CN1774403B - Apparatus for electrodeionization and method for operating the same - Google Patents
Apparatus for electrodeionization and method for operating the same Download PDFInfo
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- CN1774403B CN1774403B CN2004800100555A CN200480010055A CN1774403B CN 1774403 B CN1774403 B CN 1774403B CN 2004800100555 A CN2004800100555 A CN 2004800100555A CN 200480010055 A CN200480010055 A CN 200480010055A CN 1774403 B CN1774403 B CN 1774403B
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- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000009296 electrodeionization Methods 0.000 title description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 276
- 238000011033 desalting Methods 0.000 claims abstract description 121
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910052796 boron Inorganic materials 0.000 claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 claims description 42
- 230000004087 circulation Effects 0.000 claims description 30
- 239000003014 ion exchange membrane Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000009792 diffusion process Methods 0.000 abstract description 9
- 238000002242 deionisation method Methods 0.000 abstract description 4
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 30
- 238000007872 degassing Methods 0.000 description 15
- 238000001223 reverse osmosis Methods 0.000 description 15
- 239000000377 silicon dioxide Substances 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 125000000129 anionic group Chemical group 0.000 description 13
- 239000002351 wastewater Substances 0.000 description 12
- 150000001450 anions Chemical class 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 10
- 239000012528 membrane Substances 0.000 description 10
- 230000002411 adverse Effects 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 125000002091 cationic group Chemical group 0.000 description 8
- 229960001866 silicon dioxide Drugs 0.000 description 8
- 235000012239 silicon dioxide Nutrition 0.000 description 8
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 239000004020 conductor Substances 0.000 description 7
- 238000005342 ion exchange Methods 0.000 description 7
- 239000003456 ion exchange resin Substances 0.000 description 7
- 229920003303 ion-exchange polymer Polymers 0.000 description 7
- 238000011049 filling Methods 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003011 anion exchange membrane Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005192 partition Methods 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000004941 influx Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000008400 supply water Substances 0.000 description 2
- 238000009849 vacuum degassing Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000005586 carbonic acid group Chemical group 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
An electric deionization apparatus capable of inhibiting the boron concentration diffusion from concentrating chamber to thereby enable obtaining a product water of extremely low boron concentration; and a method of operating the electric deionization apparatus. Raw water is introduced in desalting chamber (16), and product water is withdrawn from the desalting chamber (16). Portion of the product water is fed in a counterflow one-passage manner into concentrating chamber (15) in the direction opposite to the direction of water passage in the desalting chamber (16). Outflow water from the concentrating chamber (15) is discharged outside the system. Inflow port for the concentrating chamber (15) is disposed on the product water withdrawing side of the desalting chamber (16), and outflow port for the concentrating chamber (15) is disposed on the raw water inflow side of the desalting chamber (16). The boron concentration of concentrated water outflowing from the concentrating chamber is 10 ppb or less or up to 500 times that of the product water.
Description
Invention field
The present invention relates to be used to produce the electric deionizer and the working method thereof of the low production water of low production water of boron concentration or anion concentration.
Background technology
At use electric deionizers such as the fields of making pure water, ultrapure water etc.The plate and frame electric deionizer, have anode, negative electrode and between this anode, negative electrode, alternately form the concentration compartments and desalting chamber (dilution chamber) and alternately the configuration flat membranaceous cationic exchange membrane and anion-exchange membrane.In desalting chamber, filling the ion exchanger of ion exchange resin etc.Treat the water of desalting treatment to the circulation of this desalting chamber, the ion in the water sees through ion-exchange membrane and moves to the concentration compartments from desalting chamber.
The spy opens record in 2002-205069 number: in order to produce the low production water of silica concentration and boron concentration, the water that silicon-dioxide or the former water of boron concentration ratio is low as condensed water when the side near the deionized water conveying end of desalting chamber is incorporated in this concentration compartments, among this concentration compartments, make it to go out, will be discharged to outside the system from least a portion of this effusive condensed water in concentration compartments from a effluent near the former water inlet of desalting chamber.
In this communique, use silicon-dioxide or the low water of the former water of boron concentration ratio as condensed water, and, the water that such water quality is good is passed to the concentration compartments along the direction that the deionized water (production water) from desalting chamber takes out side direction Yuan Shui inflow side, can access the production water that silicon-dioxide, boron concentration is reduced to the high water quality of extremely low concentration in view of the above.
Summary of the invention
The objective of the invention is, the concentration diffusion of abundant inhibition from the boron of concentration compartments is provided, can access the working method and the electric deionizer of the electric deionizer of the production water that extremely hangs down boron concentration in view of the above.In addition, the objective of the invention is, the anionic concentration diffusion of the carbanion of abundant inhibition from the concentration compartments etc. is provided, can access the working method and the electric deionizer of electric deionizer of the production water of utmost point low carbon acid concentration in view of the above.
The working method of the electric deionizer of relevant the 1st form of the present invention, be between anode and negative electrode, to utilize ion-exchange membrane to divide the working method of the electric deionizer of concentration compartments and desalting chamber, it is characterized in that, when condensed water is circulated in this concentration compartments, former water is made it to circulate in desalting chamber as processed water, as producing water from the working method that this desalting chamber takes out, making from the boron concentration of this effusive condensed water in concentration compartments is to produce below 500 times of boron concentration of water, or is below the 10ppb.
The electric deionizer of relevant the 2nd form of the present invention, be between anode and negative electrode, to utilize ion-exchange membrane to divide concentration compartments and desalting chamber, condensed water circulates in this concentration compartments, former water circulates in desalting chamber as processed water, the electric deionizer that takes out as producing water, it is characterized in that possessing the boron concentration that makes from this effusive condensed water in concentration compartments is below 500 times of boron concentration of production water, or be the following device of 10ppb.
In the 1st form and the 2nd form, significantly low in order to make boron concentration, for example the following highly purified production water of 0.1ppb reduces the boron concentration from the effusive condensed water in concentration compartments.
At flow direction the occasion of a plurality of desalting chamber and concentration compartments is set, preferably makes from the boron concentration of the effusive condensed water in concentration compartments in downstream side to be below 500 times or of boron concentration for below the 10ppb from the effusive production water of desalting chamber in downstream side along processed water.In view of the above, even near the outlet of concentration compartments, the boron concentration gradient from the concentration compartments to the desalting chamber is also smaller, and the diffusion of the boron from the concentration compartments to the desalting chamber is suppressed, and can reduce the boron concentration of producing water.
In the 1st form and the 2nd form, the former water that preferably will import to electric deionizer carries out pre-treatment, after particularly former water such as tap water being carried out dechlorinations such as turbidity removal such as MF film or gac and handling, wishes to carry out RO and handles.Processing also can further outgas.
Be 0.005ppb when following particularly, further wish to carry out 2 step RO (reverse osmosis) and handle, reduce the feedwater load (for example 3ppb is following) of electric deionizer making the boron concentration of producing water.
Also can fill ion exchanger to desalting chamber.
When the water that water quality is good, when the current of promptly low conductivity, high resistivity passed in the concentration compartments, the resistance of concentration compartments uprised, and the possibility that can not guarantee current value is arranged.Therefore, also can be in the concentration compartments also ion exchanger, gac or other the electric conductor of filling ion-exchange resin etc., guarantee necessary electric current.
The working method of the electric deionizer of relevant the 3rd form of the present invention, it is characterized in that, it is the working method of deionizer, be that processed water is circulated in this desalting chamber, the working method that condensed water is circulated in this concentration compartments, in this working method, make adopt negatively charged ion remove low anion concentration water that treatment unit handles as this condensed water near a side inflow of desalting chamber's outlet the time to this concentration compartments, circulation is to make it to go out from the effluent near desalting chamber's inlet in this concentration compartments.
The electric deionizer of relevant the 4th form of the present invention, it is characterized in that, be between anode and negative electrode, to utilize ion-exchange membrane to divide concentration compartments and desalting chamber, processed water circulates in this desalting chamber, the electric deionizer that condensed water circulates in this concentration compartments, in this device, condensed water gatherer and bleeder are set, so that make this condensed water near a side inflow of desalting chamber outlet the time to this concentration compartments, go out from a effluent near desalting chamber's inlet, and the condensed water that is being provided with from flow into this concentration compartments is removed anionic device.
In the 3rd form and the 4th form,, reduce the anion concentration of the carbonic acid that supplies to the condensed water in the concentration compartments etc. for the remarkable low highly purified production water of the anion concentration of making carbonic acid etc.
In view of the above, even near the anion concentration gradient ratio the outlet of concentration compartments from the concentration compartments to the desalting chamber is less, the diffusion of the carbonic acid from the concentration compartments to the desalting chamber is suppressed, and can reduce the carbonate concentration of producing water.
In the 3rd form and the 4th form, by the total inorganic carbon (TIC) acid concentration that makes the condensed water that flow into the concentration compartments is below the 50ppb, can suppress the diffusion that the concentration gradient of the carbanion from the concentration compartments to the desalting chamber causes, produce significantly low production water of total inorganic carbon (TIC) acid concentration.
In the 3rd form and the 4th form, be below the 100ppb similarly by the silica concentration that makes the condensed water that flow into the concentration compartments, and making boron concentration is below the 10ppb, can suppress the diffusion that the concentration gradient of these ions from the concentration compartments to the desalting chamber causes, significantly reduce silica concentration and the boron of producing in the water.
In order to reduce total inorganic carbon (TIC) acid concentration, silica concentration or the boron concentration in the condensed water that flow into condensed water, also can will use as condensed water from the part of the effusive production water of desalting chamber.In addition, also can handle the water of supplying with the concentration compartments with ion exchange unit or electric deionizer.
In order to reduce the total inorganic carbon (TIC) acid concentration in the condensed water that flow into the concentration compartments, also can use de-gassing vessels such as degassing film device.
In the 3rd form and the 4th form, also former water can be made negatively charged ion and remove treatment and supplied in desalting chamber, in view of the above, can further reduce the anion concentration of producing water.Remove processing as this negatively charged ion, the preferred reverse-osmosis treated and the degassing are handled, preferred especially multistage reverse-osmosis treated, degassing processing again.
The simple declaration of accompanying drawing
Fig. 1 is the schematic sectional view of the electric deionizer of relevant embodiment.
Fig. 2 is the water circulation system figure of the electric deionizer of Fig. 1.
Fig. 3 is the water circulation system figure of the electrodeionization system of relevant another embodiment.
Fig. 4 is the water circulation system figure of the electrodeionization system of relevant another embodiment.
Fig. 5 is the water circulation system figure about the electrodeionization system of different embodiments.
Fig. 6 is the water circulation system figure of the electrodeionization system of relevant embodiment.
Fig. 7 a is the approximate three-dimensional map of the electric deionizer of relevant another embodiment, and Fig. 7 b is its system diagram.
Fig. 8 is the schematic sectional view about the electric deionizer of the embodiment of the 3rd form.
Fig. 9 is the water circulation system figure of the electric deionizer of Fig. 8.
Figure 10 is the water circulation system figure of the electrodeionization system of relevant another embodiment.
Figure 11 is the water circulation system figure of the electrodeionization system of relevant another embodiment.
Figure 12 is the water circulation system figure about the electrodeionization system of different embodiments.
Figure 13 is the water circulation system figure of the electrodeionization system of relevant embodiment.
Figure 14 is the water circulation system figure of the electrodeionization system of relevant embodiment.
Figure 15 is the water circulation system figure of the electrodeionization system of relevant embodiment.
Figure 16 is the water circulation system figure of the electrodeionization system of relevant embodiment.
The embodiment of invention
Below the preferred version that present invention will be described in detail with reference to the accompanying.
Fig. 1 is the schematic sectional view of electric deionizer 10 ' of an example of expression the 1st and the 2nd form.This electric deionizer is alternately to arrange a plurality of anion-exchange membranes (A film) 13 and cationic exchange membrane (C film) 14 between electrode (anode 11, negative electrode 12), alternately formed the device of concentration compartments 15 and desalting chamber 16, in desalting chamber 16, mixed or many anion ion exchange body and cation exchange columns that comprises ion exchange resin, ion-exchange fiber or grafting permutoid etc. of layeredly filling.
In concentration compartments 15 and anolyte compartment 17 and cathode compartment 18, filling the electric electrical conductor of ion exchanger, gac or metal etc.
Former water is directed in the desalting chamber 16, takes out from desalting chamber 16 and produces water.The part of this production water is passed in the concentration compartments 15 in adverse current one way (singlepass) mode in the opposite direction in the logical side of current with desalting chamber 16, and the outflow water of concentration compartments 15 is discharged to outside the system.That is, in this electric deionizer, concentration compartments 15 and desalting chamber 16 are set alternately, take out the influx that side is being provided with concentration compartments 15, the spout of concentration compartments 15 is being set in the Yuan Shui inflow side of desalting chamber 16 at the production water of desalting chamber 16.A part of producing water is fed to the inlet side of anolyte compartment 17, and the outflow water of anolyte compartment 17 is fed to the inlet side of cathode compartment 18, and the outflow water of cathode compartment 18 is discharged to outside the system as waste water.
Like this, by with desalting chamber 16 adverse current one way modes to the concentration compartments 15 circulations produce water, the approaching more production water of the concentration of the condensed water in the concentration compartments 15 takes out that side is low more, and the influence to desalting chamber 16 that the concentration diffusion causes diminishes, and can improve the ionic clearance of boron etc. by leaps and bounds.
In this embodiment, because by to the logical water of producing in concentration compartments, the resistance of electric deionizer uprises, therefore in the concentration compartments, filling the electrical conductor of ion exchanger etc.In view of the above, do not need to reduce resistance to ionogen such as condensed water interpolation salt.
In the electric deionizer 10 ' of Fig. 1, also to supply with and produce water to electrode vessel 17,18, electrode vessel 17,18 is also same with concentration compartments 15, in order to ensure electric current, preferably fills ion exchanger, gac or as the metal of electric electrical conductor etc.In view of the above, even the water of the logical contour water quality of ultrapure water also can be guaranteed necessary electric current.
Owing to cause in electrode vessel, the particularly generation of oxygenant such as chlorine in the anolyte compartment or ozone,,, preferably use gac compared with making spent ion exchange resin etc. chronically therefore as weighting material.Supply with the situation of producing water to electrode vessel as shown in Figure 1, owing in electrode vessel supply water, almost do not have Cl
-, therefore can prevent the generation of chlorine,, be desirable therefore for the long term stabilization of weighting material or electrode.
Fig. 2 is the figure that simplify to show to the water circulation system of the desalting chamber of the electric deionizer 10 ' of this Fig. 1 and concentration compartments's circulation water.According to diagram, former water is passed in the desalting chamber 16, becomes production water.A part of producing water is passed in the concentration compartments 15, is discharged from as concentrated waste water.The flow direction of the water in the concentration compartments is opposite (adverse current) direction in the desalting chamber 16.
Boron concentration 500 times below or for 10ppb below of boron concentration by making this concentrated waste water for producing water, the boron concentration of producing water for example significantly step-down and can produce extremely low concentration production water below the boron concentration 0.05ppb about 0.1ppb below.
Fig. 7 a is the electric deionizer 10 of another example of relevant the 2nd form of expression " the approximate three-dimensional map of another embodiment, Fig. 7 b is the water circulation system figure of this device.
Such as shown, this electric deionizer 10 "; between anode 11 and negative electrode 12, alternately arrange cationic exchange membrane and anion-exchange membrane; alternately formed concentration compartments 15 and desalting chamber 16; be the formation same on this aspect with the electric deionizer 10 ' of Fig. 1; but concentration compartments 15 is divided into the condensed water throughput 15a of 2 or above (at Fig. 7 a; among the 7b be 2) by partition 15S, 15b, each condensed water throughput 15a, the current of the condensed water of 15b lead to direction, for with desalting chamber 16 in the logical direction of the current direction of intersecting, this puts different with the electric deionizer 10 ' of Fig. 1.
That is, in Fig. 7 a, 7b, desalting chamber 16, the upside among Fig. 7 a is an inlet side, and downside is an outlet side, and water flows from the top down in desalting chamber 16.
On the other hand, in concentration compartments 15, be provided with along with this desalting chamber 16 in the logical direction of the current direction of intersecting (be orthogonal directions in Fig. 7 a.Moreover, this orthogonal directions may not be proper, comprise the scope about the 80-100 degree) the partition 15S that extend to exist, be divided into 2 sections up and down in the drawings in the concentration compartments 15, in each of each condensed water throughput 15a, 15b, circulate to rear side from the front side of figure.
Shown in Fig. 7 b, the part of the production water that takes out from desalting chamber 16 is directed to the recycle system by pump round-robin condensed water throughput 15b, circulates in producing the condensed water throughput 15b that water takes out side.The part of the circulation condensed water of this recycle system is directed in the recycle system by pump round-robin condensed water throughput 15a, circulates in the condensed water throughput 15a of Yuan Shui inflow side, and its part is discharged to outside the system.
Even this electric deionizer 10 "; produce water in producing the condensed water throughput 15b that water takes out side after the circulation; flow among the condensed water throughput 15a of Yuan Shui inflow side and circulate;; to flow into effluent from the former water of the taking-up side direction of producing water logical for condensed water as a result; a part is discharged to outside the system then, also obtain to become the circulate same effect of occasion of water of adverse current one way mode with desalting chamber with shown in Figure 1 then by outside the system of being discharged to.
With partition separate the concentration compartments and the condensed water throughput that forms also can be 3 or more than.Complicated etc. the occasion that consider to increase that increase, the device of the scantling numeral that the partition number causes constitute is preferably with the condensed water throughput that is divided into 2 or 3 in the concentration compartments.
By electric deionizer is set multistagely, multistage ground of Jiang Yuanshui deionization is handled, and thus as above-mentioned, can produce significantly low production water of boron concentration effectively, and, also can produce the production water of the following super extremely low concentration of 0.005ppb.
Fig. 3-the 6th is provided with the water circulation system figure of the electrodeionization system of electric deionizer in this wise multistagely, and the 1st electric deionizer 1 and the 2nd electric deionizer 2 all are being connected in series.Device 1,2 also can be a said apparatus 10 ', 10 " any.
In the electrodeionization system of Fig. 3, the former water of boron concentration 3ppb is passed among the 16A of desalting chamber of the 1st electric deionizer, becomes 1 the production water of boron concentration 0.1ppb.Producing water this 1 time is divided among the 16B of desalting chamber and the 15B of concentration compartments of the 2nd electric deionizer.The circulating direction of the condensed water of the 15A of concentration compartments, 15B is the direction that also flows with the 16A of desalting chamber, 16B.Take out 2 production water (production water) of boron concentration 0.01ppb from the 16B of this desalting chamber.From the effusive condensed water of the 15B of concentration compartments of the 2nd electric deionizer 2 are the low condensed water that reach 1ppb of boron concentration, and its part is recycled to the inlet side of the 15B of this concentration compartments, and remainder for example turns back in the former water.
From the concentrated waste water of the 15A of concentration compartments of the 1st electric deionizer 1, be the concentrated waste water of boron concentration up to 30ppb, a part turns back to the inlet side of the 15A of this concentration compartments, and remainder is discharged from as concentrating waste water.
In the electrodeionization system of Fig. 4, to be that whole amounts that water is produced in 1 time of 0.1ppb are passed among the 16B of desalting chamber of the 2nd electric deionizer 2 from the boron concentration of the 16A of desalting chamber of the 1st electric deionizer 1, and make following 2 times of boron concentration 0.005ppb and produce water.A part of these 2 times being produced water is passed among the 15B of concentration compartments with reflux type.For example turn back to the former water from 2 condensed water of the effusive boron concentration of the 15B of concentration compartments 1ppb.
Former water with and stream mode to the 15A of concentration compartments of the 1st electric deionizer 1 circulation, become 1 condensed water of boron concentration 30ppb, be discharged from.
In the electrodeionization system of Fig. 5, whole amounts of former water are pressed along the order of the 16A of desalting chamber, the 16B of device 1 and are flowed, and become 2 times following production water of boron concentration 0.005ppb.Moreover, be 0.05ppb from the effusive boron concentration of producing water for 1 time of the 16A of desalting chamber.From the effusive part of producing water for 2 times of the 16B of desalting chamber with the order of the 15B of concentration compartments, 15A respectively with the reflux type circulation, form the concentrated waste water of boron concentration 15ppb and be discharged from.From the boron concentration of effusive 1 condensed water of the 15B of concentration compartments is 0.25ppb.
In the electrodeionization system of Fig. 6, whole amounts of former water are fed among the 16A of desalting chamber, become 1 the production water of boron concentration 0.02ppb.A part of producing water for 1 time is passed among the 15A of concentration compartments with reflux type, forms the concentrated waste water of boron concentration 30ppb and is discharged from.The remainder of producing water for 1 time is passed among the 16B of desalting chamber, and becoming boron concentration is 2 times following production water of 0.005ppb.A part of producing water for these 2 times is passed among the 15B of concentration compartments with reflux type, forms 2 condensed water of boron concentration 0.2ppb and flows out.These 2 condensed water for example are returned in the former water.
The occasion of electric deionizer is set as Fig. 3-6 multistagely, when the thickness of the desalting chamber of the 1st electric deionizer 1 is more than the 7mm, 8-30mm particularly, the thickness of the desalting chamber of the 2nd electric deionizer 2 is less than 7mm, particularly during 2-5mm, separate material and hardness components with the light current that the 1st electric deionizer 1 is removed silicon-dioxide, boron etc., further remove silicon-dioxide and boron with the 2nd electric deionizer 2.Because the 2nd electric deionizer 2 is removed the alkali composition of missing from the electric deionizer 1 of prime, therefore obtains the treating water of high water quality.
The thickness of the desalting chamber by making the 1st electric deionizer 1 is more than the 7mm, and the pH in the 16A of desalting chamber of this device 1 rises, and the weak electrolyte and the hardness components of silicon-dioxide or boron etc. are removed expeditiously.
In the above-described embodiment, by supply with producing water to the concentration compartments, the boron concentration of the concentration compartments that is positioned at desalting chamber's outlet side being reduced, producing water but also can replace using, perhaps with itself and usefulness, making the concentration compartments supply with water is the water that has carried out going the boron processing.
Boron removal method can be to use the method for ion exchange resin or boron polymeric adsorbent or use reverse osmosis membrane method etc. any.
According to above-mentioned,, can produce significantly low production water of boron concentration conscientiously according to the electric deionizer and the working method thereof of the 1st, the 2nd form.
Fig. 8 is the schematic sectional view of electric deionizer 10 of the embodiment of expression the 3rd form of the present invention.This electric deionizer 10, be between electrode (anode 11, negative electrode 12), alternately to arrange a plurality of anion-exchange membranes (A film) 13 and cationic exchange membrane (C film) 14, alternately formed the device of concentration compartments 15 and desalting chamber 16, in desalting chamber 16, mixed or many anion ion exchange body and cation exchange columns that comprises ion exchange resin, ion-exchange fiber or grafting permutoid etc. of layeredly filling.
In concentration compartments 15 and anolyte compartment 17 and cathode compartment 18, also can fill the electric electrical conductor of ion exchanger, gac or metal etc.
Processed water is directed in the desalting chamber 16, takes out from desalting chamber 16 and produces water.The part of processed water is sent in the negatively charged ion removal device 9, carries out negatively charged ion and removes processing.Removed anionic water with this negatively charged ion removal device 9, led in the concentration compartments 15 with the adverse current one-way stream in the opposite direction with the logical side of current of desalting chamber 16, the outflow water of concentration compartments 15 is discharged to outside the system.In this electric deionizer, concentration compartments 15 and desalting chamber 16 alternately are set, take out the influx that side is being provided with concentration compartments 15 at the production water of desalting chamber 16, the spout of concentration compartments 15 is being set in the Yuan Shui inflow side of desalting chamber 16.In view of the above, condensed water flows into from desalting chamber's outlet side (downside of Fig. 8) for concentration compartments 15, flows out from desalting chamber's inlet side (upside of Fig. 8).
Be fed to the inlet side of anolyte compartment 17 from the part of negatively charged ion removal device 9 effusive water, and the outflow water of anolyte compartment 17 is fed to the inlet side of cathode compartment 18, the outflow water of cathode compartment 18 is discharged to outside the system as waste water.The inlet water of anolyte compartment 17 also can be the processed water without the negatively charged ion removal device.
Like this, by to remove treating water to concentration compartments's 15 circulation negatively charged ion with desalting chamber 16 adverse current one way modes, the near more production water of the concentration of the condensed water in the concentration compartments 15 takes out side step-down more, the influence to desalting chamber 16 that the concentration diffusion causes diminishes, reinforcing yin essence ion not only, the clearance of the weak anionic of carbonic acid, silicon-dioxide, boron etc. also can improve by leaps and bounds.Adopting this electric deionizer, can production resistivity be the above production water of 18M Ω cm.
When the resistance of removing electric conductivity step-down, the electric deionizer for the treatment of water at the negatively charged ion that is passed to the concentration compartments uprises, fill the electrical conductor of ion exchanger etc. to the concentration compartments.In view of the above, do not need to reduce resistance to ionogen such as condensed water interpolation salt.In order to ensure electric current, preferably in electrode vessel 17,18, also fill ion exchanger, gac or as metal of electric electrical conductor etc.In view of the above, even the water of the logical contour water quality of ultrapure water also can be guaranteed necessary electric current.
Owing to cause in electrode vessel, the particularly generation of oxygenant such as chlorine in the anolyte compartment or ozone,,, preferably use gac compared with making spent ion exchange resin etc. chronically therefore as weighting material.Supply with the situation of producing water to electrode vessel as shown in Figure 8, owing in electrode vessel supply water, almost do not have Cl
-, therefore can prevent the generation of chlorine,, be desirable therefore for the long term stabilization of weighting material or electrode.
Fig. 9 is the figure that simplify to show to the water circulation system of the desalting chamber of the electric deionizer of this Fig. 8 and concentration compartments's circulation water.According to diagram, processed water is passed in the desalting chamber 16, becomes production water.The part of processed water is passed in the concentration compartments 15 after carrying out negatively charged ion removal processing, is discharged from as concentrated waste water.The flow direction of the water in the concentration compartments is opposite (adverse current) direction in the desalting chamber 16.
By adopting this negatively charged ion removal device 9 to make the total inorganic carbon (TIC) acid concentration is below the 50ppb, below the preferred 30ppb, produces the remarkable step-down of total inorganic carbon (TIC) acid concentration in the water.In addition, be below the 100ppb, below the preferred 80ppb by adopting negatively charged ion removal device 9 to make silica concentration, making boron concentration is below following, the preferred 8ppb of 10ppb, can significantly reduce the silica concentration and the boron concentration of producing in the water.
As above-mentioned negatively charged ion removal device 9, except the de-gassing vessel of degassing film device, decarburization acid tower, vacuum degassing tower etc., also exemplify out reverse osmosis membrane separation device, electrodialysis device, contain the ion exchange unit or the electric deionizer of the exchange resin tower etc. of anion ion exchange body.
In order to remove carbonic acid, wish to comprise the de-gassing vessel of degassing film, decarburization acid tower, vacuum degassing tower etc.Vacuum take-off mode (for example 20Torr following) or adopt the purging mode of nitrogen etc. or carry out both degassing film treatment unit particularly, carbonic acid is removed the efficient excellence.
Figure 10 is the occasion of electric deionizer 8 has been adopted in expression as negatively charged ion removal device 9 the system diagram of an example.This electric deionizer 8 is the devices that formed the 8D of desalting chamber and the 8A of concentration compartments, 8B between anode and negative electrode by anionic membrane 8a and cationic membrane 8c.Processed water adopts and stream circulates among each chamber 8A, 8B, the 8D, is fed into desalting chamber's outlet side of the condensed water 15 of electric deionizer 10 from the de-salted water of the 8D of desalting chamber with from the condensed water of the 8B of concentration compartments, flows out from desalting chamber's inlet side.In this electric deionizer 8, the 8A of concentration compartments of anionic membrane 8a side of the 8D of desalting chamber and the 8B of concentration compartments of cationic membrane 8c side are arranged, only be concentrated the spissated anionic component of chamber 8A and discharge, positively charged ion is concentrated chamber 8B and concentrates and be fed in the concentration compartments 15 of electric deionizer 10 with the de-salted water from the 8D of desalting chamber.This electric deionizer 8 is devices of only removing, reducing anionic component in this wise.
In the present invention, also can use the water that has carried out negatively charged ion removal processing as the processed water that supplies to desalting chamber, by doing like this, the negatively charged ion load of desalting chamber is alleviated, and therefore can access weak anionic concentration further reaches low-level production water.Remove processing as this negatively charged ion, preferred degassing processing, reverse-osmosis treated etc.Also preferably adopt charcoal absorption to remove organic composition, or chlorine is carried out ionization.
Handle the occasion of removing carbanion from removing by negatively charged ion,, especially preferably use de-gassing vessel (particularly film de-gassing vessel) as the negatively charged ion removal device to the feedwater of desalting chamber.In addition, wish to make the part of degassing treating water to be recycled to the de-gassing vessel inlet, improve carbonic acid and remove efficient.
In the degassing processing that is used for removing carbonic acid, hope will flow into water and be adjusted to acidity, preferred pH4-6, further preferred pH4-5, improve carbonic acid and remove efficient.
With the occasion that vacuum pump aspirates the gas side of degassing film, wish that on the point that improves carbonic acid removal efficient making vacuum tightness is below the 50Torr, more preferably below the 20Torr.
Former water is carried out the occasion of reverse-osmosis treated (following be called sometimes RO handle), wish by multistage, for example 2 grades of ground are handled, and fully reduce the weak anionic composition of carbonic acid, silicon-dioxide, boron etc.
Under this occasion, be alkalescence (pH8-10), improve the removal efficient of weak anionic composition by the RO inlet water that makes the 1st grade and/or the 2nd grade.
As being used to form this alkaline alkali generating apparatus, desalting chamber's thickness that also can use the spy to open to illustrate for 2001-113281 number as (preferred 15mm) more than the 7mm, filled the electric deionizer of negatively charged ion/cationic hybrid ionic permutoid.Like this, giving birth to the alkaligenous while, also reduce the weak anionic composition.Such electric deionizer wishes to be configured between the RO device of the 1st grade and the 2nd grade.
For the ultrapure water that obtains ultra-high purity, the treating water more than for example resistivity 18.2M Ω cm, below the silica concentration 0.05ppb, below the boron 0.005ppb,, especially preferably comprise the above-mentioned 2 grades of RO processing and the degassing and handle as pre-treatment.
Fig. 4-7 expresses the configuration example that above-mentioned pretreating device is configured in the prime of electric deionizer 10.
In Figure 11, the degassing film device 101 that former hydromining is used as pretreating device outgases, and makes the processed water of electric deionizer 10.Moreover the part of the degassing treating water of degassing film device 101 is returned to the upstream side of this device 101, is repeated to handle.
In Figure 12, former current are led in the RO device 103,103 as the activated carbon adsorber 102 of pretreating device and 2 grades make processed water.
In Figure 13, adopt activated carbon adsorber 102,1RO device 103, electric deionizer 104,2RO device 103 to handle former water, make the processed water of electric deionizer 10.Moreover, as electric deionizer 104, for example can use the spy to open 2001-113281 number electric deionizer, but be not limited thereto.
In Figure 14, adopt the RO device 103,103 of 102,2 grades of activated carbon adsorbers, degassing film device 101 to handle former water, make the processed water of electric deionizer 10.
In the present invention, removing anionic device from the condensed water that supplies to the concentration compartments, also can be that electric deionizer 10 is own.That is, as shown in Figure 15, whole amounts of processed water are circulated in the desalting chamber 16 of electric deionizer 10, the part of this production water is passed to the concentration compartments 15 towards desalting chamber's inlet side from desalting chamber's outlet side.
In the present invention, also electric deionizer 10 can be set multistagely, multistage ground of Jiang Yuanshui deionization is handled.
Figure 16 is the water circulation system figure of electrodeionization system that is provided with multistagely and installs electric deionizer 10A, the 10B of 10 same structures, is being connected in series the 1st electric deionizer 10A and the 2nd electric deionizer 10B.
In the electrodeionization system of Figure 16, processed water is passed among the 16A of desalting chamber of the 1st electric deionizer 10A, becomes 1 time and produces water.Producing current this 1 time leads among the 16B of desalting chamber of the 2nd electric deionizer 10B.The circulating direction of the condensed water of the 15A of concentration compartments, 15B is the direction with the 16A of desalting chamber, 16B adverse current.2 production water (production water) from the 16B of this desalting chamber are removed, and its part is fed among the 15B of concentration compartments.From the effusive condensed water of the 15B of concentration compartments of the 2nd electric deionizer 2 are the low condensed water of anion concentration, are fed among the 15A of this concentration compartments.
Outflow water from the 15A of concentration compartments of the 1st electric deionizer 1 is discharged from as concentrated waste water.
In the 3rd, the 4th form of the present invention, the thickness of preferred desalting chamber is 2-7mm, and flow velocity is LV=60-120m/h, SV=100-200/h.The thickness of preferred concentration compartments is 2-7mm, and flow velocity is LV=10-30m/h, SV=25-50/h.Ion exchanger is all filled by preferred desalting chamber, concentration compartments, particularly fills with the cationic mixed form of negatively charged ion, with current density 300-700mA/dm
2Make it operation.Supply with to give the water of concentration compartments, wish to be recycled to concentration compartments's inlet, and be the one way mode without recycle pump etc.
As shown in Figure 16, in the occasion that in series circulates to a plurality of desalting chamber, the thickness of the desalting chamber of preferred especially final level is 2-7mm, and flow velocity is LV=60-120m/h, SV=100-200/h.
According to above-mentioned,, can produce significantly low production water of anion concentration, particularly total inorganic carbon (TIC) acid concentration effectively according to electric deionizer of the present invention and working method thereof.
Claims (5)
1. the working method of an electric deionizer, it is to utilize ion-exchange membrane to divide the working method of the electric deionizer of concentration compartments and desalting chamber between anode and negative electrode, when condensed water is circulated in this concentration compartments, former water is made it to circulate in desalting chamber as processed water, and as producing water from this desalting chamber's taking-up, it is characterized in that: the flow direction along processed water is provided with the 1st electric deionizer and the 2nd electric deionizer, the whole amounts that to produce water from 1 time of the desalting chamber of the 1st electric deionizer are passed in the desalting chamber of the 2nd electric deionizer, make 2 times following production water of boron concentration 0.005ppb, a part of these 2 times being produced water is passed in the concentration compartments of the 2nd electric deionizer with reflux type, effusive 2 condensed water turn back to the former water from this concentration compartments, former water with and stream mode to the circulation of the concentration compartments of the 1st electric deionizer, become 1 condensed water and be discharged from.
2. the working method of electric deionizer according to claim 1, it is characterized in that: 2 production water in the concentration compartments that supplies to the 2nd electric deionizer are supplied with from the side that the desalting chamber near the 2nd electric deionizer exports, and an effluent that enters the mouth from the desalting chamber near the 2nd electric deionizer goes out.
3. electric deionizer, this device utilizes ion-exchange membrane to divide concentration compartments and desalting chamber between anode and negative electrode, condensed water is circulated in this concentration compartments, former water is circulated in desalting chamber as processed water, and take out as producing water, it is characterized in that: the flow direction along processed water is provided with the 1st electric deionizer and the 2nd electric deionizer, the whole amounts that to produce water from 1 time of the desalting chamber of the 1st electric deionizer are passed in the desalting chamber of the 2nd electric deionizer, make 2 times following production water of boron concentration 0.005ppb, a part of these 2 times being produced water is passed in the concentration compartments of the 2nd electric deionizer with reflux type, effusive 2 condensed water turn back to the former water from this concentration compartments, former water with and stream mode to the circulation of the concentration compartments of the 1st electric deionizer, become 1 condensed water and be discharged from.
4. electric deionizer according to claim 3, it is characterized in that: supply in the concentration compartments of the 2nd electric deionizer 2 times and produce water and supply with, go out from a effluent near desalting chamber's inlet of the 2nd electric deionizer from a side near desalting chamber's outlet of the 2nd electric deionizer.
5. electric deionizer according to claim 3 is characterized in that: possess the device of removing boron from the water of the concentration compartments of the concentration compartments that supplies to the 1st electric deionizer and the 2nd electric deionizer.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003036310A JP2004261643A (en) | 2003-02-14 | 2003-02-14 | Electrodeionization apparatus, and operating method therefor |
| JP036310/2003 | 2003-02-14 | ||
| JP2003043701A JP3901107B2 (en) | 2003-02-21 | 2003-02-21 | Electrodeionization apparatus and operation method thereof |
| JP043701/2003 | 2003-02-21 | ||
| PCT/JP2004/001528 WO2004071968A1 (en) | 2003-02-14 | 2004-02-13 | Electric deionization apparatus and method of operating the same |
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| CNA2007101379424A Division CN101121555A (en) | 2003-02-14 | 2004-02-13 | Electrodeionization apparatus and operating method therefor |
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| CN1774403A CN1774403A (en) | 2006-05-17 |
| CN1774403B true CN1774403B (en) | 2010-06-09 |
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| CNA2007101379424A Pending CN101121555A (en) | 2003-02-14 | 2004-02-13 | Electrodeionization apparatus and operating method therefor |
| CN2004800100555A Expired - Fee Related CN1774403B (en) | 2003-02-14 | 2004-02-13 | Apparatus for electrodeionization and method for operating the same |
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| CNA2007101379424A Pending CN101121555A (en) | 2003-02-14 | 2004-02-13 | Electrodeionization apparatus and operating method therefor |
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| CN108137354A (en) * | 2015-09-30 | 2018-06-08 | 奥加诺株式会社 | Water treatment facilities and method for treating water |
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| JP2007000827A (en) * | 2005-06-27 | 2007-01-11 | Japan Organo Co Ltd | Water treatment method and apparatus |
| MX2010005876A (en) * | 2007-11-30 | 2010-06-15 | Siemens Water Tech Corp | Systems and methods for water treatment. |
| JP5346038B2 (en) * | 2007-12-17 | 2013-11-20 | ベン グリオン ユニバーシティ オブ ザ ネジェブ リサーチ アンド ディベラップメント オーソリティ | Apparatus and system for deionization |
| JP4993136B2 (en) * | 2008-08-08 | 2012-08-08 | 栗田工業株式会社 | Pure water production apparatus and pure water production method |
| JP5379025B2 (en) * | 2010-01-06 | 2013-12-25 | オルガノ株式会社 | Electric deionized water production equipment |
| JP2012016696A (en) * | 2010-06-09 | 2012-01-26 | Kobelco Eco-Solutions Co Ltd | Fresh water generating apparatus and method |
| JP5606841B2 (en) * | 2010-09-14 | 2014-10-15 | オルガノ株式会社 | Electric deionized water production equipment |
| JP5158393B2 (en) * | 2012-03-23 | 2013-03-06 | 栗田工業株式会社 | Pure water production apparatus and pure water production method |
| TW201434525A (en) * | 2013-03-15 | 2014-09-16 | Ritedia Corp | Electrodialysis device and electrodialysis method using the same |
| JP2014000575A (en) * | 2013-10-10 | 2014-01-09 | Kurita Water Ind Ltd | Apparatus and method for producing purified water |
| JP6119886B1 (en) * | 2016-01-28 | 2017-04-26 | 栗田工業株式会社 | Ultrapure water production apparatus and operation method of ultrapure water production apparatus |
| WO2018117035A1 (en) * | 2016-12-22 | 2018-06-28 | オルガノ株式会社 | Deionized water manufacturing system, deionized water manufacturing device, and deionized water manufacturing method |
| WO2018235366A1 (en) * | 2017-06-23 | 2018-12-27 | 栗田工業株式会社 | Method for controlling and method for designing electrical deionization device |
| JP7262353B2 (en) * | 2019-09-18 | 2023-04-21 | オルガノ株式会社 | Deionized water production method and production system |
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| CN1172077A (en) * | 1997-08-14 | 1998-02-04 | 王方 | Method for preparing soft water by electro-deionization and its device |
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| JP3575260B2 (en) * | 1997-12-26 | 2004-10-13 | 栗田工業株式会社 | Pure water production equipment |
| JP3826690B2 (en) * | 1999-08-11 | 2006-09-27 | 栗田工業株式会社 | Electrodeionization device and pure water production device |
| JP3794268B2 (en) * | 2001-01-05 | 2006-07-05 | 栗田工業株式会社 | Electrodeionization apparatus and operation method thereof |
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| CN1172077A (en) * | 1997-08-14 | 1998-02-04 | 王方 | Method for preparing soft water by electro-deionization and its device |
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| JP特开2000-61271A 2000.02.29 |
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| CN108137354A (en) * | 2015-09-30 | 2018-06-08 | 奥加诺株式会社 | Water treatment facilities and method for treating water |
| CN108137354B (en) * | 2015-09-30 | 2021-05-14 | 奥加诺株式会社 | Water treatment apparatus and water treatment method |
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| CN101121555A (en) | 2008-02-13 |
| JP2004261643A (en) | 2004-09-24 |
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