CN108456893A - A kind of automatically controlled ion exchange coupling electrolytic water device and technique - Google Patents

A kind of automatically controlled ion exchange coupling electrolytic water device and technique Download PDF

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CN108456893A
CN108456893A CN201810232265.2A CN201810232265A CN108456893A CN 108456893 A CN108456893 A CN 108456893A CN 201810232265 A CN201810232265 A CN 201810232265A CN 108456893 A CN108456893 A CN 108456893A
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automatically controlled
controlled ion
chamber
ion
electrode
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CN108456893B (en
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郝晓刚
郝晓琼
张迪
杜晓
蒋仲庆
高凤凤
杨言言
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Taiyuan University of Technology
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Taiyuan University of Technology
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/02Hydrogen or oxygen
    • C25B1/04Hydrogen or oxygen by electrolysis of water
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70Assemblies comprising two or more cells
    • C25B9/73Assemblies comprising two or more cells of the filter-press type
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/42Treatment of water, waste water, or sewage by ion-exchange
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/14Alkali metal compounds
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/42Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/422Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention discloses a kind of automatically controlled ion exchange coupling electrolytic water device and techniques, belong to wastewater treatment and new energy field, can solve two big hot issue of metal ion treatment and electrolytic hydrogen production in water body simultaneously, to realize that high efficiency of energy utilizes.The present invention uses two cell structure of a chamber, a Room is by giving automatically controlled ion exchanging function electrode to impose oxidation or recovery voltage wherein, while realizing the reversible absorption of target metal ions and desorption, in addition the efficient utilization of hydrogen, oxygen or chlorine high added value product is realized in a Room.This technique has the advantages that energy loss is low, ion selectivity is high, process is reversible, environmental-friendly, easy to operate, is a kind of novel, efficient water treatment technology.

Description

A kind of automatically controlled ion exchange coupling electrolytic water device and technique
Technical field
The present invention relates to a kind of automatically controlled ion exchange coupling electrolytic water device and techniques, and in particular to a kind of synchronous output hydrogen Gas, the method for generating metal ion in acid, energy-efficient processing waste water, belong to wastewater treatment and new energy field.
Background technology
In recent years, the process problem of metal ion receives extensive attention in water body.It such as removes and poisons heavy metal ion, returns Receive high value metals lithium ion etc..Its reason includes mainly the following aspects:1)Due to mining, sewage irrigation and use weight Heavy metal caused by the factors such as the exceeded product of metal makes environmental quality deteriorate, and is directly detrimental to health;2)In many In industrial processes, micro impurity metal ion seriously affects product quality and production efficiency;3)Electronic product is increasingly Development is so that the problem of lithium resource scarcity is serious.Therefore, how efficiently to remove harmful metal ion and recycling is valuable Metal ion becomes the focal issue of water treatment field.
In addition, as petroleum resources are increasingly short, reserves increasingly decline and fossil fuel utilizes a series of rings brought Border problem getting worse, exploitation new cleaning fuel are extremely urgent.Wherein, hydrogen energy source as a kind of high heating value, it is environmental-friendly, Preparation process is simple, the convenient new cleaning fuel of storage and transportation receives favor, has extensive researching value and application prospect.And water Hydrogen manufacturing is solved because of advantages such as its product purity height, abundant raw materials, becomes the hot spot studied instantly.
However, the single consideration cathode adsorption desorption of the electrochemical treatments technology for metal ion reported at present, as in State's patent publication No. is:A kind of " the automatically controlled ion-exchange process recycling metal ion in weak solution " of CN102583664A, it is right Charge on electrode is not utilized rationally.That is reported at present prepares novel hydrogen energy source, only concentrates research electro-catalysis mostly The performance of material, as China Patent Publication No. is:CN105483744A " a kind of porous liberation of hydrogen catalyst and preparation method thereof and Electrode containing the liberation of hydrogen catalyst " is only focused in surface liberation of hydrogen overpotential and catalytic activity, about to electrode electric energy loss There is no any discussion.Existing patented technology is never by the energy consumption problem at negative and positive the two poles of the earth, product cost problem and energy environment Problem combines well.
Although the existing research at present of automatically controlled ion exchange technique and electrolysis water technology, automatically controlled ion exchange coupling electrolysis Hydraulic art handles metal ion, precipitation hydrogen, the theoretical of generation acid and is had not been reported with technique simultaneously.
Invention content
The present invention is intended to provide a kind of automatically controlled ion exchange coupling electrolytic water device and technique, in automatically controlled ion exchange technique On the basis of, realize the coupling application of automatically controlled ion exchange and electro-catalysis, the synchronous adsorption desorption for realizing ion and hydrogen, oxygen, The secondary pollution in existing ion-exchange is eliminated in the generation of acid solution, improves the utilization of power of original automatically controlled ion exchange technique Rate, and make product multipolarity.
Automatically controlled ion exchange coupling electrolysis hydraulic art proposed by the invention can solve above-mentioned water body metal ion simultaneously Recovery processing and two big hot issue of novel Hydrogen Energy output.Wherein, automatically controlled ion exchange technique(Electrochemically Switched ion exchange, ESIX)It is that electrode is made in electroactive ion exchanging function material and conducting base, passes through Regulate and control electrode potential, switch the redox state of electrode, the object ion in solution is made reversibly to be placed in and discharge, to real Enrichment, the recycling of existing effects of ion.Automatically controlled ion exchange technique have easy to operate, high selectivity, process it is reversible, without secondary The advantages of pollution is a kind of environmental-friendly new and effective isolation technics, and chief motivation is electrode potential.Automatically controlled ion is handed over Changing coupling electrolysis hydraulic art is handed over by installation anion between in the reactor on the basis of traditional automatically controlled ion-exchange process It changes film and forms " class chloralkali process " reactor of one " two Room of a chamber " to carry out.Wherein a Room is ion-exchange chamber, in addition one Room is tank house.Electroactive ion exchanging function electrode and electro-catalysis functional electrode are installed respectively in two interiors, give a wherein Room Electrode impose oxidation voltage, the electrode of another room imposes recovery voltage to realize.In adsorption process, cathode merging metal from While sub-, anode realizes oxygen(Or chlorine etc.)Precipitation and acid solution formation.In desorption process, Concentration of Gold is discharged in anode While belonging to ion, cathode realizes the precipitation of hydrogen.Two reactions of cathode anode are catalyzed by means respectively of different functions lives Property material mutually promote, collaboration carry out.
The present invention provides a kind of automatically controlled ion exchanges to couple electrolytic water device, which is two cell structure of a chamber, that is, is existed Two chambers are separated by electrolytic bath, electrolytic bath middle part is divided into left chamber and right chamber by anion-exchange membrane;Left chamber Side is equipped with the first inlet, and top is equipped with gas outlet, and bottom is equipped with the first liquid outlet;Right chamber side is equipped with the second feed liquor Mouthful, bottom is equipped with the second liquid outlet;Electro-catalysis functional electrode, the automatically controlled ion exchanging function of right chamber indoor location are equipped in left chamber Electrode, electrolytic bath outside are equipped with DC power supply, and electro-catalysis functional electrode and automatically controlled ion exchanging function electrode are separately connected directly Galvanic electricity source;Gas outlet connects gas collection bag.
The present invention provides a kind of automatically controlled ion exchange coupling electrolysis hydraulic arts to be had in installation using two cell structure of a chamber There is a Room of the electrode of automatically controlled ion exchanging function by imposing oxidation or recovery voltage to electrode, realizes that target metal ions can While inverse absorption and desorption, in addition the efficient utilization of hydrogen, oxygen or chlorine high added value product is realized in a Room.
Above-mentioned technique is divided into absorption and desorption process, and concrete operations are:
In adsorption process, with the automatically controlled ion exchanging function electrode of the connected chamber indoor location of cathode;With the connected chamber of anode Anion-exchange membrane is installed in indoor location electro-catalysis functional electrode, two Room centre;With the connected chamber of cathode in inject metal Waste water solution or salt lake bittern solution, with the connected chamber of anode in inject dilute acid soln, the gas of generation is from gas outlet It is discharged and collects, collect the acid solution of generation, discharge corresponding treatment fluid in reactor, washing reactor;
In desorption process, with the connected chamber of anode in the automatically controlled ion exchanging function electrode of above-mentioned adsorption saturation is installed; Contribute to the electro-catalysis functional electrode that hydrogen generates with installation in the connected chamber of cathode, anion exchange is installed among two Room Film, with the connected chamber of anode in inject dilute salting liquid, with the connected chamber of cathode in inject dilute acid soln, collect and generate Gas, collect the metal ion solution of enrichment method, discharge corresponding treatment fluid in reactor, washing reactor;
It is carried out by the intermittent cycle of above-mentioned steps, realizes the enriching and recovering to metal ion in solution, and collect object gas With acid solution.
Above-mentioned technique specifically includes following steps:
(1)When absorption, dilute acid soln is added into left chamber, metallic wastewater solution is added to right chamber or salt lake bittern is molten Liquid adsorbs metal ion by adjusting voltage;
(2)Collect the gas and acid solution generated;Discharge corresponding treatment fluid in reactor;
(3)When desorption, the electrode of left chamber is replaced, dilute acid soln is added to left chamber, it is molten that corresponding dilute salt is added to right chamber Liquid adjusts voltage, metal ion is desorbed;
(4)The target concentrate collected the gas generated and be rich in metal ion;Discharge corresponding treatment fluid in reactor;
(5)It recycles and carries out by above-mentioned steps, realize the enriching and recovering to metal ion in solution, realize the height to a variety of by-products Effect is used.
In above-mentioned technique, the automatically controlled ion exchanging function electrode is sunk on carbon-based conductive matrix or metallic conduction matrix Product or coating have highly selective, high-throughput electroactive ion exchanging function material for object ion.
In above-mentioned technique, the anion-exchange membrane is quaternary amine type anion-exchange membrane, the friendship of aromatic amine groups type anion Change one kind in film or quaternary amine type anion-exchange membrane.
The technique can solve the problems, such as the problem of recycling enrichment of metal ion and novel hydrogen energy source generate simultaneously.
The present invention is a kind of automatically controlled ion exchange coupling electrolysis hydraulic art, and compared with prior art, innovation is:
(1)The recyclable recycling of automatically controlled ion exchanging function electrode;
(2)Electro-catalysis technology and automatically controlled ion exchange technique are coupled, waste water treatment efficiency and energy utilization efficiency can be improved, with And a variety of high added value products of recycling, to effectively improve economic benefit;The different automatically controlled ion exchange electrodes of functionality is optional The different target metal ions of the adsorption desorption of selecting property;While handling metal ion, the productions such as hydrogen, oxygen, chlorine, acid are generated Object;Electro-catalysis functional material is in the reaction rate for promoting the while of hydrolyzing also to accelerate ion adsorption desorption;
(3)The present invention is a kind of novel hydrogen energy source for recycling metal ion in waste water, being enriched with lithium resource in salt lake, generating high heating value Multifunctional combined technique, realize product multipolarity, device multifunctionality, reduce operating cost;
(4)Coupling technique device can be automatically controled, easy to operate, easy to use;
(5)Simulated waste both can one way flow through, also be recycled multiple adsorption desorption;
(6)Flow velocity can be passed in and out by control to control ion isolation rate;
(7)It is combined system with two electrodes, is conducive to industrialized production.
Description of the drawings
Fig. 1 be synchronous absorption lithium ion in this process example one, precipitated oxygen process schematic diagram.
Fig. 2 is synchronous desorption lithium ion in this process example one, the schematic diagram of hydrogen process is precipitated.
Fig. 3 be synchronous absorption copper ion in this process example two, precipitated oxygen process schematic diagram.
Fig. 4 is synchronous desorption copper ion in this process example two, the schematic diagram of hydrogen process is precipitated.
Fig. 5 is synchronous absorption lithium ion in this process example three, the schematic diagram of chlorine process is precipitated.
Fig. 6 is synchronous desorption lithium ion in this process example three, the schematic diagram of hydrogen process is precipitated.
In figure:A- electro-catalysis functional electrodes;The automatically controlled ion exchanging function electrodes of B-;C- anion-exchange membranes;D- liberation of hydrogen electricity Catalysis electrode;1- electrolytic baths;2- DC power supplies;The gas outlets 3-;The first inlets of 4-;The second inlets of 5-;6- first Liquid outlet;The second liquid outlets of 7-.
Specific implementation mode
It is further illustrated the present invention below by embodiment, but is not limited to following embodiment.
The present invention uses device shown in FIG. 1.The device is two cell structure of a chamber, i.e., is separated by two in electrolytic bath 1 A chamber, 1 middle part of electrolytic bath are divided into left chamber and right chamber by anion-exchange membrane C;Left chamber side is equipped with the first feed liquor Mouth 4, top are equipped with gas outlet 3, and bottom is equipped with the first liquid outlet 6;Right chamber side is equipped with the second inlet 5, and bottom is equipped with the Two liquid outlets 7;It is equipped with electro-catalysis functional electrode A in left chamber, automatically controlled ion exchanging function electrode B, electrolysis are equipped in right chamber DC power supply 2 is equipped with outside liquid bath, electro-catalysis functional electrode and automatically controlled ion exchanging function electrode are separately connected DC power supply 2; Gas outlet 3 connects gas collection bag.
Embodiment one:
Lithium ion in processing recycling waste water:
Lithium ion adsorbs and precipitated oxygen process is as shown in Figure 1, installation different functionalities electrode:It is electro-catalysis functional electrode A, automatically controlled Dilution heat of sulfuric acid injects in ion exchanging function electrode B, anion-exchange membrane C, the first inlet 4, left chamber, opens the first feed liquor Mouth 5, right chamber inject pending lithium sulfate waste liquid.Gas outlet 3 is opened again, connects gas collection bag.Apply voltage carry out lithium from Son absorption, oxygen discharge.After saturation to be adsorbed, opens the first liquid outlet 6 and collect the sulfuric acid solution that concentration improves(Discharge liquor can be with Adsorption system is re-injected by the first inlet 4 to recycle).Open the lithium sulfate that the second liquid outlet 7 discharge concentration reduces Solution.After injecting cleaning solution cleaning, cleaning solution is discharged.
Lithium ion is desorbed and hydrogen process is precipitated as shown in Fig. 2, switching 2 current direction of DC power supply, by electro-catalysis function Electrode A is taken out, and Electrocatalytic Activity for Hydrogen Evolution Reaction functional electrode D is changed to, and opens the first inlet 4, and dilution heat of sulfuric acid injects in left chamber, opens First inlet 5, right chamber inject regenerated liquid:Dilute sulfuric acid lithium waste liquid.Gas outlet 3 is opened again, connects gas collection bag.Apply electricity Pressure carries out lithium ion desorption, hydrogen discharge.After desorption empties, opens the first liquid outlet 6 and waste acid liquor is discharged.Second is opened to go out Liquid mouth 7 collects the target product of enrichment:The lithium sulfate solution of high concentration.After injecting cleaning solution cleaning, cleaning solution is discharged.
Above-mentioned process cycles carry out, and by constantly switching adsorption/desorption process, realize that the processing to metal-lithium ion is returned It receives.The reasonable utilization of hydrogen, oxygen, sulfuric acid is also realized simultaneously.Accelerate to reduce energy loss while reaction.
When concrete application, described to lithium, selectively functional automatically controlled ionic material is λ-MnO2/Pt、 H1.33Mn1.67O4、H1.6Mn1.6O4Or λ-MnO2One kind in/PPy/PSS.
When concrete application, the material of the automatically controlled ion exchanging function electrode B and Electrocatalytic Activity for Hydrogen Evolution Reaction functional electrode D are gold Belong to oxide, metal phosphide, metal-organic framework material(MOF), one kind in carbonitride and its compound.
When concrete application, the anion-exchange membrane C is quaternary amine type anion-exchange membrane, aromatic amine groups type anion One kind in exchange membrane and quaternary amine type anion-exchange membrane.
Embodiment two:
Copper ion in processing recycling waste water:
Copper absorption and precipitated oxygen process are as shown in figure 3, installation different functionalities electrode:It is electro-catalysis functional electrode A, automatically controlled Ion exchanging function electrode B, anion-exchange membrane C open the first inlet 4, and dilution heat of sulfuric acid injects in left chamber, opens first Inlet 5, right chamber inject pending bluestone waste.Gas outlet 3 is opened again, connects gas collection bag.Apply voltage to carry out Copper absorption, oxygen discharge.After saturation to be adsorbed, opens the first liquid outlet 6 and collect the sulfuric acid solution that concentration improves(Discharge liquor Adsorption system recycling can be re-injected by the first inlet 4).Open the sulphur that the second liquid outlet 7 discharge concentration reduces Sour copper solution.After injecting cleaning solution cleaning, cleaning solution is discharged.
Copper ion is desorbed and hydrogen process is precipitated as shown in figure 4, switching 2 current direction of DC power supply, by electro-catalysis function Electrode A is taken out, and Electrocatalytic Activity for Hydrogen Evolution Reaction functional electrode D is changed to, and opens the first inlet 4, and dilution heat of sulfuric acid injects in left chamber, opens First inlet 5, right chamber inject regenerated liquid depleted copper sulfate waste liquid.Gas outlet 3 is opened again, connects gas collection bag.Apply electricity Pressure carries out copper ion desorption, hydrogen discharge.After desorption empties, opens the first liquid outlet 6 and waste acid liquor is discharged.Second is opened to go out Liquid mouth 7 collects the copper-bath of the target product high concentration of enrichment.After injecting cleaning solution cleaning, cleaning solution is discharged.
It is carried out with above-mentioned process cycles, by constantly switching adsorption/desorption process, realizes the recycling to metal copper ion Processing.The reasonable utilization of hydrogen, oxygen, sulfuric acid is also realized simultaneously.Accelerate to reduce energy loss while reaction.
When concrete application, described to copper, selectively functional automatically controlled ionic material is chitosan magnetic Nano material In material, the functionalized modification material of mesoporous SBA-15, amino modified carbon nano-quantum point or calcium alginate/porous silicon composite material One kind.
When concrete application, the material of the automatically controlled ion exchanging function electrode B and Electrocatalytic Activity for Hydrogen Evolution Reaction functional electrode D are gold Belong to one kind in oxide, metal phosphide, MOF, carbonitride and its compound.
When concrete application, the anion-exchange membrane C is quaternary amine type anion-exchange membrane, aromatic amine groups type anion One kind in exchange membrane and quaternary amine type anion-exchange membrane.
Embodiment three:
Extraction and enrichment lithium ion in salt lake bittern:
Lithium ion adsorbs and chlorine process is precipitated as shown in figure 5, installation different functionalities electrode:It is electro-catalysis functional electrode A, automatically controlled Ion exchanging function electrode B, anion-exchange membrane C open the first inlet 4, and dilute hydrochloric acid solution injects in left chamber, opens first Inlet 5, salt lake aqueous solution of the right chamber injection rich in lithium chloride.Gas outlet 3 is opened again, connects gas collection bag.Apply electricity Pressure carries out lithium ion absorption, chlorine discharge.After saturation to be adsorbed, opens the first liquid outlet 6 and collect the acid solution that concentration improves(Row Adsorption system recycling can be re-injected by the first inlet 4 by going out liquid).Opening the second liquid outlet 7 discharge concentration reduces Lithium chloride solution.After injecting cleaning solution cleaning, cleaning solution is discharged.
Lithium ion is desorbed and hydrogen process is precipitated as shown in fig. 6, switching 2 current direction of DC power supply, by electro-catalysis function Electrode A is taken out, and Electrocatalytic Activity for Hydrogen Evolution Reaction functional electrode D is changed to, and opens the first inlet 4, and dilute hydrochloric acid solution injects in left chamber, opens First inlet 5, right chamber inject the dilute lithium chloride waste liquid of regenerated liquid.Gas outlet 3 is opened again, connects gas collection bag.Apply electricity Pressure carries out lithium ion desorption, hydrogen discharge.After desorption empties, opens the first liquid outlet 6 and waste acid liquor is discharged.Second is opened to go out Liquid mouth 7 collects the lithium chloride solution of the target product high concentration of enrichment.After injecting cleaning solution cleaning, cleaning solution is discharged.
It is carried out with above-mentioned process cycles, by constantly switching adsorption/desorption process, realizes the enrichment to metal-lithium ion. The reasonable utilization of hydrogen, chlorine is also realized simultaneously.Accelerate to reduce energy loss while reaction.
When concrete application, described to lithium, selectively functional automatically controlled ionic material is λ-MnO2/Pt、 H1.33Mn1.67O4、H1.6Mn1.6O4、λ-MnO2One kind in/PPy/PSS.
When concrete application, the material of the automatically controlled ion exchanging function electrode B is TiO2Nano-tube array (TNTs) is negative Carry one kind in Sn, Sb codope oxide containing ruthenium coating.
When concrete application, the material of the Electrocatalytic Activity for Hydrogen Evolution Reaction functional electrode D be metal oxide, metal phosphide, One kind in MOF, carbonitride and its compound.
When concrete application, the anion-exchange membrane C is quaternary amine type anion-exchange membrane, aromatic amine groups type anion One kind in exchange membrane and quaternary amine type anion-exchange membrane.

Claims (9)

1. a kind of automatically controlled ion exchange couples electrolytic water device, it is characterised in that:The device is two cell structure of a chamber, that is, is being electrolysed Two chambers are separated by liquid bath, electrolytic bath middle part is divided into left chamber and right chamber by anion-exchange membrane;Left chamber side Equipped with the first inlet, top is equipped with gas outlet, and bottom is equipped with the first liquid outlet;Right chamber side is equipped with the second inlet, bottom Portion is equipped with the second liquid outlet;It is equipped with electro-catalysis functional electrode in left chamber, automatically controlled ion exchanging function electrode is equipped in right chamber, DC power supply is equipped with outside electrolytic bath, electro-catalysis functional electrode and automatically controlled ion exchanging function electrode are separately connected direct current Source;Gas outlet connects gas collection bag.
2. a kind of automatically controlled ion exchange coupling electrolysis hydraulic art, using automatically controlled ion exchange coupling electrolysis described in claim 1 Water installations, it is characterised in that:Using two cell structure of a chamber, in right chamber by giving automatically controlled ion exchanging function electrode to impose oxidation Or recovery voltage, while realizing the reversible absorption of target metal ions and desorption, in addition hydrogen, oxygen or chlorine are realized in a Room The efficient utilization of high added value product.
3. automatically controlled ion exchange coupling electrolysis hydraulic art according to claim 2, it is characterised in that:
In adsorption process, with the automatically controlled ion exchanging function electrode of the connected chamber indoor location of cathode;With the connected chamber of anode Anion-exchange membrane is installed in indoor location electro-catalysis functional electrode, two Room centre;With the connected chamber of cathode in inject metal Waste water solution or salt lake bittern solution, with the connected chamber of anode in inject dilute acid soln, the gas of generation is from gas outlet It is discharged and collects, collect the acid solution of generation, discharge corresponding treatment fluid in reactor, washing reactor;
In desorption process, with the connected chamber of anode in the automatically controlled ion exchanging function electrode of above-mentioned adsorption saturation is installed; Contribute to the electro-catalysis functional electrode that hydrogen generates with installation in the connected chamber of cathode, anion exchange is installed among two Room Film, with the connected chamber of anode in inject dilute salting liquid, with the connected chamber of cathode in inject dilute acid soln, collect and generate Gas, collect the metal ion solution of enrichment method, discharge corresponding treatment fluid in reactor, washing reactor;
It is carried out by the intermittent cycle of above-mentioned steps, realizes the enriching and recovering to metal ion in solution, and collect object gas With acid solution.
4. automatically controlled ion exchange coupling electrolysis hydraulic art according to claim 2 or 3, it is characterised in that:Including following step Suddenly:
(1)When absorption, dilute acid soln is added into left chamber, metallic wastewater solution is added to right chamber or salt lake bittern is molten Liquid adsorbs metal ion by adjusting voltage;
(2)Collect the gas and acid solution generated;Discharge corresponding treatment fluid in reactor;
(3)When desorption, the electrode of left chamber is replaced, dilute acid soln is added to left chamber, it is molten that corresponding dilute salt is added to right chamber Liquid adjusts voltage, metal ion is desorbed;
(4)The target concentrate collected the gas generated and be rich in metal ion;Discharge corresponding treatment fluid in reactor;
(5)It recycles and carries out by above-mentioned steps, realize the enriching and recovering to metal ion in solution, realize the height to a variety of by-products Effect is used.
5. automatically controlled ion exchange coupling electrolysis hydraulic art according to claim 3, it is characterised in that:The automatically controlled ion is handed over It is to have high selection for object ion in carbon-based conductive matrix or metallic conduction substrate deposit or coating to change functional electrode Property, high-throughput automatically controlled ion exchanging function material.
6. automatically controlled ion exchange coupling electrolysis hydraulic art according to claim 5, it is characterised in that:The automatically controlled ion is handed over The material for changing functional electrode is in metal oxide, metal phosphide, metal-organic framework material, carbonitride and its compound One kind.
7. automatically controlled ion exchange coupling electrolysis hydraulic art according to claim 3, it is characterised in that:The anion exchange Film is one kind in quaternary amine type anion-exchange membrane, aromatic amine groups type anion-exchange membrane or quaternary amine type anion-exchange membrane.
8. automatically controlled ion exchange coupling electrolysis hydraulic art according to claim 3, it is characterised in that:It is selective to lithium Automatically controlled ion exchanging function material is λ-MnO2/Pt、H1.33Mn1.67O4、H1.6Mn1.6O4Or λ-MnO2One kind in/PPy/PSS.
9. automatically controlled ion exchange coupling electrolysis hydraulic art according to claim 3, it is characterised in that:It is selective to copper Automatically controlled ion exchanging function material is the functionalized modification material, amino modified of chitosan magnetic Nano material, mesoporous SBA-15 One kind in carbon nano-quantum point or calcium alginate/porous silicon composite material.
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CN110357220A (en) * 2019-07-01 2019-10-22 太原理工大学 A kind of electrochemical couple removes the method and device of chloride ion in desulfurization wastewater
CN110747488A (en) * 2019-11-12 2020-02-04 上海莒纳新材料科技有限公司 Water electrolysis oxygen production equipment
CN110747487A (en) * 2019-11-12 2020-02-04 上海莒纳新材料科技有限公司 Water electrolysis oxygen generation system and air quality control system of closed space
CN110863212A (en) * 2019-11-12 2020-03-06 上海莒纳新材料科技有限公司 Water electrolysis oxygen generation system and air quality control system of closed space
WO2023067101A3 (en) * 2021-10-20 2023-06-15 IIDC International Investment Development Corporation Method and electrochemical filter cell for extracting lithium

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CN109351363A (en) * 2018-10-16 2019-02-19 安徽理工大学 A kind of evolving hydrogen reaction catalyst of layered mesoporous structure and preparation method thereof
CN109778218A (en) * 2019-02-01 2019-05-21 南京大学 A kind of electrochemistry hydrogen manufacturing and the device and method for proposing lithium coproduction
CN109778218B (en) * 2019-02-01 2021-04-06 南京大学 Device and method for co-production of hydrogen production and lithium extraction by electrochemistry
CN110357220A (en) * 2019-07-01 2019-10-22 太原理工大学 A kind of electrochemical couple removes the method and device of chloride ion in desulfurization wastewater
CN110357220B (en) * 2019-07-01 2021-12-03 太原理工大学 Method and device for removing chloride ions in desulfurization wastewater through electrochemical coupling
CN110747488A (en) * 2019-11-12 2020-02-04 上海莒纳新材料科技有限公司 Water electrolysis oxygen production equipment
CN110747487A (en) * 2019-11-12 2020-02-04 上海莒纳新材料科技有限公司 Water electrolysis oxygen generation system and air quality control system of closed space
CN110863212A (en) * 2019-11-12 2020-03-06 上海莒纳新材料科技有限公司 Water electrolysis oxygen generation system and air quality control system of closed space
WO2023067101A3 (en) * 2021-10-20 2023-06-15 IIDC International Investment Development Corporation Method and electrochemical filter cell for extracting lithium

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