the reactor is operably connected to anode chamber, and be configured as using in an aqueous medium in higher oxidation state Metal halide or metal sulfate carry out halogenation or sulfonation to unsaturated hydrocarbons or saturated hydrocarbons, and the wherein aqueous medium is comprised more than 5wt% water, or more than 5.5wt% or more than 6wt% or 5-90wt% or 5-95wt% or 5-99wt% water, or 5.5- 90wt% or 5.5-95wt% or 5.5-99wt% water, or 6-90wt% or 6-95wt% or 6-99wt% water.

In some embodiments there is provided a kind of system, it is included：Contact and be configured as in sun with anodolyte Metal halide or metal sulfate are oxidized to the anode of higher oxidation state at pole from low oxidation state, connect with catholyte Tactile negative electrode, and reactor, the reactor are operably connected to anode chamber, and are configured as making to be in an aqueous medium The metal halide or metal sulfate of higher oxidation state contact to form acid such as hydrochloric acid or sulfuric acid, wherein aqueous Jie with hydrogen Matter comprises more than 5wt% water, or more than 5.5wt% or more than 6wt%'s or 5-90wt% or 5-95wt% or 5-99wt% Water, or 5.5-90wt% or 5.5-95wt% or 5.5-99wt% water, or 6-90wt% or 6-95wt% or 6-99wt% Water.

In some embodiments of said system, negative electrode is configured as producing hydroxide ion.The one of said system In a little embodiments, negative electrode is configured as producing hydrogen.In some embodiments of said system, negative electrode is configured as producing Water.In some embodiments of said system, negative electrode is ODC.In some embodiments of such method and system, it is not required to Water is carried out azeotropic distillation to reduce the water in anodolyte.In some embodiments, the system further comprises The separator of reactor is operably connected to, metal of the separator by product such as acid or halogenated hydrocarbons with being in low oxidation state Ion isolation.In some embodiments, the system further comprises the recirculating system for being operably connected to the separator, And the anode chamber of the electro-chemical systems is configured as metal ion of at least a portion in low oxidation state from separator It is recycled back into electrochemical cell.Such recirculating system can be used for conduit, pipeline, pipe of transfer solution etc.. Suitable control valve and computer control system can be associated with the recirculating system.

In some embodiments, said system is configured as at anode not producing chlorine.In some embodiments, Said system is configured as not needing oxygen and/or chlorine to be halogenated hydrocarbons by unsaturated hydrocarbons or saturated hydrocarbons chlorination.

In some embodiments, method described herein and system include：Metal ion solution is being recycled back to electrification Before learning battery, by halogenated hydrocarbons and/or other organic products (it is as described herein, it is higher with being in by saturated hydrocarbons or unsaturated hydrocarbons Formed after the metal ion reaction of oxidation state) and separation of metal ions.In some embodiments, it may be necessary to by metal Organic matter is removed to prevent in electrochemical cell by solion before being circulated back to electrochemical cell from metal ion solution Fouling membrane.As described above, the aqueous medium containing metal ion with after unsaturated hydrocarbons or saturation hydrocarbon reaction comprising organic Product, such as, but not limited to halogenated hydrocarbons and other accessory substances (can be with trace presence).For example, containing in higher oxidation state The metal ion solution of metal ion and metal ion and ethylene dichloride of the ethylene reaction formation in low oxidation state.Can be with Form other accessory substances, including but not limited to chlorethanol, dichloro acetaldehyde, trichloroacetaldehyde etc..There is provided herein for that will contain The aqueous medium of metal ion is recycled back to the separation of metal ions of organic product and aqueous medium before electrochemical cell Method and system.Aqueous medium can be the metal ion in low oxidation state and the metal ion two in higher oxidation state The mixture of person, the ratio of relatively low and higher oxidation state by according to the aqueous medium from electrochemical cell (wherein compared with suboxides State changes into higher oxidation state) and with the aqueous medium (wherein higher oxidation state changes into low oxidation state) after hydrocarbon reaction without Together.

In some embodiments, the separation of organic product and the metal ion of aqueous medium is carried out using adsorbent. " adsorbent " includes having organic compound high-affinity and not having metal ion or with very as used herein The compound of low affinity.In some embodiments, adsorbent except do not have to metal ion or with low-affinity in addition to, Do not have to water or with low-down affinity yet.Therefore, adsorbent can be hydrophobic compound, its adsorb organic matter but Repel metal ion and water." organic matter " or " organic compound " or " organic product " are included in it and had as used herein Any compound of carbon.

In some embodiments, preceding method (is such as, but not limited to activated carbon, alumina, activity including the use of adsorbent Silica, polymer etc.) so that organic product to be removed from metal ion solution.These adsorbents are commercially available.It can use Include but is not limited in the example of the activated carbon of the inventive method：Powdered active carbon, granular active carbon, the activity of extrusion Charcoal, beaded activated carbon, impregnated carbon, the carbon of polymer overmold, carbon cloth etc.." the absorption used in the content of this paper adsorbent Agent polymer " or " polymer " include having organic compound high-affinity and not having or with low metal ion and water The polymer of affinity.It can be used as the example including but not limited to polyolefin of the polymer of adsorbent." polyene used herein Hydrocarbon " or " polyene " include the polymer produced by alkene (or alkene) as monomer.The alkene or alkene can be aliphatic compounds Or aromatic compound.The example includes but is not limited to：Polyethylene, polypropylene, polystyrene, polymethylpentene, PB Polybutene-1, Polyolefin elastomer, polyisobutene, ethylene propylene rubber, PMA, poly- (methyl methacrylate), poly- (methyl-prop Olefin(e) acid isobutyl ester) etc..

In some embodiments, adsorbent used herein is from containing the aqueous of metal ion, organic compound and water Organic compound of the absorption more than 90%w/w in medium；Organic compound more than 95%w/w；Or more than 99%w/w or exceed 99.99%w/w organic compound；Or the organic compound more than 99.999%w/w.In some embodiments, this paper institutes Adsorbent is less than 2%w/w metal ion from the aqueous medium absorption containing metal ion, organic compound and water； Or less than 1%w/w metal ion；Or less than 0.1%w/w metal ion；Or less than 0.01%w/w metal ion；Or Metal ion less than 0.001%w/w.In some embodiments, adsorbent used herein is not adsorbed from aqueous medium Metal ion.In some embodiments, through the aqueous medium that (and being recycled back into electrochemical cell) is obtained after adsorbent Organic compound containing less than 100ppm, or less than 50ppm, or less than 10ppm, or less than 1ppm.

Adsorbent can be used with any commercially available shape or form.For example, in certain methods and being In the embodiment of system, adsorbent is powdery, tabular, netted, pearl, cloth-like, threadiness, pellet, flake, bulk etc.. In the embodiment of certain methods and system, adsorbent is the forms such as bed, packed column.In certain methods and the embodiment of system In, adsorbent can be a series of beds or the form of post of the sorbing material of filling.For example, in the implementation of certain methods and system In scheme, adsorbent is one or more packed columns containing active carbon powder, polystyrene bead or Polystyrene powder (to go here and there Join or be arranged in parallel).

In the embodiment of certain methods and system, adsorbent is after absorption organic product by using various desorption skills Art is regenerated, and these desorption techniques include but is not limited to：With inert fluid (such as water) purge, change electrochemical conditions (such as pH), Temperature, reduction partial pressure are improved, concentration is reduced, uses inert gas purge (such as, but not limited to exist at high temperature>With steaming at 100 DEG C Vapour, nitrogen, argon gas purging), etc..

In the embodiment of certain methods and system, adsorbent can be handled, burns or abandoned after desorption process.One In the embodiment of a little method and systems, adsorbent is reused for adsorption process after desorption.In certain methods and the reality of system Apply in scheme, adsorbent is reused in the repeatedly circulation of absorption and regeneration before being disposed.In certain methods and the reality of system Apply in scheme, adsorbent is reused for once before being disposed, twice, three times, four times, five times or more absorption and regeneration In circulation.

In some embodiments, there is provided herein a kind of method, it includes：

Anode is set to be contacted with anodolyte, wherein the anodolyte includes metal ion,

Metal ion is oxidizing to higher oxidation state from low oxidation state at anode,

Negative electrode is set to be contacted with catholyte,

By unsaturated hydrocarbons or saturated hydrocarbons with containing the anodolyte of the metal ion in higher oxidation state in an aqueous medium React to form one or more organic compounds comprising halogenated hydrocarbons and the metal in low oxidation state in an aqueous medium Ion, and

By one or more organic compounds from the aqueous medium separation comprising the metal ion in low oxidation state.

In some embodiments of preceding method, methods described further comprises comprising the gold in low oxidation state The aqueous medium of category ion is recycled back into anodolyte.

In some embodiments of preceding method, unsaturated hydrocarbons (such as Formulas I), saturated hydrocarbons (such as formula III), halogenated hydrocarbons are (such as Formula II and IV), metal ion etc. is all described in detail herein.

In some embodiments, there is provided herein a kind of method, it includes：

Negative electrode is set to be contacted with catholyte,

Ethene is reacted with aqueous in an aqueous medium with the anodolyte comprising the metal ion in higher oxidation state One or more organic compounds comprising ethylene dichloride and the metal ion in low oxidation state are formed in medium,

By one or more organic compounds from the aqueous medium separation comprising the metal ion in low oxidation state, And

Aqueous medium comprising the metal ion in low oxidation state is recycled back into anodolyte.

In some embodiments of preceding method, aqueous medium comprises more than 5wt% water or more than 5.5wt% or super Cross 6wt% or the water or 5.5-90wt% or 5.5-95wt% or 5.5- for 5-90wt% or 5-95wt% or 5-99wt% 99wt% water or 6-90wt% or 6-95wt% or 6-99wt% water.It is organic in some embodiments of preceding method Compound is further comprising the one or more in chlorethanol, dichloro acetaldehyde, trichloroacetaldehyde or its combination.The one of preceding method In a little embodiments, metal ion is copper.Metal ion in low oxidation state is Cu (I) and the gold in higher oxidation state It is Cu (II) to belong to ion.In some embodiments of preceding method, metal salt is copper halide.Metal in low oxidation state It is Cu (II) Cl that ion, which is Cu (I) Cl and is in the metal ion of higher oxidation state,₂。

In some embodiments of preceding method, by one or more organic compounds from comprising in low oxidation state The aqueous medium of metal ion the step of separate including the use of one or more adsorbents.In some implementations of preceding method In scheme, adsorbent is activated carbon.In some embodiments of preceding method, adsorbent is polymer, is such as selected from but does not limit In polyethylene, polypropylene, polystyrene, polymethylpentene, PB Polybutene-1, polyolefin elastomer, polyisobutene, ethylene, propylene rubber The polyolefin of glue, PMA, poly- (methyl methacrylate), poly- (Isobutyl methacrylate) and combinations thereof.Preceding In some embodiments for stating method, adsorbent is polystyrene.

In some embodiments, there is provided herein a kind of method, it includes：

Negative electrode is set to be contacted with catholyte,

By unsaturated hydrocarbons or saturated hydrocarbons and the anodolyte comprising the metal ion in higher oxidation state in an aqueous medium React to form one or more organic compounds comprising halogenated hydrocarbons and the metal in low oxidation state in an aqueous medium Ion,

In some embodiments, there is provided herein a kind of method, it includes：

Negative electrode is set to be contacted with catholyte,

By using adsorbent, by one or more organic compounds from including the metal ion in low oxidation state Aqueous medium is separated, and

In some embodiments, in preceding method, adsorbent is activated carbon.In some embodiments, foregoing In method, adsorbent is polyolefin, such as polystyrene.

In some embodiments of preceding method, adsorbent adsorbs organising more than 90%w/w from aqueous medium Compound；Or the organic compound more than 95%w/w；Or more than 99%w/w；Or more than 99.99%w/w；Or more than 99.999% W/w organic compound.In some embodiments of preceding method, through adsorbent after obtained aqueous medium (it is followed again It is looped back to anodolyte) organic compound containing less than 100ppm, or less than 50ppm, or less than 10ppm, or less than 1ppm Thing.

In some embodiments of the above method, negative electrode produces water, alkali and/or hydrogen.In some realities of the above method Apply in scheme, negative electrode is the ODC for producing water.In some embodiments of the above method, negative electrode is the ODC for producing alkali.Upper In some embodiments for stating method, negative electrode produces hydrogen.In some embodiments of the above method, negative electrode is by oxygen and water It is reduced into the oxygen depolarization negative electrode of hydroxide ion；Negative electrode is that the hydrogen that water is reduced into hydrogen and hydroxide ion generates the moon Pole；Negative electrode is that the hydrogen that hydrochloric acid is reduced into hydrogen generates negative electrode；Or negative electrode is the oxygen that hydrochloric acid and oxygen reaction are generated to water Depolarized cathode.

In some embodiments of the above method, metal ion is any metal ion as described herein.In above-mentioned side In some embodiments of method, metal ion be selected from iron, chromium, copper, tin, silver, cobalt, uranium, lead, mercury, vanadium, bismuth, titanium, ruthenium, osmium, europium, Zinc, cadmium, gold, nickel, palladium, platinum, rhodium, iridium, manganese, technetium, rhenium, molybdenum, tungsten, niobium, tantalum, zirconium, hafnium and combinations thereof.In some embodiments, Metal ion is selected from iron, chromium, copper and tin.In some embodiments, metal ion is copper.In some embodiments, metal The low oxidation state of ion is 1+, 2+, 3+, 4+ or 5+.In some embodiments, the higher oxidation state of metal ion is 2+, 3 +, 4+, 5+ or 6+.

In some embodiments, there is provided herein a kind of method, it includes：

Anode is set to be contacted with anodolyte, wherein the anodolyte includes copper ion,

Copper ion is oxidizing to higher oxidation state from low oxidation state at anode,

Negative electrode is set to be contacted with catholyte,

Ethene and the anodolyte comprising the copper ion in higher oxidation state are reacted in an aqueous medium aqueous to be situated between One or more organic compounds comprising ethylene dichloride and the copper ion in low oxidation state are formed in matter,

By using the adsorbent selected from activated carbon, polyolefin, active silica and combinations thereof, the one or more are had Machine compound is less than 100ppm from the aqueous medium separation comprising the copper ion in low oxidation state to produce to include, or Less than 50ppm, or less than 10ppm, or less than 1ppm organic compound and aqueous Jie of copper ion in low oxidation state Matter, and

Aqueous medium comprising the copper ion in low oxidation state is recycled back into anodolyte.

In some embodiments, method provided above can further comprise providing turbulent flow in anodolyte changing The step of mass transfer being apt at anode.Such turbulent flow in the anode using turbulence promoter is retouched above State.In some embodiments, method provided above can further comprise making the diffusion of such as, but not limited to porous anode to increase Strong anode is contacted with anodolyte.Such as, but not limited to such diffusion-enhanced anode of porous anode is carried out below Description.

In some embodiments, there is provided herein a kind of system, it is included：

The anode contacted with the anodolyte comprising metal ion, the wherein anode are configured as metal ion from compared with hypoxemia Change state and be oxidized to higher oxidation state；

The negative electrode contacted with catholyte；

Reactor, it is operably coupled to anode chamber and is configured as making comprising the metal ion in higher oxidation state Anodolyte reacts to form one comprising halogenated hydrocarbons in an aqueous medium in an aqueous medium with unsaturated hydrocarbons or saturated hydrocarbons Plant or a variety of organic compounds and the metal ion in low oxidation state, and

Separator, it is operably coupled to reactor and anode and is configured as one or more organic compounds From comprising the metal ion in low oxidation state aqueous medium separation, and by comprising the metal in low oxidation state from The aqueous medium of son is recycled back into anodolyte.

In some embodiments of aforementioned system, unsaturated hydrocarbons (such as Formulas I), saturated hydrocarbons (such as formula III), halogenated hydrocarbons are (such as Formula II and IV), metal ion etc. is all described in detail herein.

The anode contacted with the anodolyte comprising metal halide or metal sulfate, the wherein anode are configured as gold Category halide or metal sulfate are oxidized to higher oxidation state from low oxidation state；

The negative electrode contacted with catholyte；

Reactor, it is operably coupled to anode chamber and is configured as using metal halide or metal sulphur in an aqueous medium Hydrochlorate carries out halogenation or sulfonation to form one comprising halogenated hydrocarbons or sulfonated hydrocarbon in an aqueous medium to unsaturated hydrocarbons or saturated hydrocarbons Plant or a variety of organic compounds and the metal ion in low oxidation state, and

Separator, it is operably coupled to reactor and anode and is configured as one or more organic compounds From the aqueous medium separation comprising the metal halide in low oxidation state or metal sulfate, and it will include in relatively low The metal halide of oxidation state or the aqueous medium of metal sulfate are recycled back into anodolyte.

The negative electrode contacted with catholyte；

Reactor, it is operably coupled to anode chamber and is configured as making ethene and the metal ion in higher oxidation state React to form one or more organic compounds comprising ethylene dichloride in an aqueous medium and be in an aqueous medium The metal ion of low oxidation state, and

Separator, it is operably coupled to reactor and anode and is configured as one or more organic compounds From comprising the metal ion in low oxidation state aqueous medium separation, and by comprising the metal in low oxidation state from The aqueous medium of son is recycled to anodolyte.

In some embodiments of aforementioned system, aqueous medium comprises more than 5wt% water, or more than 5.5wt% or More than 6wt% or be 5-90wt% or 5-95wt% or 5-99wt% water, or 5.5-90wt% or 5.5-95wt% or 5.5- 99wt% water, or 6-90wt% or 6-95wt% or 6-99wt% water.

In some embodiments of aforementioned system, separator, which is further included, to include the metal in low oxidation state The aqueous medium of ion is recycled to the recirculating system of anodolyte.

In some embodiments of aforementioned system, one or more organic compounds include chlorethanol, dichloro acetaldehyde, three One or more in chloroacetaldehyde or its combination.In some embodiments of aforementioned system, metal ion is copper.In relatively low It is Cu (II) that the metal ion of oxidation state, which is Cu (I) and is in the metal ion of higher oxidation state,.In some realities of aforementioned system Apply in scheme, metal halide is copper halide and metal sulfate is copper sulphate.

In some embodiments of aforementioned system, by one or more organic compounds from comprising in low oxidation state The separator of aqueous medium separation of metal ion include one or more adsorbents.In some embodiment party of aforementioned system In case, separator is activated carbon.In some embodiments of aforementioned system, separator is polymer, is selected from but does not limit In polyethylene, polypropylene, polystyrene, polymethylpentene, PB Polybutene-1, polyolefin elastomer, polyisobutene, ethylene, propylene rubber The polyolefin of glue, PMA, poly- (methyl methacrylate), poly- (Isobutyl methacrylate) and combinations thereof.Preceding In some embodiments for stating system, separator is polystyrene.

The negative electrode contacted with catholyte；

The separator of one or more adsorbents is included, it is operably coupled to reactor and anode and is configured as institute One or more organic compounds are stated from the aqueous medium separation comprising the metal ion in low oxidation state, and will be included The aqueous medium of metal ion in low oxidation state is recycled to anodolyte.

The negative electrode contacted with catholyte；

In some embodiments, in aforementioned system, adsorbent is activated carbon.In some embodiments, foregoing In system, adsorbent is polyolefin, such as polystyrene.

In some embodiments of aforementioned system, adsorbent adsorbs organising more than 90%w/w from aqueous medium Compound；Or the organic compound more than 95%w/w；Or more than 99%w/w；Or more than 99.99%w/w；Or more than 99.999% W/w organic compound.In some foregoing embodiments, through adsorbent after obtained aqueous medium (it is recirculated back to To anodolyte) organic compound containing less than 100ppm, or less than 50ppm, or less than 10ppm, or less than 1ppm.

In some embodiments of said system, negative electrode is configured as producing water, alkali and/or hydrogen.In said system Some embodiments in, negative electrode be configured as produce water ODC.In some embodiments of said system, negative electrode is It is configured as producing the ODC of alkali.In some embodiments of said system, negative electrode is configured as producing hydrogen.In above-mentioned system In some embodiments of system, negative electrode is configured as oxygen and water being reduced into the oxygen depolarization negative electrode of hydroxide ion；Negative electrode It is configured as the hydrogen that water is reduced into hydrogen and hydroxide ion generating negative electrode；Negative electrode is configured as hydrochloric acid being reduced into The hydrogen generation negative electrode of hydrogen；Or negative electrode is configured as generating hydrochloric acid and oxygen reaction the oxygen depolarization negative electrode of water.

In some embodiments of said system, metal ion is any metal ion as described herein.In above-mentioned system System some embodiments in, metal ion be selected from iron, chromium, copper, tin, silver, cobalt, uranium, lead, mercury, vanadium, bismuth, titanium, ruthenium, osmium, europium, Zinc, cadmium, gold, nickel, palladium, platinum, rhodium, iridium, manganese, technetium, rhenium, molybdenum, tungsten, niobium, tantalum, zirconium, hafnium and combinations thereof.In some embodiments, Metal ion is selected from iron, chromium, copper and tin.In some embodiments, metal ion is copper.In some embodiments, metal The low oxidation state of ion is 1+, 2+, 3+, 4+ or 5+.In some embodiments, the higher oxidation state of metal ion is 2+, 3 +, 4+, 5+ or 6+.

The anode contacted with the anodolyte comprising copper ion, the wherein anode are configured as copper ion from low oxidation state It is oxidized to higher oxidation state；

The negative electrode contacted with catholyte；

Reactor, it is operably coupled to anode chamber and is configured as making ethene and the copper ion in higher oxidation state anti- Should be to form one or more organic compounds comprising ethylene dichloride and the copper in low oxidation state in an aqueous medium Ion,

The separator of one or more adsorbents selected from activated carbon, polyolefin, active silica and combinations thereof is included, it can It is operably connected to reactor and anode and is configured as one or more organic compounds from comprising in relatively low The aqueous medium of the metal ion of oxidation state is separated, and generation includes and is less than 100ppm, or less than 50ppm, or less than 10ppm, or less than 1ppm organic compound and the aqueous medium of copper ion in low oxidation state, and

Recirculating system, a part for the aqueous medium comprising the metal ion in low oxidation state is recycled into sun Pole electrolyte.

In some embodiments of system described herein, separator be a series of adsorbent being connected to each other bed or Packed column.

In some embodiments of aforementioned system, recirculating system can be can be used for the transfer conduit of solution, pipeline, Pipe etc..Suitable control valve and computer control system can be associated with such recirculating system.

In the embodiment of some systems, the system further includes regenerator, and the regenerator is adsorbed in organic product Afterwards by using include but is not limited to inert fluid (such as water) purge, change electrochemical conditions (such as pH), improve temperature, reduction point Press, reduce concentration, use inert gas purge (such as, but not limited to exist at high temperature>Blown at 100 DEG C with steam, nitrogen, argon gas Sweep) etc. various desorption technique reproducing adsorbents.

In some embodiments, the reactor and/or separator assembly in system of the invention may include control station, should Control station is configured as the amount of hydrocarbon that control is introduced into reactor, the amount for the anodolyte being introduced into reactor, into separation Temperature in amount, the adsorption time of adsorbent, reactor and the separator of the aqueous medium comprising organic matter and metal ion of device The recovery time of adsorbent, aqueous medium in degree and pressure condition, the flow velocity for flowing in and out reactor and separator, separator Return to time and flow velocity of electrochemical cell etc..

Control station may include one group of manual, mechanical or numerically controlled valve or many valve systems, or can using it is any its His easily flow regulator scheme.In some cases, control station may include that (wherein regulation is computer aided manufacturing to computer interface It is helping or complete controlled by computer), the computer interface is configured as providing a user input and output parameter controlling Amount and condition as described above.

The method and system of the present invention may also include one or more detectors, and the detector is configured as monitoring ethylene gas Concentration of organic matter of concentration or aqueous medium of the flow of body or the metal ion of aqueous medium etc..Monitoring may include but It is not limited to, gathers the data on pressure, temperature and aqueous medium and the composition of gas.Detector can be any suitable The device of monitoring is configurable for, for example, pressure sensor (for example, electromagnetic pressure sensor, differential pressure sensor etc.), Temperature sensor (resistance temperature detector, thermocouple, gas thermometer, thermal resistor, pyrometer, infrared radiation sensor Deng), volume sensor (for example, geophysics diffraction tomograph art, X-ray topography, underwater acoustic measurement device etc.), and For the chemical component that determines aqueous medium or gas device (for example, infrared spectrometer, nuclear magnetic resonance spectrometer, it is ultraviolet can See spectrometer, high performance liquid chromatograph, inductive coupling plasma emission spectrograph, icp mses, from Sub- chromatograph, X-ray diffractometer, gas chromatograph, gas chromatograph-mass spectrometer, Flow Injection Analysis, scintillation counter, acid amount Titration and flame emission spectrometer etc.).

In some embodiments, detector can also include computer interface, and the computer interface is configured as to user The data of the relevant aqueous medium, metal ion and/or the organic matter that are gathered are provided.For example, detector can determine that aqueous medium, The concentration of metal ion and/or organic matter, and computer interface can provide aqueous medium, metal ion and/or organic matter Constitute the summary changed with time.In some embodiments, the summary can be deposited as mechanized data file Storage is printed as user's readable documents.

In some embodiments, detector can be that monitoring device allows it to collect relevant aqueous medium, metal The real time data (for example, internal pressure, temperature etc.) of ion and/or organic matter.In other embodiments, detector can be One or more detectors, it is configured as the parameter that aqueous medium, metal ion and/or organic matter are determined with fixed intervals, It is for example every 1 minute, every 5 minutes, every 10 minutes, every 30 minutes, every 60 minutes, every 100 minutes, every 200 minutes, every 500 minutes Or determine that it is constituted with some other intervals.

In some embodiments, electro-chemical systems described herein and method, which include containing, has more than the aqueous of 5wt% water Medium.In some embodiments, the aqueous medium comprises more than 5wt% water；Or more than 6wt%；Or more than 8wt%'s Water；Or the water more than 10wt%；Or the water more than 15wt%；Or the water more than 20wt%；Or the water more than 25wt%；Or exceed 50wt% water；Or the water more than 60wt%；Or the water more than 70wt%；Or the water more than 80wt%；Or more than 90wt%'s Water；Or about 99wt% water；Or 5-100wt% water；Or 5-99wt% water；Or 5-90wt% water；Or 5-80wt% Water；Or 5-70wt% water；Or 5-60wt% water；Or 5-50wt% water；Or 5-40wt% water；Or 5-30wt% Water；Or 5-20wt% water；Or 5-10wt% water；Or 6-100wt% water；Or 6-99wt% water；Or 6-90wt% Water；Or 6-80wt% water；Or 6-70wt% water；Or 6-60wt% water；Or 6-50wt% water；Or 6-40wt% Water；Or 6-30wt% water；Or 6-20wt% water；Or 6-10wt% water；Or 8-100wt% water；Or 8-99wt% Water；Or 8-90wt% water；Or 8-80wt% water；Or 8-70wt% water；Or 8-60wt% water；Or 8-50wt% Water；Or 8-40wt% water；Or 8-30wt% water；Or 8-20wt% water；Or 8-10wt% water；Or 10-100wt% Water；Or 10-75wt% water；Or 10-50wt% water；Or 20-100wt% water；Or 20-50wt% water；Or 50- 100wt% water；Or 50-75wt% water；Or 50-60wt% water；Or 70-100wt% water；Or 70-90wt% water； Or 80-100wt% water.In some embodiments, the aqueous medium can include water-miscible organic solvent.

In some embodiments of method described herein and system, the amount of total metal ion in anodolyte, Or in anodolyte copper amount, or in anodolyte iron amount, or in anodolyte chromium amount, or in anodolyte The amount of tin, or platinum amount, or the metal ion contacted with unsaturated hydrocarbons or saturated hydrocarbons amount be 1-12M；Or 1-11M；Or 1- 10M；Or 1-9M；Or 1-8M；Or 1-7M；Or 1-6M；Or 1-5M；Or 1-4M；Or 1-3M；Or 1-2M；Or 2-12M；Or 2-11M； Or 2-10M；Or 2-9M；Or 2-8M；Or 2-7M；Or 2-6M；Or 2-5M；Or 2-4M；Or 2-3M；Or 3-12M；Or 3-11M；Or 3- 10M；Or 3-9M；Or 3-8M；Or 3-7M；Or 3-6M；Or 3-5M；Or 3-4M；Or 4-12M；Or 4-11M；Or 4-10M；Or 4-9M； Or 4-8M；Or 4-7M；Or 4-6M；Or 4-5M；Or 5-12M；Or 5-11M；Or 5-10M；Or 5-9M；Or 5-8M；Or 5-7M；Or 5- 6M；Or 6-12M；Or 6-11M；Or 6-10M；Or 6-9M；Or 6-8M；Or 6-7M；Or 7-12M；Or 7-11M；Or 7-10M；Or 7- 9M；Or 7-8M；Or 8-12M；Or 8-11M；Or 8-10M；Or 8-9M；Or 9-12M；Or 9-11M；Or 9-10M；Or 10-12M；Or 10-11M；Or 11-12M.In some embodiments, the total ionic weight in anodolyte described herein is in compared with hypoxemia The amount for changing the metal ion of state adds the amount of the metal ion in higher oxidation state；Or the metal ion in higher oxidation state Total amount；Or the total amount of the metal ion in low oxidation state.

In some embodiments of method described herein and system, the anodolyte comprising metal ion can contain The mixture of metal ion in low oxidation state and the metal ion in higher oxidation state.In some embodiments, It may want to that there is the metal ion in low oxidation state and the metal ion in higher oxidation state in anodolyte Mixture.In some embodiments, the anodolyte contacted with unsaturated hydrocarbons or saturated hydrocarbons, which is included, to be in compared with suboxides The metal ion of state and the metal ion in higher oxidation state.In some embodiments, the metal in low oxidation state Ion and metal ion in higher oxidation state exist with a certain ratio so that occur metal ion and unsaturated hydrocarbons or saturation The reaction of hydrocarbon formation halogenated hydrocarbons or sulfo group.In some embodiments, the metal ion in higher oxidation state with compared with The ratio of the metal ion of low-oxidation-state is 20:1 to 1:20；Or 14:1 to 1:2；Or 14:1 to 8:1；Or 14:1 to 7:1；Or 2: 1 to 1:2；Or 1:1 to 1:2；Or 4:1 to 1:2；Or 7:1 to 1:2.

In some embodiments of method described herein and system, the sun in electro-chemical systems and method of the invention Pole electrolyte contain the 4-7M metal ion in higher oxidation state, 0.1-2M metal ion in low oxidation state and 1-3M sodium chloride.The anodolyte optionally contains 0.01-0.1M hydrochloric acid.The one of method described herein and system In a little embodiments, and the anodolyte of hydrogen or unsaturated hydrocarbons or saturation hydrocarbon reaction contains 4-7M is in higher oxidation state Metal ion, 0.1-2M metal ion in low oxidation state and 1-3M sodium chloride.The anodolyte can be optional Contain 0.01-0.1M hydrochloric acid in ground.

In some embodiments of method described herein and system, anodolyte can also contain in addition to the metal ion There is another cation.Other cations include but is not limited to alkali metal ion and/or alkaline-earth metal ions, such as, but not limited to Lithium, sodium, calcium, magnesium etc..The amount for other cations being added in anodolyte can be 0.01-5M；Or 0.01-1M；Or 0.05-1M；Or 0.5-2M；Or 1-5M.

In some embodiments of method described herein and system, anodolyte can contain acid.It can add an acid to Into anodolyte so that the pH of anolyte reaches 1 or 2 or smaller.The acid can be hydrochloric acid or sulfuric acid.

Provided herein is system include being operably connected to the reactor of anode chamber.The reactor is configured as making anode Metal chloride in electrolyte is contacted with hydrogen or unsaturated hydrocarbons or saturated hydrocarbons.The reactor can be used to make anode electrolysis Any device that metal chloride in matter is contacted with hydrogen or unsaturated hydrocarbons or saturated hydrocarbons.Such device or such reactor are It is well known in the art, and a series of including but not limited to pipe, conduit, tank, tanks, container, tower, pipeline etc..This paper Fig. 7 A, Fig. 7 B, Figure 10 A and Figure 10 B describe some examples of such reactor.Reactor can come equipped with one or more controllers Temperature sensor, pressure sensor, controlling organization, inert gas injection device etc. are controlled, so as to monitor, control and/or promote and be anti- Should.In some embodiments, metal chloride and unsaturated hydrocarbons or saturation containing the metal ion in higher oxidation state The reaction of hydrocarbon is in the reactor in 100-200 DEG C or 100-175 DEG C or 150-175 DEG C of temperature and 100-500psig or 100- Carried out under 400psig or 100-300psig or 150-350psig pressure.In some embodiments, in the component of reactor Teflon (Teflon) is served as a contrast, to avoid component from being corroded.Fig. 7 A and Fig. 7 B are shown for carrying out the gold in higher oxidation state Belong to some examples of the reactor of the reaction of ion and hydrogen.

In some embodiments, unsaturated hydrocarbons or saturated hydrocarbons can be provided to anode chamber, wherein containing place in anode chamber It is respective to be formed in the metal halide or metal sulfate and unsaturated hydrocarbons or saturation hydrocarbon reaction of the metal of higher oxidation state Product.In some embodiments, unsaturated hydrocarbons or saturated hydrocarbons can be provided to anode chamber, wherein containing in higher oxidation state The metal chloride of metal and unsaturated hydrocarbons or saturation hydrocarbon reaction are to form chlorohydrocarbon.Such system includes unsaturated hydrocarbons or saturation Hydrocarbon delivery system, the delivery system is operably connected to anode chamber, and is configured as unsaturated hydrocarbons or saturated hydrocarbons delivering To anode chamber.The unsaturated hydrocarbons or saturated hydrocarbons can be solid, liquid or gas.Can be used is used for unsaturated hydrocarbons or saturated hydrocarbons Any device of anode chamber, which is directed to, from external source by unsaturated hydrocarbons or saturated hydrocarbons is supplied to anode.For by unsaturated hydrocarbons or The such device or unsaturated hydrocarbons or saturated hydrocarbons delivery system that saturated hydrocarbons is directed to anode chamber from external source be it is well known that , and including but not limited to pipe, tank, conduit, pipeline etc..In some embodiments, the system or unsaturated hydrocarbons or full With conduit of the hydrocarbon delivery system including unsaturated hydrocarbons or saturated hydrocarbons to be directed to anode from external source.It should be appreciated that can be by not Saturated hydrocarbons or saturated hydrocarbons are directed to anode from battery bottom, battery top or side.In some embodiments, by unsaturated hydrocarbons Or saturation appropriate hydrocarbon gas by make unsaturated hydrocarbons or saturation appropriate hydrocarbon gas do not contacted directly with anolyte in the way of be directed to anode. In some embodiments, unsaturated hydrocarbons or saturated hydrocarbons can be directed to anode by multiple entrances.Provided herein is method In system, unsaturated hydrocarbons or the saturated hydrocarbons source for providing unsaturated hydrocarbons or saturated hydrocarbons to anode chamber include known in the art Why not saturated hydrocarbons or saturated hydrocarbons source.Such source includes but is not limited to unsaturated hydrocarbons or saturated hydrocarbons and/or the insatiable hunger of commerical grade With hydrocarbon or saturated hydrocarbons factory, such as petrochemical refinery enterprise.

In some embodiments there is provided following method and system, wherein the electrochemical cell of the present invention is set up At the scene of production unsaturated hydrocarbons or saturated hydrocarbons, such as refinery, to carry out the halogenation such as chlorination of unsaturated hydrocarbons or saturated hydrocarbons. In some embodiments, the anolyte of the metal ion from electro-chemical systems is transported to form unsaturated hydrocarbons or full With the refinery of hydrocarbon to carry out the halogenation of unsaturated hydrocarbons or saturated hydrocarbons, such as chlorination.In some embodiments, side of the invention Method and system are using the ethylene gas from refinery, without filtering or purifying ethylene gas.Generally, ethylene gas is produced The factory of body washs the gas to remove impurity.In some embodiments of the method and system of the present invention, it is not necessary to and can Avoid this advance washing of gas.

In some embodiments, metal generation and halogenation such as chlorination reaction occur in same anode chamber.Fig. 9 is shown The illustrative example of such embodiment.It should be appreciated that Fig. 9 system 900 is for illustration purposes only, with different oxidation state Other metal ions, other unsaturated hydrocarbons or saturated hydrocarbons, its for forming product such as water or hydrogen in addition to alkali in the cathodic compartment He is equally applicable to the system by electro-chemical systems with other unsaturated hydrocarbons or saturation appropriate hydrocarbon gas.In some embodiments, such as Fig. 9 Shown, electro-chemical systems 900 include being located at the anode close to AEM position.System 900 also includes gas diffusion layers (GDL).Sun Pole electrolyte is contacted in side and positive contact in opposite side with GDL.In some embodiments, anode, which can be located at, makes sun The position that the resistance of pole electrolyte is minimized, for example, anode can be located at close to AEM position or be bonded to AEM.In some implementations In scheme, the metal ion in low oxidation state is converted into the metal ion in higher oxidation state by anode.For example, anode Metal ion is converted into 2+ oxidation state from 1+ oxidation state.Cu²⁺Ion and chloride binding formation CuCl₂.Ethylene gas is pressed In the gas compartment for entering GDL sides.Ethylene gas then by gas diffusion layers spread and with the metal chlorine in higher oxidation state Compound reacts to form chlorohydrocarbon, such as ethylene dichloride.Metal chloride CuCl₂Then undergo the reduction to low oxidation state To form CuCl.In some embodiments, anodolyte is can be taken off, and isolation technics well known in the art can be used (including but not limited to filtering, vacuum distillation, fractionation, fractional crystallization, ion exchange resin etc.) separates two from anodolyte Ethlyene dichloride.In some embodiments, ethylene dichloride may it is denser than anodolyte and can in anode chamber shape Into separation layer.In such embodiment, ethylene dichloride can be removed from battery bottom.In some embodiments, it can open The gas compartment of GDL sides is to remove gas.In some embodiments, anode chamber can be opened to remove gaseous ethylene or gaseous state pair Product.System 900 also includes the oxygen depolarization negative electrode that hydroxide ion is produced by water and oxygen.Hydroxide ion can undergo to be retouched herein Any carbonate precipitation process stated.In some embodiments, negative electrode is not gas diffusion cathode, but such as Fig. 4 A or Fig. 4 B Shown negative electrode.In some embodiments, system 900 can be applied to the electro-chemical systems of any generation alkali.

In some embodiments of system and method described herein, formed at negative electrode without gas.It is being described herein System and method some embodiments in, at negative electrode formed hydrogen.In some realities of system and method described herein Apply in scheme, formed at anode without gas.In some embodiments of system and method described herein, at anode not Use the gas in addition to gaseous state unsaturated hydrocarbons or saturated hydrocarbons.

Figure 10 A show another illustrative example for the reactor being connected with electro-chemical systems.As shown in Figure 10 A, the electricity The anode chamber of chemical system (electro-chemical systems can be any electro-chemical systems described herein) is connected with reactor, the reaction Device is also connected with unsaturated hydrocarbons or saturated hydrocarbons source, and the unsaturated hydrocarbons or the example of saturated hydrocarbons shown in Figure 10 A is ethene (C₂H₄).In some embodiments, the electro-chemical systems are connected with reactor in same unit and in the unit.Will Contain containing the metal ion in higher oxidation state and optionally the anodolyte of the metal ion in low oxidation state It is supplied to together with ethene (for example, bricking) reactor of prestress.The chlorination of ethene occurs to be formed in reactor Ethylene dichloride (EDC or dichloroethanes DCE) and the metal ion in low oxidation state.The reactor can be at 340-360 °F Run with the range of 200-300psig.Can set other reactor conditions, such as, but not limited to concentration of metal ions, in compared with The partial pressure of the metal ion of low-oxidation-state and the ratio of the metal ion in higher oxidation state, DCE and vapor, to ensure height Selective operation.Reaction heat can be removed by evaporating water.In some embodiments, cooling table is may not be needed in the reactor Face, it is thus possible to do not need thermograde or rigid temperature control.It can be used in (for example, bricking) packed tower of prestress Water quenching reactor discharge gas (being shown as " being quenched " reactor in Figure 10 A).Leaving the liquid of tower can further cool down simultaneously It is separated into aqueous phase and DCE phases.Aqueous phase can be separated, a part is recycled in tower as quenching water, and remainder is recyclable Into reactor or electro-chemical systems.DCE products can further cool down and flash to isolate the ethene of more water and dissolving. The ethene of the dissolving can be recycled as shown in Figure 10 A.In addition to the purging air-flow for removing inert gas, from rapid The non-condensing gas of cold tower is recyclable to arrive reactor.Purging air-flow may pass through ethylene recovery system to keep the entirety of ethene Utilization rate is higher, and such as up to 95%.Flammability limits of the ethylene gas under actual processing temperature, pressure and composition can be carried out Measuring.The construction material of factory may include the brick lining of prestress, Hastelloy (Hastealloys) B and C, Inconel (inconel), doping level titanium (such as AKOT, II grade), tantalum, Kynoar (Kynar), Teflon, PEEK, Glass or other polymers or plastics.Reactor is also designed to make anodolyte constant flow pass in and out reactor.

Another illustrative example for the reactor being connected with electro-chemical systems is as shown in Figure 10 B.As shown in Figure 10 B, react Device system 1000 is glass container A, and glass container A is by means of being welded to the metal ball-and-socket of flange head from metal flange B top Suspention is got off, and flange B is connected with discharge pipe C.The glass reactor is in electrical heating metal shell D.Automatic warm can be passed through Adjuster is spent to control heat input and temperature.Hydrocarbon can be introduced in metal-back by opening E and by glass tube F, glass tube F can With equipped with sintered glass seat.It is balanced that this set can provide pressure in the both sides of glass reactor.Hydrocarbon can be in reactor bottom Contacted with metallic solution (metal for being in higher oxidation state), and may pass through medium bubbling.Volatile products, vapor and/ Or unreacted hydrocarbon can leave via pipeline C, pipeline C is optionally equipped with valve H, and valve H can make pressure be down to atmospheric pressure.Discharge Gas may pass through suitable capture systems to remove product.The device can also be provided with by-pass collar G, and it allows gas through pressure Power area, and it is not passed through water-based metal medium.In some embodiments, the gold of the reduction in low oxidation state in a reservoir is stayed Category ion process electrolysis as described herein is in the metal ion of higher oxidation state to regenerate.

The illustrative embodiment of the present invention is as shown in figure 11.As shown in figure 11, Fig. 6 electro-chemical systems 600 (or Alternatively, Fig. 4 A system 400) can be integrated with CuCl-HCl electro-chemical systems 1100 (being also illustrated as the system in Fig. 4 B). In CuCl-HCl electro-chemical systems 1100, that inputted at anode is CuCl and HCl, and it causes to generate CuCl₂And hydrogen ion.Hydrogen Ion reaches negative electrode through PEM, and it forms hydrogen at negative electrode.In some embodiments, it is possible to use chloride Conductive membranes.In some embodiments, it is contemplated that CuCl-HCl batteries can be run under 0.5V or more low-voltage, and system 600 can Run under 0V or more low-voltage.Due to resistance loss, can occur and expection voltage certain deviation.

On the one hand, provided herein is system and method in, the CuCl formed in anodolyte₂Life available for copper Production.For example, the CuCl formed in the system and method for the present invention₂Available for the extract technology that copper is extracted from copper mineral.Only For example, chalcopyrite be can be in chloride environment by means of oxidant Cu²⁺The copper mineral being leached.Cupric can leach Huang The copper of copper mine and other sulfide.Once copper is leached, other recyclable mineral matters such as iron, sulphur, gold, silver etc..In some implementations In scheme, the CuCl that will can be produced by electrochemical cell described herein₂It is added in copper mineral concentrate.Cu²⁺Ion can oxygen Change copper mineral and form CuCl.CuCl solution from the concentrate can be reversely fed to electrochemical cell as described herein CuCl can be converted into CuCl by anode chamber, the anode chamber₂.Then can be by CuCl₂Reversely mineral concentrates are fed to further oxygen Change copper mineral.Once copper is leached, silver can be replaced out, while zinc, lead etc. are further precipitated.Then by using can be by the electricity The alkali that the cathode chamber of chemical cell is produced is handled, and copper can be made to be precipitated out as Cu oxide.It is heavy as oxide in copper Behind shallow lake, filtrate NaCl can return in the electrochemical cell.The hydrogen produced at negative electrode can be used for reducing copper oxides with shape Into metallic copper (at high temperature).Molten copper can be cast into copper product such as copper wires.This method can be used for low-grade ore or a variety of The copper mineral of type.Electrochemical plants can be close to stone pit or close to ore dressing plant (concentrator), to eliminate waste products Cost of transportation and allow only transport metal values product.

Method described herein and system can be batch processing method or system either continuous stream method or system.

In terms of this paper and as described in embodiment, hydrogen or unsaturated hydrocarbons or saturated hydrocarbons and the gold in higher oxidation state The reaction of category ion is carried out in an aqueous medium.In some embodiments, the reaction can enter in non-aqueous liquid medium OK, the medium can be hydrocarbon or the solvent of hydrogen feed.The liquid medium or solvent can be aqueous or non-aqueous.Properly Non-aqueous solvent be polarity and apolar aprotic solvent, such as dimethylformamide (DMF), dimethyl sulfoxide (DMSO), halogen For hydrocarbon (only for example, dichloromethane, carbon tetrachloride and 1,2- dichloroethanes) and organic nitrile such as acetonitrile.Organic solvent can Containing can with low oxidation state metal formation chemical bond so that the metal ion in low oxidation state have increase The nitrogen-atoms of strong stability.In some embodiments, the organic solvent is acetonitrile.

In some embodiments, when organic solvent is used between the metal ion in higher oxidation state and hydrogen or hydrocarbon Reaction when, it may be necessary to water is removed from the medium containing metal.Therefore, the metal obtained from electro-chemical systems described herein Ion may contain water.In some embodiments, can be by carrying out azeotropic distillation from Jie comprising metal ion to mixture Water is removed in matter.In some embodiments, comprising the metal ion and hydrogen or unsaturated hydrocarbons in higher oxidation state or full It can contain 5%-90%, or 5%-80%, or 5%-70%, or 5%-60%, or 5%- in reaction medium with the solvent of hydrocarbon 50%, or 5%-40%, or 5%-30%, or 5%-20%, or 5%-10% (weight) water.It is permissible in reaction medium The specific halide carrier that water may depend in medium, for example, the permissible water of copper chloride is permissible more than iron chloride Water.When using aqueous medium in the reaction, this azeotropic distillation can be avoided.

In some embodiments, the metal ion in higher oxidation state and hydrogen or unsaturated hydrocarbons or saturated hydrocarbons is anti- Should can in reaction temperature more than 50 DEG C until 350 DEG C when occur.In an aqueous medium, reaction can be in up to 1000psi or lower Superatmospheric pressure under carry out, using at a temperature of 50 DEG C -200 DEG C, normally about 120 DEG C to about 180 DEG C maintenance reaction medium as Liquid phase.

In some embodiments, the reaction of the metal ion in higher oxidation state and unsaturated hydrocarbons or saturated hydrocarbons can be wrapped Halide carrier.In some embodiments, halide ion：The ratio of metal ion total amount in higher oxidation state is 1: 1；Or more than 1:1；Or 1.5:1；Or more than 2:1；And/or at least 3:1.Thus, for example, ratio of the halogenation copper solution in concentrated hydrochloric acid Example can be about 2:1 or 3:1.In some embodiments, due to the high utilization rate of halide carrier, it may be desirable to using highly concentrated The metal halide and use saturation or the metal halide solution close to saturation of degree.If desired, in the halogenation phase Between can enter row buffering to solution pH is maintained to required level.

In some embodiments, the non-of metal can be added into the solution comprising the metal ion in higher oxidation state Halogen.The metal salt of addition can be solvable in the metal halide solution.It is adapted to the example of salt added in copper chloride solution Including but not limited to copper sulphate, copper nitrate and tetrafluoro boric acid copper.In some embodiments, it can add and described method and system The different metal halide of the middle metal halide used.For example, can be added in unsaturated hydrocarbons halogenation into copper chloride system Iron chloride.

Unsaturated hydrocarbons or saturation hydrocarbon feed can be continuously or intermittently supplied into halogenation container.Efficient halogenation can be dependent on Reach the close contact of raw material and metal ion in solution, and can be by this contacting the skill designed to improve or maximizing Art carries out halogenation.By stirring or it can vibrate or any desired technology agitation metal ion solution, for example, reaction can To be carried out in the tower or trickle bed reactor or reactions described herein device of such as packed tower.For example, when unsaturated hydrocarbons or full When with hydrocarbon being gas, it can be used reverse flow technique, wherein unsaturated hydrocarbons or saturated hydrocarbons is upward through tower or reactor, and metal ion Solution is passed down through tower or reactor.Except strengthening in solution, unsaturated hydrocarbons or saturated hydrocarbons are in addition to the contact of metal ion, originally The technology of text description can also strengthen the rate of dissolution of unsaturated hydrocarbons or saturated hydrocarbons in the solution, be the aqueous solution and unsaturation in solution Hydrocarbon or saturated hydrocarbons it is water-soluble it is low in the case of this be probably gratifying.Higher pressure can also contribute to the molten of raw material Solution.

The mixture of saturation, unsaturated hydrocarbons and/or partially halogenated hydrocarbon can be used.In some embodiments, one can be entered Partially halogenated product that walk halogenation, the inventive method can be by product recovery stage and (if appropriate) compared with suboxides State metal ion regeneration stage is recycled to reaction vessel.In some embodiments, halogenation can be in halogenation container Outside, for example continue in single regeneration container, and may need to carefully control the reaction to avoid unsaturated hydrocarbons or satisfy With the halogenation excessively of hydrocarbon.

In some embodiments, electro-chemical systems described herein are built up in production unsaturated hydrocarbons or saturated hydrocarbons or life Near the factory of hydrogen producing.In some embodiments, electro-chemical systems described herein are built up near PVC factory.For example, In some embodiments, electro-chemical systems are 100 miles near ethylene gas, hydrogen, VCM and/or PVC factories Radius in.In some embodiments, electro-chemical systems described herein are built up in ethylene plant or outside factory so as to Ethene is set to be reacted with metal ion.In some embodiments, with electro-chemical systems described herein to factory as described above Transformed.In some embodiments, the anodolyte comprising the metal ion in higher oxidation state is transported to State the place of factory.In some embodiments, the anodolyte comprising the metal ion in higher oxidation state is transported Into 100 mile ranges of above-mentioned site.In some embodiments, by electro-chemical systems described herein be built up in as Upper described factory is nearby and near bivalent cation source so that the alkali and bivalent cation generated in catholyte React to form carbonate/bicarbonate product.In some embodiments, by electro-chemical systems described herein be built up in as Upper described factory nearby, near bivalent cation source and/or carbon dioxide source so that generated in catholyte Alkali can sequestering carbon dioxide to form carbonate/bicarbonate product.In some embodiments, by formed unsaturated hydrocarbons or The carbon dioxide of refinery's generation of saturated hydrocarbons is used in electro-chemical systems or in the precipitation of carbonate/bicarbonate product Use.Therefore, in some embodiments, electro-chemical systems described herein are built up near factory as described above, two Near the refinery in valency cation source and/or carbon dioxide source such as production unsaturated hydrocarbons or saturated hydrocarbons so that in negative electrode electricity The alkali of Xie Zhizhong generations can sequestering carbon dioxide to form carbonate/bicarbonate product.

Any number of halogenated hydrocarbons or sulfo group can the metal chloride as described herein by higher oxidation state with not The reaction generation of saturated hydrocarbons or saturated hydrocarbons.Chlorohydrocarbon can be used in chemistry and/or process industry.Chlorohydrocarbon can be used as in chemistry Mesosome or solvent.Solvent purposes includes numerous applications, including metal and clean fabric, grease are extracted and for chemical synthesis Reaction medium.

In some embodiments, unsaturated hydrocarbons such as ethene reacts to form two with the metal chloride in higher oxidation state Ethlyene dichloride.Ethylene dichloride can be used for multiple use, including but not limited to produce in plastics, rubber and synthetic textile The chemicals being related to, such as, but not limited to vinyl chloride, trichloro ethylene and tetrachloro-ethylene, vinylidene chloride, trichloroethanes, ethylene glycol, Diamino-vinyl, polyvinyl chloride, nylon, viscose silk (viscose rayon), butadiene-styrene rubber and a variety of plastics；As de- Fat agent and the solvent of paint stripper；As for resin, pitch, pitch, rubber, fat, oil, wax, natural gum, photo, photocopy, cosmetic The solvent of product, leather cleaning and medicine；Fumigant for cereal, orchard, mushroom house, upholstery and carpet；It is used as acid Lotion；As construction unit reagent, the intermediate in such as production of a variety of organic compounds such as ethylenediamine；As remove ethene and The chlorine source of chloride；It is used as the precursor of the 1,1,1- trichloroethanes used in dry-cleaning；It is used as the antiknock addition in leaded fuel Agent；For extracting spices such as annatto, chilli powder and turmeric；It is used as the dilution of insecticide；In paint, coating and adhesive In use；And combinations thereof.

In method described herein and system, in some embodiments, without hydrochloric acid is formed in the anode compartment.Herein In the method and system of description, in some embodiments, formed at anode without gas.In method described herein and system In, in some embodiments, without using gas at anode.In method described herein and system, in some embodiment party In case, hydrogen is formed at negative electrode.In method described herein and system, in some embodiments, the hydrogen-free at negative electrode Gas is formed.

In some embodiments, electric wire is connected between a cathode and an anode so that electric current passes through battery.In such reality Apply in scheme, battery may act as battery pack (battery), and the electric current produced by battery can be used for generation alkali, the alkali from Taken out in battery.In some embodiments, the resistance of battery can increase, and electric current can be reduced.In such embodiment party In case, voltage can be applied to the electrochemical cell.The resistance of battery can due to include but is not limited to electrode corrosion, solution resistance, The many reasons such as fouling membrane and increase.In some embodiments, Ampere load can be used to draw electric current from battery.

In some embodiments, with chlor-alkali or using ODC chlor-alkali or in the anode compartment by metal ion from compared with Any other method that low-oxidation-state is oxidized to higher oxidation state is compared, and the system that the present invention is provided causes low-voltage to no-voltage Production alkali system.In some embodiments, system described herein is less than 2V；Or less than 1.2V；Or less than 1.1V； Or less than 1V；Or less than 0.9V；Or less than 0.8V；Or less than 0.7V；Or less than 0.6V；Or less than 0.5V；Or less than 0.4V；Or Less than 0.3V；Or less than 0.2V；Or less than 0.1V；Or at 0 volt；Or 0-1.2V；Or 0-1V；Or 0-0.5V；Or 0.5-1V；Or 0.5-2V；Or 0-0.1V；Or 0.1-1V；Or 0.1-2V；Or 0.01-0.5V；Or 0.01-1.2V；Or 1-1.2V；Or 0.2-1V； Or 0V；Or 0.5V；Or 0.6V；Or 0.7V；Or 0.8V；Or 0.9V；Or run under 1V voltage.

As used herein " voltage " include put on electrochemical cell or drawn from electrochemical cell, drive the electrification Learn the voltage or bias of the required reaction between galvanic anode and negative electrode.In some embodiments, the required reaction can be Electro transfer between anode and negative electrode is to form alkaline solution, water or hydrogen in catholyte and metal ion exists It is oxidized at anode.In some embodiments, the required reaction can be the electro transfer between anode and negative electrode to cause The metal ion in higher oxidation state is formed by the metal ion in low oxidation state in anodolyte.Can be by appointing What applies a voltage to electrochemical cell across the means of anode and negative electrode the application electric current of electrochemical cell.Such means are these Known to field, include but is not limited to the devices such as power supply, fuel cell, solar energy device, wind energy driving device And combinations thereof.The power supply type for providing electric current can be any power supply well known by persons skilled in the art.For example, in some implementations In scheme, voltage can be applied by the way that the anode and negative electrode of battery are connected on external dc (DC) power supply.Power supply can be The rectified alternating current (AC) for DC.D/C power can have adjustable voltage and current, to apply necessary to electrochemical cell The voltage of amount.

In some embodiments, the electric current for putting on electrochemical cell is at least 50mA/cm²；Or at least 100mA/cm²； Or at least 150mA/cm²；Or at least 200mA/cm²；Or at least 500mA/cm²；Or at least 1000mA/cm²；Or at least 1500mA/ cm²；Or at least 2000mA/cm²；Or at least 2500mA/cm²；Or 100-2500mA/cm²；Or 100-2000mA/cm²；Or 100- 1500mA/cm²；Or 100-1000mA/cm²；Or 100-500mA/cm²；Or 200-2500mA/cm²；Or 200-2000mA/cm²； Or 200-1500mA/cm²；Or 200-1000mA/cm²；Or 200-500mA/cm²；Or 500-2500mA/cm²；Or 500- 2000mA/cm²；Or 500-1500mA/cm²；Or 500-1000mA/cm²；Or 1000-2500mA/cm²；Or 1000-2000mA/ cm²；Or 1000-1500mA/cm²；Or 1500-2500mA/cm²；Or 1500-2000mA/cm²；Or 2000-2500mA/cm²。

In some embodiments, when the electric current of application is 100-250mA/cm²Or 100-150mA/cm²Or 100- 200mA/cm²Or 100-300mA/cm²Or 100-400mA/cm²Or 100-500mA/cm²Or 150-200mA/cm²Or 200- 150mA/cm²Or 200-300mA/cm²Or 200-400mA/cm²Or 200-500mA/cm²Or 150mA/cm²Or 200mA/cm²Or 300mA/cm²Or 400mA/cm²Or 500mA/cm²Or 600mA/cm²When, battery is run under 0-3V voltages.In some embodiment party In case, battery is run under 0-1V.In some embodiments, when the electric current of application is 100-250mA/cm²Or 100- 150mA/cm²Or 150-200mA/cm²Or 150mA/cm²Or 200mA/cm²When, battery is run under 0-1.5V.In some implementations In scheme, battery is in 100-250mA/cm²Or 100-150mA/cm²Or 150-200mA/cm²Or 150mA/cm²Or 200mA/cm² Ampere load under in 0-1V operation.In some embodiments, battery is in 100-250mA/cm²Or 100-150mA/cm²Or 150-200mA/cm²Or 150mA/cm²Or 200mA/cm²Electric current or Ampere load under in 0.5V operation.

In some embodiments, provided herein is system and method further comprise anode and amberplex and/or Percolation filter (percolator) and/or spacer region between negative electrode and amberplex.Electricity comprising percolation filter and/or spacer region Chemical system is the U.S. Provisional Application 61/442 submitted for 14th for 2 months in 2011, and described in 573, this application is herein by drawing With being integrally incorporated in present disclosure.

Provided herein is system be applied to or available for any one or more method as described herein.In some embodiment party In case, provided herein is system further comprise the oxygen supply or delivery system for being operably connected to cathode chamber.The oxygen Delivery system is configured as providing oxygen to gas diffusion cathode.In some embodiments, the oxygen delivery system is configured To deliver gas to gas diffusion cathode, the gas, which is catalyzed, at the gas diffusion cathode is reduced to hydroxide ion.One In a little embodiments, oxygen and water are reduced to hydroxide ion；Unreacted oxygen is recovered in system；And it is recycled to the moon Pole.It can be used and supply oxygen for from external source oxygen to be directed into any device of negative electrode to negative electrode.For by oxygen from The such device or oxygen delivery system that external source is directed to negative electrode be it is well known in the art, including but not limited to pipe, lead Pipe, pipeline etc..In some embodiments, the system or oxygen delivery system include oxygen being directed to negative electrode from external source Conduit.It should be appreciated that can be by oxygen is from battery bottom, battery top or is directed to negative electrode sideways.In some embodiments, Oxygen is directed to cathode back, oxygen is not contacted directly with catholyte here.In some embodiments, it can pass through Oxygen is directed to negative electrode by multiple entrances.Provided herein is method and system in gas diffusion cathode provide oxygen oxygen Source includes any oxygen sources known in the art.Such source includes but is not limited to surrounding air, from gas cylinder (cylinders) commerical grade oxygen, the oxygen obtained by the fractional distillation of liquefied air, by passing air through zeolite beds The oxygen of acquisition, the oxygen obtained by the electrolysis of water, the pottery based on zirconium dioxide forced air through by high pressure or electric current Porcelain film and oxygen, chemical oxygen generators, the oxygen as the liquid in insulatedtanker (insulated tanker) obtained, Or its combination.In some embodiments, oxygen sources can also provide carbon dioxide.In some embodiments, come from The oxygen of oxygen sources can be purified before cathode chamber is supplied to.In some embodiments, make as former state in the cathodic compartment With the oxygen from oxygen sources.

Alkali in cathode chamber

Catholyte containing alkali can take out from cathode chamber.Techniques known in the art can be used, including but does not limit In diffusion dialysis, alkali is separated from catholyte.In some embodiments, by provided herein is method and system in The alkali of generation is used for commercial or in commercial process known in the art as former state.The shape in described method and system Into the purity of alkali can be changed according to final use demand.For example, provided herein is use equipped with film electrochemical cell Method and system can be formed may substantially free from admixture film quality alkali.In some embodiments, can also be by avoiding making The alkali compared with low-purity is formed with film or by adding carbon into catholyte.In some embodiments, in catholyte The alkali formed in matter is more than 2%w/w or more than 5%w/w or is 5-50%w/w.

In some embodiments, the alkali produced in cathode chamber can be used for various commercial processes as described herein In.In some embodiments, being adapted to the system of this kind of purposes can be operably connected with electrochemical cell, or can transport alkali To appropriate site for using.In some embodiments, system includes being configured as collecting alkali from cathode chamber and being connected The collector of appropriate process is connected to, the collector can be collection and any device for handling alkali, and including but is not limited to can Collect, handle and/or shift tank, collector, pipe that the alkali produced in the cathodic compartment uses for various commercial processes Road etc..

In some embodiments, by the alkali produced in catholyte for example sodium hydroxide as former state be used for commercial use or Handled in a variety of methods well known in the art.For example, the sodium hydroxide formed in catholyte can be used as chemical work Alkali in industry, the alkali of family expenses and/or paper pulp, paper, textile, drinking water, soap, the manufacture of detergent and drainpipe cleaning agent. In some embodiments, sodium hydroxide can be used in papermaking.Sodium hydroxide can be kraft process together with vulcanized sodium It is used for the composition of white liquor (white liquor) solution for separating lignin and cellulose fibre in (Kraft process). It is also likely to be useful in rear several stages of the process for the brown paper pulp that bleaching is produced by pulping process.These stages can Including oxygen lignification removal, oxidative extraction and simple extraction, all these stages may need pH in the last of stage>10.5 Strong basicity environment.In some embodiments, sodium hydroxide can be used for digesting tissue.The process may include to put corpse Enter in closed chamber, corpse is put into the mixture of sodium hydroxide and water afterwards, this can make the complete chemical bond of holding body break Split.In some embodiments, sodium hydroxide can be used for Bayer process, and wherein sodium hydroxide is in the ore (bauxite) containing alumina Used in refining, to produce alumina (aluminum oxide).Alumina produces metallic aluminium available for via Hall-H é roult electrolysis Raw material.Alumina may be dissolved in sodium hydroxide, leave the relatively low impurity of solubility at a high ph after high alkalinity red soil is formed, such as Iron oxide.In some embodiments, sodium hydroxide can be used in soap manufacturing process.In some embodiments, hydroxide Sodium can be used in the production of biodiesel, and wherein sodium hydroxide can be used as the catalyst of the Trans-esterification of methanol and triglycerides. In some embodiments, sodium hydroxide can be used as cleaning agent, such as, but not limited to, the degreasing of stainless steel and glass bakee Agent.

In some embodiments, sodium hydroxide can be used in food production.The food applications of sodium hydroxide are included but not It is limited to, the washing or chemical peeling of fruits and vegetables, the processing of chocolate and cocoa, caramel coloring production, poultry scalding, soft drink Material processing and thickening ice cream.Olive can be dipped in sodium hydroxide so that it softens, and pretzels and German alkali lye are rolled up With sodium hydroxide surface can be made smooth before baking makes it become fragile.In some embodiments, sodium hydroxide in the family may be used It is used to clear up the drainpipe blocked as drainpipe cleaning agent.In some embodiments, sodium hydroxide can be used as stretching hair Detanglers.In some embodiments, sodium hydroxide can be used for oil plant and for oil drilling, because it can increase viscosity And prevent weight depression.In chemical industry, sodium hydroxide can provide acid neutralization, hydrolysis, condensation, saponification and hydroxyl from Son is to functions such as the displacements of other groups in organic compound.In some embodiments, sodium hydroxide can be used for textile industry. Mercerization finish available bigger tensile strength and consistent gloss are carried out to fiber with sodium hydroxide solution.Can also be from fiber Paraffin removal and oil are removed with so that fiber is easier to receive bleaching and dyed.Sodium hydroxide is also used in the production of viscose silk.One In a little embodiments, sodium hydroxide can be used for preparing the sodium hypochlorite that can be used as household bleach and disinfectant, and for making It is standby to can be used for preservative and for the sodium phenate in aspirin production.

Contact of the carbon dioxide with catholyte

On the one hand there is provided method described herein and system, it includes making carbon dioxide in cathode chamber or in the moon Pole room is outer to be contacted with catholyte.There is provided the method comprised the following steps on the one hand：Make anode and sun in the anode compartment Metal ion contact in the electrolyte of pole；Metal ion is converted into or is oxidized in the anode compartment higher oxygen from low oxidation state Change state；Negative electrode is set to be contacted with catholyte in the cathodic compartment；Alkali is formed in the cathodic compartment；And make the alkali in catholyte Contacted with the carbon (carbon dioxide such as originated from carbon dioxide) from carbon source.In some embodiments, this method enters one Step includes the metal in higher oxidation state that uses (as described herein) to be formed in the anode compartment as former state, or use it for and Hydrogen react or with (as described herein) unsaturated hydrocarbons or saturation hydrocarbon reaction.There is provided one kind side in some embodiments Method, this method includes：Anode is set to be contacted with anodolyte；Metal ion is oxidized to from low oxidation state at anode higher Oxidation state；Negative electrode is set to be contacted with catholyte；Hydroxide ion is produced in catholyte；And make catholyte with Industrial waste gas containing carbon dioxide is contacted with the dioxide solution containing bicarbonate ion.

There is provided the system for including following component on the other hand：Anode chamber, it is included and the metal in anodolyte The anode of contacted with ions, the wherein anode are configured as metal ion being converted into higher oxidation state from low oxidation state；Negative electrode Room, it includes the negative electrode contacted with catholyte, and the wherein negative electrode is configured as producing alkali；And contactor, it is operationally Cathode chamber is connected to, and the carbon dioxide and catholyte for being configured as making the carbon from carbon source such as to be originated from carbon dioxide Alkali contact in matter.In some embodiments, the system further comprises reactor, and the reactor is operably coupled to sun Pole room, and be configured as making the metal ion in higher oxidation state with hydrogen or with (as described herein) unsaturated hydrocarbons or Saturation hydrocarbon reaction.

In some embodiments, handle the carbon from carbon source to be formed in the alkali of catholyte with catholyte The solution of carbon dioxide is dissolved.Alkali present in catholyte can promote the dissolving of carbon dioxide in the solution.Containing molten The solution of the carbon dioxide of solution includes carbonic acid, bicarbonate, carbonate or its any combination.In such method and system, Carbon from carbon source includes the gaseous carbon dioxide from industrial process or the dioxide solution from gas/liquid contactor, should Contactor is contacted with the gaseous carbon dioxide from industrial process.This contactor is further defined herein.Including contact In some embodiments of the system of device, in addition to hydroxide ion, cathode chamber also includes bicarbonate ion and carbonate Ion.

One illustrative examples of integrated electro-chemical systems are as shown in Figure 12 with the carbon from carbon source.It should be appreciated that Figure 12 system 1200 is for illustration purposes only, other metal ions (for example, chromium, tin etc.) with different oxidation state, herein Other described electro-chemical systems, such as Figure 1A, 1B, 2,3A, 3B, 4A, 5A, 5C, 6,8A, 8B, 9 and 11 electro-chemical systems, with And the 3rd electrolyte in addition to sodium chloride, such as sodium sulphate, all it is the version for being equally applicable to the system.Figure 12 electrification System 1200 includes the anode and negative electrode separated by anion-exchange membrane and cation-exchange membrane, so as to create containing the 3rd Electrolyte NaCl the 3rd Room.Metal ion is oxidized to higher oxidation state from low oxidation state in the anode compartment, then at this In higher oxidation state metal be used for react in the reactor, such as with hydrogen reaction or with unsaturated hydrocarbons or saturation hydrocarbon reaction.This Text is described reacts the product formed by such.Negative electrode is shown as hydrogen formation negative electrode in fig. 12, but ODC is equally applicable In the system.Cathode chamber is connected with gas/liquid contactor, and the latter contacts with gaseous carbon dioxide.Containing alkali such as hydroxide and/or The catholyte of sodium carbonate is recycled to gas/liquid contactor so that catholyte is contacted with gaseous carbon dioxide, causes carbonic acid The formation of hydrogen sodium/sodium carbonate liquor.This solution for having dissolved carbon dioxide then loops to cathode chamber, in the cathodic compartment, Bicarbonate ion is converted into carbanion by the alkali formed at negative electrode so that the pH of catholyte is less than 12.This transfers So that the voltage of battery is decreased below 2V.The sodium carbonate liquor that is thusly-formed is recyclable to be returned to gas/liquid contactor to enter one Step is contacted with gaseous carbon dioxide, or is drawn off carrying out precipitation of calcium carbonate process as described herein.In some embodiments In, gaseous carbon dioxide is supplied directly into cathode chamber, and gas/liquid contactor is used without centre.In some embodiments, Bicarbonate solution from gas/liquid contactor is not supplied to cathode chamber, but for the precipitation of bicarbonate product.

It is as described herein and such as Figure 12 institutes with the carbon from carbon source not compared with the method and system that catholyte is contacted It is showing, be related to method and be that carbon from carbon source contacts with catholyte (when negative electrode is ODC or hydrogen generation negative electrode) System can cause voltage to be saved.Voltage, which is saved, can then cause relatively low power consumption and the less carbon dioxide caused by generating to be arranged Put.This can cause to produce the more green chemicals formed by efficient, energy-conservation the method and system of the present invention, such as carbonic acid Sodium, sodium acid carbonate, calcium bicarbonate/magnesium bicarbonate or calcium carbonate/magnesium carbonate, halogenated hydrocarbons and/or acid.In some embodiments, Wherein from the carbon and the moon of carbon source (such as carbon dioxide or the sodium carbonate/bicarbonate solution from gas/liquid contactor) The electrochemical cell for the alkali contact that pole is produced, is not contacted with wherein carbon with the alkali from negative electrode such as ODC or hydrogen generation negative electrode Electrochemical cell is compared, with more than 0.1V, or more than 0.2V, or more than 0.5V, or more than 1V, or more than 1.5V, or be 0.1-1.5V, or 0.1-1V, or 0.2-1.5V, or 0.2-1V, or 0.5-1.5V, or 0.5-1V theoretical cathode half-cell voltage Save or theoretical full cell voltage is saved.In some embodiments, it is to use 7-13 that this voltage, which is saved, or 6-12, or 7-12, Or 7-10, or 6-13 catholyte pH realize.

Based on the Nernst equation illustrated before, when the metal in low oxidation state is oxidized to place at anode When the metal of higher oxidation state：

Cu⁺→Cu²⁺+2e^-

The E of concentration based on II valency copper species_AnodeFor 0.159-0.75V.

When water is reduced to hydroxide ion and hydrogen (as shown in Fig. 4 A or Figure 12) at negative electrode, and hydroxyl from (carbon dioxide that is such as directly dissolved in catholyte is recycled to from gas/liquid contactor for son and bicarbonate ion Sodium carbonate/bicarbonate solution in catholyte) contacted to be formed during carbonate, the pH of catholyte is under 14 It is decreased to less than 14, it is as follows：

E_{Negative electrode}=-0.059pH_c, wherein pH_cFor the pH=10 of catholyte

E_{Negative electrode}=-0.59

According to the concentration of copper ion in anodolyte, E is 0.749 to 1.29.For not with bicarbonate ion/carbonic acid For the hydrogen generation negative electrode of radical ion contact, E_{Negative electrode}=-0.59 and E_{Negative electrode}=-0.83 compares saving more than 200mV or 200mV- 500mV or 100-500mV.For not generating negative electrode with the hydrogen that bicarbonate ion/carbanion is contacted, E_Always= 0.749-1.29 and E_Always=0.989-1.53 is compared to saving more than 200mV or 200mV-1.2V or 100mV-1.5V.

Equally, when water is reduced to hydroxide ion (as shown in Figure 5 A), and hydroxide ion and carbonic acid at ODC (carbon dioxide that is such as directly dissolved in catholyte is recycled to catholyte to hydrogen radical ion from gas/liquid contactor Sodium carbonate/bicarbonate solution in matter) contacted to be formed during carbonate, the pH of catholyte is deteriorated to less than from 14 14, it is as follows：

E_{Negative electrode}=1.224-0.059pH_c, wherein pH_c=10

E_{Negative electrode}=0.636V

According to the concentration of copper ion in anodolyte, E_AlwaysFor -0.477 to 0.064V.For not with bicarbonate ion/ For the ODC of carbanion contact, E_{Negative electrode}=0.636 and E_{Negative electrode}=0.4 compared to saving more than 100mV or 100mV-200mV or 100-500mV or 200-500mV.For not for the ODC that bicarbonate ion/carbanion is contacted, E_Always=-0.477- 0.064V and E_Always=-0.241-0.3 is compared to saving more than 200mV or 200mV-1.2V or 100mV-1.5V.

As described above, when catholyte is increased into pH 14 or higher, anodic half-cell potential and cathode half-cell Difference between potential will increase.Without CO₂In the case that addition or other interventions are such as diluted with water, during with battery operation duration Between increase, required cell voltage potential will continue to increase.Negative electrode pH provides for the operation of 7-13 or 7-12 electrochemical cell Significant energy-conservation.

Therefore, for different catholyte pH value, when putting on the voltage between anode and negative electrode less than 2.9, or Less than 2.5, or less than 2.1, or 2.0, or less than 1.5, or less than 1.0, or less than 0.5, or be 0.5-1.5V, while negative electrode is electric Solve matter pH be 7-13 or 7-12 or 6-12 or 7-10 when, in catholyte produce hydroxide ion, carbanion and/ Or bicarbonate ion.

In some embodiments, carbon source is any gas source of carbon dioxide and/or the dissolving for providing carbon dioxide Any source of form or solution.The dissolved form of carbon dioxide or the solution of carbon dioxide include carbonic acid, bicarbonate ion, Carbanion or its combination.Come from this there is provided oxygen and/or carbon dioxide to negative electrode in some embodiments Any oxygen source and carbon dioxide source known to field.Oxygen sources and carbon dioxide source can be identicals or can To be different.Oxygen sources and some examples in carbon dioxide source are as described herein.

In some embodiments, the alkali produced in cathode chamber can use the dissolving of carbon dioxide gas stream and/or carbon dioxide Form is to handle to form carbonate/bicarbonate product, and the product can be used for commercial use as former state, or can use bivalent cation Such as, but not limited to alkaline-earth metal ions handle to form alkaline earth metal carbonate and/or alkali metal bicarbonates.

" carbon from carbon source " includes the gaseous form of carbon dioxide or the dissolved form of carbon dioxide as used herein Or solution.Carbon from carbon source includes CO₂, carbonic acid, bicarbonate ion, carbanion or its combination.As used herein " carbon source " includes gaseous form and/or any source of dissolved form for providing carbon dioxide.Carbon source includes but is not limited to provide CO₂The waste stream or industrial process of air-flow；Offer contains CO₂, carbonic acid, bicarbonate ion, carbanion or its combination it is molten The gas/liquid contactor of liquid；And/or bicarbonate brine solution.

In some embodiments, gaseous state CO₂It is waste stream or product from industrial plant.In these embodiments In, the property of industrial plant can be different.Industrial plant includes but is not limited to, the refinery of formation unsaturated hydrocarbons or saturated hydrocarbons, Power plant is (for example, in " Methods of sequestering CO submit, entitled on December 24th, 2008₂" the world Be described in detail in application PCT/US08/88318, the disclosure of which is incorporated herein by reference in their entirety), chemical process Factory, steel rolling mill, paper mill, cement plant (for example, further retouch in detail in the U.S. Provisional Application of Serial No. 61/088,340 State, the disclosure of which is incorporated herein by reference in their entirety) and generation CO₂Other industrial plants of accessory substance.It is useless Logistics refers to the air-flow (or similar stream) produced as the accessory substance of industrial plant active procedure.The air-flow can be basic Pure CO₂Or including CO₂With the multi-component gas stream of other one or more gases.It can be used as CO in the embodiment of this method₂ The multi-component gas stream in source (contains CO₂) include also Primordial Qi, for example, synthesis gas, synthesis gas, natural gas and the hydrogen of conversion etc., with And oxidizing condition air-flow, for example, carrying out the flue gas of spontaneous combustion such as methyl hydride combustion.Waste gas containing NOx, Sox, VOC, particulate and Hg The carbonate in these compounds and precipitated product will be merged.The specific multicomponent gas interested that can be handled according to the present invention Stream includes but is not limited to, oxygen containing thermal power plant flue gas, turbocharging boiler product gas, coal gasification product gas, turn Coal gasification product gas, anaerobic digester product gas, well head natural gas flow, reforming natural gas or methane hydrate of change etc.. In the case where gas contains carbon dioxide and oxygen simultaneously, the gas can be used as carbon dioxide source and oxygen source.For example, by oxygen and The flue gas that the burning of methane is obtained can contain oxygen, and can provide the source of carbon dioxide and oxygen.

Therefore, waste stream can be produced by a variety of different types of industrial plants.Suitable for the present invention waste stream include by Combustion of fossil fuels (for example, coal, oil, natural gas) or naturally occurring organic-fuel deposit (for example, Tar sands, heavy oil, Oil shale etc.) artificial fuel Products industrial plant produce waste stream such as flue gas.In some embodiments, it is adapted to this The waste stream of the system and method for invention derives from coal-fired power plant, and such as pulverized coal plant, overcritical coal-fired power plant, concentration are burnt Burn coal-fired power plant, fluidized bed burned-coal power plant.In some embodiments, waste stream derives from combustion gas or oil burning boiler and vapour Turbine power plant, combustion gas or oil burning boiler simple cycle gas turbine engine power plant or combustion gas or oil burning boiler combined cycle gas wheel Machine power plant.In some embodiments, (produced using by burn synthesis gas by the gasification of the organic matter such as coal, biomass Raw gas) power plant produce waste stream.In some embodiments, using from integrated gasification combined cycle plants (IGCC) waste stream of factory.In some embodiments, according to provided herein is system and method using being steamed by waste heat recovery The waste stream that vapour generator (HRSG) factory produces produces composition.

The waste stream produced by cement plant be also suitable for provided herein is system and method.Cement plant waste stream includes coming from Wet method and the waste stream of dry method factory, these factories can use shaft furnace or rotary kiln, and may include precalcining stove.These industry Factory can each spontaneous combustion single-fuel or two or more fuel that can sequentially or simultaneously burn.

Although carbon dioxide may be present in common surrounding air, in view of its low-down concentration, environment titanium dioxide Carbon possibly can not provide enough carbon dioxide to realize the carbon such as obtained when the carbon from carbon source is contacted with catholyte The formation of sour hydrogen salt and/or carbonate.In some embodiments of the system and method, the pressure inside electro-chemical systems can Higher than the environment atmospheric pressure in surrounding air, and it therefore can generally prevent ambient carbon dioxide from penetrating into catholyte.

Contact system or contactor include being used to make the carbon from carbon source and the negative electrode inside cathode chamber or outside cathode chamber Any device of electrolyte contact.It is this kind of to be used to make the device that carbon is contacted with catholyte, or be configured to make from carbon source The contactor that carbon is contacted with cathode chamber, is well known in the art, including but not limited to syringe, pipe, conduit, pipeline etc..One In a little embodiments, the system is including carbon to be guided to the conduit in the catholyte to cathode chamber.Come from it should be appreciated that working as , can be according to carbon amounts required in cathode chamber from battery bottom, battery when the carbon of carbon source is contacted with the catholyte in cathode chamber Carbon is injected catholyte by side entrance and/or all entrances in top, battery.The amount of carbon from carbon source in cathode chamber It may depend on the flow velocity of solution, the required pH of catholyte and/or the size of battery.To this of the amount of the carbon from carbon source Optimization is entirely within the ambit of the present invention.In some embodiments, the carbon from carbon source is selected from the gaseous state from industrial process Carbon dioxide or the dioxide solution from the gas/liquid contactor contacted with the gaseous carbon dioxide from industrial process.

In some embodiments, cathode chamber promotes carbon dioxide and/or dioxide solution in the moon including help The septal area of conveying in pole room.In some embodiments, septal area can help prevent carbon dioxide and oxygen mix and/or Carbon dioxide in cathode chamber is mixed with the hydrogen in anode chamber.In some embodiments, septal area causes catholyte Liquid contains the gaseous form of carbon dioxide and the dissolved form of carbon dioxide.In some embodiments, provided herein is system Including catholyte to be divided into the septal area of the first cathode electrolyte portion and the second cathode electrolyte portion, wherein including dissolving Carbon dioxide the second cathode electrolyte portion Contact cathod；And carbon dioxide and gaseous state titanium dioxide wherein comprising dissolving The second cathode electrolyte portion under the first cathode electrolyte portion contact septal area of carbon.Within the system, septal area is located at negative electrode In electrolyte, to cause the gas (for example, carbon dioxide) in the first cathode electrolyte portion and the second cathode electrolyte portion In catholyte keep apart.Therefore, septal area may act as preventing the gas on negative electrode and/or the gas from anode and/or The device of steam mixing.Retouched in the US publication 2010/0084280 that on November 12nd, 2009 submits this septal area State, this application is incorporated herein by reference in their entirety in this disclosure.

In some embodiments, carbon source is to provide containing CO₂, carbonic acid, bicarbonate ion, carbanion or its group The carbon dioxide solubility form or the gas/liquid contactor of solution of conjunction.In some embodiments, by by CO₂Jet-impingement or Diffuse through slurries or solution and contain CO to be made₂Water, contain the CO that partially or substantially dissolves so as to be made₂Solution.At some In embodiment, contain CO₂Slurries or solution include the matter as described herein obtained from the catholyte of electrochemical cell Sub- remover.In some embodiments, gas/liquid contactor may include bubble chamber, the CO in bubble chamber₂Gas is by containing matter The slurries or solution bubbling of sub- remover.In some embodiments, contactor may include spray column, and matter is contained in spray column The slurries or solution spraying of sub- remover circulate through CO₂Gas.In some embodiments, contactor may include packed bed To increase CO₂Contact surface area between gas and solution containing proton remover.For example, gas/liquid contactor or absorber The slurries or solution or packed bed of sodium carbonate can be included.CO₂Injection is situated between through the slurries or solution or packed bed, here alkalescence Matter promotes CO₂Dissolving in the solution.CO₂After dissolving, solution can include bicarbonate, carbonate or its combination.In some realities Apply in scheme, typical absorber or contactor fluid temperature (F.T.) is 32-37 DEG C.For the CO in absorbent solution₂Absorber or Contactor is described in the U. S. application for the Serial No. 12/721,549 that on March 10th, 2010 submits, and this application is herein It is entirely incorporated by reference in this disclosure.It can be taken out from gas/liquid contactor containing carbonate/or bicarbonate species Solution is to form bicarbonate/carbonate product.In some embodiments, carbonate/bicarbonate solution can be transferred to In catholyte containing alkali.It is molten to form carbonate that bicarbonate can be gone up or be completely converted into substantially carbonate by the alkali Liquid.Carbonate solution is recyclable to return to gas/liquid contactor, or can be taken out from cathode chamber and handle to be formed with bivalent cation Bicarbonate/carbonate product.

In some embodiments, the alkali produced in catholyte can be delivered to gas/liquid contactor, in the contact Carbon dioxide is contacted with alkali in device.Carbon dioxide can be resulted in after being contacted with alkali carbonic acid, bicarbonate radical from Son, carbanion or its combination.The dissolved form of carbon dioxide can be handed back to cathode chamber afterwards, alkali can in the cathode chamber It is carbonate by bicarbonate conversion.Then carbonate/bicarbonate mixture can be used for commercial use as former state, or positive with divalence Ion such as alkaline-earth metal ions handle to form alkaline earth metal carbonate/bicarbonate.

In some embodiments, the system includes the negative electrode electricity suitable for taking out and circulating in systems catholyte Solve the matter circulatory system.In some embodiments, the catholyte circulatory system is included in the gas/liquid contactor outside negative electrode room, The gas/liquid contactor is suitable for making the carbon from carbon source to be contacted with the catholyte circulated, and in recirculating system Electrolyte.Due to catholyte can be adjusted by the way that catholyte/carbon from carbon source is taken out and/or circulated from system PH, so can be taken out by adjusting from system, it is by gas/liquid contactor and/or be recycled back into cathode chamber The amount of catholyte adjusts the pH of catholyte compartment.

In some embodiments, carbon source is bicarbonate brine solution.Bicarbonate brine solution was January 18 in 2011 In the U.S. Provisional Application 61/433,641 of day submission and the U.S. Provisional Application 61/408,325 submitted on October 29th, 2010 It is described, the two is incorporated herein by reference in their entirety in this disclosure.As used herein " bicarbonate brine solution " Including any salt solution for including bicarbonate ion.In some embodiments, salt solution is synthesis salt solution, for example, contain bicarbonate The saline solution of salt such as sodium acid carbonate, saleratus, lithium bicarbonate etc..In some embodiments, salt solution is naturally occurring Bicarbonate brine, for example, for example naturally occurring lake water of saline groundwater.In some embodiments, bicarbonate brine is by ground Lower salt solution (such as, but not limited to, carbonate salt solution, base brine, kieserohalosylvite water and/or alkaline kieserohalosylvite water) is made.In some implementations In scheme, bicarbonate brine is made up of mineral matter, wherein mineral matter is crushed and is dissolved in salt solution and optionally carries out Further processing.Mineral matter can be under the surface in lake, the discovery of surface Shang Huoci top layers.Bicarbonate brine can also be by evaporite It is made.Bicarbonate brine removes bicarbonate ion (HCO₃ ^-) outside can also include other oxo-anions of carbon, for example but not It is limited to carbonic acid (H₂CO₃) and/or carbanion (CO₃ ^2-)。

In some embodiments of electrochemical cell as described herein, the system is configured as by the carbon from carbon source Such as CO₂, carbonic acid, bicarbonate ion, carbanion or its combination with the alkali from catholyte such as sodium hydroxide reaction And produce carbanion.(it is not shown) in some embodiments, the gaseous state of such as carbon dioxide of the carbon from carbon source Form can be contacted with the catholyte in cathode chamber, and can be taken out from cathode chamber and contained hydroxide/carbon hydrochlorate/carbonic acid The catholyte of hydrogen salt is simultaneously contacted with the gas/liquid contactor outside negative electrode room.In such embodiments, connect from gas/liquid The catholyte of tentaculum can be contacted with the catholyte in cathode chamber again.

The system contacted for carbon wherein from carbon source with the catholyte outside negative electrode room, can take from cathode chamber Go out the catholyte containing alkali and can be added into being configured as in the container containing the carbon from carbon source.The container can With carbon source input module, such as pipe or pipeline or and CO₂Air-flow, contain CO₂The solution and/or bicarbonate salt of dissolved form The pipeline of water connection.The container can also with that can produce wherein, it is modified and/or storage carbon source such as bicarbonate brine solution anti- Device is answered to be in fluid communication.

System for being contacted in the carbon wherein from carbon source with the catholyte in cathode chamber, can take from cathode chamber Go out the catholyte containing alkali, bicarbonate and/or carbonate, and as described herein it can be made to be contacted with alkaline-earth metal ions To form bicarbonate/carbonate product.

The component of electrochemical cell

Provided herein is method and system include one or more following components.

In some embodiments, anode can include corrosion resistant conductive seat support.Such as, but not limited to, amorphous carbon Such as carbon black, fluorocarbons, such as in United States Patent (USP) 4, described in 908,198 and the special fluorination that can be obtained under trade mark SFCTM carbon Carbon.Other examples of conductive seat material include but is not limited to, the titanium oxide of substoichiometric, as with formula TiOx The titanium oxide of Magneli phase substoichiometrics, wherein x is about 1.67 to about 1.9.For example, titanium oxide Ti₄O₇.In some realities Apply in scheme, carbon-based material provides machinery support for GDE, or improves as mixing material electric conductivity, but is not used as urging Agent carrier carrys out anticorrosion.

In some embodiments, gas-diffusion electrode as described herein or ordinary electrode, which are included, is used to help electrochemistry solution The elctro-catalyst of metal ion oxidation from the hydrogen reduction for example at negative electrode or at anode.The example of elctro-catalyst include but Be not limited to, the metal or alloy of the high degree of dispersion of platinum group metal, such as platinum, palladium, ruthenium, rhodium, iridium or its combination as platinum-rhodium, platinum-ruthenium, It is coated with the titanium net of PtIr mixed-metal oxides or is coated with the titanium of zinc-plated platinum；Electrocatalytic metal oxide, for example but is not limited In IrO₂；Gold；Tantalum；Carbon；Graphite；Organic metal macrocyclic compound, and the electrochemical reduction or gold well known in the art for oxygen Belong to other elctro-catalysts of oxidation.

In some embodiments, electrode as described herein is related to porous homogeneous composite construction and heterogeneous laminated devices is multiple Structure is closed, each of which layer can have different physics and composition to constitute, such as porous, and conductive seat, to prevent Overflow and the forfeiture of three phase boundary and cause electrode performance.

In some embodiments, provided herein is electrode may include that anolyte or catholyte in electrode are molten On liquid side or the anode and negative electrode with porous polymeric nitride layer adjacent thereto, this can help to reduce infiltration and electrode fouling. Stable fluoropolymer resin or film may include that in the composite electrode layers neighbouring with anolyte it is included by non-ionic polymeric Thing (such as polystyrene, polyvinyl chloride, polysulfones) or ionic charged polymer are (such as by polystyrolsulfon acid, styrene and second The sulfonation or carboxylation polymerization of the sulfonated copolymer of alkenyl benzene, carboxylated polymers derivative, hydrocarbon chain with partly or completely perfluorinate Thing and ammonification polymer for example polyvinylpyridine formation polymer) formed resin.The micro- of stabilization can also be included in dry side Pore polymer film is to suppress electrolyte osmosis.In some embodiments, gas diffusion cathode includes being coated with noble metal such as gold And/or this kind of negative electrode known in the art of the high surface area coatings of silver, precious metal alloys, nickel etc..

In some embodiments, provided herein is method and system include allow improve anode at and surrounding electrolyte Diffusion anode.It has been found that the shape and/or geometry of anode can be to the anode electrolysis around anode chamber's Anodic The flow or flow velocity of matter produce influence, and this can improve mass transfer and reduction cell voltage again.In some embodiments, originally The method and system that text is provided is included for the anode of " diffusion enhancing " anode." diffusion enhancing " anode includes carrying as used herein At high anode and/or surrounding electrolyte diffusion so as to strengthening the anode of reaction at anode.In some embodiments, expand It is porous anode to dissipate enhancing anode." porous anode " includes the porose anode of tool in it as used herein.Applicant is unexpected simultaneously It has surprisingly been found that diffusion-enhanced anode, such as, but not limited to provided herein is method and system in the porous anode that uses, with Non-diffusing or non-porous anode in electro-chemical systems, which are compared, has some advantages, includes but is not limited to, higher surface area；It is living Increase in property site；Voltage is reduced；The resistance reduction as caused by anodolyte is eliminated；Current density increase；Anodolyte In turbulent flow increase；And/or improved mass transfer.

Diffusion-enhanced anode, such as, but not limited to porous anode, can be flat or non-flat.For example, at some In embodiment, diffusion-enhanced anode, such as, but not limited to porous anode are flat forms, are included but is not limited to, extension Flattened version, porous plate, network structure etc..In some embodiments, diffusion-enhanced anode, such as, but not limited to porous sun Pole, includes the net or flat extension net anode of extension.

In some embodiments, diffusion-enhanced anode, such as, but not limited to porous anode, are non-flat or with ripple Line shape geometry.In some embodiments, the corrugated geometry of anode can provide the volume of turbulent flow to anodolyte Outer advantage simultaneously improves the mass transfer at anode.As used herein " ripple " or " corrugated geometry " or " corrugated sun It not is flat or non-flat anode that pole ", which includes,.The corrugated geometry of anode includes but is not limited to, non-flat, The non-flat of extension, stair shape, undulated, wavy, three-dimensional, curling, groove, pleated, gauffer, carinate, pleated ribbon, pleat Pleat shape, corrugated, woven mesh, perforation tab style etc..

Diffusion-enhanced anode is such as, but not limited to some examples of the flat and undulatory geometry of porous anode As shown in figure 16.These examples are for illustration purposes only, and any other change of these geometries is complete in the present invention Within the scope of.Figure A in Figure 16 is the example of flat expanded anode, and the figure B in Figure 16 is the example of corrugated anode.

In some embodiments, there is provided herein a kind of method, it includes：It is such as, but not limited to diffusion-enhanced anode Porous anode is contacted with anodolyte, and wherein the anodolyte contains metal ion；In diffusion-enhanced anode for example but not It is limited to porous anode and metal ion is oxidizing to higher oxidation state from low oxidation state；Negative electrode is set to be contacted with catholyte； And hydroxyl is produced at negative electrode.

In some embodiments, there is provided herein a kind of method, it includes：It is such as, but not limited to diffusion-enhanced anode Porous anode is contacted with anodolyte, and wherein the anodolyte contains metal ion；In diffusion-enhanced anode for example but not It is limited to porous anode and metal ion is oxidizing to higher oxidation state from low oxidation state；Negative electrode is set to be contacted with catholyte； And make unsaturated hydrocarbons or saturated hydrocarbons with producing halogen comprising the anode electrolysis qualitative response of the metal ion in higher oxidation state For hydrocarbon.

In some embodiments, there is provided herein a kind of method, it includes：It is such as, but not limited to diffusion-enhanced anode Porous anode is contacted with anodolyte, and wherein the anodolyte contains metal ion；In diffusion-enhanced anode for example but not It is limited to porous anode and metal ion is oxidizing to higher oxidation state from low oxidation state；Negative electrode is set to be contacted with catholyte； And make unsaturated hydrocarbons or saturated hydrocarbons and the anodolyte comprising the metal ion in higher oxidation state in an aqueous medium Reaction is to produce halogenated hydrocarbons, and the wherein aqueous medium comprises more than 5% water.

In some embodiments of preceding method, aqueous medium comprises more than 5wt% water, or more than 5.5wt% or More than 6wt% or 5-90wt% or 5-95wt% or 5-99wt% water, or 5.5-90wt% or 5.5-95wt% or 5.5- 99wt% water, or 6-90wt% or 6-95wt% or 6-99wt% water.

In some embodiments, there is provided herein a kind of method, it includes：It is such as, but not limited to diffusion-enhanced anode Porous anode is contacted with anodolyte, and wherein the anodolyte contains copper ion；For example but do not limited in diffusion-enhanced anode Copper ion is oxidizing to higher oxidation state from low oxidation state in porous anode；Negative electrode is set to be contacted with catholyte；And Hydroxyl is produced at negative electrode.

In some embodiments, there is provided herein a kind of method, it includes：It is such as, but not limited to diffusion-enhanced anode Porous anode is contacted with anodolyte, and wherein the anodolyte contains copper ion；For example but do not limited in diffusion-enhanced anode Copper ion is oxidizing to higher oxidation state from low oxidation state in porous anode；Negative electrode is set to be contacted with catholyte；And Make unsaturated hydrocarbons or saturated hydrocarbons with producing halogenated hydrocarbons comprising the anode electrolysis qualitative response of the copper ion in higher oxidation state.

In some embodiments, there is provided herein a kind of method, it includes：It is such as, but not limited to diffusion-enhanced anode Porous anode is contacted with anodolyte, and wherein the anodolyte contains copper ion；For example but do not limited in diffusion-enhanced anode Copper ion is oxidizing to higher oxidation state from low oxidation state in porous anode；Negative electrode is set to be contacted with catholyte；And Unsaturated hydrocarbons or saturated hydrocarbons and the anodolyte comprising the copper ion in higher oxidation state is reacted in an aqueous medium with Halogenated hydrocarbons is produced, the wherein aqueous medium comprises more than 5wt% water.

In some embodiments, there is provided herein a kind of method, it includes：It is such as, but not limited to diffusion-enhanced anode Porous anode is contacted with anodolyte, and wherein the anodolyte contains copper ion；For example but do not limited in diffusion-enhanced anode Copper ion is oxidizing to higher oxidation state from low oxidation state in porous anode；Negative electrode is set to be contacted with catholyte；And Make ethene with producing ethylene dichloride comprising the anode electrolysis qualitative response of the copper ion in higher oxidation state.

In some embodiments, there is provided herein a kind of method, it includes：It is such as, but not limited to diffusion-enhanced anode Porous anode is contacted with anodolyte, and wherein the anodolyte contains copper ion；For example but do not limited in diffusion-enhanced anode Copper ion is oxidizing to higher oxidation state from low oxidation state in porous anode；Negative electrode is set to be contacted with catholyte；And Ethene is set to react to produce dichloride second in an aqueous medium with the anodolyte comprising the copper ion in higher oxidation state Alkene, the wherein aqueous medium comprise more than 5wt% water.

In some embodiments of preceding method and embodiment, compared with non-diffusing or non-porous anode, diffusion increases The use that strong anode is such as, but not limited to porous anode causes 10-500mV, or 50-250mV, or 100-200mV, or 200- 400mV, or 25-450mV, or 250-350mV, or 100-500mV voltage are saved.

In some embodiments of preceding method and embodiment, compared with non-diffusing or non-porous anode, corrugated The use of anode causes 10-500mV, or 50-250mV, or 100-200mV, or 200-400mV, or 25-450mV, or 250- 350mV, or 100-500mV voltage are saved.

Diffusion-enhanced anode, which is such as, but not limited to porous anode, to be characterized with various parameters, and the parameter is included but not Be limited to mesh number (i.e. the line number of the net of per inch), hole size, silk thickness or silk diameter, perforated area percentage, the amplitude of ripple, Repetition period of ripple etc..These features that diffusion-enhanced anode is such as, but not limited to porous electrode can influence the property of porous anode Can, such as, but not limited to, the reduction of increase, solution resistance for the surface area of anode reaction, apply across anode and negative electrode The reduction of voltage, the mass transfer at the whole anode at the enhancing of electrolyte turbulent flow and/or improved anode.

In some embodiments of preceding method and embodiment, diffusion-enhanced anode is such as, but not limited to porous anode There can be scope for 2x1mm to 20x10mm, or 2x1mm to 10x5mm, or 2x1mm to 5x5mm, or 1x1mm is to 20x10mm, or 1x1mm to 10x5mm, or 1x1mm to 5x5mm, or 5x1mm to 10x5mm, or 5x1mm to 20x10mm, 10x5mm are to 20x10mm Deng perforate size.It should be appreciated that the hole size of porous anode may also depend upon the shape in hole.For example, the geometry in hole can To be rhombus or square.For the geometry of rhombus, hole size can be such as transverse direction 3mm, longitudinal direction 10mm 3x10mm The rhombus of (vice versa).For the geometry of square, hole size can be that such as each side is 3mm.Mesh grid can be with It is the net with square opening, and it can be the net with diamond hole to extend net.

In some embodiments of preceding method and embodiment, diffusion-enhanced anode is such as, but not limited to porous anode There can be scope for 0.5mm to 5mm, or 0.5mm to 4mm, or 0.5mm to 3mm, or 0.5mm to 2mm, or 0.5mm is to 1mm, or 1mm to 5mm, or 1mm to 4mm, or 1mm to 3mm, or 1mm to 2mm, or 2mm to 5mm, or 2mm to 4mm, or 2mm is to 3mm, or 0.5mm to 2.5mm, or 0.5mm to 1.5mm, or 1mm to 1.5mm, or 1mm to 2.5mm, or 2.5mm to 3mm, or 0.5mm, or 1mm, or 2mm, or 3mm hole silk thickness or thickness of net (as shown in figure 16).

In some embodiments of preceding method and embodiment, when diffusion-enhanced anode is such as, but not limited to porous sun When pole is corrugated anode, corrugated anode can have scope for 1mm to 8mm, or 1mm to 7mm, or 1mm to 6mm, or 1mm is extremely 5mm, or 1mm to 4mm, or 1mm to 4.5mm, or 1mm to 3mm, or 1mm to 2mm, or 2mm to 8mm, or 2mm to 6mm, or 2mm To 4mm, or 2mm to 3mm, or 3mm to 8mm, or 3mm to 7mm, or 3mm to 5mm, or 3mm to 4mm, or 4mm to 8mm, or 4mm To 5mm, or 5mm to 7mm, or 5mm to 8mm ripple magnitude (as shown in figure 16).

In some embodiments of preceding method and embodiment, when diffusion-enhanced anode is such as, but not limited to porous sun When pole is corrugated anode, corrugated anode can have scope for 2mm to 35mm, or 2mm to 32mm, or 2mm is to 30mm, or 2mm to 25mm, or 2mm to 20mm, or 2mm to 16mm, or 2mm to 10mm, or 5mm to 35mm, or 5mm to 30mm, or 5mm is extremely 25mm, or 5mm to 20mm, or 5mm to 16mm, or 5mm to 10mm, or 15mm to 35mm, or 15mm to 30mm, or 15mm is extremely 25mm, or 15mm to 20mm, or 20mm to 35mm, or 25mm to 30mm, or 25mm to 35mm, or 25mm to 30mm ripple are all Phase (not shown).

In some embodiments, there is provided herein a kind of method, it includes：It is such as, but not limited to diffusion-enhanced anode Porous anode is contacted with anodolyte, and wherein the anodolyte contains metal ion；In diffusion-enhanced anode for example but not It is limited to porous anode and metal ion is oxidizing to higher oxidation state from low oxidation state；Negative electrode is set to be contacted with catholyte； And hydroxyl is produced at negative electrode, the wherein anode includes one or more following parameters：

Scope is 2x1mm to 20x10mm, or 2x1mm to 10x5mm, or 2x1mm to 5x5mm, or 1x1mm is to 20x10mm, or 1x1mm to 10x5mm, or 1x1mm to 5x5mm, or 5x1mm to 10x5mm, or 5x1mm to 20x10mm, or 10x5mm is extremely 20x10mm perforate size；

Scope is 0.5mm to 5mm, or 0.5mm to 4mm, or 0.5mm to 3mm, or 0.5mm to 2mm, or 0.5mm is to 1mm, or 1mm to 5mm, or 1mm to 4mm, or 1mm to 3mm, or 1mm to 2mm, or 2mm to 5mm, or 2mm to 4mm, or 2mm is to 3mm, or 0.5mm to 2.5mm, or 0.5mm to 1.5mm, or 1mm to 1.5mm, or 1mm to 2.5mm, or 2.5mm to 3mm, or 0.5mm, or 1mm, or 2mm, or 3mm hole silk thickness or thickness of net；

Scope is 1mm to 8mm, or 1mm to 7mm, or 1mm to 6mm, or 1mm to 5mm, or 1mm to 4mm, or 1mm is to 4.5mm, Or 1mm to 3mm, or 1mm to 2mm, or 2mm to 8mm, or 2mm to 6mm, or 2mm to 4mm, or 2mm to 3mm, or 3mm is to 8mm, Or 3mm to 7mm, or 3mm to 5mm, or 3mm to 4mm, or 4mm to 8mm, or 4mm to 5mm, or 5mm to 7mm, or 5mm to 8mm Ripple magnitude；And

Scope is 2mm to 35mm, or 2mm to 32mm, or 2mm to 30mm, or 2mm to 25mm, or 2mm to 20mm, or 2mm To 16mm, or 2mm to 10mm, or 5mm to 35mm, or 5mm to 30mm, or 5mm to 25mm, or 5mm to 20mm, or 5mm is extremely 16mm, or 5mm to 10mm, or 15mm to 35mm, or 15mm to 30mm, or 15mm to 25mm, or 15mm to 20mm, or 20mm is extremely 35mm, or 25mm to 30mm, or 25mm to 35mm, or 25mm to 30mm corrugated periodic.In some embodiments, carry herein A kind of method is supplied, it includes：Make diffusion-enhanced anode be such as, but not limited to porous anode to contact with anodolyte, wherein should Anodolyte contains metal ion；It is such as, but not limited to porous anode by metal ion from compared with hypoxemia in diffusion-enhanced anode Change state and be oxidizing to higher oxidation state；Negative electrode is set to be contacted with catholyte；And be in unsaturated hydrocarbons or saturated hydrocarbons with containing The anode electrolysis qualitative response of the metal ion of higher oxidation state is to produce halogenated hydrocarbons, and wherein the anode is comprising one or more following Parameter：

Scope is 2mm to 35mm, or 2mm to 32mm, or 2mm to 30mm, or 2mm to 25mm, or 2mm to 20mm, or 2mm is extremely 16mm, or 2mm to 10mm, or 5mm to 35mm, or 5mm to 30mm, or 5mm to 25mm, or 5mm to 20mm, or 5mm is to 16mm, Or 5mm to 10mm, or 15mm to 35mm, or 15mm to 30mm, or 15mm to 25mm, or 15mm to 20mm, or 20mm is to 35mm, Or 25mm to 30mm, or 25mm to 35mm, or 25mm to 30mm corrugated periodic.

In some embodiments, there is provided herein a kind of method, it includes：It is such as, but not limited to diffusion-enhanced anode Porous anode is contacted with anodolyte, and wherein the anodolyte contains metal ion；In diffusion-enhanced anode for example but not It is limited to porous anode and metal ion is oxidizing to higher oxidation state from low oxidation state；Negative electrode is set to be contacted with catholyte； And by unsaturated hydrocarbons or saturated hydrocarbons with containing the anodolyte of the metal ion in higher oxidation state in an aqueous medium Reaction is to produce halogenated hydrocarbons, and the wherein aqueous medium comprises more than 5wt% water, and wherein the anode is comprising one or more following Parameter：

In some embodiments, it is by being coated with elctro-catalyst that diffusion-enhanced anode, which is such as, but not limited to porous anode, Metal is as titanium is made.The example of elctro-catalyst is having been described above, and includes but is not limited to, the high degree of dispersion of platinum group metal Metal or alloy, such as platinum, palladium, ruthenium, rhodium, iridium or its combination such as platinum-rhodium, platinum-ruthenium, the titanium for being coated with PtIr mixed-metal oxides Net or the titanium for being coated with zinc-plated platinum；Electrocatalytic metal oxide, such as, but not limited to, IrO₂；Gold；Tantalum；Carbon；Graphite；Organic gold Belong to macrocyclic compound, and other elctro-catalysts known in the art.Diffusion-enhanced anode is such as, but not limited to porous anode can business Purchase is obtained or can manufactured by appropriate metal.Method coating elctro-catalyst well known in the art can be used in electrode.For example, can be by Metal immerses in the catalytic solution for coating and can carry out the techniques such as heating, sandblasting.Manufacture anode simultaneously coats catalysis Such method of agent is well known in the art.

In some embodiments, provided herein is system and method in electrolyte (including catholyte or the moon Pole electrolyte and/or anolyte or anodolyte, or the 3rd electrolyte being placed between AEM and CEM) include but do not limit In salt water or fresh water.Salt water includes but is not limited to seawater, salt solution and/or brackish water.In some embodiments, provided herein is Catholyte in system and method includes but is not limited to seawater, fresh water, salt solution, brackish water, hydroxide such as sodium hydroxide Or its combination." salt water " is used with its conventional meaning, refers to many different types of aqueous fluids in addition to fresh water, wherein term " salt water " include but is not limited to brackish water, seawater and salt solution (including naturally occurring saline groundwater or artificial saline groundwater and Artificial salt solution, for example, underground heat plant chimney stalk, desalinization wastewater etc.) and salinity with higher than fresh water other salt solution.Salt solution is With salt loading or close to the water of saturation, and with 50ppt (permillage) or higher salinity.Brackish water be it is more salty than fresh water but There is no the water that seawater is salty, the salinity with 0.5-35ppt.Seawater is the water from sea or ocean, and with 35-50ppt Salinity.Salt water source can be the naturally occurring source such as sea, ocean, lake, marsh, river mouth, Diarrhea lakes or artificial next Source.In some embodiments, provided herein is system include the salt water from land salt solution.In some embodiments, to The salt water for the consumption taken out from electrochemical cell supplements salt and is recycled back into electrochemical cell.

In some embodiments, electrolyte (including catholyte and/or anodolyte and/or the 3rd electrolyte, Such as salt water) include the chloride such as NaCl containing content more than 1%；Or the NaCl more than 10%；Or the NaCl more than 20%；Or NaCl more than 30%；Or the NaCl more than 40%；Or the NaCl more than 50%；Or the NaCl more than 60%；Or more than 70% NaCl；Or the NaCl more than 80%；Or the NaCl more than 90%；Or 1-99% NaCl；Or 1-95% NaCl；Or 1- 90% NaCl；Or 1-80% NaCl；Or 1-70% NaCl；Or 1-60% NaCl；Or 1-50% NaCl；Or 1- 40% NaCl；Or 1-30% NaCl；Or 1-20% NaCl；Or 1-10% NaCl；Or 10-99% NaCl；Or 10- 95% NaCl；Or 10-90% NaCl；Or 10-80% NaCl；Or 10-70% NaCl；Or 10-60% NaCl；Or 10-50% NaCl；Or 10-40% NaCl；Or 10-30% NaCl；Or 10-20% NaCl；Or 20-99% NaCl；Or 20-95% NaCl；Or 20-90% NaCl；Or 20-80% NaCl；Or 20-70% NaCl；Or 20- 60% NaCl；Or 20-50% NaCl；Or 20-40% NaCl；Or 20-30% NaCl；Or 30-99% NaCl；Or 30-95% NaCl；Or 30-90% NaCl；Or 30-80% NaCl；Or 30-70% NaCl；Or 30-60% NaCl；Or 30-50% NaCl；Or 30-40% NaCl；Or 40-99% NaCl；Or 40-95% NaCl；Or 40- 90% NaCl；Or 40-80% NaCl；Or 40-70% NaCl；Or 40-60% NaCl；Or 40-50% NaCl；Or 50-99% NaCl；Or 50-95% NaCl；Or 50-90% NaCl；Or 50-80% NaCl；Or 50-70% NaCl；Or 50-60% NaCl；Or 60-99% NaCl；Or 60-95% NaCl；Or 60-90% NaCl；Or 60- 80% NaCl；Or 60-70% NaCl；Or 70-99% NaCl；Or 70-95% NaCl；Or 70-90% NaCl；Or 70-80% NaCl；Or 80-99% NaCl；Or 80-95% NaCl；Or 80-90% NaCl；Or 90-99% NaCl；Or 90-95% NaCl water.In some embodiments, above-described percentage is suitable as electrolyte Ammonium chloride, iron chloride, sodium bromide, sodium iodide or sodium sulphate.Percentage as described herein includes wt% or wt/wt% or wt/ V%.It should be appreciated that the sodium chloride that contains of all electro-chemical systems as described herein can with other suitable electrolyte (for example but It is not limited to, ammonium chloride, sodium bromide, sodium iodide, sodium sulphate or its combination) replace.

In some embodiments, catholyte such as salt water, fresh water and/or sodium hydroxide does not include alkaline-earth metal ions Or bivalent cation.Bivalent cation as used herein includes alkaline-earth metal ions, such as, but not limited to calcium, magnesium, barium, strontium, Radium etc..In some embodiments, catholyte such as salt water, fresh water and/or sodium hydroxide includes the divalence less than 1%w/w Cation.In some embodiments, catholyte such as seawater, fresh water, salt solution, brackish water and/or sodium hydroxide is comprising low In 1%w/w bivalent cation.In some embodiments, catholyte for example seawater, fresh water, salt solution, brackish water and/or Sodium hydroxide includes bivalent cation, and the bivalent cation includes but is not limited to calcium, magnesium and combinations thereof.In some embodiments In, catholyte such as seawater, fresh water, salt solution, brackish water and/or sodium hydroxide include the bivalent cation less than 1%w/w, The bivalent cation includes but is not limited to calcium, magnesium and combinations thereof.

In some embodiments, catholyte such as seawater, fresh water, salt solution, brackish water and/or sodium hydroxide is comprising low In 1%w/w；Or less than 5%w/w；Or less than 10%w/w；Or less than 15%w/w；Or less than 20%w/w；Or less than 25%w/ w；Or less than 30%w/w；Or less than 40%w/w；Or less than 50%w/w；Or less than 60%w/w；Or less than 70%w/w；Or it is low In 80%w/w；Or less than 90%w/w；Or less than 95%w/w；Or 0.05-1%w/w；Or 0.5-1%w/w；Or 0.5-5%w/ w；Or 0.5-10%w/w；Or 0.5-20%w/w；Or 0.5-30%w/w；Or 0.5-40%w/w；Or 0.5-50%w/w；Or 0.5-60%w/w；Or 0.5-70%w/w；Or 0.5-80%w/w；Or 0.5-90%w/w；Or 5-8%w/w；Or 5-10%w/w； Or 5-20%w/w；Or 5-30%w/w；Or 5-40%w/w；Or 5-50%w/w；Or 5-60%w/w；Or 5-70%w/w；Or 5- 80%w/w；Or 5-90%w/w；Or 10-20%w/w；Or 10-30%w/w；Or 10-40%w/w；Or 10-50%w/w；Or 10- 60%w/w；Or 10-70%w/w；Or 10-80%w/w；Or 10-90%w/w；Or 30-40%w/w；Or 30-50%w/w；Or 30-60%w/w；Or 30-70%w/w；Or 30-80%w/w；Or 30-90%w/w；Or 50-60%w/w；Or 50-70%w/w； Or 50-80%w/w；Or 50-90%w/w；Or 75-80%w/w；Or 75-90%w/w；Or 80-90%w/w；Or 90-95%w/w Bivalent cation, the bivalent cation includes but is not limited to calcium, magnesium and combinations thereof.

In some embodiments, catholyte includes but is not limited to sodium hydroxide, sodium acid carbonate, sodium carbonate or its group Close.In some embodiments, catholyte includes but is not limited to sodium hydroxide or potassium hydroxide.In some embodiments In, catholyte includes but is not limited to sodium hydroxide, bivalent cation or its combination.In some embodiments, negative electrode electricity Solution matter includes but is not limited to sodium hydroxide, sodium acid carbonate, sodium carbonate, bivalent cation or its combination.In some embodiments, Catholyte includes but is not limited to sodium hydroxide, calcium bicarbonate, calcium carbonate, magnesium bicarbonate, magnesium carbonate, miemite or its group Close.In some embodiments, catholyte include but is not limited to salt water, sodium hydroxide, bicarbonate brine solution or its Combination.In some embodiments, catholyte includes but is not limited to salt water and sodium hydroxide.In some embodiments, Catholyte includes but is not limited to fresh water and sodium hydroxide.In some embodiments, catholyte include alkali or The fresh water of bivalent cation.In some embodiments, catholyte includes but is not limited to fresh water, sodium hydroxide, bicarbonate Sodium, sodium carbonate, bivalent cation or its combination.

In some embodiments, anodolyte includes but is not limited to fresh water and metal ion.In some embodiments In, anodolyte includes but is not limited to salt water and metal ion.In some embodiments, anodolyte include metal from Sub- solution.

In some embodiments, the salt water of the consumption from battery can be circulated back to battery.In some embodiments In, catholyte includes 1-90%；1-50%；Or 1-40%；Or 1-30%；Or 1-15%；Or 1-20%；Or 1-10%； Or 5-90%；Or 5-50%；Or 5-40%；Or 5-30%；Or 5-20%；Or 5-10%；Or 10-90%；Or 10-50%；Or 10-40%；Or 10-30%；Or 10-20%；Or 15-20%；Or 15-30%；Or 20-30% sodium hydroxide solution.One In a little embodiments, anodolyte includes 0-5M；Or 0-4.5M；Or 0-4M；Or 0-3.5M；Or 0-3M；Or 0-2.5M；Or 0- 2M；Or 0-1.5M；Or 0-1M；Or 1-5M；Or 1-4.5M；Or 1-4M；Or 1-3.5M；Or 1-3M；Or 1-2.5M；Or 1-2M；Or 1-1.5M；Or 2-5M；Or 2-4.5M；Or 2-4M；Or 2-3.5M；Or 2-3M；Or 2-2.5M；Or 3-5M；Or 3-4.5M；Or 3- 4M；Or 3-3.5M；Or 4-5M；Or 4.5-5M metal ion solution.In some embodiments, anode does not form oxygen. In some embodiments, anode does not form chlorine.

In some embodiments, catholyte and anodolyte be ion exchanged film partially or even wholly every Open.In some embodiments, amberplex is anion-exchange membrane or cation-exchange membrane.In some embodiments, Cation-exchange membrane in an electrochemical cell is conventional as disclosed herein, and can be from such as Tokyo Asahi Kasei or Membrane International of the Glen Rock, NJ or DuPont in the U.S. are obtained.CEM reality Example includes but is not limited to N2030WX (Dupont), F8020/F8080 (Flemion) and F6801 (Aciplex).The present invention's Preferable CEM has minimum resistance loss, the selectivity more than 90% and the height in dense corrosive agent in method and system Stability.AEM in the method and system of the present invention is exposed to dense metal salt anolyte and saturated salt current.Expect AEM Allow salt ion such as chlorion therethrough into anolyte but retain the species of metal ion from anolyte.One In a little embodiments, metal salt can form different kinds of ions species (cation, anion and/or neutral ion), including but not limit In MCl⁺、MCl₂ ^-、MCl₂ ⁰、M²⁺Deng, and it is expected that this kind of compound is not passed through AEM or not polluted membrane.One is provided in embodiment Carried out test for the method and system of the present invention a bit, find that it can prevent the film of metal spans.

Therefore, there is provided herein the method comprised the following steps：Make anode and the gold in anodolyte in the anode compartment Belong to contacted with ions；Metal ion is converted into higher oxidation state from low oxidation state at anode；Make in the cathodic compartment negative electrode with Catholyte is contacted；Alkali, water or hydrogen are formed at negative electrode；And by using anion-exchange membrane prevent metal ion from Anodolyte is migrated to catholyte, and wherein the anion-exchange membrane, which has, is less than 3 Ω cm²Or less than 2 Ω cm²Or less than 1 Ωcm²Ohmic resistance.In some embodiments, anion-exchange membrane has 1-3 Ω cm²Ohmic resistance.In some implementations There is provided the method comprised the following steps in scheme：Anode is set to be contacted with the metal ion in anodolyte in the anode compartment； Metal ion is converted into higher oxidation state from low oxidation state at anode；Negative electrode is set to be connect with catholyte in the cathodic compartment Touch；Alkali, water or hydrogen are formed at negative electrode；And by using anion-exchange membrane prevent metal ion from anodolyte to Catholyte migrate, wherein the anion-exchange membrane retention all metal ions from anodolyte in more than 80% Or more than 90% or more than 99% or about 99.9%.

Additionally providing includes the system of following component：The sun contacted in the anode compartment with the metal ion in anodolyte Pole, the wherein anode are configured as that metal ion is converted into higher oxidation state from low oxidation state in the anode compartment；In negative electrode The negative electrode contacted in room with catholyte, the wherein negative electrode are configured as forming alkali, water or hydrogen in the cathodic compartment；And it is cloudy Amberplex, the wherein anion-exchange membrane, which have, is less than 3 Ω cm²Or less than 2 Ω cm²Or less than 1 Ω cm²Ohmic resistance. In some embodiments, anion-exchange membrane has 1-3 Ω cm²Ohmic resistance.There is provided bag in some embodiments The system for including following component：The anode contacted in the anode compartment with the metal ion in anodolyte, the wherein anode by with It is set to and metal ion is converted into higher oxidation state from low oxidation state in the anode compartment；Connect in the cathodic compartment with catholyte Tactile negative electrode, the wherein negative electrode are configured as forming alkali, water or hydrogen in the cathodic compartment；And anion-exchange membrane, wherein should Anion-exchange membrane retention all metal ions from anodolyte in more than 80% or more than 90% or more than 99% Or about 99.9%.

The method comprised the following steps is also provided herein：Make in the anode compartment metal in anode and anodolyte from Son contact；Metal ion is converted into higher oxidation state from low oxidation state at anode；Make negative electrode and negative electrode in the cathodic compartment Electrolyte is contacted；Alkali is formed at negative electrode；Anodolyte is separated with salt solution compartment using anion-exchange membrane；Use cation Exchange membrane separates catholyte with salt solution compartment；And by using with less than 3 Ω cm²Or less than 2 Ω cm²Or less than 1 Ωcm²The anion-exchange membrane of Ohmic resistance prevents metal ion from being migrated from anodolyte to salt solution compartment.In some implementations In scheme, anion-exchange membrane has 1-3 Ω cm²Ohmic resistance.There is provided comprise the following steps in some embodiments Method：Anode is set to be contacted with the metal ion in anodolyte in the anode compartment；By metal ion from relatively low at anode Oxidation state is converted into higher oxidation state；Negative electrode is set to be contacted with catholyte in the cathodic compartment；Alkali is formed at negative electrode；Utilize the moon Amberplex separates anodolyte with salt solution compartment；With cation-exchange membrane by catholyte and salt solution compartment every Open；And by using retention all metal ions from anodolyte in more than 80% or more than 90% or exceed 99% or about 99.9% anion-exchange membrane prevents metal ion from being migrated from anodolyte to salt solution compartment.

Additionally providing includes the system of following component：The sun contacted in the anode compartment with the metal ion in anodolyte Pole, the wherein anode are configured as that metal ion is converted into higher oxidation state from low oxidation state in the anode compartment；In negative electrode The negative electrode contacted in room with catholyte, the wherein negative electrode are configured as forming alkali in the cathodic compartment；By anodolyte with The anion-exchange membrane that salt solution compartment is separated；And the cation-exchange membrane for separating catholyte and salt solution compartment, wherein The anion-exchange membrane, which has, is less than 3 Ω cm²Or less than 2 Ω cm²Or less than 1 Ω cm²Ohmic resistance.In some embodiments In, the anion-exchange membrane has 1-3 Ω cm²Ohmic resistance.There is provided including following component in some embodiments System：The anode contacted in the anode compartment with the metal ion in anodolyte, the wherein anode are configured as in anode chamber It is middle that metal ion is converted into higher oxidation state from low oxidation state；The negative electrode contacted in the cathodic compartment with catholyte, its In the negative electrode be configured as forming alkali in the cathodic compartment；The anion-exchange membrane that anodolyte and salt solution compartment are separated；With And the cation-exchange membrane for separating catholyte and salt solution compartment, wherein anion-exchange membrane retention is from anode electrolysis In all metal ions of matter more than 80% or more than 90% or more than 99% or about 99.9%.

The above-described method and system comprising AEM further comprises use hydrogen as described herein, unsaturated hydrocarbons or full The anodolyte of the metal ion in higher oxidation state is included with hydrocarbon processing.

The example of cation-exchange membrane includes but is not limited to by containing the complete of anionic group such as sulfonic group and/or carboxyl The cationic membrane of fluorinated polymer composition.However, in some embodiments, it will be appreciated that, according to limiting or allow specific The need for cation or anion species are migrated between electrolyte, it can be used restricted bigger and therefore allow a kind of cation Migration limits the cation-exchange membrane of another cation transport simultaneously, for example, can be used allows sodium ion from anodolyte Migrate to catholyte and migrated while limiting other ions from anodolyte to the cation-exchange membrane of catholyte.Together Sample, in some embodiments, according to limiting or allow the need for specific anion species migrate between electrolyte, to can be used It is restricted more simultaneously therefore to allow a kind of anion transport while limiting the anion-exchange membrane of another anion transport, example greatly Such as, can be used allows chlorion to be migrated from catholyte to anodolyte while limiting hydroxide ion from catholyte Migrate to the anion-exchange membrane of anodolyte.Such restricted cation-exchange membrane and/or anion-exchange membrane are can business What purchase was obtained, and can be selected by those of ordinary skill in the art.

In some embodiments there is provided a kind of system, it is included positioned at one or more between anode and negative electrode Anion-exchange membrane and cation-exchange membrane.In some embodiments, it should be chosen so that they can be in acid to film Suitably played a role in property and/or alkaline electrolyte solution.Other desired characteristics of film are included in 0 DEG C to 100 DEG C or higher At a temperature of macroion selectivity in acidic electrolyte solution, low ionic resistance, high bursting strength and high stability, Huo Zheke So that the alkaline solution in similar temperature range.In some embodiments, it is desirable that amberplex prevents metal ion Transported from anolyte to cathode electrode liquid.In some embodiments, 0 DEG C to 90 DEG C, or 0 DEG C to 80 DEG C are may be used at, Or 0 DEG C to 70 DEG C, or 0 DEG C to 60 DEG C, or 0 DEG C to 50 DEG C, or 0 DEG C to 40 DEG C, or 0 DEG C to 30 DEG C, or 0 DEG C to 20 DEG C, or 0 DEG C To 10 DEG C, or film stable in more high scope.In some embodiments, it may be used at 0 DEG C to 90 DEG C；Or 0 DEG C to 80 DEG C；Or 0 DEG C to 70 DEG C；Or 0 DEG C to 60 DEG C；Or 0 DEG C to 50 DEG C；Or it is stable but unstable at a higher temperature in the range of 0 DEG C to 40 DEG C Film.For other embodiments, using allowing a kind of cation transport without allowing another cationic ion to migrate, or allow A kind of anion transport without allow the ion specific ion exchange membrane of another anion transport be probably it is useful, with Product needed for a kind of product is obtained in electrolyte or be a variety of.In some embodiments, at 0 DEG C to 90 DEG C；Or 0 DEG C to 80 DEG C； Or 0 DEG C to 70 DEG C；Or 0 DEG C to 60 DEG C；Or 0 DEG C to 50 DEG C；Or 0 DEG C to 40 DEG C；Or 0 DEG C to 30 DEG C；Or 0 DEG C to 20 DEG C；Or 0 DEG C To 10 DEG C and higher and/or lower temperature, in systems in desired time span such as a couple of days, several weeks or several months or In several years, film can be stable and with functional.In some embodiments, for example, 100 DEG C, 90 DEG C, 80 DEG C, 70 DEG C, 60 DEG C, 50 DEG C, 40 DEG C, 30 DEG C, 20 DEG C, 10 DEG C, under 5 DEG C and higher or lower electrolyte temperature, at least 1 day, extremely Few 5 days, 10 days, 15 days, 20 days, 100 days, 1000 days, 5-10 or in the longer time, film can be stable and have a function Property.

The Ohmic resistance of film can influence the voltage drop between anode and negative electrode, for example, with the Ohmic resistance increase of film, sun Voltage between pole and negative electrode can increase, and vice versa.Workable film includes but is not limited to have relatively low Ohmic resistance The film of relatively high ionic mobility；And with the increased high hydration properties relatively with temperature and therefore ohm electricity Hinder the film of reduction.By selecting the film known in the art having compared with low ohmic resistance, it is possible to decrease anode at a certain temperature Voltage drop between negative electrode.

Ion channel including acid group may be interspersed within film.These ion channels can extend to outer from the inner surface of matrix Surface, and acid group can easily turn into hydrate water in reversible reaction with reference to water.The knot of this water as hydrate water Conjunction can follow first-order kinetics so that reaction rate is directly proportional to temperature.Therefore, film may be selected relatively low to provide Ohmic resistance and ionic resistance, while providing improved intensity and resistance in operating temperature range built-in system.

In some embodiments, when being contacted with the catholyte in cathode chamber, carbon and hydroxyl from carbon source Ionic reaction and water and carbanion are produced according to the pH of catholyte.Carbon from carbon source is added into catholyte In can reduce the pH of catholyte.Therefore, the basicity according to needed for catholyte, the pH of adjustable cathode electrolyte, And 6-12 in some embodiments, can be held it in；7-14 or higher；Or 7-13；Or 7-12；Or 7-11；Or 7-10； Or 7-9；Or 7-8；Or 8-14 or higher；Or 8-13；Or 8-12；Or 8-11；Or 8-10；Or 8-9；Or 9-14 or higher；Or 9- 13；Or 9-12；Or 9-11；Or 9-10；Or 10-14 or higher；Or 10-13；Or 10-12；Or 10-11；Or 11-14 or higher； Or 11-13；Or 11-12；Or 12-14 or higher；Or 12-13；Or 13-14 or higher.In some embodiments, can be by negative electrode The pH of electrolyte is adjusted to any value between 7-14 or higher, the pH less than 12, pH 7.0,7.5,8.0,8.5,9.0,9.5, 10.0th, 10.5,11.0,11.5,12.0,12.5,13.0,13.5,14.0 and/or higher.

Equally, in some embodiments of the system, adjust the pH of anodolyte and hold it in 0-7；Or 0-6；Or 0-5；Or 0-4；Or 0-3；Or 0-2；Or 0-1.Voltage between anode and negative electrode can be dependent on several factors, including sun PH poor (being determined such as by Nernst equation well known in the art) between pole electrolyte and catholyte, therefore one In a little embodiments, operating voltage that can be according to needed between anode and negative electrode adjusts the pH of anodolyte to 0-7 value, Including 0,0.5,1.0,1.5,2.0,2.5,3.0,3.5,4.0,4.5,5.0,5.5,6.0,6.5 and 7.Therefore, it is desirable that reducing In the equivalent system of voltage between the energy and/or reduction anode and negative electrode that use, for example, such as in chlor-alkali, can be in the future Added to from the carbon of carbon source in catholyte as disclosed herein, so as to be obtained between anodolyte and catholyte Required pH is poor.

The system can be configured as by hydrogen in the pH, the pH of catholyte, catholyte that adjust anodolyte The concentration of oxide, the taking-up of anodolyte or supplement, the taking-up of catholyte or supplement and/or addition catholyte In the carbon from carbon source amount, and it is poor that any required pH is produced between anodolyte and catholyte.By adjusting The pH saved between anodolyte and catholyte is poor, can adjust the voltage between anode and negative electrode.In some embodiment party In case, the system is configured as between anodolyte and catholyte producing at least four pH units；At least five pH is mono- Position；At least six pH units；At least seven pH units；At least eight pH units；At least nine pH units；At least ten pH units；Extremely Few 11 pH units；At least 12 pH units；At least 13 pH units；At least 14 pH units；Or 4-12 pH unit；Or 4- 11 pH units；Or 4-10 pH unit；Or 4-9 pH unit；Or 4-8 pH unit；Or 4-7 pH unit；Or 4-6 pH Unit；Or 4-5 pH unit；Or 3-12 pH unit；Or 3-11 pH unit；Or 3-10 pH unit；Or 3-9 pH is mono- Position；Or 3-8 pH unit；Or 3-7 pH unit；Or 3-6 pH unit；Or 3-5 pH unit；Or 3-4 pH unit；Or 5- 12 pH units；Or 5-11 pH unit；Or 5-10 pH unit；Or 5-9 pH unit；Or 5-8 pH unit；Or 5-7 PH units；Or 5-6 pH unit；Or 6-12 pH unit；Or 6-11 pH unit；Or 6-10 pH unit；Or 6-9 pH is mono- Position；Or 6-8 pH unit；Or 6-7 pH unit；Or 7-12 pH unit；Or 7-11 pH unit；Or 7-10 pH unit； Or 7-9 pH unit；Or 7-8 pH unit；Or 8-12 pH unit；Or 8-11 pH unit；Or 8-10 pH unit；Or 8- 9 pH units；Or 9-12 pH unit；Or 9-11 pH unit；Or 9-10 pH unit；Or 10-12 pH unit；Or 10- 11 pH units；Or the pH of 11-12 pH unit is poor.In some embodiments, the system is configured as in anodolyte The pH that at least four pH units are produced between catholyte is poor.

In some embodiments, provided herein is method and system in, anodolyte in electrochemical cell and Catholyte at room or elevated temperature, such as higher than 40 DEG C, or higher than 50 DEG C, or higher than 60 DEG C, or higher than 70 DEG C, or operated higher than at 80 DEG C, or 30-70 DEG C.

The generation of bicarbonate and/or carbonate product

In some embodiments, provided herein is method and system be configured as processing catholyte with from carbon The carbonate/bicarbonate solution obtained after the carbon contact in source.In some embodiments, with such as, but not limited to calcium and/or Solution of the bivalent cation processing containing carbonate and/or bicarbonate of magnesium, thus formed calcium carbonate and/or magnesium carbonate and/ Or calcium bicarbonate and/or magnesium bicarbonate.An exemplary of this class process is provided in fig. 13.

As shown in Figure 13, process 1300 illustrates to obtain after catholyte is contacted with the carbon from carbon source for handling The method and system of the carbonate/bicarbonate solution obtained.In some embodiments, solution undergoes heavy in settling vessel 1301 Form sediment.In some embodiments, solution includes sodium hydroxide, sodium carbonate and/or sodium acid carbonate.In some embodiments, should System is configured to, with alkaline-earth metal ions or bivalent cation (including but is not limited to calcium, magnesium and combinations thereof) processing negative electrode electricity Solve the bicarbonate ion and/or carbanion in matter.As used herein " bivalent cation " include containing divalence sun from Any solid or solution of son such as alkaline-earth metal ions, or any aqueous medium containing alkaline-earth metal.Alkaline-earth metal include calcium, Magnesium, strontium, barium etc. or its combination.Bivalent cation is (for example, alkaline earth metal cation, such as Ca²⁺And Mg²⁺) be found in industrial waste, In seawater, salt solution, hard water, mineral matter and many other suitable sources.According to the method using water, the water containing alkaline-earth metal Including fresh water or salt water.In some embodiments, the water used in this process includes one or more alkaline-earth metal, example Such as, magnesium, calcium etc..In some embodiments, the content of alkaline-earth metal ions is the 1%- of the solution containing alkaline-earth metal ions 99%wt；Or 1%-95%wt；Or 1%-90%wt；Or 1%-80%wt；Or 1%-70%wt；Or 1%-60%wt；Or 1%-50%wt；Or 1%-40%wt；Or 1%-30%wt；Or 1%-20%wt；Or 1%-10%wt；Or 20%-95%wt； Or 20%-80%wt；Or 20%-50%wt；Or 50%-95%wt；Or 50%-80%wt；Or 50%-75%wt；Or 75%- 90%wt；Or 75%-80%wt；Or 80%-90%wt.In some embodiments, alkaline-earth metal ions are present in salt water such as In seawater.In some embodiments, bivalent cation source is hard water or naturally occurring kieserohalosylvite water.In some embodiments In, the water rich in calcium can be combined with magnesium silicate mineral such as olivine or serpentine.

In some embodiments, gypsum (for example, from ammonia-soda process (Solvay process)) provide divalence sun from Son (such as, but not limited to calcium ion) source.Use the carbonate/bicarbonate solution from cathode chamber and the calcium from gypsum After winnofil/calcium bicarbonate, the supernatant containing sodium sulphate can be made to be recycled in electro-chemical systems as described herein.Sulphur Acid sodium solution can be used in combination with metal sulfate such as copper sulphate so that Cu (I) ion is oxidized to Cu (II) in the anode compartment Ion, and it is further used for the sulfonation of hydrogen or the sulfonation for unsaturated hydrocarbons or saturated hydrocarbons.In such embodiments, Electro-chemical systems are fully integrated with precipitation process.The U.S. that gypsum was submitted on the 3rd as this purposes of calcium source in August in 2011 It is described in provisional application 61/514,879, this application is incorporated herein by reference in their entirety.

In some places, (and in some cases, the industrial Waste Stream from multiple industrial process provides cation Useful other materials, such as metal hydroxides in this process) convenient source.This kind of waste stream includes but is not limited to Mining wastes；Combustion of fossil fuel ash content (for example, flying dust, bottom ash, boiler slag)；Clinker (for example, scum, phosphorus slag)；Cement kiln Waste (for example, cement kiln dust)；Oil plant/petrochemical refinery factory refuse (for example, oil field and methane layer salt solution)；Coal seam refuse (for example, aerogenesis salt solution and coal seam salt solution)；Paper conversion refuse；Water softens effluent brine (for example, ion exchange efflux)；Silicon is processed Waste；Agricultural wastes；Intermetallic composite coating waste；High pH weavings waste；And alkaline residue.In some embodiments, the water of cation Solution includes 10-50,000ppm；Or 10-10,000ppm；Or 10-5,000ppm；Or 10-1,000ppm；Or 10-100ppm； Or 50-50,000ppm；Or 50-10,000ppm；Or 50-1,000ppm；Or 50-100ppm；Or 100-50,000ppm；Or 100-10,000ppm；Or 100-1,000ppm；Or 100-500ppm；Or 1,000-50,000ppm；Or 1,000-10, 000ppm；Or 5,000-50,000ppm；Or 5,000-10,000ppm；Or the calcium and/or magnesium of 10,000-50,000ppm contents.

Fresh water can be cation (for example, alkaline earth metal cation, such as Ca²⁺And Mg²⁺) Suitable sources.It can use Many suitable freshwater sources, including the freshwater source from the relative source without mineral matter to the relative source rich in mineral matter.It is rich in The freshwater source of mineral matter can be naturally occurring, including many hard water sources, lake or interior marine any one.Some are rich in ore deposit The freshwater source of material such as alkaline lake or inland sea (for example, LakeVan (Lake Van) of Turkey) additionally provide pH modifying agent Source.Freshwater source rich in mineral matter can also be artificial.For example, poor (soft) water of mineral matter can be with cation such as alkaline earth gold Belong to cation (for example, Ca²⁺、Mg²⁺Deng) source contact, with produce suitable method described herein and system rich in mineral matter Water.Can be used any convenient scheme (for example, addition solid, suspension or solution) by cation or its precursor (for example, salt, Mineral matter) add into fresh water (or water of any other type as described herein).In some embodiments, Ca will be selected from²⁺ And Mg²⁺Bivalent cation add fresh water in.In some embodiments, containing Ca²⁺Fresh water and magnesium silicate (for example Olivine or serpentine) or its product or form processing combination, produce the solution containing calcium and magnesium cation.

The sediment including but not limited to carbon that carbon from carbon source is obtained after being contacted with catholyte and bivalent cation Sour calcium, magnesium carbonate, calcium bicarbonate, magnesium bicarbonate, miemite or its combination.In some embodiments, sediment can undergo One or more steps, including but not limited to mixing, stirring, temperature, pH, precipitation, the holdup time of sediment, sediment it is de- Water, sediment, ion ratio, the concentration of additive, drying, crushing, grinding, storage, aging and solidification is washed with water, to be made The carbonate composition of the present invention.In some embodiments, deposition condition causes carbonate product to be metastable state form, for example But it is not limited to vaterite, aragonite, amorphous calcium carbonate or its combination.

Settling vessel 1301 can be a tank or a series of tanks.Contact scheme includes but is not limited to direct contact scheme, example Such as, make certain volume water containing cation such as alkaline-earth metal ions flow through certain volume containing sodium hydroxide Catholyte；Current contacting method, for example, being contacted between the liquid phase stream of one-way flow；And countercurrent method, for example, Contact, etc. between the liquid phase stream of reverse flow.Accordingly, it is possible to it is expedient to, can be by using injector, bubbler, jet Venturi reactor, sprayer, pneumatic filter, injector, pallet or filling column type reactor etc. complete contact.In some implementations In scheme, contact is by injection.In some embodiments, contact is by packed column.In some embodiments, in the future It is added to from the carbon of carbon source in cationic source and catholyte containing hydroxide.In some embodiments, by sun from Component is added in the carbon from carbon source with the catholyte containing alkali.In some embodiments, for the heavy of precipitation Both carbon in the device of shallow lake by cationic source and from carbon source is added in the catholyte containing alkali simultaneously.

The carbon from carbon source is added in some embodiments in the catholyte in cathode chamber, hydrogen will be included The catholyte of the taking-up of oxide, bicarbonate and/or carbonate is fed in settling vessel to enter with bivalent cation Single step reaction.In some embodiment party for having added to carbon and bivalent cation from carbon source in the catholyte in cathode chamber In case, by including sodium hydroxide, calcium carbonate, magnesium carbonate, calcium bicarbonate, magnesium bicarbonate, miemite or the taking-up of its combination Catholyte is fed in settling vessel for further processing.

Settling vessel containing calcium carbonate, magnesium carbonate, calcium bicarbonate, magnesium bicarbonate, miemite or the solution of its combination 1301 are subjected to deposition condition.In settling step, carbonate compound is precipitated, and it can be unbodied or crystallization. The reaction product that these carbonate compounds can be formed including carbonic acid, bicarbonate, carbonate or its mixture.Carbonate Sediment can, from binding composition, and can be stored in as former state in mother liquor, or can further handle that cement is made Product.Or, sediment can be subjected to further processing and be combined with obtaining water cement or complementary cementing material (SCM) Thing.From the U.S. of binding composition, water cement and the SCM Serial No. 12/857,248 submitted for 16th in August in 2010 It is described in application, this application is entirely incorporated by reference in this disclosure.

One or more conditions interested or one or more deposition conditions include changing the physical environment of water producing Those conditions of raw required precipitated product.Such one or more conditions or deposition condition include but is not limited to, temperature, One or more of pH, precipitation, the dehydration of sediment or separation, drying, crushing and storage.For example, water temperature can be adapted to hair In the range of the precipitation of composition needed for raw.For example, water temperature can be improved to the precipitation of the carbonate compound to needed for suitable generation Level.In such embodiments, water temperature can be 5-70 DEG C, such as 20-50 DEG C, including 25-45 DEG C.Equally, although given A group precipitation condition can have 0-100 DEG C of temperature, but in certain embodiments, temperature can be raised with needed for producing Sediment.In certain embodiments, using by low or zero CO2 emission source, such as solar energy source, wind energy, water The energy of the generations such as electric energy raises temperature.

Holdup time of the sediment in settling vessel can be different before sediment is taken out from solution.In some implementations In scheme, the holdup time of sediment in the solution more than 5 seconds, or for 5 seconds to 1 hour, or 5 seconds to 1 minute, or 5 seconds to 20 Second, or 5 seconds to 30 seconds, or 5 seconds to 40 seconds.System not limited by any theory, it is contemplated that the holdup time of sediment can influence particle Size.For example, the shorter holdup time can obtain the particle or more dispersed particle of reduced size, and the longer holdup time Particle can be condensed or large-size.In some embodiments, the holdup time in process of the invention can be used for Single batch or many batches manufacture small size and large-sized particle, these particles can separate or can keep mixing for the process Afterwards the step of.

The property of sediment can also be influenceed by the selection of appropriate leading ion ratio.Leading ion ratio can influence polycrystalline The formation of type thing so that carbonate product is metastable state form, such as, but not limited to vaterite, aragonite, amorphous calcium carbonate or It is combined.In some embodiments, carbonate product may also include calcite.This kind of polymorphic sediment is in August, 2010 It is described in the U. S. application for the Serial No. 12/857,248 submitted for 16th, this application is integrally incorporated the disclosure by quoting In content.For example, magnesium can stabilize vaterite and/or amorphous calcium carbonate in sediment.Settling rate can also influence chemical combination The formation of thing polymorphic phase, and can be controlled in the way of being enough precipitated product needed for producing.By using required polycrystalline Type relative solution carries out seeding, it is possible to achieve most fast precipitation., can be by quickly increasing the pH of seawater in the case of not seeding To realize rapid precipitation.PH is higher, and precipitation can be faster.

In some embodiments, one group from water produce needed for sediment condition include but is not limited to water temperature and Ionic species in pH, and the concentration and water of (in some cases) additive.Deposition condition, which may also include, such as mixes speed The factor of rate, whipped form (as ultrasound) and crystal seed, catalyst, the presence of film or substrate etc.In some embodiments, Deposition condition includes supersaturated condition, temperature, pH and/or concentration gradient, or circulation or these any parameters of change.According to this It can be scheme or continuous scheme in batches to invent the scheme for preparing carbonate compound precipitation thing.It will be appreciated that, even It is probably different compared with batch system that the deposition condition of given sediment is produced in continuous running system.

As shown in Figure 13 step 1302, produced from water after carbonate sediment, can be by the carbonate of obtained precipitation Composition separates or is dehydrated to produce sediment product from mother liquor.Or, sediment is stayed in into mother liquor or mother liquor supernatant as former state In liquid, and it is used as binding composition.Any convenient method can be used to realize the separation of sediment, methods described includes Mechanical means, for example, most of excessive water is discharged from precipitation, for example, passes through single gravity or applying vacuum, machinery Pressurization, by from mother liquor filtering precipitate to produce filtrate etc..The separation of a large amount of water produces wet dehydration lees.Dehydrating plant Can be any amount of dehydrating plant being connected to each other so that dewatering slurries (for example, parallel, series connection or its combination).

Such scheme causes the generation of sediment slurries and mother liquor.This sediment in mother liquor and/or slurries can be produced It is born from binding composition.In some embodiments, part or all of dehydration lees or slurries are further handled to make Standby water cement or SCM compositions.

When needed, can be after precipitation and the composition being made up of sediment and mother liquor is stored one section by further before processing Time.For example, composition can store 1-1000 days or longer a period of time, such as 1- at a temperature of 1-40 DEG C such as 20-25 DEG C 10 days or longer.

Slurry constituents can be separated afterwards.Embodiment may include the processing of mother liquor, wherein mother liquor can exist with product or It is not present in identical composition.Any suitable scheme can be used to handle for obtained reaction mother liquor.In some embodiment party In case, tailings pond 1307 can be passed to and handled.In certain embodiments, can be by it in naturally occurring water body, example As handled in ocean, sea, lake or river.In certain embodiments, mother liquor is returned to the feedwater of the inventive method Source, such as ocean or sea.Or, mother liquor can be further subjected to processing, for example, being subjected to as submitted on June 27th, 2008 The desalination scheme further described in the U. S. application of Serial No. 12/163,205；This public affairs is incorporated herein by reference in this application Open in content.

The dehydration lees being dried to obtain afterwards as shown in Figure 13 step 1304 with produce the present invention carbonate combination Thing.Drying can be completed by air-drying sediment.When air-drying sediment, air-drying can be as needed in -70-120 DEG C of temperature Degree is lower to be carried out.In certain embodiments, drying is realized by being freeze-dried (i.e. desivac), when freezing precipitation thing, drop Ambient pressure simultaneously adds enough heats, to cause the water freezed in material mutually directly to be distilled from the sediment of freezing as gas Body.In still another embodiment, sediment is spray-dried with dry sediment, wherein the liquid containing sediment is It is dried by being conveyed through hot gas (the off-gas stream of the spontaneous power plant of Tathagata), for example, wherein passing through spray Liquid material is pumped to main hothouse by day with fog, and hot gas passes through relative to sprayer direction cocurrent or countercurrent.According to being The specific drying proposal of system, dry station may include filter element, freeze-drying structure, spray-dried structure etc..Drying steps can Discharge air and fines 1306.

In some embodiments, spray drying step may include the separation of different size of precipitate particles.Such as Figure 13 Step 1303 shown in, when needed, the washable sediment product from 1302 dehydration before the drying.It can be washed with fresh water Sediment is washed, for example, to remove desalination (such as NaCl) from the sediment of dehydration., can be by used slurry if convenient Handled, for example, by being processed in tailings pond.Slurry can contain the metals such as iron, nickel.

In some embodiments, dry sediment refined, crushed, aging and/or solidification (are such as walked refined Shown in rapid 1305), for example, with the physical property needed for offer, such as granularity, surface area, eletrokinetic potential (zeta Potential) etc., or into sediment add one or more compositions, such as adulterating agent, gather materials, complementary cementing material, with Produce carbonate composition.It is refined to may include a variety of different schemes.In certain embodiments, product experience machine finish, For example, grinding, so as to obtain the product with required physical property such as granularity.Dry sediment can be crushed or ground Grind to obtain required granularity.

In some embodiments, metastable state shape is in by the lime deposit of the method and system formation of the present invention Formula, including but not limited to vaterite, aragonite, amorphous calcium carbonate or its combination.In some embodiments, pass through the present invention's Method and system formation lime deposit be in metastable state form, including but not limited to vaterite, amorphous calcium carbonate or It is combined.Calcium carbonate composition containing vaterite is converted into the polycrystalline of the stabilization with high compression-strength after being contacted with water Type thing form, such as aragonite, calcite or its combination.

The carbonate composition or binding composition being thusly-formed have the carbon from carbon source for coming from and being used during this Element or mark.Carbonate composition has at least 14MPa after solidification (setting) and hardening；Or at least 16MPa； Or at least 18MPa；Or at least 20MPa；Or at least 25MPa；Or at least 30MPa；Or at least 35MPa；Or at least 40MPa；Or extremely Few 45MPa；Or at least 50MPa；Or at least 55MPa；Or at least 60MPa；Or at least 65MPa；Or at least 70MPa；Or at least 75MPa；Or at least 80MPa；Or at least 85MPa；Or at least 90MPa；Or at least 95MPa；Or at least 100MPa；Or 14- 100MPa；Or 14-80MPa；Or 14-75MPa；Or 14-70MPa；Or 14-65MPa；Or 14-60MPa；Or 14-55MPa；Or 14-50MPa；Or 14-45MPa；Or 14-40MPa；Or 14-35MPa；Or 14-30MPa；Or 14-25MPa；Or 14-20MPa；Or 14-18MPa；Or 14-16MPa；Or 17-35MPa；Or 17-30MPa；Or 17-25MPa；Or 17-20MPa；Or 17-18MPa；Or 20-100MPa；Or 20-90MPa；Or 20-80MPa；Or 20-75MPa；Or 20-70MPa；Or 20-65MPa；Or 20-60MPa； Or 20-55MPa；Or 20-50MPa；Or 20-45MPa；Or 20-40MPa；Or 20-35MPa；Or 20-30MPa；Or 20-25MPa； Or 30-100MPa；Or 30-90MPa；Or 30-80MPa；Or 30-75MPa；Or 30-70MPa；Or 30-65MPa；Or 30- 60MPa；Or 30-55MPa；Or 30-50MPa；Or 30-45MPa；Or 30-40MPa；Or 30-35MPa；Or 40-100MPa；Or 40-90MPa；Or 40-80MPa；Or 40-75MPa；Or 40-70MPa；Or 40-65MPa；Or 40-60MPa；Or 40-55MPa；Or 40-50MPa；Or 40-45MPa；Or 50-100MPa；Or 50-90MPa；Or 50-80MPa；Or 50-75MPa；Or 50-70MPa； Or 50-65MPa；Or 50-60MPa；Or 50-55MPa；Or 60-100MPa；Or 60-90MPa；Or 60-80MPa；Or 60- 75MPa；Or 60-70MPa；Or 60-65MPa；Or 70-100MPa；Or 70-90MPa；Or 70-80MPa；Or 70-75MPa；Or 80-100MPa；Or 80-90MPa；Or 80-85MPa；Or 90-100MPa；Or 90-95MPa；Or 14MPa；Or 16MPa；Or 18MPa；Or 20MPa；Or 25MPa；Or 30MPa；Or 35MPa；Or 40MPa；Or 45MPa compressive strength.For example, in foregoing side In some embodiments of face and foregoing embodiments, composition has 14MPa-40MPa after solidification and hardening；Or 17MPa-40MPa；Or 20MPa-40MPa；Or 30MPa-40MPa；Or 35MPa-40MPa compressive strength.In some embodiment party In case, compressive strength as described herein is the compressive strength after 1 day or 3 days or 7 days or 28 days.

In some embodiments, the sediment comprising such as calcium carbonate and magnesium carbonate and calcium bicarbonate and magnesium bicarbonate It can be used as construction material, for example, as cement and gather materials, the commonly assigned United States Patent (USP) such as submitted on May 23rd, 2008 Application 12/126, described in 776, this application is incorporated herein by reference in their entirety in this disclosure.

There is provided following examples be in order to those of ordinary skill in the art provide on how to implement and using the present invention Entire disclosure and description, and be not intended to limit the present inventor be considered as its invention scope, be also not intended to expression with Lower experiment is all experiments or only experiment carried out.Based on preceding description and accompanying drawing, in addition to content as described herein, Various modifications to the present invention also will be apparent to those skilled in the art.These modifications fall in appended right It is required that in the range of.Make efforts to ensure the degree of accuracy of numeral (such as amount, temperature) used, it is contemplated that some Experimental error and deviation.Unless otherwise indicated, number is parts by weight, and molecular weight is weight average molecular weight, temperature for degree Celsius, and Pressure is atmospheric pressure or close to atmospheric pressure.

Neutralized elsewhere in embodiment, abbreviation has following meanings：

The invention provides including but not limited to embodiments below：

1. a kind of method, including：

Anode is set to be contacted with anodolyte, wherein the anodolyte includes metal ion；

The metal ion is oxidized to higher oxidation state from low oxidation state at the anode；

Negative electrode is set to be contacted with catholyte；

Make unsaturated hydrocarbons or saturated hydrocarbons with the anodolyte comprising the metal ion in higher oxidation state in water Property medium in react, with the aqueous medium formation comprising halogenated hydrocarbons one or more organic compounds and in relatively low The metal ion of oxidation state；And

By one or more organic compounds from aqueous Jie comprising the metal ion in low oxidation state Separated in matter.

2. the method according to embodiment 1, it further comprises the institute comprising the metal ion in low oxidation state Aqueous medium is stated to be recycled back into the anodolyte.

3. the method according to embodiment 1 or 2, wherein the aqueous medium includes 5-95wt% water.

4. the method according to any one of foregoing embodiments, its further comprise being formed at the negative electrode alkali, water or Hydrogen.

5. the method according to any one of foregoing embodiments, wherein the metal ion be selected from iron, chromium, copper, tin, silver, Cobalt, uranium, lead, mercury, vanadium, bismuth, titanium, ruthenium, osmium, europium, zinc, cadmium, gold, nickel, palladium, platinum, rhodium, iridium, manganese, technetium, rhenium, molybdenum, tungsten, niobium, tantalum, Zirconium, hafnium and combinations thereof.

6. the method according to any one of foregoing embodiments, wherein the metal ion is selected from iron, chromium, copper and tin.

7. the method according to any one of foregoing embodiments, wherein the metal ion is from Cu⁺It is converted into Cu²⁺'s Copper, the metal ion is from Fe²⁺It is converted into Fe³⁺Iron, the metal ion is from Sn²⁺It is converted into Sn⁴⁺Tin, the gold It is from Cr to belong to ion²⁺It is converted into Cr³⁺Chromium, the metal ion is from Pt²⁺It is converted into Pt⁴⁺Platinum, or its combination.

8. the method according to any one of foregoing embodiments, wherein the unsaturated hydrocarbons is compound of formula I, it is in halogenation Production II compounds afterwards：

Wherein, n is 2-10；M is 0-5；And q is 1-5；

X is the halogen selected from chlorine, bromine and iodine.

9. the method according to embodiment 8, wherein the compound of formula I is ethene, propylene or butylene, and the Formula II Compound is respectively ethylene dichloride, propylene dichloride or 1,4- dichloroetane.

10. the method according to any one of foregoing embodiments, wherein one or more organic compounds are further Including chlorethanol, dichloro acetaldehyde, trichloroacetaldehyde or its combination.

11. the method according to any one of foregoing embodiments, wherein by one or more organic compounds from bag The step of aqueous medium separation containing the metal ion in low oxidation state is including the use of adsorbent.

12. the method according to embodiment 11, wherein the adsorbent be selected from activated carbon, it is alumina, active silica, poly- Compound and combinations thereof.

13. the method according to embodiment 11 or 12, wherein the adsorbent is to be selected from polyethylene, polypropylene, polyphenyl second Alkene, polymethylpentene, PB Polybutene-1, polyolefin elastomer, polyisobutene, ethylene propylene rubber, PMA, poly- (first Base methyl acrylate), the polyolefin of poly- (Isobutyl methacrylate) and combinations thereof.

14. the method according to any one of embodiment 11-13, wherein the adsorbent is polystyrene.

15. the method according to any one of embodiment 11-14, wherein adsorbent absorption having more than 95%w/w Machine compound.

16. the method according to any one of embodiment 11-15, its further comprise using purged selected from inert fluid, Change electrochemical conditions, improve the technology regeneration of temperature, reduction partial pressure, reduction concentration, inert gas or steam blowing and combinations thereof The adsorbent.

17. the method according to any one of foregoing embodiments, it further comprises providing in the anodolyte Turbulent flow is to improve the mass transfer at anode.

18. the method according to any one of foregoing embodiments, it further comprises making diffusion-enhanced anode and the sun Pole electrolyte contact.

19. a kind of system, comprising：

The anode contacted with the anodolyte comprising metal ion, wherein the anode be configured as by the metal ion from Low oxidation state is oxidized to higher oxidation state；

The negative electrode contacted with catholyte；

Reactor, it is operably coupled to anode chamber, and is configured as making comprising the metal for being in higher oxidation state The anodolyte of ion reacts in an aqueous medium with unsaturated hydrocarbons or saturated hydrocarbons, to be formed in the aqueous medium One or more organic compounds comprising halogenated hydrocarbons and the metal ion in low oxidation state, and

Separator, it is operably coupled to the reactor and the anode, and is configured as the one or more Organic compound is separated from the aqueous medium comprising the metal ion in low oxidation state.

20. the system according to embodiment 19, wherein the separator further includes recirculating system, the recycling system System is operably coupled to the anode to recycle the aqueous medium comprising the metal ion in low oxidation state To the anodolyte.

21. the system according to embodiment 19 or 20, wherein the anode is diffusion-enhanced anode.

22. the system according to any one of embodiment 19-21, wherein the separator include selected from activated carbon, alumina, The adsorbent of active silica, polymer and combinations thereof.

23. the system according to any one of embodiment 19-22, wherein the metal ion is copper.

24. the system according to any one of embodiment 19-23, wherein the unsaturated hydrocarbons is ethene, and described one kind Or a variety of organic compounds are selected from ethylene dichloride, chlorethanol, dichloro acetaldehyde, trichloroacetaldehyde and combinations thereof.

25. the system according to any one of embodiment 19-24, wherein the separator is one or more to include polyphenyl The filling column of ethene.

Embodiment

Embodiment 1

Halogenated hydrocarbons is formed by unsaturated hydrocarbons

EDC is formed by ethene using copper chloride

This experiment is directed to use with copper chloride and forms ethylene dichloride (EDC) by ethene.This experiment is carried out in pressure vessel. It is the outer layer chuck of copper chloride solution and for ethylene gas to be blasted into copper chloride solution that the pressure vessel, which is included containing catalyst, In air inlet.The concentration of reactant is as shown in following table 1.Pressure vessel is heated to 160 DEG C in this experiment, and Ethylene gas 30min to 1hr is passed through into the container containing 200mL solution under 300psi.By container before being vented and opening It is cooled to 4 DEG C.The product formed in solution is extracted with ethyl acetate, is separated afterwards using separatory funnel.To the acetic acid containing EDC Ethyl ester extract carries out gas chromatographic analysis (GC).

Table 1

Dichloropropane is formed by propylene using copper chloride

This experiment is directed to use with copper chloride and forms 1,2- dichloropropanes (DCP) by propylene.This experiment is entered in pressure vessel OK.It is the outer layer chuck of copper chloride solution and molten for propylene gas to be blasted into copper chloride that the pressure vessel, which is included containing catalyst, Air inlet in liquid.By 150mL 5M CuCl₂, 0.5M CuCl, 1M NaCl and 0.03M HCl solution be placed in 450mL liners In the stirring pressure vessel of glass.With N₂Purge after the closed container, be heated to 160 DEG C.Reach after the temperature, by third Alkene adds in container that the pressure rise of self-generated pressure (mainly due to vapor) will be come to 130psig pressure.15 points Zhong Hou, adds more propylene pressure is increased into 140psig from 120psig.After after 15 minutes, pressure is 135psig. Now, reactor is cooled to 14 DEG C, depressurizes and open.Using ethyl acetate rinse reactor parts, extraction is used as afterwards Take solvent.By gas chromatography analysis product, it is shown in 1, the 2- dichloropropanes that 0.203g has been reclaimed in ethyl acetate phase.

Embodiment 2

Recycling of the aqueous phase from catalytic reactor to electro-chemical systems

This example illustrates the Cu produced from catalytic reactor (I) solution to containing PtIr net electrodes (gauze Electrode the recycling of electrochemical cell).4.5M Cu (II), 0.1M Cu (I) and 1.0M NaCl solution will be contained It is fitted into Parr bomb reactors and reacts 60min under 160 DEG C and 330psi.Pass through anode before and after being catalyzed Cyclic voltammetry (CV) tests same solution to seek the influence of organic residue such as EDC or residual extractant to anode performance. Each CV experiments are in 70 DEG C and 10mVs^-1Sweep speed under carry out five circulation, be relative to saturated calomel electrode (SCE) 0.3-0.8V。

Figure 14 shows before and after catalysis the PtIr net electrodes obtained in (before and after being respectively labeled as) solution (6cm²) V/I response.As shown in figure 14, as desired by for the increased Nernst equation of Cu (I) concentration, redox Potential (voltage in zero current) is changed into voltage after relatively low catalysis.The increase of Cu (I) concentration is due in catalytic reaction Period EDC generation and Cu (I) regeneration.Due to the mass transfer and limit in low Cu (I) concentration, before catalysis, CV curves, which reach, connects Nearly 0.5A carrying current.The Cu (I) indicated during operation is catalyzed that significantly improves of dynamic behavior is generated after catalysis, Precipitous linear I/V slopes are shown as in Figure 14, without the electric current that reaches capacity.What is obtained after catalysis in CV is typical reversible I/V curves show that residual EDC or other organic matters are substantially without negative effect.

Embodiment 3

The bubbling of air in anodal compartment

This example illustrates the reduction of the cell voltage when air bubbling around anode.As described herein, air exists Circulation in anodal compartment improves the mass transfer at anode, so as to reduce cell voltage.

The solution for being introduced to fuel cell be 0.9M Cu (I), 4.5M Cu (II) and 2.5M NaCl anolytes and 10wt%NaOH catholytes.Anion-exchange membrane is FAS-PK-130.The flow velocity of anolyte is 1.7l/min and sun The spacing of pole and rear wall is 3mm.In the side of anode using fishing net so that anode to be separated with anion-exchange membrane.Such as Figure 15 institutes Show, when each bubble enters anodal compartment, voltage declines 100-200mV.

Embodiment 4

Influence of the geometry of anode to cell voltage

This example illustrates compared with using flat expanded anode, battery is electric when in the battery using corrugated anode The decline of pressure.

The solution for being introduced to fuel cell be 0.9M Cu (I), 4.5M Cu (II) and 2.5M NaCl anolytes and 10wt%NaOH catholytes.Anion-exchange membrane is FAS-130 separators and temperature is 70 DEG C.As shown in A in Figure 16 Flat expanded anode shows 3.30V and 3.32V cell voltage, and the corrugated anode as shown in B in Figure 16 show 3.05V with 2.95V cell voltage.The voltage that there is 250mV to 370mV is saved.

Embodiment 5

The absorption of organic matter on the sorbent

In this experiment, test and organic matter is adsorbed from aqueous metal solution using different adsorbents.The absorption of test Agent is：Activated carbon (Aldrich, 20-60 mesh), microspheroidal PMMA (measure the poly- (first of mean molecule quantity~120,000 by GPC Base methyl acrylate), Aldrich) and microspheroidal PBMA (poly- (Isobutyl methacrylate) of mean molecule quantity~130,000, Aldrich) (PMMA and PBMA are shown as PXMA in fig. 17) and crosslinking PS (DowexL-493, Aldrich)。PS(Dowex L-493, Aldrich) be 20-50 mesh bead, it has 1100m²/ g table Area, 4.6nm average pore size and the crushing strength of 500g/ pearls.

Staticadsorption experiment is carried out in 20mL screw cap vials.Contain 4M CuCl₂(H₂O)₂, 1M CuCl and 2M NaCl Aqueous stock solutions doped with a small amount of ethylene dichloride (EDC), chlorethanol (CE), dichloro acetaldehyde (DCA) and trichloroacetaldehyde (TCA).The content of organics of the solution extracts the aqueous solution by using 1mL EtOAc and analyzes the organic matter of EtOAc extracts Concentration is analyzed.6mL stock solutions stir as shown in figure 17 show at 90 DEG C together with different amounts of sorbent material Indicated special time in figure.After filtering, extraction and GCMS analytic approach by organic phase are analyzed in the handled aqueous solution Content of organics.It has been observed that the gradually increase of the amount with sorbent material, the drop of the content of organics gradually increased It is low.Highest reduction amount is observed under crosslinking PS.

In this experiment, the power of regeneration of adsorbent is tested as follows：With given sorbing material (DowexOrganic matter 495-L) is repeatedly adsorbed from the solution containing Cu, with cold water and the hot wash material, drying should Material, is then re-used for absorption by the material after washing.The result of the experiment is shown in Figure 18.It has been observed that absorption property is Make still to be very similar to unworn material after second regenerates.It was additionally observed that, adsorb right after organic matter with Dowex materials Ultraviolet (UV) measurement of Cu concentration does not show significant changes.Using not used material, it was observed that about 10% it is total The reduction of Cu concentration, and 1-2% Cu concentration reduction is only observed using regrown material.These results of study indicate that polymerization is inhaled The advantage of the Reusability of enclosure material, because polymeric material adsorbs organic matter from the solution of copper ions, and even multiple Using not retaining substantial amounts of Cu ions after circulation.So sorbent material can regenerate after its adsorption capacity exhausts, and again Sorbent material after life can be reused for absorption.

Then Dowex is evaluated in dynamic adsorption post (figure 19 illustrates)495-L materials, to set up The transmission time under the flow conditions.Contain 511g CuCl₂(H₂O)₂, 49g CuCl, 117g NaCl and 500g water deposit it is molten Liquid is doped with EDC (1.8mg/mL), CE (0.387mg/mL), TCA (0.654mg/mL) and DCA (0.241mg/mL).Pass through extraction Take and analyze initial organic concentration with GCMS analytic approach.91-94 DEG C of hot reserve solution is pumped by filled with 13.5g Dowex V495L post (diameter 1.25cm, length 15.2cm).The temperature measured in exit is 78-81 DEG C. Flow velocity is 18mL/min.After 60 minutes, charging is converted into hot DI water from stock solution, starts regeneration cycle.With shown in Figure 20 Curve map in indicated time interval sampling.Extraction and content of organics of the GCMS analytic approach to sample by organic phase Analyzed.It has been observed that CE, followed by DCA, with the earliest transmission time, is followed by TCA.EDC observes the latest saturating Spend the time.

The regeneration curve of organic matter is followed and absorption identical order：Clean the CE of absorption first with hot water, followed by Be DCA.The next organic compound for cleaning adsorbent is TCA, is finally EDC.It has been observed that absorption and desorption curve and when Between may be influenceed by parameters such as flow velocity, temperature, column dimensions.These parameters can be used for optimization and enter electrochemistry electricity The technology of organic matter is removed before pond from outlet stream.

Claims

1. a kind of method, including：

Negative electrode is set to be contacted with catholyte；

2. according to the method described in claim 1, it further comprises the institute comprising the metal ion in low oxidation state Aqueous medium is stated to be recycled back into the anodolyte.

3. method according to claim 1 or 2, wherein the aqueous medium includes 5-95wt% water.

4. according to any method of the preceding claims, its further comprise at the negative electrode formed alkali, water or Hydrogen.

5. according to any method of the preceding claims, wherein the metal ion be selected from iron, chromium, copper, tin, silver, Cobalt, uranium, lead, mercury, vanadium, bismuth, titanium, ruthenium, osmium, europium, zinc, cadmium, gold, nickel, palladium, platinum, rhodium, iridium, manganese, technetium, rhenium, molybdenum, tungsten, niobium, tantalum, Zirconium, hafnium and combinations thereof.

6. according to any method of the preceding claims, wherein the metal ion is selected from iron, chromium, copper and tin.

7. according to any method of the preceding claims, wherein the metal ion is from Cu⁺It is converted into Cu²⁺'s Copper, the metal ion is from Fe²⁺It is converted into Fe³⁺Iron, the metal ion is from Sn²⁺It is converted into Sn⁴⁺Tin, the gold It is from Cr to belong to ion²⁺It is converted into Cr³⁺Chromium, the metal ion is from Pt²⁺It is converted into Pt⁴⁺Platinum, or its combination.

8. according to any method of the preceding claims, wherein the unsaturated hydrocarbons is compound of formula I, it is in halogenation Production II compounds afterwards：

Wherein, n is 2-10；M is 0-5；And q is 1-5；

X is the halogen selected from chlorine, bromine and iodine.

9. method according to claim 8, wherein the compound of formula I is ethene, propylene or butylene, and the Formula II Compound is respectively ethylene dichloride, propylene dichloride or 1,4- dichloroetane.

10. according to any method of the preceding claims, wherein one or more organic compounds are further Including chlorethanol, dichloro acetaldehyde, trichloroacetaldehyde or its combination.