CN107555619A - A kind of electric deionizing method and device for strengthening antiscale - Google Patents
A kind of electric deionizing method and device for strengthening antiscale Download PDFInfo
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- CN107555619A CN107555619A CN201710900971.5A CN201710900971A CN107555619A CN 107555619 A CN107555619 A CN 107555619A CN 201710900971 A CN201710900971 A CN 201710900971A CN 107555619 A CN107555619 A CN 107555619A
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Landscapes
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of electric deionizing method and device for strengthening antiscale, fresh water stream is two sections of one-level in this method, and concentrated stream is one-level one-part form flow, and dense, fresh water stream is mutually adverse current in the first paragraph flow of fresh water stream.The electric deionizer includes positive plate, cathode chamber dividing plate, the n repeatable groundwork unit, 1 groundwork unit, m repeatable groundwork units, the 1 groundwork unit and negative plate with anode chamber dividing plate replacement concentrated stream dividing plate with the light water flow partition board of fresh water commutation dividing plate replacement that are stacked successively in order, and n, m are integer and n >=m >=1.The internal water flow scheme design and operation process of electric deionizing method and device provided by the invention, so that electrodeionization desalination processes can both be run and non-scaling under 5 10mg/L water inlet stiffness conditions, the performance of excellent tolerance influent quality fluctuation is also equipped with simultaneously, is had concurrently and is strengthened anti-scaling property and high operation stability.
Description
Technical field
The present invention relates to a kind of method and apparatus of water desalination, particularly one kind possesses reinforcing anti-scaling property, for depth
Desalination prepares the electric deionizing method and device of high purity water, belongs to energy-conserving and environment-protective technical fiel.
Background technology
Electrodeionization (Electrodeionization, abbreviation EDI), is referred to as packed-bed electrodialysis earliest, is by ion
The electric drive membrane separation technique that exchanger resin and electrodialysis organically combine.EDI is that ion exchange resin is filled in into thickness increase
Electrodialytic freshwater room in, under DC electric field effect, positive and negative ion in freshwater room water is along ion exchange resin and ion
The ion channel that exchange membrane is formed migrates to negative pole and positive extreme direction respectively, cation permselective cation-exchange membrane, cloudy
Ion selectivity passes through anion-exchange membrane, respectively enters and is arrested in adjacent concentrated water room.EDI both make use of electrodialysis
Can the advantages of continuously desalination and ion exchange resin can be with deep desaltings, it is not thorough to overcome electrodialysis desalination again, it is impossible to straight
Connect the negative effect of high purity water, and ion exchange resin needs frequently to consume a large amount of acid-alkali regenerations, exhaust emission gives up
Liquid, the defects of can not continuously working, water process processed can be carried out continuously for a long time.
EDI membrane technologies have obtained wide application in prepared by the high purity water in the fields such as the energy, electronics, bio-pharmaceuticals, but
Existing various business EDI technologies still have its limitation so that fail large area so far in pure water market segment and substitute tradition
Mixed bed ion switching technology.It is very harsh to flow condition requirement that this limitation is mainly manifested in EDI, wherein requiring water inlet
Hardness have to be lower than 1mg/L, or even below 0.5mg/L is key point.
Why EDI has rigors to the hardness of raw water, is because its technical process is easy to hardness ions be present
Under conditions of fouling is formed in compartment so that irreversible destruction occurs for process.High purity water is prepared for deep desalting
For EDI, the relatively conventional water body of ion concentration of its raw water is very low, and such as the most frequently used raw water is counter-infiltration (RO) production
Water, its typical salt content are essentially 1-10mg/L.Under the conditions of this low concentration raw water, resin and film in diluting compartment connect with water
Water decomposition reaction in tactile boundary layer persistently be present：H2O→H++OH-, then certain density Ca is contained in raw water2+、Mg2+Deng
When hardness ions and high valence ion, the easy OH with one of water decomposition reaction product-Ions binding, generation Mg (OH)2、Ca
(OH)2Deng slightly solubility metal hydroxides, the constantly improve of its concentration will cause serious scale.Due under EDI working condition,
Water decomposition reaction is requirement, OH-The dynamic regeneration that ion pair fills negative resin is essential, because to avoid fouling shape
Into the Ca in accurate control water inlet2+、Mg2+Ion concentration turns into the key means of conventional EDI technologies.
Reality engineering of water treatment in, to reach above-mentioned water inlet hardness number, using two-stage RO as EDI prime at
Science and engineering skill turns into a realistic choice.For most water bodys, by two-stage RO film desalinations, it produces the salt content of water and existed more
Below 3mg/L, wherein hardness are more in 0.5mg/L, or even below 0.2mg/L, it is sufficient to ensure EDI safe and stable operation.For
For identical aquifer yield, pre-treatment is compared using two-stage RO with one-level RO, and its cost of investment and the consumption to raw water differ
It is very greatly different.For example, the RO film dosages of two-stage RO techniques, will be 2.5 times or so of one-level RO technique film dosages, the RO of discharge is dense
Water is also higher by more than 50% compared with the latter.Prior, to considerable use " exchange of one-level RO- mixed bed ions ", technique was both
For having the high-purity water system of industry, because pre-treatment is only one-level RO, its producing water water quality is difficult to the inflow requirement for meeting EDI, led
Causing can not be directly using the mixed bed ion switching equipment in EDI replacements downstream；And if upstream RO techniques are transformed, upgraded
For two-stage RO, then investment is not only dramatically increased, and often also do not possess transformation condition in place etc..Therefore, although
EDI belongs to more advanced, efficient and environment-friendly advanced desalination technology, but its share in Purewater Technique market in theory
Still less than 10%.The situation that mixed bed ion switching technology occupies about 90% market share is difficult to change always.It can be seen that continuing pair
Conventional EDI technologies optimize development, relax its influent quality requirement so that its be resistant to most one-level RO production water and
Direct high purity water has highly important society, economy and environmental benefit, has milestone meaning to the future of Purewater Technique
Justice.
Patent CN105198133A discloses a kind of ultrapure water production system and method for preventing electric deionizer fouling,
It is mainly made up for the treatment of nature water system, counter-infiltration system, electrodeionization system.By increasing additionally dense in this technique
Water treatment system realizes antiscale purpose, and concrete operations are that the water outlet of EDI concentrated waters is sequentially connected demineralizer and precision by a water pump
Filter, the concentrated water after processing carry out alone cycle；Concentrated water cyclic system is controlled by the cationic ion-exchange resin in external water softener
Hardness ions in system and prevent the fouling of concentrated water room.This method not only increases system investments and operation energy consumption, improves technique
Numerous and diverse degree, key in the fouling in it actually can not effectively prevent concentrated water room.Once because shape in concentrated water room
Into fouling, it does not discharge EDI devices with current, but is accumulated in concentrated water room.The main purpose of the technique is to realize
The part of concentrated water recycles, and can not prevent that fouling generates in EDI because of possible higher hardness in raw water.Actually should
In, the risk of softening resin replacement not in time also be present.
United States Patent (USP) US6056878 is then prevented in EDI using the method that antisludging agent is added into concentrated stream and electrode water
Portion's fouling；Method is then the pH value for adjusting EDI raw waters used by patent EP0916620 and US6017433, by into raw water
Acid medicine is added to prevent fouling.Add the desalination principle that antisludging agent and raw water acid adding consume with EDI without extra chemicals
Disagree, and make it that operation process is more responsible, also increase cost of investment.
Patent CN101195081A discloses a kind of method and apparatus for preventing scaling in electrodeionization units, and it is logical
The mode of overrich fresh water whole process adverse current so that just migrate into the metal cation can of concentrated water room by concentrated stream from freshwater room
Device is taken out of so as to prevent fouling.In the patented technology, fresh water and concentrated water are the type of flow of one section of one-level, but its current side
To opposite.This deep or light aqueous phase mutually in adverse current water flow mode cause residence time of the metal ion in EDI concentrated water room compared with
The mode of deep or light water following current greatly shortens, to preventing fouling advantageously.
However, the conventional EDI technologies including above-mentioned patented technology, are also closed in the presence of the general character that some not yet achieve a solution
Key problem, these problems are how relevant with the Water flow-path design inside EDI.One problem is that most existing business EDI technologies are adopted
Designed with one section of Water flow-path of one-level, i.e. fresh water and concentrated water raw water, or enter from bottom of device, by the long flow path of a dividing plate
After degree, just discharged from top；Or in contrast, arranged after entering from top after the operation length of a dividing plate from bottom
Go out.In this design, the current in multiple diluting compartments in parallel, after the desalting processing of a compartment, compartment is expelled directly out；
It is the water outlet of whole device after the lightening products water mixing of multiple compartments.Because ultra-pure water requires that ion concentration therein is necessary
The extremely low level of micrograms per litre rank, if therefore have the current desalination in some compartment not thorough, have it is a small amount of do not remove from
Son discharge compartment, then just directly affect the producing water water quality of whole device；On the other hand, if certain fluctuation occurs for water inlet raw water
When, as electrical conductivity from below 5 μ S/cm improve to 10 μ S/cm levels when, due to lacking enough regeneration mixed bed buffering area, produce water
Resistivity can be directly reduced to below 5M Ω cm from more than 15M Ω cm.This illustrates that existing EDI technologies are improving tolerance water inlet
Obvious deficiency in terms of the fluctuation of salt content and the stability of desalination processes be present.
Another problem of existing EDI technologies is relevant with electrode water system, and the problem is directly related to whole water process
The security of system.In most existing EDI technologies including above-referenced technology, the current in its electrode chamber are final
It is mutually mixed with concentrated stream, is favourable for this design and assembling to device, the facility of production, but it is negative to bring other
Face rings.For example, oxidation reaction can occur in cathode chamber, the Cl in water-Ionic valence condition raises, and turns into Cl2Gas, goes forward side by side one
Step, which is dissolved in the water, generates HCl, HClO and NaClO.In this series of course of reaction, product is all the very strong oxidation of destructive power
Agent, have a strong impact on the life-span of resin and film.And in actual applications, because EDI condensed water is not general in line, but reclaim
To upstream RO water inlet, due to wherein containing the electrode water lumped together, then Cl therein is brought into by electrode water2, hypochlorous acid
HClO, sodium hypochlorite NaClO will be to the polyamide RO films of resistance to oxidation do not play destruction completely.In order to avoid this to whole
The destruction of individual water treatment system, need to add reproducibility medicament such as NaHSO again before RO films again3, Cl is neutralized using it2、
HClO and NaClO.This adds inconvenience to practical application, because it is difficult to accurately hold chlorine caused by electrode reaction and
Hypochlorous amount, thus can only in the feed water flow of RO films excessive addition reproducibility medicament, so as to additionally increase desalination burden.
EDI electrode water is that the flow of electrode water and pressure can not be separately adjustable with another potential risk that condensed water mixes,
But distributed automatically depending on the number of electrode water dividing plate and concentrated stream dividing plate.This may cause specifically running compared with high workload electric current
Under the conditions of, electrode water-carrying capacity is relatively low and is not enough to heat caused by electrode reaction discharging EDI membrane stacks in time, so as to certain
After run time accumulation, because accumulation of heat, electrode room temperature improve the water flow partition board of corresponding plastic material is deformed, to whole
Individual EDI membrane stacks device band carrys out high risks.In view of this, completely self-contained electrode water piping system is designed, very small amount is contained
The electrode water and the dense of EDI, fresh water stream of harmful substance are mutually isolated, and individually discharge is to improving EDI and whole water treatment system
Operation stability is favourable.
It can be seen that existing EDI technologies can not yet provide a feasible technical scheme so that it can effectively relax into water
Hardness limits, and improves the operation stability of EDI resistance to raw water quality fluctuation simultaneously, and provides and can be completely independent, isolate
Electrode water lines, to ensure EDI and whole water treatment system safety in operation.
The content of the invention
The deficiency of the present invention existing electrodeionization technology for more than, there is provided a kind of to be both suitable for the higher hard of 5-10mg/L
Flow condition is spent, while is more tolerant of influent quality fluctuation, possesses completely self-contained electrode water system, has high ant-scaling and height concurrently
Stable desalting performance, the electric deionizing method and device of more stable, the safe reinforcing antiscale of operation.EDI provided by the invention takes off
The core thinking of salt technology, it is that EDI fresh water stream is designed as two sections of one-level, and concentrated stream is then one section of one-level, and in fresh water
In the first paragraph flow of stream, dense, fresh water stream is mutually adverse current.This aspect causes hardness ions and OH-、CO3 2-Plasma enters
It is difficult to combine inside EDI, or, EDI modules have been discharged before it is not yet combined；On the other hand, EDI fresh water stream
For one-level two-piece design so that whole fresh water is realized and remixed and redistribution process between one, two section of EDI, this energy
The enough stability for fundamentally improving operation, it is advantageous to be resistant to the fluctuation of influent quality.In addition, pass through special battery lead plate
Frame designs so that electrode water completely with it is dense, fresh water stream is mutually isolated, so as at utmost avoiding to EDI and whole water process system
The damaging influence of system.
Wherein, in the electric deionizing method of above-mentioned reinforcing antiscale, the fresh water is referred to by the way of two sections of one-level：It is light
Water is intake to be imported in each light water flow partition board of EDI fresh water stream first paragraph by the upper end fresh water hole of side battery lead plate, directly
It is prevented to arrival fresh water commutation dividing plate and carries out current commutation, the water (flow) direction in fresh water stream first paragraph is from top to bottom；Fresh water
Each light water flow partition board water outlet for flowing first paragraph re-mixes in interconnected fresh water hole, and enters the after redistributing automatically
In two sections of each light water flow partition board, from bottom to top, last fresh water outlet is from opposite side battery lead plate for water (flow) direction in second segment
The fresh water hole export at end.
Wherein, in the electric deionizing method of above-mentioned reinforcing antiscale, the fresh water is referred to by the way of two sections of one-level：It is light
Water is intake to be imported in each light water flow partition board of EDI fresh water stream first paragraph by the lower end fresh water hole of side battery lead plate, directly
It is prevented to arrival fresh water commutation dividing plate and carries out current commutation, the water (flow) direction in fresh water stream first paragraph is from bottom to top；Fresh water
Each light water flow partition board water outlet for flowing first paragraph re-mixes in interconnected fresh water hole, and enters the after redistributing automatically
In two sections of each light water flow partition board, from top to bottom, last fresh water outlet is under opposite side battery lead plate for water (flow) direction in second segment
The fresh water hole export at end.
Between two sections, current, which realize, to be remixed and reallocates：The water outlet of each dividing plate is being interconnected in first paragraph
Fresh water hole composition water stream channel in re-mix, then again mean allocation enter second segment each dividing plate in；In addition,
If necessary, the water inlet of concentrated stream can be distributed offer by fresh water outlet, and remaining fresh water outlet then enters production water for ultrapure product water
Case.
Wherein, in the electric deionizing method of above-mentioned reinforcing antiscale, the concentrated water is referred to by the way of one section of one-level：It is dense
Water water inlet imports electricity by side battery lead plate lower end or the concentrated water hole of upper end (depending on the water (flow) direction of fresh water stream in the first paragraph)
Deionization membrane stack, it is evenly distributed on each dividing plate in interconnected concentrated water hole in each enriched chamber's dividing plate, from bottom to top or certainly
Each enriched chamber's dividing plate is above flowed through lowerly, and concentrated water apopore exports directly as corresponding to the battery lead plate other end；Wherein, each concentrated water
Flow dividing plate in water (flow) direction with fresh water stream first paragraph fresh water stream it is in opposite direction.
Wherein, in the electric deionizing method of above-mentioned reinforcing antiscale, methods described also includes independent electrode water disengaging mode,
Which refers specifically to：Pole water water inlet is imported the electrode chamber of the side by the electrode water inlet opening of side battery lead plate lower end, at this
EDI membrane stacks are discharged in lateral electrode room upper end, and further pass through another electrode water hole of the lateral electrode plate lower end through external pipe
Reenter EDI membrane stacks, through all in dense, light water flow partition boards corresponding position electrode water hole, opposite side is entered by lower end
Electrode chamber, by the electrode water hole of opposite side electrode chamber upper end, and all corresponding another electrode waters in dense, light water flow partition board
Hole returns, final to discharge EDI membrane stacks.
Wherein, in the electric deionizing method of above-mentioned reinforcing antiscale, the electrode water is under in the flow direction of positive and negative pole room
On and, EDI membrane stacks are effectively discharged so as to be advantageous to the various gases of electrode reaction generation.
The device of the electric deionizing method provided by the present invention for implementing above-mentioned reinforcing antiscale, including closed assembly successively in order
Positive plate together, cathode chamber dividing plate, the n groundwork unit repeated, 1 with fresh water commutation dividing plate substitute fresh water stream every
The groundwork unit of plate, the m groundwork unit repeated, 1 basic work that concentrated stream dividing plate is substituted with anode chamber dividing plate
Make unit and negative plate；The groundwork unit is by from positive pole to the anion-exchange membrane in negative pole direction successively closed assembly, fresh water
Dividing plate, cation-exchange membrane and concentrated stream dividing plate is flowed to form；N, m is integer and n >=m >=1.
Wherein, in the electric deionizer of above-mentioned reinforcing antiscale, the positive and negative of the light water flow partition board are equipped with reinforcement
And seal groove.
Further, seal groove is additionally arranged at the outer periphery of whole water flow holes and to filling ion-exchange resin
Central cavity outer periphery.
Wherein, clamping plate is matched somebody with somebody in the outside of the positive/negative plate at the electric deionizer both ends of above-mentioned reinforcing antiscale, and uses spiral shell
Bar is fastened whole device.
Wherein, the electric deionizer of above-mentioned reinforcing antiscale, when using positive plate as fresh water influent side battery lead plate, negative pole
Plate is then used as fresh water outlet lateral electrode plate.
Wherein, the electric deionizer of above-mentioned reinforcing antiscale, when using positive plate as fresh water outlet lateral electrode plate, negative pole
Plate is then used as fresh water influent side battery lead plate.
Wherein, in the electric deionizer of above-mentioned reinforcing antiscale, one end of the fresh water influent side battery lead plate is provided with fresh water
Inlet opening；One end of the fresh water outlet lateral electrode plate is provided with fresh water outlet hole, concentrated water apopore, pole water apopore, dynode
Water leadout hole, concentrated water inlet opening, pole water inlet opening and dynode water entrance hole are provided with the other end of fresh water outlet lateral electrode plate.
Compared with prior art, the present invention has obvious advantage and beneficial effect, embodies in the following areas：1、
By two sections of fresh water stream one-level, one section of concentrated stream one-level inside EDI devices, and dense, fresh water stream is in the first paragraph of fresh water stream
Unique construction and the Water flow-path design of adverse current, effectively prevent the internal fouling because of generation precipitate metal hydroxides, significantly put
Wide water inlet stiffness conditions limitations；2nd, fresh water stream is one-level two-part flow so that current can occur again in first and second section
Mixing and reallocation effect, make EDI possess more stable desalting performance, the fluctuation into water salt content are more tolerant of, relatively
High entering can still stablize high purity water under the conditions of water conductivity；3rd, possess completely self-contained electrode water piping system, electrode water
With it is dense, fresh water stream is completely isolated, avoid destruction of harmful electrode reaction to EDI devices and whole water treatment system；4th, fresh water
Stream dividing plate positive and negative are equipped with the reinforcement of large area distribution and place the seal groove of O-ring seal, and battery lead plate is towards membrane stack
Corresponding O-ring seal groove is also equipped with medial surface, between dividing plate and amberplex, between dividing plate and dividing plate, dividing plate with
Good airproof performance between battery lead plate, it can thoroughly prevent from altering leakage in current；
Brief description of the drawings
Fig. 1 is a kind of internal water schematic flow sheet of existing EDI technologies；
Fig. 2 is a kind of internal water schematic flow sheet of the electric deionizing method of reinforcing antiscale provided by the present invention；
Fig. 3 is another internal water schematic flow sheet of the electric deionizing method of reinforcing antiscale provided by the present invention；
Fig. 4 be it is provided by the present invention reinforcing antiscale electric deionizing method groundwork unit in Ion transfer,
Prevent the principle schematic of fouling；
Fig. 5 is a kind of electrode water idiographic flow schematic diagram of electric deionizing method for strengthening antiscale provided by the present invention；
Fig. 6 is the closed assembly schematic diagram of the electric deionizer of reinforcing antiscale provided by the present invention；
Fig. 7 is the assembling schematic diagram of the electric deionizer of reinforcing antiscale provided by the present invention；
Fig. 8 is the main structure chart of the light water flow partition board of the electric deionizer of reinforcing antiscale provided by the present invention；
Fig. 9 is the flow chart of embodiment device provided by the present invention；
Figure 10 is that the production water resistance rate of embodiment provided by the present invention changes over time curve map；
Figure 11 is that the ton water body energy consumption of embodiment provided by the present invention changes over time curve map.
In figure, 1- positive plates, 2- negative plates, 3- anion-exchange membranes, 4- cation-exchange membranes, the water inlet of 5- fresh water, 6- are light
Water water outlet, the water inlet of 7- concentrated waters, the water outlet of 8- concentrated waters, the water inlet of 9- cathode chambers, the water outlet of 10- cathode chambers, the water inlet of 11- anode chambers, 12- negative poles
Room water outlet, the water inlet of 13- poles water, the water water outlet of 14- poles, 15- groundworks unit, 16- anode chambers dividing plate, the light water flow partition boards of 17-,
18- concentrated streams dividing plate, 19- fresh water commutation dividing plate, 20- cathode chambers dividing plate, 21- reinforcements, 22-O type circles seal groove, 23- raw waters
Case, 24- regulating valves, 25- water pumps, the online conductivity meters of 26-, 27- flowmeters, 28-EDI devices, 29- D.C. regulated power supplies, 30-
Online resistance rate instrument, 31-EDI production water tanks.
Embodiment
The invention will be further described with reference to the accompanying drawings and examples.
A kind of electric deionizing method for strengthening antiscale provided by the invention, this method include：Fresh water stream uses two sections of one-level
Water flow-path mode, concentrated stream uses the Water flow-path mode of one section of one-level, and dense, fresh water is reverse in the 1st section of fresh water stream
Flowing；In addition, the electrode current of whole EDI devices with it is dense, fresh water stream is completely isolated, its flow, pressure can be with separately adjustable.
Fig. 1 is a kind of internal water schematic flow sheet of existing EDI technologies.Fresh water stream, concentrated stream are one-part form stream in figure
Journey, two bursts of flow reversal flowings；Electrode water mixes with concentrated stream, and the flow and pressure of electrode water can not be separately adjustable.
Fig. 2 is a kind of internal water schematic flow sheet of the electric deionizing method of reinforcing antiscale provided by the present invention, wherein
Fresh water raw water enters from side of the positive electrode, and n, m are 2；Fig. 3 is the another kind of the electric deionizing method of reinforcing antiscale provided by the invention
Internal water schematic flow sheet, wherein fresh water raw water enter from negative side, and n, m are also 2.EDI devices involved in the present invention it is light
Change equal filling ion-exchange resin in room, enriched chamber and positive and negative electrode room, carried out in figure exemplified by filling uniform mixed-bed resin
Illustrate, specific filling Strategy can make the appropriate adjustments according to water quality treatment.
According to Fig. 2, fresh water water inlet 5 imports the 3rd light water flow partition board entered in the 1st section, the 1st section by positive pole upper end
For the dividing plate 19 that commutates, i.e. the top fresh water hole of the dividing plate allows current to enter, but completely closed towards the water hole bottom of negative side,
So as to force current to commutate.Water (flow) direction from top to bottom, connects in the fresh water hole of the 1st, 2 section of whole dividing plate bottoms in 1st section
Re-mix, and redistributed automatically into the 2nd section of 3 light water flow partition boards in the 2nd section, water in the water stream channel of formation
Flow direction from bottom to top, last fresh water outlet 6 exports from negative plate upper end.This design make it that the desalination stroke of fresh water stream is longer
More fully, desalting effect is insufficient in the 1st section some compartment, and its salinity can also be through the entrance that remixes, reallocates
Thoroughly removed in 2nd section, so as to which device effluent quality will not be directly affected, drastically increase the resistance to raw water quality fluctuations of EDI
Operation stability.
In Fig. 2, fresh water outlet 6 distributes one as concentrated water water inlet 7, and remaining is largely ultrapure product water.Concentrated water
Water inlet 7 is imported by negative plate lower end, is evenly distributed in each concentrated stream compartment, is flowed from bottom to top, concentrated water water outlet 8 is by negative plate
Upper end exports.The specific Principle of Scale Prevention of this design is as shown in Figure 4.In a groundwork unit 15, laterally born from positive pole
Pole side is anion-exchange membrane 3, diluting compartment, cation-exchange membrane 4, enriched chamber successively, wherein two strands of current are counter-current flow.It is former
Salt ion in water, including Ga2+、Mg2+Hardness ions, the i.e. lateral transfer in the presence of DC electric field after diluting compartment is entered,
And enter adjacent enriched chamber through cation-exchange membrane 4, and in opposite direction flowing, the condensed water of only one section of short route
Stream can take it out of EDI membrane stacks within the shortest time；In addition, concentration polarization and water decomposition in diluting compartment mainly salt from
The downstream for the water (flow) direction that sub- concentration progressively reduces just acutely occurs, therefore water decomposition product H+、OH-Concentration be along fresh water
The direction of stream gradually increases, and including Ga2+、Mg2+Salt ionic concentration including hardness ions is gradual along the direction of fresh water stream
Reduce, this allows for the Ga of rather high concentration2+、Mg2+Hardness ions and OH-Ion can not be formed at same Water flow-path position, it
Be respectively at the entrance and exit of fresh water stream.It can be seen that in electric deionizing method provided by the invention, hardness ions can be rapid
Discharge EDI devices, and the hardness ions and OH of high concentration-Ion distribution is at the entrance and exit of fresh water stream, so as to maximum journey
Degree avoids to form Mg (OH)2、Ga(OH)2Precipitated Deng fouling.Dense, fresh water stream counter-flow pattern and concentrated water water inlet is shunted by fresh water
Design method, similarly avoid CO3 2-Ion continues to build up in concentrated water flow, and it is with Ga2+、Mg2+Ion is the same,
It is quickly discharged outside EDI, therefore also avoids GaCO well3Fouling precipitation.Electric deionizing method provided by the invention
Two sections of the fresh water one-level of use, the unique design that one section of concentrated water one-level, effective anti-scaling property and efficient, stable are taken into account and have taken off
Salt performance so that under the conditions of the higher raw water salt content of more existing EDI technologies, original water hardness, EDI still can efficiently, stably
Prepare ultra-pure water.
Fig. 5 be Fig. 3 shown in electrodeionization internal water flow in electrode water current schematic diagram.Electrode water water inlet 13, by
The pole water hole of positive plate bottom enters, as positive pole water inlet 9.Because the perforate of positive pole dividing plate in this place causes electrode water only
Positive pole dividing plate can be entered, and at the pole water hole on positive plate top, be expelled directly out in a manner of positive pole water outlet 10.Positive pole water outlet 10
Through ft connection pipeline, EDI membrane stacks are entered by another pole water hole of positive plate bottom again, are horizontally through whole the lower partition
The reserved pole water hole of corresponding site, reach negative pole dividing plate as negative pole intake 11, equally flowed from lower to upper in negative pole dividing plate,
Negative pole water outlet 12 continues to be horizontally through the reserved pole water hole of whole dividing plate tops corresponding site, another pole water from positive plate top
Sentence electrode water water outlet 14 and discharge EDI membrane stacks in hole.When electrode water is through the reserved pole water hole at position above and below each dividing plate, due to
The sealing function of the O-ring on water hole periphery, electrode water and the dense of each dividing plate, fresh water stream are completely isolated, will not also leak.
This design causes electrode water lines to be completely independent, and can regard scale, the size and water quality of whole device processing water of membrane stack,
By the pump of outside, flowmeter and respective valves opening and closing flexibly, be independently adjusted its operating pressure and flow；It is in addition, positive and negative
Current in electrode chamber are from bottom to top, to be advantageous to H caused by electrode reaction2、O2、Cl2Deng the discharge of gas.These effects
Damaging influence of the electrode reaction noxious products to whole system is fundamentally prevented.Further, electrode water from positive pole to
Negative pole serial communication, the acidity of positive pole current can be made mutually to be neutralized with the alkalescence of negative pole current, be also beneficial to improve anode chamber
Operational reliability.Both positive and negative polarity water Natural communication inside membrane stack, only there are a small amount of connecting pipe, pole water outside the battery lead plate of side
Water-in and water-out in battery lead plate side, avoid traditional multiple, complicated exterior line connected mode, beneficial to whole EDI systems
The simplification of operation, arrangement and management.
Present invention also offers the electric deionizer for implementing the above method, Fig. 6 and Fig. 7 are respectively provided by the present invention
A kind of the closed assembly schematic diagram and assembling schematic diagram of the electric deionizer for strengthening antiscale, each groundwork unit 15 is same in Fig. 7
Sample contains each 1 cation-exchange membrane, anion-exchange membrane, light water flow partition board and concentrated stream dividing plate, but order of arranging is by just
Pole is followed successively by concentrated stream dividing plate 18, anion-exchange membrane 3, light water flow partition board 17 and cation-exchange membrane 4 to negative pole.The device bag
The positive plate 1 being stacked successively in order, cathode chamber dividing plate 20, n repeatable groundwork units 15,1 are included with light
Water commutation dividing plate 19 substitutes the groundwork unit of light water flow partition board 17, m repeatable groundwork units 15,1 with negative pole
Room dividing plate 16 substitutes the groundwork unit and negative plate 2 of concentrated stream dividing plate 18；
The groundwork unit 15 by the anion-exchange membrane 3 from positive pole to negative pole direction successively closed assembly, fresh water stream every
Plate 17, cation-exchange membrane 4 and concentrated stream dividing plate 18 are formed.N+m+2 groundwork unit 15 forms membrane stack, groundwork list
Member is also referred to as film pair.The quantity of motor-driven adjustment groundwork unit 15, it is possible to the processing water of adjustment equipment.In parallel is basic
The number of working cell 15 is more, and the aquifer yield of EDI devices is bigger.
Specifically, the electric deionizer is at work, it is independent when fresh water raw water enters EDI by negative side
Electrode water raw water by positive plate lower end electrode water water inlet import cathode chamber dividing plate, cathode chamber dividing plate upper end i.e. discharge electricity go
Ion membrane stack, and EDI is further reentered by another electrode water hole of positive plate lower end through external pipe,
The electrode water hole of corresponding position, enters opposite side anode chamber dividing plate by lower end, passes through negative pole on through whole dense, light water flow partition boards
The electrode water hole of room dividing plate upper end, and all corresponding another electrode water hole return, final discharge electricity in dense, light water flow partition board
Deionization membrane stack；Or when fresh water raw water enters EDI by side of the positive electrode, independent electrode water raw water is by cathode chamber
The pole water hole of dividing plate lower end imports, and is exported in the pole water hole of cathode chamber dividing plate upper end, through all dense, light water flow partition board, negative pole
The pole water hole of room dividing plate and negative plate upper end exports, and is further entered through external pipe by the electrode water hole of negative plate lower end
Anode chamber dividing plate, EDI is finally discharged by another pole water hole of anode chamber dividing plate and negative plate upper end.
Fig. 8 is a kind of agent structure of the diluting compartment dividing plate of electric deionizer for strengthening antiscale provided by the present invention
Figure.Shown in figure, the positive and negative of diluting compartment dividing plate 17 are equipped with widely distributed reinforcement 21 and place the close of O-ring seal
Sealing groove 22.Between dividing plate and amberplex, good airproof performance between dividing plate and dividing plate, prevent from altering leakage in current.Different dividing plates
The water hole of same position is interconnected, the closed corresponding water stream channel of composition under membrane stack impaction state by O-ring.
Fig. 9 is a kind of process chart of embodiment device provided by the present invention.Shown according to flow in figure, raw water box
First-stage reverse osmosis production water in 23 additionally adds the CaCl of debita spissitudo again2、MgCl2Solution, conduct after regulating into the water hardness
EDI is intake, and enters EDI modules 28 through water pump 25, flow of inlet water is controlled regulation by flowmeter 27, enters water conductivity by online
Conductivity meter 26 is monitored in real time.EDI fresh water productions water 6 is used as concentrated water water inlet 7 to enter dense outdoor except part, and remaining all enters production
Water tank 31, fresh water producing water water quality are detected by online resistance rate instrument 30.Pole water water outlet 15 and the directly outer row of concentrated water water outlet 8, it is dense
Aquatic products water conductivity is detected by online conductivity meter.D.C. regulated power supply 29 provides direct current for whole EDI modules.
Embodiment
In the example, EDI devices use two sections of fresh water one-level, the frame mode that one section of concentrated water one-level, containing 10 basic works
Make unit.Diluting compartment dividing plate specification is 668mm × 330mm × 10mm, concentrated stream and electrode chamber dividing plate specification be 668mm ×
330mm × 4.9mm, effective membrane area of each dividing plate is 888cm2.The number of the groundwork unit, i.e. film pair of EDI membrane stacks
For 10.Amberplex used in EDI is the special heterogeneous ion-exchange membranes of EDI, is produced by Hangzhou Ai Er Environmental Protection Technology Co., Ltd；
Ion exchange resin is the Marathon cationic ion-exchange resins (Na of DOW companies production+Type) and Marathon anion exchanges
Resin (Cl-Type).The volume ratio of yin, yang resin is 1 in whole compartments:1.
Ca in raw water box 232+Ion concentration is 1.71mg/L, mg2+Ion concentration is 0.78mg/L.According to based on CaCO3
The hardness conversion formula of calculating, then the calcium hardness in raw water is 1.71* (100/40), i.e., 4.275, and magnesium hardness is 0.78*
(100/24.4), i.e., 3.223, then total hardness is 7.5mg/L (with CaCO3Meter).The raw water is that one-level RO production water additionally adds
CaCl2And MgCl2Salting liquid is prepared and obtained, and produces water to simulate the RO of higher hardness, its electrical conductivity is 17.5 μ S/cm.
Fresh water flow of inlet water is 1m3/ h, fresh water outlet shunting 0.2m3/ h flow as concentrated water intake, lightening products water and
The flow of condensed water is respectively then 0.8m3/ h and 0.2m3/h.Electrode water is intake by directly being provided in raw water box, flow 60L/h.
Adjustment at initial stage EDI operating current is 1.6A, after running 10h under galvanostatic conditions, lightening products water resistance rate
15.0M Ω cm are gradually increased to by 0.1M Ω cm, persistently raised thereafter, it is stable between 16.0-17.6M Ω cm.About
After 100h, the operating current for properly increasing EDI is 1.8A, hereafter continuous service.In accumulative 500h, it is equal to fade out water resistance rate
It is stable that corresponding membrane stack operating voltage is persistently increased by initial 20V between 16.0-17.5M Ω cm (as shown in Figure 10),
It is final stable in 40V.This be by EDI processes anion-exchange membrane and anion exchange resin with the passage of run time,
Under the working condition of water decomposition, partial function group quaternary ammonium group occurs caused by tertiary-aminated degraded institute nature.With the work under stable state
Make voltage 40V, operating current 1.8A, fresh water production water 0.8m3/ h is calculated, and EDI ton water body energy consumption is by initial in the embodiment
0.04kWh step up, finally stabilize to 0.09kWh (as shown in figure 11).Relatively existing commodity EDI technologies and product
0.15-0.3kWh/m3Normal energy consumption for, it is seen that also there is electric deionizing method provided by the invention significant energy-conservation to imitate
Fruit.
In the present embodiment, the EDI water hardness of entering has reached 7.5mg/L (with CaCO3Meter), more existing EDI is to entering the water hardness
Common demands will much relax less than 1.0mg/L.Estimation is guarded to the steady removal rate 99% of hardness ions in water with RO films,
The Ca of its upstream RO raw water allowed2+Ion concentration can reach 170mg/L, while also allow the mg for having 78mg/L2+Ion is deposited
.For most city tap-waters, surface water and groundwater, the Ca in its water2+、Mg2+Ion is substantially lower than this water
It is flat.Obviously, using only the pre-treatment that single-stage RO is EDI, it produces water hardness index all in electric deionizing method provided by the invention
Disposal ability within.For another angle, for existing EDI technologies it is necessary enter the water hardness less than 1mg/L harshness will
Ask, such as when RO production water contains 0.4mg/L Ca2+Ion, or, the Ca containing 0.3mg/L simultaneously2+With 0.063mg/L Mg2 +During ion, its total hardness is just up to 1.0mg/L.Equally using single-stage RO as pre-treatment, steady removal rate of the RO films to hardness
In terms of 99%, it is clear that use " when the existing EDI " of RO/ integrated technique prepares ultra-pure water, must contain in the raw water handled by it
Ca no more than 40mg/L2+Ion, or simultaneously containing the Ca for being no more than 30mg/L respectively2+The Mg of ion and 6.3mg/L2+Ion,
Or the combination of other calcium ions and magnesium ions suitable with this.It can be seen that for most of running water, surface water and groundwater,
This is all implacable condition.In the present embodiment, electric deionizing method provided by the present invention so that whole water process system
The handled raw water of system and the more existing EDI technologies of hardness number of upstream RO production water relax 7.5 times, and to most running water,
For surface water and groundwater, all cause so that " single-stage RO/EDI " integrated technique stably prepares ultra-pure water and possesses practicable
Property.This is to the production of the pure water, ultra-pure water of numerous industrial departments such as electric power, electronics, bio-pharmaceuticals, really promoting the use of EDI
This green, cleaning, environment-friendly membrane technology, save significantly on upstream UF, RO film dosage, and saving RO concentrated water drainages all has
Significance.
Described above is only the preferred embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, under the premise without departing from the principles of the invention, some improvement can also be made, including but not limited to change EDI
Two sections of fresh water streams in water (flow) direction be from top to bottom or from bottom to top, the appropriate negative and positive tree changed in diluting compartment and enriched chamber
The particle size range of institute's filling ion-exchange resin in fat ratio, suitable control diluting compartment and enriched chamber, directly using RO produce water as
The raw water of concentrated water and electrode water or shunted completely by fresh water outlet also same as concentrated water and the raw water of electrode water etc., these improvement
Sample belongs within protection scope of the present invention.
Claims (10)
1. a kind of electric deionizing method for strengthening antiscale, it is characterised in that possess the Water flow-path of uniqueness inside EDI
Mode, i.e. fresh water stream are two sections of one-level and concentrated stream is one section of one-level, and dense, fresh water stream is in the first paragraph flow of fresh water stream
Mutual counter-current flow.
2. a kind of electric deionizing method for strengthening antiscale according to claim 1, it is characterised in that the fresh water stream is one
The mode of two sections of level refers to：Fresh water is intake imports EDI fresh water stream first by the upper end fresh water hole of side battery lead plate
In each light water flow partition board of section, it is prevented from until reaching fresh water commutation dividing plate and carries out current commutation, in fresh water stream first paragraph
Water (flow) direction is from top to bottom；Each light water flow partition board water outlet of fresh water stream first paragraph re-mixes in interconnected fresh water hole,
And enter after redistributing automatically in each light water flow partition board of second segment, water (flow) direction is from bottom to top, last light in second segment
Water water outlet exports from the fresh water hole of opposite side battery lead plate upper end.
3. a kind of electric deionizing method for strengthening antiscale according to claim 1, it is characterised in that the fresh water stream is one
The mode of two sections of level refers to：Fresh water is intake imports EDI fresh water stream first by the lower end fresh water hole of side battery lead plate
In each light water flow partition board of section, it is prevented from until reaching fresh water commutation dividing plate and carries out current commutation, in fresh water stream first paragraph
Water (flow) direction is from bottom to top；Each light water flow partition board water outlet of fresh water stream first paragraph re-mixes in interconnected fresh water hole,
And enter after redistributing automatically in each light water flow partition board of second segment, water (flow) direction is from top to bottom, last light in second segment
Water water outlet exports from the fresh water hole of opposite side battery lead plate lower end.
4. the electric deionizing method of a kind of reinforcing antiscale according to any one of claims 1 to 3, it is characterised in that described
Concentrated stream refers to for the mode of one section of one-level：Concentrated water is intake is gone by the lower end of side battery lead plate or the concentrated water hole importing electricity of upper end
Ion membrane stack, it is evenly distributed in each enriched chamber's dividing plate in the concentrated water hole being interconnected on each dividing plate, from bottom to top or from upper
And flow through each enriched chamber's dividing plate lowerly, then as corresponding to the battery lead plate other end concentrated water apopore export, wherein, each concentrated stream every
Water (flow) direction in plate with fresh water stream first paragraph fresh water stream it is in opposite direction.
5. a kind of electric deionizing method for strengthening antiscale according to claim 1, it is characterised in that methods described also includes
Independent electrode water disengaging mode, which refer specifically to：The water water inlet of single pole is entered just by cathode chamber bottom pole water hole
Pole room dividing plate, discharged by cathode chamber dividing plate top pole water hole, continued through EDI internal poles water lines or external pipe
Anode chamber dividing plate is entered by anode chamber bottom pole water hole, EDI is discharged by the pole water hole on anode chamber dividing plate top.
6. a kind of electric deionizer for strengthening antiscale, it is characterised in that the device includes what is be stacked successively in order
Positive plate, cathode chamber dividing plate, the n groundwork unit repeated, 1 the basic of light water flow partition board is substituted with fresh water commutation dividing plate
Working cell, m repeat groundwork unit, 1 with anode chamber dividing plate substitute concentrated stream dividing plate groundwork unit and
Negative plate, n, m are integer and n >=m >=1；The groundwork unit is by from positive pole to the anion in negative pole direction successively closed assembly
Exchange membrane, light water flow partition board, cation-exchange membrane and concentrated stream dividing plate are formed.
A kind of 7. electric deionizer for strengthening antiscale according to claim 6, it is characterised in that the light water flow partition board
Positive and negative be equipped with reinforcement and seal groove.
8. a kind of electric deionizer for strengthening antiscale according to claim 6, it is characterised in that whole device both ends
Clamping plate is matched somebody with somebody in the outside of positive/negative plate, and is fastened whole device using screw rod.
9. it is according to claim 6 it is a kind of strengthen antiscale electric deionizer, it is characterised in that when using positive plate as
During fresh water influent side battery lead plate, negative plate is then used as fresh water outlet lateral electrode plate；When being used as fresh water outlet lateral electrode using positive plate
During plate, negative plate is then used as fresh water influent side battery lead plate.
A kind of 10. electric deionizer for strengthening antiscale according to claim 9, it is characterised in that the fresh water water inlet
One end of lateral electrode plate is provided with fresh water inlet opening；One end of the fresh water outlet lateral electrode plate is provided with fresh water outlet hole, concentrated water goes out
Water hole, pole water apopore, dynode water leadout hole, concentrated water inlet opening, pole water are provided with the other end of fresh water outlet lateral electrode plate
Inlet opening and dynode water entrance hole.
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