CN106630040A - Selective bipolar membrane electrodialysis system and application thereof - Google Patents
Selective bipolar membrane electrodialysis system and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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- Y02A20/124—Water desalination
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a selective bipolar membrane electrodialysis system and application thereof. The selective bipolar membrane electrodialysis system comprises an electrodialysis membrane pile, a positive electrode plate and a negative electrode plate, wherein the positive electrode plate and the negative electrode plate are fixed at the two sides of the electrodialysis membrane pile through clamping plates; the electrodialysis membrane pile is formed by sequentially and alternately laminating several kinds of functional membranes and adding a flow passage separation net and a sealing gasket; the functional membranes comprise a bipolar membrane and a multiple valence ion selective passing membrane; an anion exchange layer of the bipolar membrane faces the positive electrode plate; the cation exchange layer faces the negative electrode plate. The selective bipolar membrane electrodialysis system provided by the invention has the advantages that the bipolar membrane electrodialysis and the selective electrodialysis are combined in the same device; when the system is used for salt-containing material desalting and acid-base production, the bipolar membrane electrodialysis and the selective electrodialysis are merged into one operation; the flow process is simplified; the operation quantity is reduced; the electrode reaction energy consumption is reduced; the production efficiency is improved.
Description
Technical field
The present invention relates to a kind of selective bipolar membrane electrodialysis technology, is in particular that one kind is selected using a multivalent ion
The electrodialytic technique that selecting property combines through film and Bipolar Membrane.
Background technology
Electrodialysis is a kind of new mass transfer isolation technique, using having amberplex of different nature, can make electricity
Dialysis is used for different field, such as the desalination and concentration process of water process, environmental protection, bio-pharmaceuticals, industrial material.Due to waiting to locate
The composition of reason material is different, and during the process target of material is had nothing in common with each other, the species of amberplex can be thin
It is divided into many kinds, common amberplex is anion/cation exchange membrane.Anion-exchange membrane is usually by lotus positively charged polymer
Polymer after inversion of phases be obtained, with compact texture, it is allowed to the transmission of anion and hinder cation.Cation exchange
Film is usually to be obtained through phase inversion by the high molecular polymer of bear electricity, with compact texture, it is allowed to the transmission of cation
And hinder anion.Common electrodialysis is referred to as using the electrodialytic process of traditional anion/cation exchange membrane.With special separation
Property simultaneously can be used for the amberplex of extraordinary feed separation and generally comprise a multivalent ion selectively through film and Bipolar Membrane.
One multivalent ion selectively can realize the separation between the ion of the same race with different valence state through film, its typically via it is cloudy/
Cation-exchange membrane is modified prepared through surface.Calcium, magnesium, the chromium cation of lithium, sodium, potassium and the multivalence of monovalence can such as be realized
Between a detached polyvalent cation selectively pass through film, be by cation-exchange membrane through the surface coating positive electric functional layer of lotus,
Different using the Donnan repulsive forces between the cation with different charge numbers are realized separating, and this process is commonly referred to as selected
Property electrodialysis.Bipolar Membrane can realize the dissociation of water, so as to being used to produce acid, producing alkali technique.Bipolar Membrane is typically handed over via cation
Change film to be superimposed with anion-exchange membrane, and be obtained in middle functional compounds of the addition with water decomposition ability, thus it is bipolar
Film generally comprises anion exchange layer, cation-exchange membrane and intermediate layer.Under the impetus of electric field, the centre of Bipolar Membrane
There is water decomposition in layer, obtain hydrogen ion and hydroxide ion, and hydrogen ion is migrated to sour room, hydroxide ion by cation exchange layer
Migrated to alkali room by anion exchange layer, with after corresponding ions binding acid/base target product is obtained, this process is commonly referred to as double
Pole EDBM.
Selective electrodialysis in general is developed with bipolar membrane electrodialysis by common electrodialysis, and common electrodialysis can be with
For the desalination of ordinary material, concentration process.As patent CN104370396 B reports a kind of sea water desalinization strong brine zero-emission
Method, is passed through the strong brine of sea water desalinating unit by-product electrodialysis plant and proceeds concentration, and it is near that electrodialysis is concentrated to give
Saturated brine is used for subsequent evaporation salt manufacturing, and the light salt brine of discharge again returns to sea water desalinating unit after may be processed.Patent
CN105668519 A report the technique that watery hydrochloric acid is concentrated reuse for a kind of use electrodialysis and Membrane Materials, what electrodialysis gave off
Content of hydrochloric acid is less than 0.2% in light liquid, and processing cost is lower, while the dope of electrodialysis acquisition salt after the operation such as Membrane Materials
Acid content is used directly for production more than 12%.Patent CN205328675 U reports a kind of solar powered electric osmose
Bleed processing system, desalination and concentration process is carried out using electrodialysis membrane stack to waste water.
Selective electrodialysis can be used for salt lake and put forward the processes such as lithium, strong brine process, soda acid recovery.Patent CN87102881
A report isolate in a kind of electrolyte using selective anion/cation exchange membrane by zinc sulfate chloride, cyanide and
The mixture of thallium.Patent WO2011130809 A2 report it is a kind of using selective electrodialysis by isolating in the solution for mixing
The process of monovalent anion, due to ionic radius and the difference of charge number, by using common cation-exchange membrane and unit price
Selective anion-exchange membrane, by sub-argument in waste water phosphoric acid product is gone out.Document (Preliminary study on
recovering lithium from high Mg2+/Li+ratio brines by electrodialysis,
Separation and Purification Technology, 172 (2017) 168-177) report by selective double
Pole EDBM can realize the separation of magnesium, lithium ion, so as to avoid traditional causticization process, simplify operating procedure, while
Reduce energy consumption.
Bipolar membrane electrodialysis process can be used for the fields such as organic acid production, Fermentation Engineering, water process.Patent
CN104744280 A report the process that a kind of utilization bipolar membrane electrodialysis are produced methyl amimoacetic acid by the aqueous solution of sodium sarcosinate.Specially
Sharp CN104593809 A, CN101781190 B report a kind of fermentation of utilization bipolar membrane electrodialysis acidification technique by citric acid
The method that purifying citric acid is produced in liquid, largely reduces process energy consumption, reduces soda acid introducing.Patent
CN102167293 A report one kind and utilize bipolar membrane electrodialysis process, by production NaOH and sulfuric acid in sodium sulfate wastewater
Method, realize resource reutilization.Patent CN103882468 A reports a kind of utilization and is electrolysed bipolar membrane electrodialysis by salt lake halogen
The aquatic process for producing lithium hydroxide, after causticizing process removes calcium, magnesium ion, is concentrated in bittern by common electrodialysis, is obtained
Lithium is enriched with bittern.
Document (Integration of monopolar and bipolar electrodialysis for
valorization of seawater reverse osmosis desalination brines:Production of
strong acid and base,Desalination,398(2016)87-97；Selectrodialysis and bipolar
membrane electrodialysis combination for industrial process brines treatment:
Monovalent-divalent ions separation and acid and base production,
Desalination, 399 (2016) 88-95.) report it is a kind of using selective electrodialysis in combination with bipolar membrane electrodialysis by
Bittern come the technique of acid/base processed, bittern first after selective electrodialysis, in solution the sodium ion of monovalence, chlorion with it is many
Calcium, magnesium, sulfate radical, silicate of valency etc. are realized separating, while the monovalence salting liquid for obtaining is concentrated, it is afterwards that monovalent salt is molten
Liquid is realized producing acid/base using bipolar membrane electrodialysis process.Whole process is related to selective electrodialysis and bipolar membrane electrodialysis
Between coupling, come by bittern relieving haperacidity alkaline compared to traditional causticizing process, ion exchange membrane, extraction and electrolysis
Process, reduces to a certain extent cost, reduces pollution of the process for environment, but process operation is still very complicated.
In view of the electrode reaction for selecting electrodialysis and bipolar membrane electrodialysis to be directed to anode and negative electrode, such as following formula：
2H2O+2e-→H2+OH-
H2O+2e-→0.5O2+2H+
If the common male/female amberplex used during bipolar membrane electrodialysis is used having a multivalence selective
Amberplex replaces, and is an operation by two process simplifications, can largely reduce electrode reaction energy consumption, while
Simplify operation, this process is referred to as selective bipolar membrane electrodialysis process by the present invention.
The content of the invention
The invention discloses a kind of selective bipolar membrane electrodialysis system and its application, it is intended to by selective electrodialysis and double
Combining in the EDBM of pole, so that the system can simultaneously realize the mesh of the Selective Separation to ion in solution and acid/base processed
Mark, streamline operation reduces production cost.
The present invention solves technical problem, adopts the following technical scheme that：
The present invention selective bipolar membrane electrodialysis system, including electrodialysis membrane stack and by Boards wall in the electricity
The positive plate and minus plate of dialysis membrane stack both sides；The electrodialysis membrane stack be alternately laminated successively by several functional membranes after plus upstream
Road filter and gasket seal are constituted；The functional membrane includes that Bipolar Membrane and a multivalent ion selectively pass through film；The moon of Bipolar Membrane
, towards positive plate, cation exchange layer is towards minus plate for ion exchange layer.
The electrodialysis membrane stack adds after selectively can alternately being laminated successively through film by Bipolar Membrane and a polyvalent cation
Upper runner filter and gasket seal are constituted；Anode chamber is formed between positive plate and adjacent membranes, is formed between minus plate and adjacent membranes
Cathode chamber；The repetitive of one or more " alkali rooms-feed liquid room " is formed with the electrodialysis membrane stack.Positive plate and negative electrode
Plate is connected respectively with the positive pole and negative pole of power supply；Anode chamber and cathode chamber are communicated in parallel electrode solution hold-up tank, the connection of feed liquid room
In feed liquid hold-up tank, alkali room is communicated in alkali lye hold-up tank；Anode chamber, cathode chamber, alkali room, in feed liquid room solution respectively by driving
Pump drives, and is formed between electrodialysis system and corresponding hold-up tank and circulate；All it is provided with alkali room, feed liquid room exit
PH sensors and conductivity sensor；Each pH sensors are connected to pH meter, and each conductivity sensor is connected to conductivity meter.
After the electrodialysis membrane stack selectively can also alternately be laminated successively by Bipolar Membrane and a multivalent anions through film
Plus upper runner filter and gasket seal composition；Anode chamber is formed between positive plate and adjacent membranes, shape between minus plate and adjacent membranes
Into cathode chamber；The repetitive of one or more " sour rooms-feed liquid room " is formed with the electrodialysis membrane stack.Positive plate and the moon
Pole plate is connected respectively with the positive pole and negative pole of power supply；Anode chamber and cathode chamber are communicated in parallel electrode solution hold-up tank, and feed liquid room connects
Feed liquid hold-up tank is passed through, sour room is communicated in acid solution hold-up tank；Anode chamber, cathode chamber, sour room, in feed liquid room solution respectively by driving
Dynamic pump drives, and is formed between electrodialysis plant and corresponding hold-up tank and circulate；All arrange in sour room, feed liquid room exit
There are pH sensors and conductivity sensor；Each pH sensors are connected to pH meter, and each conductivity sensor is connected to conductivity meter.
After the electrodialysis membrane stack can be alternately to be laminated successively by Bipolar Membrane, cation-exchange membrane and anion-exchange membrane
Plus upper runner filter and gasket seal composition；Anode chamber is formed between positive plate and adjacent membranes, shape between minus plate and adjacent membranes
Into cathode chamber；The repetitive of one or more " alkali rooms-feed liquid room-sour room " is formed with the electrodialysis membrane stack；It is described
At least one of cation-exchange membrane and anion-exchange membrane selectively pass through film for a multivalent ion.Bipolar Membrane and adjacent sun
Alkali room is formed between amberplex, sour room is formed between adjacent anion-exchange membrane, cation-exchange membrane is handed over anion
Change between film and form feed liquid room.Positive plate and minus plate are connected respectively with the positive pole and negative pole of power supply；Anode chamber and cathode chamber are simultaneously
Row is communicated in electrode solution hold-up tank, and feed liquid room is communicated in feed liquid hold-up tank, and sour room is communicated in acid solution hold-up tank, and alkali room is communicated in alkali
Liquid hold-up tank；Anode chamber, cathode chamber, sour room, alkali room, solution is driven respectively by transfer tube in feed liquid room, and in electrodialysis dress
Put to be formed between corresponding hold-up tank and circulate；PH sensors and conductance are all provided with sour room, alkali room, feed liquid room exit
Rate sensor；Each pH sensors are connected to pH meter, and each conductivity sensor is connected to conductivity meter.
Above-mentioned power supply can be voltage-stabilized power supply, or stabilized current supply.Above-mentioned transfer tube can be membrane pump, wriggling
Pump, centrifugal pump, immersible pump or piston pump.
Above-mentioned selective bipolar membrane electrodialysis system can be used for producing acid while to saliferous feed liquid desalination and/or produce
Alkali.
With what is be made up of " Bipolar Membrane, a polyvalent cation selectively selectively pass through film through film and a multivalent anions "
As a example by electrodialysis membrane stack：During work, feed liquid is added into feed liquid hold-up tank, acid solution is added into acid solution hold-up tank, by alkali soluble
Liquid is added to alkali lye hold-up tank, and strong electrolytic solution is added into electrode solution hold-up tank；Then will be expected by respective transfer tube
Feed liquid circulation in liquid hold-up tank pumps into the feed liquid room of electrodialysis system, and the acid solution circulation in acid solution hold-up tank is pumped into acid
Room, by the caustic solution circulation in alkali lye hold-up tank alkali room is pumped into, and the strong electrolytic solution of electrode solution hold-up tank is distinguished into circulating pump
Enter anode chamber and cathode chamber；Applying electric current to electrodialysis system finally by current stabilization or voltage-stabilized power supply carries out electrodialysis, completes material
The desalination of liquid, production, the production of alkali room alkali of sour room acid.The feed liquid can be containing sodium ion, calcium ion, magnesium ion, lithium
Ion, potassium ion, aluminium ion, chromium ion, chlorion, sulfate ion, phosphate anion, silicate ion, hydrogen ion, hydrogen-oxygen
The mixing salt solution of radical ion.
For being made up of " Bipolar Membrane, a polyvalent cation selectively selectively pass through film through film and a multivalent anions "
Electrodialysis membrane stack, when as a example by the electrodialysis system with seawater as feed liquid, using a repetitive, its membrane stack inside is illustrated
Figure is as shown in Fig. 1 (a)：Feed liquid is passed through to electrodialysis system, by applying electric current, Bipolar Membrane occurs water decomposition and generates hydrogen-oxygen
Root and hydrogen ion, in feed liquid room sodium ion under the impetus of anode by a polyvalent cation it is selective through film migrate to
Alkali room, and the hydroxide ion dissociateed with adjacent bipolar film combined and obtains NaOH；Chlorion in feed liquid room is in negative electrode
Impetus under selectively migrated to sour room through film by a multivalent anions, and the hydrogen dissociateed with adjacent bipolar film from
Son is combined and obtains hydrochloric acid；Calcium ion, magnesium ion in feed liquid room cannot enter alkali by the way that a polyvalent cation is selective through film
Room, is retained in feed liquid room；Sulfate ion in feed liquid room cannot be entered by the way that a multivalent anions are selective through film
Sour room, is retained in feed liquid room；Electric current constantly applies, and the salt in feed liquid is constantly removed, while the hydroxide in alkali room
Hydrochloric acid in sodium and sour room is constantly accumulated.Using the electrodialysis system of multiple repetitives with the system using single chamber unit
Operating principle is identical.The operating principle of the feed liquids with different compositions with seawater selective bipolar membrane electrodialysis operating principle phase
Together.
For the electrodialysis membrane stack being made up of " Bipolar Membrane and a polyvalent cation selectively pass through film ", when with seawater as material
Liquid, using as a example by the electrodialysis system of a repetitive when, shown in its membrane stack schematic internal view such as Fig. 1 (b)：Feed liquid is passed through
To electrodialysis system, by applying electric current, there is water decomposition and generate hydroxyl and hydrogen ion, sodium ion in feed liquid room in Bipolar Membrane
Selectively migrated to alkali room through film by a polyvalent cation under the impetus of anode, and dissociateed with adjacent bipolar film
Hydroxide ion combine obtain NaOH；Calcium ion, magnesium ion in feed liquid room cannot be selected by a polyvalent cation
Property enters alkali room through film, is retained in feed liquid room；Anion in feed liquid room cannot be obtained by Bipolar Membrane in feed liquid room
Retain, and the hydrogen ion dissociateed with adjacent bipolar film is combined and obtains acid；Electric current constantly applies, and the sodium ion in feed liquid is continuous
It is removed, while the NaOH in alkali room is constantly accumulated.Using the electrodialysis system of multiple repetitives with using single chamber
The system operation principles of chamber unit are identical.The operating principle of the feed liquids with different compositions with seawater selective Bipolar Membrane electric osmose
Analysis operating principle is identical.
For the electrodialysis membrane stack being made up of " Bipolar Membrane and a multivalent anions selectively pass through film ", when with seawater as material
Liquid, using as a example by the electrodialysis system of a repetitive when, shown in its membrane stack schematic internal view such as Fig. 1 (c)：Feed liquid is passed through
To electrodialysis system, by applying electric current, there is water decomposition and generate hydroxyl and hydrogen ion in Bipolar Membrane, the chlorine in feed liquid room from
Son is selectively migrated to sour room by a multivalent anions under the impetus of negative electrode through film, and is dissociated with adjacent bipolar film
The hydrogen ion for going out is combined and obtains hydrochloric acid；Sulfate ion in feed liquid room selectively cannot be entered by a multivalent anions through film
Enter sour room, retained in feed liquid room；Sodium ion, calcium ion, magnesium ion in feed liquid room cannot be by Bipolar Membrane, in feed liquid room
Retained, and the hydroxide ion dissociateed with adjacent bipolar film is combined and obtains alkali；Electric current constantly applies, the chlorine in feed liquid
Ion is constantly removed, while the hydrochloric acid in sour room is constantly accumulated.Using the electrodialysis system of multiple repetitives with using single
The system operation principles of individual chamber unit are identical.The operating principle of the feed liquids with different compositions with seawater selective Bipolar Membrane
Electrodialysis operation principle is identical.
Compared with the prior art, beneficial effects of the present invention are embodied in：
1st, selective bipolar membrane electrodialysis system of the invention combines bipolar membrane electrodialysis and selective electrodialysis same
In one device, when for the desalination of saliferous feed liquid and the operation of product soda acid, compared to selective electrodialysis and bipolar membrane electrodialysis
Coupling process, the two is merged into an operation, simplify flow process, reduce operational ton, reduce electrode reaction energy consumption, carry
High production efficiency.
2nd, system of the invention can be used to be separated the multivalent ion in mixing salt solution, make the cation of monovalence
Into alkali room, the anion for making monovalence enters sour room, and multivalent ion is retained in feed liquid room, it is adaptable to which a various multivalent ions are mixed
Zoarium system.Compared to traditional precipitation method separating technology, it is not necessary to add extra precipitating reagent, more discarded objects are not produced,
Cost is reduced, chemical process greenization is realized.
3rd, the monovalent cation and univalent anion in mixing salt solution can be respectively transferred to alkali room and acid by the present invention
In room, so as to obtain corresponding high-purity alkali and acid, the economy of process is improve.
4th, the present invention solves the problems, such as that a multivalent ion mixed system separation process is complicated, consume and discharge higher, carries
The economic benefit of electrodialysis methods is risen.
Description of the drawings
Fig. 1 is the membrane stack internal structure schematic diagram of three kinds of multi-forms, wherein：A be by Bipolar Membrane, cation-exchange membrane and
Anion-exchange membrane alternately laminates successively the membrane stack schematic internal view of the selective bipolar membrane electrodialysis system of composition；B is by double
Inside the membrane stack of the selective bipolar membrane electrodialysis system that pole film and a polyvalent cation are selectively alternately constituted successively through film
Schematic diagram；C is the selective bipolar membrane electrodialysis being selectively alternately made up of successively through film Bipolar Membrane and a multivalent anions
The membrane stack schematic internal view of system；
Fig. 2 is a kind of schematic diagram of selectivity bipolar membrane electrodialysis system of the invention；
Fig. 3 is electrical conductivity, pH and membrane stack voltage change schematic diagram during embodiment 1；
Fig. 4 is electrical conductivity, pH and membrane stack voltage change schematic diagram during embodiment 2；
Label in figure：1 electrode solution hold-up tank；The import of 1a anode chambers；1b cathode chamber inlets；1c anode compartment outlets；1d
Cathode chamber outlet；1e electrode solution transfer tubes；2 acid solution hold-up tanks；2a sour room imports；2b sour rooms are exported；2c sour rooms pH are sensed
Device；2d sour room conductivity sensors；2e acid solution transfer tubes；3 feed liquid hold-up tanks；3a expects anolyte chamber inlet；3b feed liquids room goes out
Mouthful；3c feed liquids room pH sensors；3d feed liquids room conductivity sensor；3e feed liquid transfer tubes；4 alkali lye hold-up tanks；4a alkali rooms
Import；4b alkali rooms are exported；4c alkali room pH sensors；4d alkali room conductivity sensors；4e alkali lye transfer tubes；5 power supplys；6
PH meter；7 conductivity meters；8 electrodialysis membrane stacks.
Specific embodiment
The selective bipolar membrane electrodialysis system of the present invention includes electrodialysis membrane stack and by Boards wall in electrodialysis
The positive plate and minus plate of membrane stack both sides；Electrodialysis membrane stack be alternately laminated successively by several functional membranes after plus upper runner filter and
Gasket seal is constituted；Functional membrane includes that Bipolar Membrane and a multivalent ion selectively pass through film；The anion exchange layer court of Bipolar Membrane
To positive plate, cation exchange layer is towards minus plate.
Wherein, electrodialysis membrane stack can be selectively alternately laminated successively through film by Bipolar Membrane and a polyvalent cation after
Plus upper runner filter and gasket seal are constituted, or selectively replaced successively through film by Bipolar Membrane and a multivalent anions
Add upper runner filter and gasket seal composition after laminating, can also be by Bipolar Membrane, cation-exchange membrane and anion-exchange membrane
Add upper runner filter and gasket seal composition after alternately laminating successively.As a example by the third, its structure is as shown in Figure 2.
Electrodialysis system by electrodialysis membrane stack 8 and by Boards wall electrodialysis membrane stack both sides positive plate and negative electrode
Plate is constituted；Electrodialysis membrane stack is selectively selectively passed through through film and a multivalent anions by Bipolar Membrane, a polyvalent cation
Film adds upper runner filter and gasket seal composition after alternately laminating successively；Anode chamber, negative electrode are formed between positive plate and adjacent membranes
Cathode chamber is formed between plate and adjacent membranes；It is formed with electrodialysis membrane stack one or more " alkali rooms-feed liquid room-sour room "
Repetitive；
Positive plate and minus plate are connected respectively with the positive pole and negative pole of power supply 5；Anode chamber's import 1a of anode chamber and anode
Room outlet 1c is communicated in electrode solution hold-up tank 1, and the cathode chamber inlet 1b and cathode chamber outlet 1d of cathode chamber are also communicated in parallel electricity
Pole liquid hold-up tank 1.The material anolyte chamber inlet 3a and material chamber outlet 3b of feed liquid room is communicated in feed liquid hold-up tank 3, and the sour room of sour room is entered
Mouth 2a and sour room outlet 2b are communicated in acid solution hold-up tank 2, and the alkali room import 4a of alkali room and alkali room outlet 4b are communicated in alkali lye storage
Tank 4.
Anode chamber, cathode chamber, sour room, alkali room, solution passes through respectively transfer tube (electrode solution transfer tube 1e, acid in feed liquid room
Liquid transfer tube 2e, alkali lye transfer tube 4e, feed liquid transfer tube 3e) drive, and between electrodialysis system and corresponding solution hold-up tank
Formation is circulated；
Conductivity sensor (sour room conductivity sensor 2d, alkali room are all provided with sour room, alkali room, feed liquid room exit
Conductivity sensor 4d, feed liquid room conductivity sensor 3d) and pH sensors (sour room pH sensor 2c, alkali room pH sensor 4c,
Feed liquid room pH sensor 3c).
Each pH sensors are connected to pH meter 6, and each conductivity sensor is connected to conductivity meter 7.
The present invention selective bipolar membrane electrodialysis system can be used for while to saliferous feed liquid desalination produce acid and/or
Alkali is produced, while the Selective Separation of a multivalent ion can also be realized, concrete example is as follows：
Embodiment 1
The present embodiment is processed sea crystal solution using the selective bipolar membrane electrodialysis system shown in above-mentioned Fig. 2,
The raw materials used solution for sea crystal, sea crystal concentration is 70g/L；Concrete process step is as follows：
Electrodialysis membrane stack is cloudy selectively through film and a multivalence by Bipolar Membrane, a polyvalent cation in electrodialysis system used
After ion selectivity is alternately laminated successively through film plus upper runner filter and gasket seal composition, altogether using three Bipolar Membranes, two
Open a polyvalent cation and selectively selectively pass through film through film, two multivalent anions, in electrodialysis membrane stack 2 are formed with
The repetitive of individual " alkali room-feed liquid room-sour room ".Bipolar Membrane selectively constitutes alkali with an adjacent polyvalent cation through film
Room, selectively sour room is constituted with an adjacent multivalent anions through film；An adjacent multivalent anions selectively pass through film and more than
Valency cation permselective film composition feed liquid room.Bipolar Membrane, a polyvalent cation used in process selectively passes through film
With BP, CSO, ASV that a multivalent anions selectively adopt AGC companies through film.Single film and membrane stack single electrode are effective
Area is 189cm2。
Sea crystal solution is added to feed liquid hold-up tank, sea crystal solution is caused in feed liquid room and material using feed liquid transfer tube
Circulate between liquid hold-up tank；The hydrochloric acid solution of 0.1mol/L is added into acid solution hold-up tank, using acid solution transfer tube acid is caused
Liquid is circulated between sour room and acid solution hold-up tank；The sodium hydroxide solution of 0.1mol/L is added to alkali lye hold-up tank, profit
With alkali lye transfer tube alkali lye is circulated between alkali room and alkali lye hold-up tank；3% metabisulfite solution is added into electrode
Liquid hold-up tank, causes electrode solution to circulate between anode chamber, cathode chamber and electrode solution hold-up tank using electrode solution transfer tube；
Each chamber solution flows the constant current of 10 minutes after-applied 1.42A in electrodialysis membrane stack inner loop, and online
The voltage change at monitoring electrodialysis membrane stack two ends and the electrical conductivity of each chamber, pH changes.Using icp analysis experiment before and after alkali room,
Sodium ion, calcium ion content in feed liquid room, using chlorion, sulphur in sour room, feed liquid room before and after ion chromatography experiment
Acid ion content, concrete outcome is shown in Table 1 and Fig. 3；
When experiment proceeds to 60 minutes, electric current is removed, turn off each chamber solution transfer tube.
Embodiment 2
The present embodiment is used in the identical electrodialysis system of embodiment 1, and sea crystal solution is processed, raw materials used to be
The solution of sea crystal, sea crystal concentration is 35g/L；Concrete process step is as follows：
Sea crystal solution is added to feed liquid hold-up tank, sea crystal solution is caused in feed liquid room and material using feed liquid transfer tube
Circulate between liquid hold-up tank；The hydrochloric acid solution of 0.1mol/L is added into acid solution hold-up tank, using acid solution transfer tube acid is caused
Liquid is circulated between sour room and acid solution hold-up tank；The sodium hydroxide solution of 0.1mol/L is added to alkali lye hold-up tank, profit
With alkali lye transfer tube alkali lye is circulated between alkali room and alkali lye hold-up tank；3% metabisulfite solution is added into electrode
Liquid hold-up tank, causes electrode solution to circulate between anode chamber, cathode chamber and electrode solution hold-up tank using electrode solution transfer tube；
Each chamber solution flows the constant current of 10 minutes after-applied 1.89A in electrodialysis membrane stack inner loop, and online
The voltage change at monitoring electrodialysis membrane stack two ends and the electrical conductivity and pH change of each chamber.Using alkali before and after icp analysis experiment
Sodium ion, calcium ion content in room, feed liquid room, using the chlorion before and after ion chromatography experiment in sour room, feed liquid room,
Sulfate ion content, concrete outcome is shown in Table 1 and Fig. 4；
When experiment proceeds to 60 minutes, electric current is removed, turn off each chamber solution transfer tube.
Each chamber ion concentration, ion select coefficient situation in the electrodialytic process of table 1
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (8)
1. a kind of selective bipolar membrane electrodialysis system, it is characterised in that：The selective bipolar membrane electrodialysis system includes electricity
Dialysis membrane stack and by Boards wall the electrodialysis membrane stack both sides positive plate and minus plate；The electrodialysis membrane stack is
Upper runner filter and gasket seal is added to constitute after alternately being laminated successively by several functional membranes；The functional membrane includes Bipolar Membrane and
Multivalent ion selectively passes through film；, towards positive plate, cation exchange layer is towards minus plate for the anion exchange layer of Bipolar Membrane.
2. selective bipolar membrane electrodialysis system according to claim 1, it is characterised in that：The electrodialysis membrane stack is by double
Pole film and a polyvalent cation add upper runner filter and gasket seal composition after selectively alternately laminating successively through film；Positive plate
Anode chamber is formed between adjacent membranes, cathode chamber is formed between minus plate and adjacent membranes；1 is formed with the electrodialysis membrane stack
The repetitive of individual or multiple " alkali room-feed liquid room ".
3. selective bipolar membrane electrodialysis system according to claim 1, it is characterised in that：The electrodialysis membrane stack is by double
Pole film and a multivalent anions add upper runner filter and gasket seal composition after selectively alternately laminating successively through film；Positive plate
Anode chamber is formed between adjacent membranes, cathode chamber is formed between minus plate and adjacent membranes；1 is formed with the electrodialysis membrane stack
The repetitive of individual or multiple " sour room-feed liquid room ".
4. selective bipolar membrane electrodialysis system according to claim 1, it is characterised in that：The electrodialysis membrane stack is by double
Pole film, cation-exchange membrane and anion-exchange membrane add upper runner filter and gasket seal composition after alternately laminating successively；Anode
Anode chamber is formed between plate and adjacent membranes, cathode chamber is formed between minus plate and adjacent membranes；Formed in the electrodialysis membrane stack
There is the repetitive of one or more " alkali rooms-feed liquid room-sour room "；The cation-exchange membrane and the anion-exchange membrane
At least one of selectively pass through film for a multivalent ion.
5. selective bipolar membrane electrodialysis system according to claim 2, it is characterised in that：
Positive plate and minus plate are connected respectively with the positive pole and negative pole of power supply；Anode chamber and cathode chamber are communicated in parallel electrode solution storage
Tank is deposited, feed liquid room is communicated in feed liquid hold-up tank, and alkali room is communicated in alkali lye hold-up tank；
Anode chamber, cathode chamber, alkali room, solution is driven respectively by transfer tube in feed liquid room, and in electrodialysis system and corresponding storage
Deposit to be formed between tank and circulate；
PH sensors and conductivity sensor are all provided with alkali room, feed liquid room exit；
Each pH sensors are connected to pH meter, and each conductivity sensor is connected to conductivity meter.
6. selective bipolar membrane electrodialysis system according to claim 3, it is characterised in that：
Positive plate and minus plate are connected respectively with the positive pole and negative pole of power supply；Anode chamber and cathode chamber are communicated in parallel electrode solution storage
Tank is deposited, feed liquid room is communicated in feed liquid hold-up tank, and sour room is communicated in acid solution hold-up tank；
Anode chamber, cathode chamber, sour room, solution is driven respectively by transfer tube in feed liquid room, and in electrodialysis system and corresponding storage
Deposit to be formed between tank and circulate；
PH sensors and conductivity sensor are all provided with sour room, feed liquid room exit；
Each pH sensors are connected to pH meter, and each conductivity sensor is connected to conductivity meter.
7. selective bipolar membrane electrodialysis system according to claim 4, it is characterised in that：
Positive plate and minus plate are connected respectively with the positive pole and negative pole of power supply；Anode chamber and cathode chamber are communicated in parallel electrode solution storage
Tank is deposited, feed liquid room is communicated in feed liquid hold-up tank, and sour room is communicated in acid solution hold-up tank, and alkali room is communicated in alkali lye hold-up tank；
Anode chamber, cathode chamber, sour room, alkali room, solution is driven respectively by transfer tube in feed liquid room, and in electrodialysis system and phase
Answer to be formed between hold-up tank and circulate；
PH sensors and conductivity sensor are all provided with sour room, alkali room, feed liquid room exit；
Each pH sensors are connected to pH meter, and each conductivity sensor is connected to conductivity meter.
8. in a kind of claim 1～7 selective bipolar membrane electrodialysis system described in any one application, it is characterised in that：
For acid to be produced while to saliferous feed liquid desalination and/or alkali is produced.
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