CN107055713A - One kind is based on the selectively electrodialytic high rigidity brackish water method for concentration of univalent cation - Google Patents
One kind is based on the selectively electrodialytic high rigidity brackish water method for concentration of univalent cation 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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- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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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
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Abstract
The present invention is based on the selectively electrodialytic high rigidity brackish water method for concentration of univalent cation to be a kind of, and this method comprises the following steps：The first step, raw water chemical precipitation is except hard and pretreatment；Second step, reverse osmosis deaslination processing；3rd step, by the use of hydrochloric acid or sulphur acid for adjusting pH value is, as electrodialysis raw water, then to respectively enter the desalting chamber and enriched chamber formed in electrodialysis membrane stack by anode membrane and cavity block interval after 46 using reverse osmosis concentrated salt solution in second step；Obtain electrodialysis haline water and electrodialysis low-solids water.The present invention is achieved that the separation of two kinds of ions of composition scale forming matter in the case where not sacrificing the rate of recovery without extra equipment and device, so as to avoid while retaining or simultaneously through the scale formation produced.
Description
Technical field
Technical scheme is related to a kind of based on the selectively electrodialytic high rigidity brackish water concentration of univalent cation
Technique and system, belong to wastewater treatment and field of environment protection.
Background technology
Social economy's fast development drive Rapid Development of Enterprise, but thing followed environmental problem particularly discharge of wastewater
Bottleneck as restriction economy, social, environmental harmony sustainable development.The side of the industrial enterprises such as chemical industry, papermaking, printing and dyeing, leather one
Face is because salt is possibly as one of raw material in technical process, the progressively concentration of salinity in another aspect process water so that waste water contains
Salt amount is higher, if cannot dispose very well, necessarily brings water body and ecological environment of soil to pollute.Therefore to the salt of this high salinity
Water carries out the concentration of economical and efficient, it has also become the key issue of liquid zero emission process economy and feasibility.
Patent of invention CN103342432B " a kind of near-zero release technique of brine waste " discloses a kind of and a kind of saliferous
The near-zero release technique of waste water, main flow includes pretreatment, Electro Sorb, ultrafiltration, counter-infiltration, electrodialysis and evaporative crystallization.Its
Middle reverse osmosis concentrated water is as electrodialysis raw material, and electric osmose division water strong brine is evaporated crystallization treatment, produces fresh water and enters water supply
System, water comprehensive recovery can reach 99.5%.The B of patent of invention CN 104016529 " are based on multi-stage countercurrent pole-reversing electroosmosis
Salt-containing waste water treatment method disclosed in the coal chemical industry salt-containing waste water treatment method of device " includes catalytic ozonation multimedium mistake
Filter, membrane filtration multi-stage countercurrent pole-reversing electroosmosis device, realize advanced treating and the desalination reuse of coal chemical industry brine waste.Utility model
Patent CN205011538U " a kind of low energy consumption coal chemical industry strong brine sub-prime crystallization combination unit " its by being separated except hard softening, NF
Film, high salt counter-infiltration, production water/concentrated water ED films concentration, production water/concentrated water evaporative crystallization, production water/concentrated water mother liquor drier, AOP catalysis
A variety of devices such as oxidation, activated carbon filtering are combined, and then realize all recyclings of coal chemical industry strong brine.Utility model is special
Sharp CN201520882324.2 " processing system of coal chemical industry high-salt wastewater " discloses a kind of processing system of coal chemical industry high-salt wastewater
System, a kind of coupling of its electrodialysis+counter-infiltration constituted using nano-filtration membrane filter, ion membrane reactor and reverse osmosis filter
Technique is closed to handle coal chemical industry high-salt wastewater system.
Therefore, a point salt, crystallization are then carried out by electrodialysis and counter-infiltration progress brine concentration and have become industry
The important aspect of high salt water process.And the feature of high-salt wastewater generally existing high rigidity, prior art electrodialysis process or use
Pole-reversing electroosmosis device is pre-processed using nanofiltration, to reduce electrodialysis concentrated water film surface fouling possibility, but in such method
Pole-reversing electroosmosis needs the pipeline and control system of complexity, while reducing the rate of recovery of electrodialysis system water；Using nanofiltration as pre-
On the one hand processing adds new processing equipment, while NF membrane still suffers from scale problems, therefore its system rate of recovery is relatively low；And
Some public technologies handle electrodialysis fresh water to be used to lower degree as technique with fresh water water, increase electrodialysis process into
This；Also have simple using ED desalination water circulation conc forms, but it is dangerous to add the concentration of COD, hardness etc..
The content of the invention
The present invention is directed to current high salt industrial wastewater concentration demand, and the equipment complexity that prior art is present, and returns
The problem of yield is low, proposes a kind of hard brine waste concentration technology of the height based on Monovalent selectivity electrodialysis using cation and system,
The system, except hard, counter-infiltration, electrodialysis is cores, utilizes the hardness ions in chemical precipitation removal system using chemistry；Using anti-
Infiltration carries out desalination and the initial concentration of low concentration of salt water, output high-quality desalted water, while obtaining initial concentration salt solution；Utilize
Initial concentration salt water depth concentrate is obtained high concentration salt solution by electrodialysis, while electrodialysis plant is by univalent cation film and general
Logical anionic membrane composition, can effectively control scale-forming ion concentration in strong brine.Comparing other techniques has condensed water product design
High, fouling tendency cation concn is low, and flow is simple, the low many advantages of film fouling risk.
The technical scheme is that：
One kind is based on the selectively electrodialytic high rigidity brackish water method for concentration of univalent cation, and this method includes following step
Suddenly：
The first step, raw water chemical precipitation is except hard and pretreatment
Required processing raw water is pre-processed and chemistry is except hard, SS in raw water after processing<0.1mg/L, Ca2+<40mg/L,
SDI ≤3,S&DSI<0；
Second step, reverse osmosis deaslination processing
After above-mentioned pretreatment process production water is filtered through cartridge filter, handled, respectively obtained anti-using reverse osmosis membrane
Osmosis deaslination water and reverse osmosis concentrated salt solution, wherein reverse osmosis deaslination hydromining go out, and reverse osmosis concentrated salt solution is carried out as electrodialysis raw material
Next step processing；
Wherein, the reverse osmosis concentrated salt solution TDS values obtained are 10 000-60 000mg/L, and reverse osmosis deaslination water TDS values are
0-1000mg/L；
3rd step, electrodialysis process
As electrodialysis raw water after being 4-6 by the use of hydrochloric acid or sulphur acid for adjusting pH value using reverse osmosis concentrated salt solution in second step, so
The desalting chamber and enriched chamber formed in electrodialysis membrane stack by anode membrane and cavity block interval is respectively enterd afterwards；Into the electrodialysis of desalting chamber
Raw water, after electric field action, returns to desalination water tank, and overflow obtains electrodialysis low-solids water as product, or as next
The raw water of individual electrodialysis process；Meanwhile, into the electrodialysis raw water of enriched chamber, after electric field action, together with through anode membrane, the moon
The ion that film enters, returns to concentration water tank, and overflow obtains electrodialysis haline water as product；Described electrodialysis process is company
Continuous course of reaction；
The concrete composition of described electrodialysis membrane stack includes positive plate-desalting chamber-anode membrane-enriched chamber-cavity block-desalination
Room ... desalting chamber-anode membrane-enriched chamber-cavity block-minus plate；It is in parallel between desalting chamber, it is in parallel between enriched chamber；
Described anode membrane is Monovalent selectivity anode membrane, preferably for Japanese ASTOM Co., Ltd. Cs IMS amberplexes or
One kind in Japanese AGC Co., Ltd. Cs SO amberplexes；
Described cavity block is the selective cavity block of non-monovalention.
Described electric field action is formed under constant current or constant voltage, the electrodialysis process process constant current
During operation, current density is 100-500A/m2；When constant voltage is operated, film is to voltage 0.1-0.5V.
The mass of ion concentration of the electrodialysis haline water of described outflow enriched chamber is 12%-24%；Described outflow takes off
The mass of ion concentration of the electrodialysis low-solids water of salt room is 0.8-3%；In described mass of ion average salt solution whole sun from
The quality sum of son and anion.
Negative electrode in the electrodialysis process step, anode electrode solution it is identical or different, be electrodialysis raw water, NaCl solution
Or NaSO4One kind in solution, wherein NaCl solution or NaSO4Concentration of polymer solution 1%-5%.
Raw water TDS values are 1000-10 000mg/L in the treating nature water process.
Every grade of the electrodialysis process process is made up of 1 electrodialysis component or by 2~10 electrodialysis components series connection structures
Into each electrodialysis component is comprising 10-300 to anion and cation exchange membrane.
In the electrodialysis process process cation-exchange membrane used in electrodialysis plant be Monovalent selectivity amberplex,
Anion is the selective cavity block of non-monovalention.
The present invention substantive distinguishing features be：
In existing published high-salt wastewater handling process, concentrated, also had using anti-using electrodialysis
Infiltration and the integrated technique of electrodialysis.But for the salting liquid that hardness is larger, nanofiltration or use are either used in existing patent
Pole-reversing electroosmosis.On the one hand equipment, increase cost of investment and operating cost are individually increased as pretreatment using nanofiltration, is received simultaneously
Filter is also a kind of membrane process promoted with pressure, has certain retention to make hardness and cause incrustation ion (Ca, SO42-, CO32-)
With above-mentioned ion is trapped within retention side (concentrated water side), causes dangerous in dense water side deposition, the simultaneity factor rate of recovery is relatively low；
Pole electrodialysis pipeline, control system are complicated, while causing electrodialysis partial concentration water during pole to contain higher cause incrustation ion
It can not be wasted as product.Zwitterion film can all produce inspissation to any ion in common electrodialysis, and this technique
Anode membrane uses common cavity block using Monovalent selectivity anode membrane and cavity block in middle electrodialysis, therefore only by univalent cation and can own
Anion is concentrated, although there is substantial amounts of SO in concentrate4 2-、CO3 2-, but Ca2+Concentration is relatively low, and solution non flouling behaviour shows
As, and it is trapped in the Ca in dilute side2+Then can be by chemistry except hard removal, counter-infiltration then can be in relatively low Ca2+Salt solution is preliminary
Concentration, in terms of such electrodialysis is mainly used in high concentration concentration, also gives full play to the respective advantage of electrodialysis and counter-infiltration.
The beneficial effects of the invention are as follows：
Based on the selectively electrodialytic high rigidity brackish water method for concentration of univalent cation, Monovalent selectivity cation is used
Exchange membrane and common anion exchange membrane, univalent cation and anion are only concentrated, set without extra in concentrated water side
Standby and device, the separation of two kinds of ions of composition scale forming matter is achieved that in the case where not sacrificing the rate of recovery, so as to avoid
Retention simultaneously or simultaneously through the scale formation produced.Secondly mutually tied with Monovalent selectivity electrodialysis using cation using counter-infiltration
Close, and counter-infiltration is as leading portion, because most industrial wastewater initial salt contents are relatively low, therefore system has preferably
Adaptability, while can give full play to counter-infiltration concentrate in Low-salinity, the advantage of equipment with high desalinization and the concentration of electrodialysis high concentration, it is real
The existing efficient effect of the two, output high concentration salt solution.Last chemical precipitation removes and firmly can discharge hardness in system in solid form,
The drawbacks of membranous system formation circulation is constantly mistaken can not be discharged by preventing the hardness of other techniques presence.
Brief description of the drawings
The present invention is further described with reference to the accompanying drawings and examples.
Fig. 1 is the high-salt wastewater method for concentration schematic diagram that counter-infiltration of the present invention is integrated with electrodialysis.
Fig. 2 is electrodialysis process schematic diagram in the present invention；
Fig. 3 is electrodialysis membrane stack sketch.
Fig. 4 is electrodialysis membrane stack fluid flow inside and Ion transfer schematic diagram.
Embodiment
Embodiment illustrated in fig. 1 shows that the technological process that concentrated seawater of the present invention prepares liquid salt method is：Raw material salt solution is first
By corresponding pre-treatment step, reach that the cartridge filter through 1-10 μm of filtering accuracy is filtered after reverse osmosis requirement, is led to
Cross high-pressure pump to enter raw water supercharging after pretreatment in the counter-infiltration membrane stack that certain level segment is constituted, wherein reverse osmosis deaslination water conduct
One of product of this technique output, condensed water is 4-6 as electrodialysis raw material regulation pH value, is concentrated into electrodialysis process
Processing, is converted into the electrodialysis haline water and low concentration electrodialysis low-solids water of high concentration, wherein electrodialysis haline water is used as this work
One of product of skill output, electrodialysis low-solids water is mixed before returning to treating nature water process with raw water.
The reverse osmosis deaslination treatment process is by 1-3 sections, 1-2 grades of compositions.Counter-infiltration segment number by counter-infiltration raw water TDS with
Reverse osmosis concentrated shrink TDS demands are determined, wherein 1 section of condensed water TDS is concentrated into 2-3 times of raw water, 2 sections are 4-6 times, and 3 sections are 8-9
Times；Often increase by 1 section of reverse osmosis concentration；Counter-infiltration number of stages is determined that every grade can make by raw water TDS with reverse osmosis produced water TDS demands
Production water TDS is reduced to the 0.1-5% of this grade of raw water.
The electrodialysis process process is constituted by 1-3 grades.Electrodialysis series is by influent density and low-solids water, high salt water concentration
Together decide on, its relation approximately can be expressed by following empirical equation：Electric osmose less salt water concentration=influent density × (30-60%
)Series。
The electrodialysis process process, desalted water and concentration water circular flow determined by electrodialytic membranes logarithm, 0.01-
0.5m3/ h is to film.
Embodiment 1
This part raw water is the mixing water that certain chemical enterprise waste water and each stock return to water, and it is as shown in the table for water quality
| Composition | Concentration |
| Na2SO4/mg·L-1 | 7 000 |
| Ca2+/mg·L-1 | 20 |
| Cl-/mg·L-1 | 36 |
| COD/mg·L-1 | 3 000 |
| SS/mg·L-1 | 50 |
| pH | 8.2 |
The first step, treating nature water process
Above-mentioned raw water 98.7m3/ h, removes SS values through mechanical clarifier respectively, and aerobic/anaerobic (A/O) biological reaction pool exposes
COD in water removal is removed in gas biofilter (BAF), by production water 88m after ultrafiltration3/ h, TDS 7050mg/L, SS 0mg/L, COD 100
Mg/L, SDI value:3.Wherein ultrafiltration uses PVDF hollow-fibre membranes, using cross-flow filtration form, the rate of recovery 90%, operating pressure
0.1MPa。
Second step, reverse osmosis deaslination treatment process
Above-mentioned pretreatment process 88m3/ h produces water conservancy 10%wt salt acid for adjusting pH value to 6.5, is filtered through cartridge filter
(operating pressure 0.1MPa, 5 μm of filtering accuracy) enters reverse osmosis membrane by high-pressure pump, and counter-infiltration is constituted by 1 grade 2 sections, wherein the
One section of counter-infiltration is composed in parallel by 9 membrane modules, and single branch component is in series by 6 membrane components, flow of inlet water 88m3/ h, operation
Pressure 1.4MPa, the rate of recovery 50%, above-mentioned membrane component uses U.S.'s DOW BW30FR400 business membrane components；Second segment counter-infiltration
Composed in parallel by 4 membrane modules, single branch component is in series by 6 membrane components, flow of inlet water 44m3/ h, operating pressure
2.2MPa, the rate of recovery 50%.Above-mentioned membrane component uses U.S.'s DOW SW30XHR400i business membrane components.Counter-infiltration output is concentrated
Water 22.5m3/ h, its TDS are 27890mg/L, COD 400mg/L, Ca2+80mg/L；Desalted water amounts to 65.5m3/ h, TDS are
90mg/L.Reverse osmosis deaslination water is carried out at next step as one of the product of this technique output, condensed water as electrodialysis raw material
Reason.
3rd step, electrodialysis process process
Electrodialysis is made up of two-stage, using continuous operation, per one-level flow as shown in Fig. 2 wherein the first order is by 2 membrane stacks
(single electrodialysis membrane stack sketch is as shown in Figure 3) is composed in parallel, each membrane stack 240 is intervally arranged to negative and positive film, and two ends are respectively
Anode and negative electrode, meanwhile, frame-shaped dividing plate is intervally distributed between negative and positive film, and (effect of dividing plate separates negative and positive film, middle space
As the desalting chamber or enriched chamber for accommodating raw water) sequentially form " positive plate-desalting chamber-anode membrane-enriched chamber-cavity block-desalination
The film stacking structure of room-anode membrane-enriched chamber-cavity block ... desalting chamber-anode membrane-enriched chamber-cavity block-minus plate ", meanwhile, all is de-
Salt room is in parallel, and all enriched chambers are in parallel；Such as Fig. 4.Condensed water from concentration water tank and the desalination moisture from desalination water tank
Not Jin Ru electrodialysis lower flow passage, the desalting chamber and enriched chamber then each formed into the dividing plate between zwitterion film it
Afterwards, the respective concentration water tank of return and desalination water tank are converged respectively by upper flow passage；
Under electric field action, into the raw water of desalting chamber, remove univalent cation, cavity block through anode membrane and remove unit price and multivalence
After anion, as the solution containing polyvalent cation and monovalent anion, it is low that return desalination water tank, and overflow obtain electrodialysis
Salt solution is as product, or is used as the raw water of next electrodialysis process；Meanwhile, into the raw water of enriched chamber, together with through sun
The univalent cation of film and the unit price and multivalent anions through cavity block, as with univalent cation, unit price and multivalent anions
Based on highly concentrated solution, return to concentration water tank, and overflow obtains electrodialysis haline water as product；
Cation in desalting chamber under electric field action to movable cathode, and due to anode membrane have monovalence selectivity, only one
Valency cation permeable anode membrane enters enriched chamber；All anion Ghandler motion that faces south is moved, and enters enriched chamber (because anion through cavity block
Film is the selective cavity block of non-monovalention, so passing through together without selectivity, therefore unit price and multivalence to monovalent and multivalence
Enter) so that condensed water intermediate ion concentration is raised, because ion is moved out and concentration step-down in desalting chamber.
In described membrane stack, single film effective area 1.4m2, the first order amounts to 480 pairs of films, and total effective area 672 is to m2
(i.e. each 672m of negative and positive film2)；The second level is made up of 1 membrane stack, equally totally 240 pairs of negative and positive films, and total effective area 336 is to m2。
10%wt salt acid for adjusting pH value is utilized to be 6 reverse osmosis concentrated salt solution in second step, as raw water with 22.5m3/ h flows
Amount enters first order electrodialysis raw water box, enters first order electrodialysis membrane stack desalting chamber through desalination water-circulating pump, is taken off by electrodialysis
Desalination water tank is returned to after the outflow of salt room, overflow obtains concentration 12.8g/L, 21m3/ h first order electrodialysis low-solids waters are used as the second level
Electrodialytic raw water；Concentration water tank be also 6 using 10%wt salt acid for adjusting pH value raw water be initial soln (beginning when
Wait, raw water fills it up with concentration water tank, afterwards in system operation, raw water does not enter back into condensed water case, but relies on electric field to make
With, the hydrone in desalted water enters condensed water through amberplex, therefore concentration water volume is continuously increased, and then in concentration
Water tank overflow output concentrated water product), concentrated water-circulating pump enters electrodialysis membrane stack enriched chamber, then returns after concentration water tank,
Overflow obtains first order electrodialysis haline water 1.5m3/h。
This level uses constant current operation, current density 250A/m2.First order electrodialysis low-solids water 21m3/ h is used as second
The electrodialytic raw water of level enters second level electrodialysis raw water box, enters second level electrodialysis membrane stack desalination through desalination water-circulating pump
Room, returns to desalination water tank, overflow obtains 20.1m after the outflow of electrodialysis desalination room3/ h, the 7.5g/L second level electrodialysis less salt
Water, is used as final electrodialysis low-solids water；It is initial soln that water tank, which is concentrated, using raw water, and concentrated water-circulating pump enters electrodialytic membranes
Heap enriched chamber, is then returned after concentration water tank, overflow obtains second level electrodialysis haline water 0.9m3/ h, with first order haline water
2.4m is obtained after mixing3/ h 200g/L high salt aquatic products, the second level uses constant current operation, current density 140A/m2。
The first order uses mass concentration 3%Na with second level anodic-cathodic liquid2SO4Circulation is carried out, per one-level circular flow
3m3/h.Second level electrodialysis 20.1m3/ h, 7.5g/L low-solids water return to first step treating nature water process and mixed with raw water
Handled afterwards as raw water.
Embodiment 2
This part raw water is certain enterprise wastewater, water 360m3It is as shown in the table for/h, pH=7 water quality.
| Water quality index | Numerical value mg/L |
| K | 50 |
| Na+ | 1700 |
| Mg2+ | 100 |
| NO3 - | 260 |
| Cl- | 1100 |
| SO4 2- | 3800 |
| Total hardness | 3000 |
| TDS | 8300 |
| CODCr | 120 |
The first step, treating nature water process
By raw water regulating reservoir with 360m3/ h flows and each several part return water and enter regulating reservoir, with total Water 400m3/ h enters smelly
Oxygen+BAF processes, this process mainly removes COD in water removal, designs clearance 40%, produces water COD 70mg/L, and remaining index is basic
It is constant；It is subsequently added Na2CO3, coagulant FeCl3(mg/L) and flocculation aid PAM (mg/L) enters high dense settling pond, mainly go
Except hardness in raw water, clearance 95% is designed, while total hardness 200mg/L, COD 60mg/L in part that can be removed COD, production water,
Water about 360m3/h；Sodium bed and weak acid cation bed are sequentially entered after subsequently entering more medium filter removal partial suspended thing, to go
Except residual harness, total hardness concentration after weak acid cation bed<5mg/L, COD about 40mg/L, SS values 0mg/L, TDS 8300mg/
L, SDI value:2.
Second step, reverse osmosis deaslination treatment process
Above-mentioned pretreatment process 360m3/ h produces water conservancy 10%wt salt acid for adjusting pH value to 6, is filtered through cartridge filter
(operating pressure 0.1MPa, 10 μm of filtering accuracy) enters reverse osmosis membrane by high-pressure pump, and counter-infiltration is constituted by 1 grade 2 sections, wherein the
One section of counter-infiltration is composed in parallel by 38 membrane modules, and single branch component is in series by 6 membrane components, flow of inlet water 360m3/ h, behaviour
Make pressure 2.3MPa, production water 210m3/ h, COD 5mg/L, TDS 100mg/L；Concentrated water 150m3/ h, TDS19800 mg/L enter
Second segment counter-infiltration is composed in parallel by 18 membrane modules, and single branch component is in series by 6 membrane components, operating pressure 5.7MPa,
Counter-infiltration output condensed water about 70m3/ h, its TDS are about 50000mg/L, COD 10mg/L；Desalted water 80m3/ h, TDS are
200mg/L.Above-mentioned membrane component is using day eastern electrician's 8 inches of business membrane components of hydranauticsSWC5.Reverse osmosis deaslination water is made
One of product for this technique output, condensed water is further processed as electrodialysis raw material.
3rd step, electrodialysis process process
Electrodialysis is made up of level Four, and using continuous operation, (single electrodialysis membrane stack sketch is such as shown in Figure 2 for every grade of flow
Shown in Fig. 3), wherein the 1st, 2 grades every grade be made up of 6 membrane stacks, the 3rd, 4 grades every grade be made up of 3 membrane stacks, each 240 pairs of membrane stack
Negative and positive film is intervally arranged, and two ends are respectively anode and negative electrode, meanwhile, be intervally distributed between negative and positive film frame-shaped dividing plate (dividing plate
Effect separates negative and positive film, and middle space turns into the desalting chamber or enriched chamber for accommodating raw water) sequentially form " positive plate-desalination
Room-anode membrane-enriched chamber-cavity block-desalting chamber-anode membrane-enriched chamber-cavity block ... desalting chamber-anode membrane-enriched chamber-cavity block-minus plate "
Film stacking structure, meanwhile, all desalting chamber is in parallel, and all enriched chambers are in parallel；Such as Fig. 4.Condensed water from concentration water tank
Electrodialysis lower flow passage is respectively enterd with the desalted water from desalination water tank, the dividing plate then each entered between zwitterion film
After the desalting chamber and enriched chamber that are formed, converge the respective concentration water tank of return and desalination water tank respectively by upper flow passage；
Under electric field action, into the raw water of desalting chamber, remove univalent cation, cavity block through anode membrane and remove unit price and multivalence
After anion, as the solution containing polyvalent cation and monovalent anion, it is low that return desalination water tank, and overflow obtain electrodialysis
Salt solution is as product, or is used as the raw water of next electrodialysis process；Meanwhile, into the raw water of enriched chamber, together with through sun
The univalent cation of film and the unit price and multivalent anions through cavity block, as with univalent cation, unit price and multivalent anions
Based on highly concentrated solution, return to concentration water tank, and overflow obtains electrodialysis haline water as product；
Cation in desalting chamber under electric field action to movable cathode, and due to anode membrane have monovalence selectivity, only one
Valency cation permeable anode membrane enters enriched chamber；All anion face south Ghandler motion move, enter enriched chamber through cavity block so that condensed water
Intermediate ion concentration is raised, because ion is moved out and concentration step-down in desalting chamber.
In described membrane stack, single film effective area 1.4m2, first and second grade of difference, 1440 pairs of films, effective area is respectively
2016 couples of m2(i.e. each 2016m of negative and positive film2)；Third and fourth level distinguishes 720 pairs of negative and positive films, and effective area is respectively 1008 couples of m2。
10%wt salt acid for adjusting pH value is utilized to be 5 reverse osmosis concentrated salt solution in second step, as raw water with 70m3/ h flows
Into first order electrodialysis raw water box, enter first order electrodialysis membrane stack desalting chamber through desalination water-circulating pump, by electrodialysis desalination
Desalination water tank is returned to after the outflow of room, overflow first order electrodialysis low-solids water is as the electrodialytic raw water in the second level, by that analogy；It is dense
The raw water that shrink case is also 5 using 10%wt salt acid for adjusting pH value is that (at first, raw water fills it up with condensed water to initial soln
Case, afterwards in system operation, raw water does not enter back into condensed water case, but relies on electric field action, the moisture in desalted water
Son enters condensed water through amberplex, therefore concentration water volume is continuously increased, and then in concentration water tank overflow output concentrated water
Product), concentrated water-circulating pump enter electrodialysis membrane stack enriched chamber, then return concentration water tank after, overflow obtain the first order and
Conduct after concentrated water mixing at different levels.
This level uses constant current operation, and current densities at different levels are respectively 270A/m2, 220A/m2, 170A/m2, 150A/
m2.Wherein overflow obtains 49.7m3/ h, 7.5g/L fourth stage electrodialysis low-solids water, are used as final electrodialysis low-solids water；Concentrate water tank
It is initial soln using raw water, concentrated water-circulating pump enters electrodialysis membrane stack enriched chamber, then returns after concentration water tank, overflow
Total obtains 20.3m3/ h 200g/L high salt aquatic products.
Anodic-cathodic liquid at different levels are carried out using mass concentration 3%NaCl circulations, per one-level circular flow 3m3/h.4th
Level electrodialysis 49.7m3/ h, 8.3g/L low-solids water are returned after first step treating nature water process is mixed with raw water as raw water
Handled.
Unaccomplished matter of the present invention is known technology.
Claims (6)
1. one kind is based on the selectively electrodialytic high rigidity brackish water method for concentration of univalent cation, it is characterized in that this method includes
Following steps：
The first step, raw water chemical precipitation is except hard and pretreatment
Required processing raw water is pre-processed and chemistry is except hard, SS in raw water after processing<0.1mg/L, Ca2+<40mg/L, SDI
≤3,S&DSI<0；
Second step, reverse osmosis deaslination processing
After above-mentioned pretreatment process production water is filtered through cartridge filter, handled using reverse osmosis membrane, respectively obtain counter-infiltration
Desalted water and reverse osmosis concentrated salt solution, wherein reverse osmosis deaslination hydromining go out, and reverse osmosis concentrated salt solution carries out next as electrodialysis raw material
Step processing；
Wherein, the reverse osmosis concentrated salt solution TDS values obtained are 10 000-60 000mg/L, and reverse osmosis deaslination water TDS values are 0-
1000mg/L；
3rd step, electrodialysis process
As electrodialysis raw water after being 4-6 by the use of hydrochloric acid or sulphur acid for adjusting pH value using reverse osmosis concentrated salt solution in second step, enter respectively
Enter desalination water tank and concentration water tank；Then the desalting chamber that is formed in electrodialysis membrane stack by anode membrane and cavity block interval is respectively enterd and dense
Contracting room；Into the electrodialysis raw water of desalting chamber, after electric field action, desalination water tank is returned, and overflow obtains electrodialysis less salt
Water is as product, or is used as the raw water of next electrodialysis process；Meanwhile, into the electrodialysis raw water of enriched chamber, by electricity
After field action, together with the ion entered through anode membrane, cavity block, concentration water tank is returned, and overflow obtains electrodialysis haline water conduct
Product；Described electrodialysis process is tandem reaction sequence；
Described anode membrane is Monovalent selectivity anode membrane, and described cavity block is the selective cavity block of non-monovalention；
Described electric field action is formed under constant current or constant voltage, the electrodialysis process process constant current operation
When, current density is 100-500A/m2；When constant voltage is operated, film is to voltage 0.1-0.5V.
2. being based on the selectively electrodialytic high rigidity brackish water method for concentration of univalent cation as claimed in claim 1, it is special
Levy de- including positive plate-desalting chamber-anode membrane-enriched chamber-cavity block-desalting chamber ... for the concrete composition of described electrodialysis membrane stack
Salt room-anode membrane-enriched chamber-cavity block-minus plate；It is in parallel between desalting chamber, it is in parallel between enriched chamber.
3. being based on the selectively electrodialytic high rigidity brackish water method for concentration of univalent cation as claimed in claim 1, it is special
Levy be preferably for described anode membrane be Japanese ASTOM Co., Ltd. Cs IMS amberplexes or AGC Co., Ltd. Cs of Japan SO ions
One kind in exchange membrane.
4. being based on the selectively electrodialytic high rigidity brackish water method for concentration of univalent cation as claimed in claim 1, it is special
It is 12%-24% to levy as the mass of ion concentration of the electrodialysis haline water of described outflow enriched chamber；Described outflow desalting chamber
Electrodialysis low-solids water mass of ion concentration be 0.8-3%；In described mass of ion average salt solution whole cations and
The quality sum of anion.
5. being based on the selectively electrodialytic high rigidity brackish water method for concentration of univalent cation as claimed in claim 1, it is special
Levy identical or different for the electrode solution of negative electrode in the electrodialysis process step, anode, be electrodialysis raw water, NaCl solution or
NaSO4One kind in solution, wherein NaCl solution or NaSO4Concentration of polymer solution 1%-5%.
6. being based on the selectively electrodialytic high rigidity brackish water method for concentration of univalent cation as claimed in claim 1, it is special
It is 1000-10 000mg/L to levy as raw water TDS values in the treating nature water process.
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