CN106823815A - Electrodialysis plant - Google Patents
Electrodialysis plant Download PDFInfo
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- CN106823815A CN106823815A CN201710083797.XA CN201710083797A CN106823815A CN 106823815 A CN106823815 A CN 106823815A CN 201710083797 A CN201710083797 A CN 201710083797A CN 106823815 A CN106823815 A CN 106823815A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/445—Ion-selective electrodialysis with bipolar membranes; Water splitting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
- B01D61/48—Apparatus therefor having one or more compartments filled with ion-exchange material, e.g. electrodeionisation
- B01D61/485—Specific features relating to the ion-exchange material
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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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
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- Health & Medical Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
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- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a kind of electrodialysis plant; the electrodialysis plant is respectively provided with anodic protection room and cathodic protection room by the end of the close anode chamber of membrane stack and cathode chamber, and running, there is a protection liquid for independent loops system to realize the protection to the electrode solution of electrodialysis plant.Anodic protection room is separated by with anode chamber by an anode membrane, and cathodic protection room is then separated by with cathode chamber by another anode membrane, anodic protection room and cathodic protection room are separated by with therebetween desalting chamber and enriched chamber by cavity block, to control high-valence cationic to pass through migration of the film to cathode chamber and anode chamber, so that the high-valence cationic in desalinization liquor and concentrate is effectively isolated, significantly reduce the content of the high volence metal ion in electrode solution, avoid it from generating precipitation or reduction reaction occurs in cathode chamber and deposit to minus plate, greatly prolong the cycle period of electrode solution, significantly reduce the operating cost of electrode solution.
Description
Technical field
The invention belongs to electric drive technical field of membrane separation, specifically, it is related to a kind of electrodialysis plant.
Background technology
Electrodialysis is widely used in desalinization, brackish water desalination, food and doctor as a kind of electric drive membrane separation technique
The fields such as medicine production.In recent years, with the development of specific ion exchange membrane and the continuous innovation of conventional electrodialysis device and improvement,
Application of the electrodialysis in the field such as separation and Extraction of industrial wastewater recycling and rare precious metal increases powerful.Electrodialysis can use
In reclaiming precious metal from the industrial wastes of the metal ions such as nickeliferous, cobalt, manganese, copper, chromium, zinc；It is equipped with monovalent ion selectivity
The electrodialysis plant of exchange membrane can be used to efficiently separate the rare precious metals such as extraction lithium, rubidium, caesium from magnesium high or high calcium solution.
In electrodialytic process, main process passes through cation exchange as counter ion for rare precious metal ion from desalting chamber
Migration from film to enriched chamber.Because the conducting process in amberplex is substantially the directional migration of ion permeable film, can not keep away
Exempt from the ion exchange between the electrode solution in desalting chamber and/or enriched chamber and anode chamber and/or cathode chamber, desalinization liquor
And/or the high valent cationic more than divalence in concentrate is with sides such as counter ion migration, the infiltrations of Ion transfer of the same name, concentration difference
Formula enters electrode solution through film；After high volence metal ion in catholyte reaches finite concentration, with the hydrogen-oxygen that cathode reaction is produced
Root is combined generation precipitation, or metal reduction reaction occurs, and deposits on minus plate, influences the smooth long term running of equipment,
The cycle period of electrode solution is greatly shortened, electrode solution operating cost is significantly improved.
When electrodialysis is used to extract lithium from high Mg/Li ratio bittern, above-mentioned phenomenon is especially protruded.Membrane stack both sides desalinization liquor
Or the magnesium ion in concentrate constantly enters in electrode solution through film, when magnesium ion content is more than 1g/L in catholyte, negative electrode
Room can generate Mg (OH)2Gelatinous precipitate, adheres on cathode side face or minus plate, forces system shutdown.
At present, the method for typically taking a large amount of new electrode solutions of supplement, with magnesium ion content in keeping catholyte in relatively low
Level, but this method can cause more fresh water and NaNO3/ nitric acid or NaSO4A large amount of consumption of the reagents such as/sulfuric acid, improve point
From cost.
In addition, also there is part to study the pH value or direct using acid solution as the side of electrode solution reported by reducing electrode solution
Method, but on the one hand these methods can cause a large amount of consumption of acid, and separation costs are higher；The catholyte of another aspect highly acidity can also
There is strong corrosiveness to minus plate, without use value.
When especially using the dominant salting liquid of high volence metal ion more than divalence or divalence as desalination stoste,
Such as the high Mg/Li ratio bittern that Mg/Li ratio (i.e. the mass ratio of magnesium ion and lithium ion) is 10~2000, these how are controlled at high price
Migration amount from metal ion to electrode solution, reduce electrode solution operating cost, ensure electrodialysis safe and stable operation, to electrodialysis
The industrialization promotion of technology has decisive meaning.
The content of the invention
To solve the problems, such as above-mentioned prior art, the invention provides a kind of electrodialysis plant, the electrodialysis plant
By the both sides of membrane stack set anodic protection room and cathodic protection room, efficiently controlled high volence metal ion through film layer to
The problem of cathode chamber migration.
In order to reach foregoing invention purpose, present invention employs following technical scheme：
A kind of electrodialysis plant, including membrane stack and the anode chamber positioned at the membrane stack both sides and cathode chamber；Wherein, it is described
Some enriched chambers and desalting chamber are formed in membrane stack；The membrane stack is described in being adjacent to the first anode membrane of the anode chamber, being adjacent to
First cavity block of the first anode membrane, the second anode membrane for being adjacent to the cathode chamber, the second cavity block for being adjacent to second anode membrane, with
And it is arranged at the anion-exchange membrane being alternately arranged and cation-exchange membrane between first cavity block and second cavity block
Formed；Wherein, the desalting chamber and institute being alternately arranged are formed between the anion-exchange membrane and the cation-exchange membrane
State enriched chamber；Anodic protection room, second anode membrane and described second are formed between first anode membrane and first cavity block
Cathodic protection room is formed between cavity block.
Further, first anode membrane is the monovalent ion selectivity sun of enhanced anode membrane or outside additional protective layers
Film；Second anode membrane is enhanced anode membrane or monovalent ion selectivity anode membrane.
Further, the protective layer is obstruct Cl2The conducting film that molecule is passed through.
Further, first cavity block is monovalent ion selectivity cavity block or common cavity block；Second cavity block is one
Valency ion selectivity cavity block or common cavity block.
Further, the anion-exchange membrane is monovalent ion selectivity cavity block or common cavity block, and the cation is handed over
It is monovalent ion selectivity anode membrane or common anode membrane to change film.
Further, it is filled with filter in the anodic protection room and the cathodic protection room.
Further, the water distribution frame of the anodic protection room, the water distribution frame of the cathodic protection room, the desalting chamber and
The energization area of the enriched chamber is equal.
Further, the turnover aquaporin of the water distribution frame is furnished with multiple-limb manifold.
Further, the electrodialysis plant also includes what is be connected with the anodic protection room and the cathodic protection room
Protection liquid circulating slot, the protection liquid water inlet for being passed through the protection liquid circulating slot is wherein Na+Concentration is not less than the sodium of 0.5mol/L
Saline solution；The protection liquid water inlet is between the anodic protection room and the protection liquid circulating slot and in the negative electrode
Circulated between protection room and the protection liquid circulating slot, form protection liquid.
Further, the superficial linear vilocity for protecting liquid in the anodic protection room and the cathodic protection room is not low
In 2cm/s.
Further, the sodium-salt aqueous solution is the NaCl aqueous solution or Na2SO4The aqueous solution.
Beneficial effects of the present invention：
(1) electrodialysis plant of the invention can be greatly reduced high valent cationic to the migration amount of electrode solution,
So that more effectively generation precipitation or metal reduction deposit to the reaction of minus plate, guarantee equipment in electrode solution in control cathode chamber
Operation steady in a long-term；
(2) electrodialysis plant of the invention substantially prolongs the cycle period of electrode solution, can significantly reduce existing skill
Fresh water and reagent consumption in art, alleviate discharge or the reuse problem of electrode cycle waste liquid, and electrode solution operating cost is greatly reduced；
(3) electrodialysis plant of the invention avoids the dirt that the foreign ion such as NO3- in electrode solution produces water to concentration
Dye, advantageously reduces the cost of its post processing, and improves the quality of product；
(4) in industrial production, enriched chamber and desalting chamber are general reachable hundreds of right in membrane stack, and electrodialysis of the invention
Device only needs to two protection rooms, while using the desalination in the inspissation in anodic protection room and cathodic protection room
Cancel out each other, protection liquid consumption can approximately be ignored, and be intake as protection liquid using sodium-salt aqueous solution, its wide material sources, price
It is cheap, so as to protect the operating cost of liquid can approximately ignore；
(5) in electrodialysis plant of the invention, the second cavity block of cathodic protection indoor is had to metal cation
Iris action so that complete inspissation plays in the enriched chamber adjacent with cathodic protection room, so as to avoid equipment start
There is the problem of concentration polarization in the stage, solve now film in this place first because the ion concentration in concentrate water inlet is too low
There is water decomposition and form Mg (OH) in face2Or the problem of other high-valency metals precipitation；
(6) electrodialysis plant of the invention passes through the anode membrane of reasonable selection first, the second anode membrane, the first cavity block, second
The species of cavity block, anion-exchange membrane and cation-exchange membrane, can be applied to reclaim lithium from magnesium solution high using electroosmose process
Salt reclaims the purposes such as precious metal from non-ferrous metals industry waste liquid, is widely used；Being particularly suited for treatment has superelevation magnesium
Lithium ratio (Mg2+With Li+Mass ratio be not less than stoste containing lithium 100), for the technology that selective electroosmose process is used to carry lithium
Being generalized to the different bittern lithium resource of chemical composition has decisive meaning.
Brief description of the drawings
By the following description carried out with reference to accompanying drawing, above and other aspect of embodiments of the invention, feature and advantage
Will become clearer, in accompanying drawing：
Fig. 1 is the structural representation of electrodialysis plant of the invention；
Fig. 2 is the structural representation of membrane stack in Fig. 1.
Specific embodiment
Hereinafter, with reference to the accompanying drawings to describing embodiments of the invention in detail.However, it is possible to come real in many different forms
Apply the present invention, and the present invention should not be construed as limited to the specific embodiment that illustrates here.Conversely, there is provided these implementations
Example is in order to explain principle of the invention and its practical application, so that others skilled in the art are it will be appreciated that the present invention
Various embodiments and be suitable for the various modifications of specific intended application.In the accompanying drawings, for the sake of clarity, element can be exaggerated
Shape and size, and identical label will all the time be used to indicate same or analogous element.
Although it will be appreciated that can be used term " first ", " second " etc. to describe various elements herein, these
Element should not be limited by these terms.These terms are only used for making a distinction an element and another element.
Fig. 1 is the structural representation of electrodialysis plant of the invention, and Fig. 2 is the structural representation of membrane stack in Fig. 1.
Referring in particular to Fig. 1 and Fig. 2, electrodialysis plant of the invention includes membrane stack and positioned at membrane stack both sides anode chamber
And cathode chamber；Some enriched chambers and desalting chamber are formed in membrane stack；Membrane stack is by being adjacent to the first anode membrane K1 of anode chamber, being adjacent to
The first cavity block A1 of one anode membrane K1, the second anode membrane K2 for being adjacent to cathode chamber, the second cavity block A2 for being adjacent to the second anode membrane K2, with
And it is arranged at the anion-exchange membrane A being alternately arranged and cation-exchange membrane K shapes between the first cavity block A1 and the second cavity block A2
Into；Wherein, the desalting chamber and enriched chamber being alternately arranged are formed between anion-exchange membrane A and cation-exchange membrane K；First anode membrane
An anodic protection room is formed between K1 and the first cavity block A1, a negative electrode is formed between the second anode membrane K2 and the second cavity block A2 and is protected
Shield room.
What deserves to be explained is, in Fig. 1, the structure in membrane stack does not represent desalting chamber and concentration in the embodiment of the present invention
The specific arrangement mode of room, only represents inside membrane stack by some amberplexes (i.e. above-mentioned first anode membrane K1, the first cavity block
A1, anion-exchange membrane A, cation-exchange membrane K, the second cavity block A2 and the second anode membrane K2) it is alternately arranged the anodic protection to be formed
Room, desalting chamber, enriched chamber and cathodic protection room, and it is related to anodic protection room, desalting chamber, enriched chamber and cathodic protection room
Feed solution flow direction.
Specifically, the structure of electrodialysis plant of the invention is：One the first anode membrane K1, first cavity block A1, a n-1
Anion-exchange membrane A, n cation-exchange membrane K, an a second cavity block A2 and second anode membrane K2 are opened according to by anode
Room to the direction of cathode chamber is alternately arranged, form an anodic protection room, n enriched chamber being alternately arranged and n desalting chamber,
And a cathodic protection room；That is, in the electrodialysis plant, an anodic protection room and cathodic protection room it
Between be folded with and be desalting chamber and enriched chamber that n is alternately arranged, wherein adjacent with anodic protection room is the first desalting chamber, with
Cathodic protection room it is adjacent be the first enriched chamber, be alternately arranged n-th successively by the first desalting chamber to the direction of the first enriched chamber
Enriched chamber, the second desalting chamber, the (n-1)th enriched chamber ..., the (n-1)th desalting chamber, the second enriched chamber, the n-th desalting chamber, first concentration
Room.
First anode membrane K1 can be resistance to Cl2Corrosion enhanced anode membrane or its adjacent to anode chamber outside additional protective layers
Monovalent ion selectivity anode membrane, protective layer be preferably capable intercept Cl2The conducting film that molecule is passed through；Second anode membrane K2 can be
Resistance to Cl2Enhanced anode membrane or monovalent ion the selectivity anode membrane of corrosion；Cation-exchange membrane K selects monovalent ion choosing according to purposes
Selecting property anode membrane or common anode membrane, the first cavity block A1, the second cavity block A2 and anion-exchange membrane A select monovalent ion according to purposes
Selective cavity block or common cavity block.
Specifically, when cation-exchange membrane K is monovalent ion selectivity anode membrane, can be produced using ASTOM companies of Japan
CIMS types or K192 types film, the CSO types film (also referred to as CSV types film) of Asahi Glass company or other companies there is close selection
The anode membrane of property；When the first cavity block A1, the second cavity block A2 and anion-exchange membrane A are monovalent ion selectivity cavity block, can adopt
The ACS types or A192 types film, the ASV types film of Asahi Glass company or other companies produced with ASTOM companies have close selectivity
Cavity block.
Being equipped with outside anodic protection room and cathodic protection room has the water distribution of identical energization area with desalting chamber and enriched chamber
Frame (not shown)；Meanwhile, there is filter (figure anodic protection room and cathodic protection room in respective two film central fillers respectively
Not shown in) and there are the independent circulatory system (not shown) for protecting liquid to circulate and some settings respectively
Multiple-limb manifold (not shown) on water distribution frame water inlet/delivery port, the wherein water inlet pipe of the circulatory system and water distribution frame
Water inlet be connected；Corresponding support, sealing are played in the setting of filter, conductive and current are uniform, collect and strengthen turbulent flow
Deng effect.In this way, protection liquid be by circulating pump and circulation line (not shown) anodic protection room, cathodic protection room and
Circulated between protection liquid circulating slot；That is, first to protection liquid water inlet is passed through in protection liquid circulating slot, this part is protected
Shield liquid water inlet is passed through in anodic protection room and cathodic protection room by protection liquid circulating slot, then by anodic protection room and cathodic protection room
Protection liquid is formed when looping back protection liquid circulating slot.
Specifically, the protection liquid water inlet being passed through in protection liquid circulating slot is wherein Na+Concentration is not less than the sodium of 0.5mol/L
Saline solution；The desalination used when being generally used for the separating Li from salt lake brine with high magnesium-lithium ratio according to the electrodialysis plant is intake
Composition, protection liquid water inlet be preferably the NaCl aqueous solution or Na2SO4The aqueous solution.The protection liquid water inlet of the concentration is enough to carry larger
Operation electric current.Meanwhile, during protection liquid is circulated in protection liquid circulating slot with anodic protection room, cathodic protection room, control
Superficial linear vilocity of the system protection liquid in anodic protection room and cathodic protection room is not less than 2cm/s.
To verify heretofore described electrodialysis plant during the separating Li from salt lake brine with high magnesium-lithium ratio
Good result, is tested by specific embodiment to the electrodialysis plant that the present invention is provided.
The electrodialysis plant that the present invention is provided is when being tested, and its general operation and principle are as follows：(1) by desalination stoste
(i.e. salt lake brine with high magnesium-lithium ratio) is passed through in desalinization liquor circulating slot, and the desalination stoste passes through desalinization liquor circulating pump and desalination circulation pipe
Circulated between desalting chamber and desalinization liquor circulating slot on road；(2) electrode solution is existed by electrode solution circulating pump and electrode solution circulation line
Circulated between cathode chamber, anode chamber and electrode solution circulating slot, form electrode cycle liquid；Electrode cycle pipeline is to refer to wherein in Fig. 1
Circulation has the pipeline of electrode cycle liquid；(3) concentrate water inlet is passed through in concentrate circulating slot, concentrate water inlet is by concentration
Liquid circulating pump and concentration cycles pipeline are circulated between enriched chamber and concentrate circulating slot.In this way, in the presence of DC electric field,
Li in desalinization liquor+Migrated to enriched chamber from desalting chamber by cation-exchange membrane K Deng cation, obtaining concentration in enriched chamber produces
Water simultaneously flows back to concentration cycles groove, then be passed through enriched chamber via concentration cycles groove in concentrate form；Meanwhile, taken off in desalting chamber
Salt produces water cocurrent salt circulating slot back off, then is passed through desalting chamber via desalination circulating slot in desalinization liquor form.Desalination circulation pipe in Fig. 1
Road be refer to wherein circulation have desalinization liquor, desalination produce water pipeline, in Fig. 1 concentration cycles pipeline be refer to wherein circulation have concentrate,
The pipeline of water is produced in concentration.
In order to ensure concentration stream normal circulation and conduction, at least in electrodialytic startup stage, in concentrate circulating slot
In be passed through the water inlet of a small amount of concentrate, concentrate water inlet can be deionized water.Electro-osmosis using electrodialytic process reclaimed water shows
As in sub-fraction moisture penetration in desalting chamber to enriched chamber, so as to realize that the synchronization of water volume and ion concentration is produced in concentration
Lifting.
Hereinafter, electrodialysis plant of the invention and its application effect will be illustrated by specific embodiment.
Embodiment 1
In embodiment 1, the first anode membrane K1 and the second anode membrane K2 are resistance to Cl2Corrode enhanced anode membrane, the first cavity block A1
And second cavity block A2 be A192 type films, anion-exchange membrane A is ACS type films, and cation-exchange membrane K is CIMS types
Film.
Protection liquid water inlet is 1mol/LNaCl, and it enters volume for 3L；The main composition of desalination stoste is as shown in table 1, its
It is 4.5L into volume；The entrance volume of concentrate water inlet is 0.95L；Electrode solution is 1mol/L NaNO3With 0.01mol/L
HNO3Mixed solution, it enters volume for 2L；Protect the main composition of liquid as shown in table 1.
In electrodialytic process, it is 210Am to control average current density-2, and protection liquid is controlled in anodic protection room
It is 2.3cm/s with the superficial linear vilocity in cathodic protection room.Through the electrodialysis operation of 340min, there is not precipitation, and protection
The volume of liquid is only reduced to 2.94L；Meanwhile, to desalination produce water, concentration produce water, protection liquid and electrode cycle liquid it is main constitute into
Analysis is gone, has been listed in Table 1 below.
The desalination stoste of table 1, protection liquid, desalination are produced water, concentration and produce the main composition of water and electrode cycle liquid
Note：In table 1, "-" is represented cannot be measured or impact effect is not provided, and table 2 below, 3 are similarly.
In embodiment 1, when the electrodialysis time 340min is reached, Li+Yield is 98.2%；Mg in protection liquid2+Concentration
It is approximately concentration and produces Mg in water2+The 1/100 of concentration.
The composition of liquid is protected in contrast protection liquid water inlet and table 1, it can be seen that by after the electrodialysis of certain hour,
It is the NaCl of 1mol/L or so to protect the bulk composition of liquid, little with the composition change that protection liquid is intake, and illustrates anodic protection room
In inspissation and the desalination in cathodic protection room couple, can cancel out each other so that protection liquid can grow
Phase is run, and significantly reduces protection liquid operating cost；At the same time, the bulk composition of electrode cycle liquid is 1mol/L or so in table 1
NaNO3, there is no big change, and wherein high valent cationic Mg compared with electrode solution2+Content it is relatively low, illustrate this reality
The electrodialysis plant for applying example offer can be greatly reduced high valent cationic Mg2+To the migration amount of electrode solution, so that more effectively
Precipitation is generated in electrode solution or metal reduction deposits to the reaction of minus plate, ensure the steady in a long-term of equipment in ground control cathode chamber
Operation.
Embodiment 2
In example 2, the first anode membrane K1 is the CIMS type films of additional protective layers N801 on the outside of it, the second anode membrane K2 and sun
Amberplex K is CIMS type films, and the first cavity block A1 and the second cavity block A2 are AMX type films, and anion-exchange membrane A is
ACS type films.
Protection liquid water inlet is 1mol/LNaCl, and it enters volume for 3L；The main composition of desalination stoste is as shown in table 2, its
It is 4.5L into volume；The entrance volume of concentrate water inlet is 0.95L；Electrode solution is 1mol/L NaNO3With 0.01mol/L
HNO3Mixed solution, it enters volume for 2L；Protect the main composition of liquid as shown in table 2.
In electrodialytic process, it is 210Am to control average current density-2, and protection liquid is controlled in anodic protection room
It is 2.2cm/s with the superficial linear vilocity in cathodic protection room.Through the electrodialysis operation of 339min, there is not precipitation, and protection
The volume of liquid is only reduced to 2.95L；Meanwhile, to desalination produce water, concentration produce water, protection liquid and electrode cycle liquid it is main constitute into
Analysis is gone, has been listed in Table 2 below.
The desalination stoste of table 2, protection liquid, desalination are produced water, concentration and produce the main composition of water and electrode cycle liquid
In example 2, when the electrodialysis time being 339min, Li+Yield is 97.0%；Mg in protection liquid2+Concentration is near
It is seemingly Mg in concentration product water2+The 1/370 of concentration.
The composition of liquid is protected in contrast protection liquid water inlet and table 2, it can be seen that by after the electrodialysis of certain hour,
It is the NaCl of 1mol/L or so to protect the bulk composition of liquid, little with the composition change that protection liquid is intake, and illustrates anodic protection room
In inspissation and the desalination in cathodic protection room couple, can cancel out each other so that protection liquid can grow
Phase is run, and significantly reduces protection liquid operating cost；At the same time, the bulk composition of the electrode cycle liquid in table 2 is 1mol/L left
Right NaNO3, there is no big change, and wherein high valent cationic Mg compared with electrode solution2+Content it is relatively low, illustrate this
The electrodialysis plant that embodiment is provided can be greatly reduced high valent cationic Mg2+To the migration amount of electrode solution, so as to more have
Precipitation is generated in electrode solution or metal reduction deposits to the reaction of minus plate, ensure the long-term steady of equipment in effect ground control cathode chamber
Fixed operation.
Embodiment 3
In embodiment 3, the first anode membrane K1 and the second anode membrane K2 are resistance to Cl2Corrode enhanced anode membrane, the first cavity block A1,
Second cavity block A2 and anion-exchange membrane A are ACS type films, and cation-exchange membrane K is CIMS type films.
Protection liquid water inlet is 0.25mol/LNa2SO4, it enters volume for 3L；The main composition of the desalination stoste such as institute of table 3
Show, it enters volume for 4.5L；The entrance volume of concentrate water inlet is 0.95L；Electrode solution is 0.5mol/LNa2SO4With
0.005mol/L H2SO4Mixed solution, it enters volume for 2L；Protect the main composition of liquid as shown in table 3.
In electrodialytic process, it is 210Am to control average current density-2, and protection liquid is controlled in anodic protection room
It is 2.2cm/s with the superficial linear vilocity in cathodic protection room.Through the electrodialysis operation of 340min, there is not precipitation, and protection
The volume of liquid is only reduced to 2.94L；Meanwhile, to desalination produce water, concentration produce water, protection liquid and electrode cycle liquid it is main constitute into
Analysis is gone, has been listed in Table 3 below.
The desalination stoste of table 3, protection liquid, desalination are produced water, concentration and produce the main composition of water and electrode cycle liquid
In embodiment 3, when the electrodialysis time being 340min, Li+Yield is 97.7%；Mg in protection liquid2+Concentration is near
It is seemingly Mg in concentration product water2+The 1/420 of concentration.
The composition of liquid is protected in contrast protection liquid water inlet and table 3, it can be seen that by after the electrodialysis of certain hour,
It is the Na of 0.25mol/L or so to protect the bulk composition of liquid2SO4, it is little with the composition change that protection liquid is intake, illustrate that anode is protected
Inspissation in shield room and the desalination in cathodic protection room are coupled, and can be cancelled out each other, so that protection liquid
Can longtime running, significantly reduce protection liquid operating cost；At the same time, the bulk composition of electrode cycle liquid is 0.5mol/L or so
Na2SO4, there is no big change, and wherein high valent cationic Mg compared with electrode solution2+Content it is relatively low, illustrate this
The electrodialysis plant that embodiment is provided can be greatly reduced high valent cationic Mg2+To the migration amount of electrode solution, so as to more have
Precipitation is generated in electrode solution or metal reduction deposits to the reaction of minus plate, ensure the long-term steady of equipment in effect ground control cathode chamber
Fixed operation.
By comparative example 1-3, it can be seen that electrodialysis plant of the invention can make protection liquid period ten
It is unlikely to protection liquid to the Mg in electrode cycle liquid more than secondary2+Flux is significantly increased and causes precipitation to analyse on negative electrode face
Go out.
In order to further verify the beneficial effect of electrodialysis plant of the invention, following contrast experiment is carried out, contrasted
Example 1 is intended to be contrasted by with above-described embodiment 1, to illustrate the necessity that anodic protection room and cathodic protection room are set.
Comparative example 1
In comparative example 1, the something in common of the electrodialysis plant in the electrodialysis plant and above-described embodiment 1 that are used exists
This is repeated no more, and only describes the difference of the two.Difference is：Be not provided with the second cavity block A2 and the second cavity block A2 and
Cathodic protection room between second anode membrane K2, while the first cavity block A1 is replaced with into ACS type films, the water distribution frame of anodic protection room is more
Enriched chamber's dividing plate is changed to, and it is connected with concentrate circulating slot.That is, in the electrodialysis plant of comparative example 1, film
Heap includes the first anode membrane K1, the second anode membrane K2 of adjacent cathodes room of neighbouring anode chamber and is located in the first anode membrane K1 and second
The anion-exchange membrane A being arranged alternately and cation-exchange membrane K between anode membrane K2, wherein, the first anode membrane K1 and the second anode membrane
K2 is still using such as the resistance to Cl in embodiment 12Corrode enhanced anode membrane, and anion-exchange membrane A is ACS type films, cation is handed over
Change film K and be CIMS type films.
It is to find that a little white occur in electrode solution sinks by 348min electrodialysis using condition same as Example 1
Form sediment, Mg (OH) is accredited as through XRD2；Meanwhile, water, concentration are produced to desalination producing the main composition of water and electrode cycle liquid has been carried out point
Analysis, is listed in Table 4 below.
The desalination stoste of table 4, desalination are produced water, concentration and produce the main composition of water and electrode cycle liquid
Note：In table 4, "-" is represented cannot be measured or impact effect is not provided.
As can be seen from Table 4, after through electrodialysis after a while, Mg in electrode cycle liquid2+Concentration is substantially increased,
In this way, causing to generate precipitation in electrode solution in cathode chamber, the operation steady in a long-term of equipment is prevented, force equipment to be stopped；And
The cycle period of electrode solution is greatly shortened, electrode solution operating cost is significantly improved.
By comparative example 1 and the electrodialysis effect of comparative example 1, it can be seen that make when with high Mg/Li ratio feed liquid containing lithium
When being the stoste of desalination containing lithium, when carrying lithium using the monovalent ion selectivity electrodialysis plant with protection room, Mg2+To electrode cycle
The flux of liquid can be reduced to 1/37 or so (Mg in electrode cycle liquid in the table 1 of embodiment 12+Concentration is 38.31mg/L, the table of comparative example 1
Mg in electrode cycle liquid in 42+Concentration is 1402mg/L), the electrodialysis plant in embodiment 1 prevents electrode with minimum cost
Precipitation is generated in circulation fluid, electrode solution operating cost is reduced, and foreign ion is produced to concentration in avoiding electrode cycle liquid
The pollution of water, advantageously reduces the quality that concentration is produced the post processing cost of water and improves the lithium salts product of its acquisition.Above-mentioned contrast
Example 1 and the electrodialysis Contrast on effect of embodiment 1, also prove the electrodialysis plant middle-jiao yang, function of the spleen and stomach in above-described embodiment 1-3 from the negative
Protect the necessity of the design of room and cathodic protection room in pole.
Therefore, summary embodiment 1-3 and comparative example 1, it can be seen that electrodialysis plant of the invention is in film
Using cavity block (the first cavity block A1, the second cavity block A2), protection room, (anodic protection room, negative electrode are protected successively from inside to outside for the both sides of heap
Shield room), anode membrane (the second anode membrane K1, the second anode membrane K2) isolation, with wherein Na+Content is not less than the sodium-salt aqueous solution of 0.5mol/L
Intake as protection liquid, using independent circulation stream by anodic protection room and cathodic protection room, due to anodic protection room and
The setting of cathodic protection room so that electrode cycle liquid is adequately isolated with concentrate and desalinization liquor, the composition of protecting liquid is simple,
Raw material sources are extensive, cheap, and precipitation is generated in not only preventing electrode cycle liquid with minimum cost, reduce electrode solution
Operating cost, and pollution of the foreign ion to concentration product water in electrode cycle liquid is avoided, advantageously reduce concentration and produce water
Post processing cost and improve its acquisition product quality.In above-described embodiment 1 desalination produce water in Mg/Li ratio up to more than 800,
Can know that electrodialysis plant of the invention contributes on the premise of holding equipment steadily in the long term operation, from high Mg/Li ratio
In salt lake bittern be up to 98% yield (desalination produce water in Li+Concentration is less than 70mg/L) come enrichment method lithium salts, and the electricity
Electrodialysis apparatus are particularly suited for containing lithium desalination stoste of the treatment with superelevation Mg/Li ratio (Mg/Li >=100).
Although the present invention has shown and described with reference to specific embodiment, it should be appreciated by those skilled in the art that：
In the case where the spirit and scope of the present invention limited by claim and its equivalent are not departed from, can carry out herein form and
Various change in details.
Claims (11)
1. a kind of electrodialysis plant, including membrane stack and the anode chamber positioned at the membrane stack both sides and cathode chamber；Wherein, the film
Some enriched chambers and desalting chamber are formed in heap；Characterized in that, the membrane stack is by being adjacent to the first anode membrane, the neighbour of the anode chamber
The first cavity block for being bordering on first anode membrane, the second anode membrane for being adjacent to the cathode chamber, it is adjacent to the of second anode membrane
Two cavity blocks and the anion-exchange membrane being alternately arranged being arranged between first cavity block and second cavity block and sun from
Proton exchange is formed；Wherein, be alternately arranged described de- is formed between the anion-exchange membrane and the cation-exchange membrane
Salt room and the enriched chamber；Form anodic protection room between first anode membrane and first cavity block, second anode membrane and
Cathodic protection room is formed between second cavity block.
2. electrodialysis plant according to claim 1, it is characterised in that first anode membrane is enhanced anode membrane or outside
The monovalent ion selectivity anode membrane of additional protective layers；Second anode membrane is enhanced anode membrane or monovalent ion selectivity anode membrane.
3. electrodialysis plant according to claim 2, it is characterised in that the protective layer is to intercept Cl2What molecule was passed through leads
Electrolemma.
4. electrodialysis plant according to claim 1, it is characterised in that first cavity block is that monovalent ion selectivity is cloudy
Film or common cavity block；Second cavity block is monovalent ion selectivity cavity block or common cavity block.
5. electrodialysis plant according to claim 4, it is characterised in that the anion-exchange membrane is monovalent ion selection
Property cavity block or common cavity block, the cation-exchange membrane is monovalent ion selectivity anode membrane or common anode membrane.
6. according to any described electrodialysis plants of claim 1-5, it is characterised in that the anodic protection room and the negative electrode
Protection is indoor to be filled with filter.
7. electrodialysis plant according to claim 6, it is characterised in that the water distribution frame of the anodic protection room, described the moon
The energization area of the water distribution frame, the desalting chamber and the enriched chamber of pole protection room is equal.
8. electrodialysis plant according to claim 6, it is characterised in that the turnover aquaporin of the water distribution frame is furnished with many points
Branch manifold.
9. according to any described electrodialysis plants of claim 1-5, it is characterised in that the electrodialysis plant also includes and institute
The protection liquid circulating slot that anodic protection room is connected with the cathodic protection room is stated, the protection liquid of the protection liquid circulating slot is passed through
It is wherein Na to intake+Concentration is not less than the sodium-salt aqueous solution of 0.5mol/L；It is described protection liquid water inlet the anodic protection room with
Circulated between the protection liquid circulating slot and between the cathodic protection room and the protection liquid circulating slot, form protection
Liquid.
10. electrodialysis plant according to claim 9, it is characterised in that the protection liquid in the anodic protection room and
Superficial linear vilocity in the cathodic protection room is not less than 2cm/s.
11. electrodialysis plants according to claim 9, it is characterised in that the sodium-salt aqueous solution be the NaCl aqueous solution or
Na2SO4The aqueous solution.
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| CN107746098A (en) * | 2017-10-25 | 2018-03-02 | 中国科学技术大学 | A kind of apparatus and method of hydrogen ion selective electrodialysis recovery acid from the waste liquid containing low concentration acid and high-concentration metallic ions |
| CN108114599A (en) * | 2017-12-25 | 2018-06-05 | 中国科学技术大学 | It is a kind of based on salt error the electrodialysis reversal of production soda acid to be driven to couple bipolar membranous system and its production method |
| CN109607709A (en) * | 2019-01-12 | 2019-04-12 | 大连理工大学 | A kind of electrochemistry deoxygen apparatus |
| CN111252968A (en) * | 2020-03-04 | 2020-06-09 | 国初科技（厦门）有限公司 | Method for concentrating copper sulfate by using membrane technology |
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| CN106345304A (en) * | 2016-11-16 | 2017-01-25 | 中国科学院青海盐湖研究所 | Cathodic solution protection type electrodialysis device |
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| JPH07313098A (en) * | 1994-05-24 | 1995-12-05 | Tokuyama Corp | Production of low salt soysauce and apparatus therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107746098A (en) * | 2017-10-25 | 2018-03-02 | 中国科学技术大学 | A kind of apparatus and method of hydrogen ion selective electrodialysis recovery acid from the waste liquid containing low concentration acid and high-concentration metallic ions |
| CN108114599A (en) * | 2017-12-25 | 2018-06-05 | 中国科学技术大学 | It is a kind of based on salt error the electrodialysis reversal of production soda acid to be driven to couple bipolar membranous system and its production method |
| CN109607709A (en) * | 2019-01-12 | 2019-04-12 | 大连理工大学 | A kind of electrochemistry deoxygen apparatus |
| CN111252968A (en) * | 2020-03-04 | 2020-06-09 | 国初科技（厦门）有限公司 | Method for concentrating copper sulfate by using membrane technology |
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