CN1769192A - Electric deionisation method and apparatus for producing superpure water using bipolar membrane - Google Patents
Electric deionisation method and apparatus for producing superpure water using bipolar membrane Download PDFInfo
- Publication number
- CN1769192A CN1769192A CNA2005100321484A CN200510032148A CN1769192A CN 1769192 A CN1769192 A CN 1769192A CN A2005100321484 A CNA2005100321484 A CN A2005100321484A CN 200510032148 A CN200510032148 A CN 200510032148A CN 1769192 A CN1769192 A CN 1769192A
- Authority
- CN
- China
- Prior art keywords
- desalting chamber
- water
- chamber
- concentration compartments
- anode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 239000012528 membrane Substances 0.000 title claims description 45
- 238000002242 deionisation method Methods 0.000 title 1
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 53
- 239000012498 ultrapure water Substances 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 27
- 150000001768 cations Chemical class 0.000 claims abstract description 3
- 238000011033 desalting Methods 0.000 claims description 117
- 239000000243 solution Substances 0.000 claims description 42
- 238000009296 electrodeionization Methods 0.000 claims description 38
- 239000003011 anion exchange membrane Substances 0.000 claims description 11
- 125000002091 cationic group Chemical group 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 abstract description 15
- 150000001450 anions Chemical class 0.000 abstract description 12
- 229910052710 silicon Inorganic materials 0.000 abstract description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 10
- 239000010703 silicon Substances 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 8
- 238000010612 desalination reaction Methods 0.000 abstract description 6
- 238000009833 condensation Methods 0.000 abstract description 4
- 230000005494 condensation Effects 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000005342 ion exchange Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 238000005349 anion exchange Methods 0.000 abstract 1
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 238000005341 cation exchange Methods 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 17
- 239000011347 resin Substances 0.000 description 16
- 229920005989 resin Polymers 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 14
- 230000008569 process Effects 0.000 description 14
- 239000008399 tap water Substances 0.000 description 11
- 235000020679 tap water Nutrition 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 239000003014 ion exchange membrane Substances 0.000 description 7
- 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 6
- 239000002253 acid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002352 surface water Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000003957 anion exchange resin Substances 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 238000001223 reverse osmosis Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000003729 cation exchange resin Substances 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000010349 cathodic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- UUWCBFKLGFQDME-UHFFFAOYSA-N platinum titanium Chemical compound [Ti].[Pt] UUWCBFKLGFQDME-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a method for preparation of ultrapure water with bipolar-film electrodeionzation and the device. The device contains an anode chamber with anode, a cathode chamber with catelectrode, and several three-chamber units sequentially from anode to catelectrode comprising of a condensation chamber filled with anion exchanger, the second desalination chamber and the first desalination chamber with cation exchanger; between the chambers are sequentially equipped with cation exchange film, bipolar film, and anion exchange film. The method contains: energizing the catelectrode and anode with direct current, the electrode water flowing sequentially from the anode chamber to the cathode chamber; raw water flowing sequentially through the first desalination chamber and the second desalination chamber, electrodeionzation to produce ultrapure water; and the liquid inlet to condensation chamber being water solution of low conductivity, the solution between condensation chamber to second desalination chamber reflowing. The merit of the invention is characterized in that, compared with the prior art that ultrapure water is prepared by electrodeionzation in mixed bed, weakly-acidic anion impurity silicon, boron, CO2 and so on in water can be removed effectively, and the area of ion exchange film can be distinctively decreased and thus the investment is saved.
Description
Technical field
The present invention relates to a kind of method and equipment thereof that electrodeionization is produced ultrapure water of using, particularly a kind of Bipolar Membrane electrodeionization is produced the method and the equipment thereof of ultrapure water.
Background technology
Ultrapure water has purposes widely, and at present ultrapure water is widely used in industry such as semi-conductor, electronics, pharmacy, generating, food, chemistry and the laboratory.The mixed bed ion switching technology is adopted in traditional ultrapure water production, in this technology, need the ion exchange resin that lost efficacy to be carried out regular regeneration with strong acid, highly basic, cause production process discontinuous on the one hand, the water quality instability, make a large amount of acid of this process consumption, alkali reagent on the other hand again, but also environment is polluted.The production method of new generation of ultrapure water is the electrodeionization (Electrodeionization that twentieth century begins commercial applications the end of the eighties, EDI) technology, the electrodeionization technology is utilized electric energy continuous production ultrapure water, process need not consumption acids, alkali, also less than the problem of environmental pollution that brings because of acid, alkali regenerating resin, thereby the commercial applications of electrodeionization is the big technical progress that ultrapure water is produced, and present traditional mixed bed ion switching technology is worldwide replaced by the electrodeionization technology just more and more.Yet the conventional electrodeionization technology of commercial applications is for mixing bed electrodeionization technology at present, and the ion-exchanger that promptly is filled in the desalting chamber is a yin, yang hybrid ionic exchanger.Referring to accompanying drawing 1, the routine shown in the accompanying drawing 1 is mixed the bed electric deion equipment and is included: the anolyte compartment 7 with anode 1; Cathode compartment 8 with negative electrode 2; With one or more 2 chamber units: concentration compartments 5, desalting chamber 6; These concentration compartmentss 5 and desalting chamber 6 form by anion-exchange membrane 3 and the cationic exchange membrane of alternately arranging 4, and between anolyte compartment 7 and cathode compartment 8; In desalting chamber 6, be filled with the yin, yang mixture iron exchange resin.
When equipment carried out work, external dc power supply on cathode and anode passed to a certain amount of galvanic current.Former water is incorporated in concentration compartments and the desalting chamber, be introduced into yin, yang ion in the solution of desalting chamber and be adsorbed in respectively on the luxuriant sub-exchange resin of yin, yang and under effect of electric field and move in the concentration compartments by anion and cation exchange resin and yin, yang ion-exchange membrane respectively, utilize in the anion and cation exchange resin contact position simultaneously or the continuous water dissociating of polarized action of the contact position of the moon (sun) ion exchange resin and sun (the moon) ion-exchange membrane produces H
+And OH
-, the cyclic regeneration cationic, anionic exchange resin, finally the outlet in desalting chamber 6 obtains removing the ionic ultrapure water.Because the selection perviousness of yin, yang ion-exchange membrane, the yin, yang ion of moving to the concentration compartments from desalting chamber can not further move, thus constantly raise in concentration compartments's intermediate ion concentration, thus obtain the higher condensed water of ionic concn in the exit, concentration compartments.Part condensed water is recycled in the inlet of concentration compartments with a pump (not shown), with the utilization ratio of the water that improves this process; Another part condensed water is supplied in the anolyte compartment, and all the other condensed water are discharged system as waste water, in order to avoid ion is excessively concentrated in the recycle system.The solution that flows out the anolyte compartment is incorporated in the cathode compartment, and the solution that flows out cathode compartment is discharged system as waste water.
Though mixing the bed electrodeionization, this routine can produce very high (＞16Mohmcm) the ultrapure water of resistivity, but particularly the removal efficiency of Si and B is not high to the acidulous anion impurity that is difficult to remove most in the ultrapure water production, and a for example conventional silica removal rate of mixing bed electrodeionization technology is difficult to reach more than 99.9%.Mix in the bed electrodeionization technology in routine in addition, membrane stack can only adopt thin desalting chamber (generally≤3mm), otherwise the current efficiency of this process and impurity-eliminating effect will descend significantly, but the design of thin desalting chamber will inevitably cause the increase of film usable floor area, thereby facility investment is increased.
Summary of the invention
The objective of the invention is to overcome the above-mentioned shortcoming that the conventional mixed bed electrodeionization of prior art is produced ultrapure water, acidulous anion impurity such as a kind of silicon, boron in can more efficient removal water are provided, obtain more high quality ultrapure water, and can reduce equipment intermediate ion exchange membrane usable floor area significantly, save the method and apparatus of producing ultrapure water of investment.
Technical solution of the present invention is the method and apparatus that a kind of Bipolar Membrane electrodeionization is produced ultrapure water, this equipment comprises: have the anodic anolyte compartment, cathode compartment with negative electrode, some desalting chamber and concentration compartments between anolyte compartment and cathode compartment, and the gripping unit that said modules is fixed together, this equipment is characterised in that: desalting chamber between anolyte compartment and cathode compartment and concentration compartments form several 3 chamber units; This 3 chamber unit comprises from the concentration compartments that anode to cathode direction is arranged in order, second desalting chamber and first desalting chamber, between concentration compartments and second desalting chamber or the anolyte compartment anion-exchange membrane is arranged, between second desalting chamber and first desalting chamber Bipolar Membrane is arranged, the cavity block side anode of Bipolar Membrane, the anode membrane side of Bipolar Membrane has cationic exchange membrane to negative electrode between first desalting chamber and concentration compartments or the cathode compartment; In first desalting chamber, fill strongly acidic cation exchanger; In second desalting chamber He in the concentration compartments, fill strongly basic anionite respectively.Preparation method is to adopt aforesaid device, logical direct current on cathode and anode, electrode water flow through anolyte compartment and cathode compartment successively and directly discharge or the part pump around circuit to the anolyte compartment, the feed liquor of the concentration compartments concentration compartments that flows through, flow through successively first desalting chamber and second desalting chamber's electrodeionization of former water produces ultrapure water.Solution countercurrent flow in the concentration compartments and second desalting chamber.The feed liquor of concentration compartments is the lower aqueous solution of specific conductivity, and its conductivity range is 0.0055～30 μ S/cm.
The present invention mixes a bed electrodeionization to produce different characteristics of ultrapure water technology is that the present invention has not only used the yin, yang ion-exchange membrane with conventional, but also has used Bipolar Membrane, utilizes under effect of electric field that water dissociating produces H in Bipolar Membrane
+And OH
-Regenerate cationite in first desalting chamber and the anionite in second desalting chamber.
The present invention produces the different another one characteristics of ultrapure water technology and is with the conventional bed electrodeionization that mixes: the repeating unit that mixes in the bed electric deion equipment in routine is by 1 desalting chamber and 12 chamber unit that the concentration compartments constitutes, and the ion-exchanger that is filled in desalting chamber is a yin, yang hybrid ionic exchanger; And the repeating unit in electric deion equipment provided by the invention is by the concentration compartments, 3 chamber units that first desalting chamber and second desalting chamber constitute, cationite and anionite are filled in first desalting chamber and second desalting chamber that is arranged in the Bipolar Membrane both sides respectively, promptly in first desalting chamber, fill cationite, what fill in second desalting chamber is anionite, anion and cation exchange resin intermingling not in two desalting chamber.In the desalting chamber of the mixed bed of routine electric deion equipment, cause existing inevitably non-conductive point, also certainly exist H owing to filling hybrid resin
+And OH
-Combination again at non-conductive some place, thus the reduction of process current efficiency and resin bed specific conductivity caused; And in the desalting chamber of present device, do not exist owing to filling the non-conductive point that hybrid resin causes, eliminated H in the desalting chamber
+And OH
-Combination again at non-conductive some place, also improved the specific conductivity of desalting chamber's resin bed simultaneously, so ultrapure water preparation method provided by the invention and equipment thereof have higher current efficiency, higher resin regeneration degree, more precipitous resin bed ion distribution and littler resin bed resistivity, therefore electrodeionization technology provided by the invention has and removes acidulous anion impurity (Si more efficiently, B, CO
2) wait and equipment can adopt thicker desalting chamber (desalting chamber's thickness can reach about 10mm).
In the present invention, be filled with anionite in the concentration compartments.Be filled in the effect that the anionite in the concentration compartments has the following aspects: on the one hand, the high conductivity of anionite has reduced the resistance of concentration compartments, help the reduction of process power consumption, this equipment is allowed to use than concentration compartments's water inlet of low conductivity and the power consumption of process changes little, thereby the ionic concn that can reduce concentration compartments and desalting chamber's solution is poor, helps the raising of ultrapure water water quality; Granular or the filamentary structure of anionite can be strengthened flowing of solution in the concentration compartments on the other hand, reduces near the thickness of diffusion layer the ion-exchange face, thereby can allow to adopt less concentration compartments's solution flow, is beneficial to the rate of recovery that improves water; The 3rd aspect, it also is even more important aspect, because the high conductivity of anionite, the conduction overwhelming majority of concentration compartments is born by anionite rather than by the ion in the solution, so greatly reduce in the concentration compartments positively charged ion in the accumulation on anion-exchange membrane surface, thereby can reduce significantly in the concentration compartments micro-positively charged ion by anion-exchange membrane (its selectivity is not 100%) from the concentration compartments to the electromigration of second desalting chamber, help the raising of ultrapure water quality, particularly the raising of ultrapure water resistivity.
In the present invention, flow through in order successively first desalting chamber and second desalting chamber of former water carries out the electrodeionization desalination and produces ultrapure water under effect of electric field.Former water at first flows into the first desalting chamber's decationize that is filled with cationite and makes solution be acid, make it enter second desalting chamber that is filled with anionite-exchange resin after the outflow again and remove negatively charged ion, avoided calcium in the former water, magnesium plasma in second desalting chamber, to produce precipitation of hydroxide so on the one hand, also help Si on the other hand, B, CO
2Deng acidulous anion impurity removing in second desalting chamber.In the present invention, in first desalting chamber and second desalting chamber flow direction of solution both can be identical also can contrary.The former water that uses among the present invention is generally tap water, surface water or underground water through handling the primary pure water that obtains, for example tap water, surface water or well water pass through the reverse osmosis water that reverse-osmosis treated obtains, or other suitable with it water of water quality, its conductivity value is generally at 1～30 μ S/cm.
In the present invention, the feed liquor of concentration compartments is the lower aqueous solution of specific conductivity, its conductivity range is 0.0055～30 μ S/cm (25 ℃), its specific conductivity is low more to be that ionic concn is low more, be unfavorable for more positively charged ion in the concentration compartments by anion-exchange membrane in the electromigration of second desalting chamber and concentration compartments negatively charged ion by the diffusive migration of anion-exchange membrane, so help producing high-quality ultrapure water more to second desalting chamber.The feed liquor of concentration compartments can be the part ultrapure water in practice, also can be former water or the lower solution of other specific conductivity.In practice, in order to improve the utilization ratio of water, the less flow of preferential employing is generally 1%～15% of desalting chamber's solution flow in the concentration compartments.
In the present invention, the flow direction contrary of the flow direction of solution and second desalting chamber in the concentration compartments, promptly be incorporated in the concentration compartments, and concentration compartments's fluid is discharged at concentration compartments's one end near second desalting chamber's influent side at end concentration compartments's feed liquor that specific conductivity is lower near the water outlet of second desalting chamber.The countercurrent flow of solution in the concentration compartments and second desalting chamber, the ionic concn that has reduced anion-exchange membrane lateral condensation chamber solution and second desalting chamber's solution is poor, particularly anion concentration is poor, be unfavorable for that negatively charged ion is by anion-exchange membrane diffusion to second desalting chamber from the concentration compartments, thereby help particularly Si of anionic impurity, B, CO
2Deng acidulous anion impurity removing in second desalting chamber.The water outlet of concentration compartments all directly effluxes, and perhaps part directly effluxes, and another part is as the water inlet of electrode water.
In the present invention, electrode water flow through successively anolyte compartment and cathode compartment, electrode water at first flows into the anolyte compartment and is acid owing to electrode reaction makes solution, flow out through cathode compartment again after the outflow, make the electrode water can be in cathode compartment like this, thereby avoided calcium in the electrode water, magnesium plasma in cathode compartment, to produce precipitation of hydroxide owing to cathodic reaction does not present over-drastic alkalescence.Electrode water is generally the higher aqueous solution of specific conductivity, helps the reduction of electrode vessel resistance like this, can be through remollescent tap water, underground water or surface water in the practice, also can be the part water outlet of concentration compartments.Electrode water can also can adopt part circular flow mode once by discharging in practice, and the water outlet of promptly a part of electrode water is recycled in the inlet of electrode water by a pump, so that increase the electroconductibility of electrode water.
Description of drawings:
Fig. 1 is that the mixed bed of a routine electrodeionization is produced ultrapure water device structure composition schematic cross sectional views;
Fig. 2 is that the Bipolar Membrane electrodeionization of one embodiment of the present invention is produced ultrapure water device structure composition and solution flow line synoptic diagram;
Fig. 3 is that the Bipolar Membrane electrodeionization of another one embodiment of the present invention is produced ultrapure water device structure composition and solution flow line synoptic diagram;
Embodiment
The present invention has numerous embodiments, with reference to the accompanying drawings enforcement of the present invention is described.
Fig. 2 is that the device structure that a Bipolar Membrane electrodeionization is produced ultrapure water is formed and the solution flow line synoptic diagram, represents that Bipolar Membrane electrodeionization according to the present invention produces the method for ultrapure water and a kind of embodiment of equipment thereof.As shown in Figure 2, the Bipolar Membrane electric deion equipment comprises an anolyte compartment 18 with anode 10; Cathode compartment 19 with negative electrode 11; With several 3 chamber units: this 3 chamber unit is made up of concentration compartments 15, the second desalting chamber 17 that are arranged in order from anode to cathode direction and first desalting chamber 16; Have between concentration compartments 15 and second desalting chamber 17 or the anolyte compartment 18 between anion-exchange membrane 12, second desalting chamber 17 and first desalting chamber 16 Bipolar Membrane 13 is arranged, the cavity block side anode of Bipolar Membrane 13, the anode membrane side of Bipolar Membrane 13 has cationic exchange membrane 14 to negative electrode between first desalting chamber 16 and concentration compartments 15 or the cathode compartment.
In first desalting chamber 16, be filled with cationite 20, be filled with anionite 21, in concentration compartments 15, be filled with anionite 21 in second desalting chamber 17.
It is as follows to adopt this equipment to produce the method for ultrapure water: external dc power supply on cathode and anode, pass to a certain amount of galvanic current, former water is introduced first desalting chamber 16 that is filled with cationite 20 successively in order and is adsorbed the positive and negative ion that removes in anhydrating respectively with second desalting chamber 17 that is filled with anionite 21, under effect of electric field, water dissociates in Bipolar Membrane and constantly produces H
+And OH
-Anionite in the cationite and second desalting chamber in difference cyclic regeneration first desalting chamber, and make that positively charged ion and negatively charged ion constantly move to concentration compartments 15 from first desalting chamber 16 and second desalting chamber 17 in the water, finally the outlet in second desalting chamber 17 obtains ultrapure water; Part ultrapure water flow in the concentration compartments 15 on the direction opposite with the flow direction of second desalting chamber 17; Effusive water is discharged from system in the concentration compartments; Electrode water is introduced in the inlet of anolyte compartment 18, and 18 effusive water flow into the inlet of cathode compartment 19 from the anolyte compartment, and the outlet from cathode compartment 19 is discharged to outside the system then.Through handling the primary pure water that obtains, its conductivity value is generally at 1～30 μ S/cm as tap water, surface water or underground water for the former water that uses in the process, and for example tap water, surface water or underground water are through the ultrapure water of reverse-osmosis treated.The electrode water that uses in the process is higher and calcic, the aqueous solution that the magnesium plasma is lower as specific conductivity, for example through the remollescent tap water.
Fig. 3 is that the device structure that another Bipolar Membrane electrodeionization is produced ultrapure water is formed and the solution flow line synoptic diagram, represents that Bipolar Membrane electrodeionization according to the present invention produces the method for ultrapure water and the another kind of embodiment of equipment thereof.Embodiment shown in Figure 3 is different with embodiment shown in Figure 2 to be: in the embodiment 1. shown in Figure 2, solution coflow in the solution and first desalting chamber in second desalting chamber, and in the embodiment shown in Figure 3, solution countercurrent flow in the solution and first desalting chamber in second desalting chamber; 2. and in the embodiment shown in Figure 3, the flow direction of solution is opposite with the flow of solution direction of concentration compartments in the embodiment shown in Figure 2 in the concentration compartments; 3. electrode water difference, in embodiment shown in Figure 2, the water inlet of electrode water is through the remollescent tap water, and in embodiment shown in Figure 3, the water inlet of electrode water is the water outlet of partial concentration chamber, and electrode hydromining part circular flow mode, and the water outlet of promptly a part of electrode water directly effluxes, and the water outlet of another part electrode water is recycled in the inlet of electrode water by a pump (not showing among Fig. 3), so that increase the electroconductibility of electrode water.
The Bipolar Membrane electrodeionization is produced the equipment of ultrapure water and solution flow line as shown in Figure 2, and this electric deion equipment has 3 multiple 3 chamber units.Yin, yang ion-exchange membrane and Bipolar Membrane are respectively AHA anion-exchange membrane, CMB cationic exchange membrane and the BP-1 Bipolar Membrane that day Bender mountain Cao Da company provides.The yin, yang ion-exchanger is respectively DOW 650C UPW Zeo-karb and DOW 550A UPW anionite-exchange resin.Anode is a titanium platinum plating mesh electrode, and negative electrode is the titanium mesh electrode.
The useful area of every film is 300cm
2The thickness of each compartment is 10mm, and promptly the distance of adjacent membranes and film is 10mm; Fill the corresponding ion exchange resin of about 300mL in each desalting chamber and concentration compartments, wherein concerning Zeo-karb, about 150mL is a h type resin, all the other are sodium type resin, concerning anionite-exchange resin, about 150mL is a hydroxyl type, and all the other are chloride type resin.
Former water is to be the reverse osmosis water of raw material production with the tap water, and its specific conductivity is 2.3 ± 0.1 μ S/cm, about siliceous 100ppb, and boracic 10ppb.Former water flows into first desalting chamber and second desalting chamber successively in order, the solution coflow in first desalting chamber and second desalting chamber, and the water outlet of second desalting chamber 17 is ultrapure water; Part ultrapure water flows in the concentration compartments 15 as the water inlet of concentration compartments, and its flow direction is opposite with the flow direction of solution in second desalting chamber, and the effluent liquid of concentration compartments directly effluxes.Electrode water is through the remollescent tap water, and specific conductivity is that electrode water flows into anolyte compartment and cathode compartment successively, effluxes then about 330 μ S/cm.
Operation is carried out as follows: start the solution e Foerderanlage, allow solution flow in equipment by above-mentioned flow direction, open direct supply then, pass to direct current on cathode and anode, electric deion equipment brings into operation.
The operational condition of process is as follows: total flooding velocity of desalting chamber is 150L/h, and total flooding velocity of concentration compartments is 7.5L/h, and the flooding velocity of electrode water is 15L/h, and strength of current is 1.5A.
The electrodeionization process need experience the long time from starting to steady state, second desalting chamber goes out electrical conductivity of water and begins higher, reduce gradually subsequently, move and reach steady state after 10 days, it is constant substantially that second desalting chamber goes out electrical conductivity of water, and its value stabilization is between 0.0554 ~ 0.0555 μ S/cm, the sampling analysis silicon wherein and the concentration of boron, the result shows, silicon concentration＜1ppb, boron concentration＜0.1ppb.
The Bipolar Membrane electric deion equipment of embodiment 2 is identical with the Bipolar Membrane electric deion equipment of embodiment 1, and solution flow line is also identical with embodiment 1 except that the source difference of concentration compartments's water inlet, and in addition, the electrode water of embodiment 2 is also identical with embodiment 1.Embodiment 2 is with the difference of embodiment 1: 1. the source of concentration compartments's water inlet is different, and in embodiment 1, the water inlet of concentration compartments is the part of ultrapure water, and in embodiment 2, the water inlet of concentration compartments is former water; 2. former water difference, embodiment 1 Central Plains electrical conductivity of water is 2.3 ± 0.1 μ S/cm, about siliceous 100ppb, boracic 10ppb, and the former water conductivity among the embodiment 2 is 25 ± 2 μ S/cm, and about siliceous 150ppb, boracic 20ppb.The operation steps of embodiment 2 is identical with embodiment 1, and operational condition is as follows: the flooding velocity of desalting chamber is 150L/h, and the flooding velocity of concentration compartments is 15L/h, and the flooding velocity of electrode water is 15L/h, and strength of current is 3.0A.
Similar to embodiment 1, the electrodeionization process need experience the long time from starting to steady state, move and reach steady state substantially after 7 days, the stable conductivity of second desalting chamber water outlet is about 0.058 μ S/cm, the silicon of sampling analysis second desalting chamber water outlet and the concentration of boron, the result shows, silicon concentration＜1ppb, boron concentration＜0.1ppb.
Embodiment 3
The Bipolar Membrane electric deion equipment of embodiment 3 and solution flow line are as shown in Figure 3.Embodiment 3 is identical with the electric deion equipment of embodiment 1, and former water is also identical with embodiment 1.Embodiment 3 is with embodiment 1 difference: 1. in embodiment 1, and solution coflow in the solution and first desalting chamber in second desalting chamber, and in embodiment 3, solution countercurrent flow in the solution and first desalting chamber in second desalting chamber; 2. the water inlet of concentration compartments is the part of ultrapure water also in embodiment 3, but the flow direction of solution is opposite with the flow of solution direction of concentration compartments among the embodiment 1 in the concentration compartments; 3. electrode water difference, in embodiment 1, the water inlet of electrode water is through the remollescent tap water, and in embodiment 3, the water inlet of electrode water is the water outlet of partial concentration chamber, and electrode hydromining part circular flow mode, and the water outlet of promptly a part of electrode water directly effluxes, and the water outlet of another part electrode water is recycled in the inlet of electrode water by a pump (not showing among Fig. 3), so that increase the electroconductibility of electrode water.
The operation steps of embodiment 3 is with embodiment 1, and its operational condition is as follows: the flooding velocity of desalting chamber is 150L/h, and total flooding velocity of concentration compartments is 15L/h, 1/3 of concentration compartments's water outlet effluxes, 2/3 joins in the electrode water, and 1/3 electrode water cycle is returned, and strength of current is 1A.
With embodiment 1,2 is similar, in embodiment 3, the electrodeionization process need experience the long time from starting to steady state, moves to reach steady state substantially after 12 days, and the stable conductivity of second desalting chamber water outlet is about 0.056 μ S/cm, the silicon of sampling analysis second desalting chamber water outlet and the concentration of boron, the result shows, silicon concentration＜1ppb, boron concentration＜0.1ppb.
Embodiment 4
The Bipolar Membrane electric deion equipment of embodiment 4 is identical with embodiment 1, and except the source of electrode water and glide path were distinguished to some extent, the former water of embodiment 4, the feed liquor of concentration compartments and glide path thereof were all identical with embodiment 1.Embodiment 4 and embodiment 1 are different to be that electrode water is different, in embodiment 1, the water inlet of electrode water is through the remollescent tap water, and in embodiment 4, the water inlet of electrode water is the water outlet of partial concentration chamber, and electrode hydromining part circular flow mode, and the water outlet of promptly a part of electrode water directly effluxes, and the water outlet of another part electrode water is recycled in the inlet of electrode water by a pump, so that increase the electroconductibility (flow circuits of electrode water as shown in Figure 3) of electrode water.The operation steps of embodiment 4 is with embodiment 1, and its operational condition is as follows: total flooding velocity of desalting chamber is 150L/h, and total flooding velocity of concentration compartments is 7.5L/h, 1/3 of concentration compartments's water outlet effluxes, 2/3 joins in the electrode water, and 2/3 electrode water cycle is returned, and strength of current is 1.5A.
With embodiment 1,2,3 is similar, and in embodiment 4, the electrodeionization process need experience the long time from starting to steady state, move and reach steady state substantially after 15 days, the stable conductivity of second desalting chamber water outlet about 0.0555 μ S/cm, the silicon of sampling analysis second desalting chamber water outlet and the concentration of boron, the result shows, silicon concentration＜1ppb, boron concentration＜0.1ppb.
Advantage of the present invention is: produce ultrapure water with the conventional mixed bed electrodeionization of prior art and compare, acidulous anion impurity was (as Si, B, CO during the present invention can remove effectively and anhydrate
2Deng) can adopt thicker desalting chamber simultaneously, thus the usable floor area of ion-exchange membrane significantly reduced.
Claims (4)
1, a kind of Bipolar Membrane electrodeionization is produced the equipment of ultrapure water, this equipment comprises: have the anodic anolyte compartment, cathode compartment with negative electrode, some desalting chamber and concentration compartments between anolyte compartment and cathode compartment, and the gripping unit that said modules is fixed together, this equipment is characterised in that: some desalting chamber between anolyte compartment and cathode compartment and concentration compartments form several 3 chamber units; This 3 chamber unit comprises from the concentration compartments that anode to cathode direction is arranged in order, second desalting chamber and first desalting chamber; Between concentration compartments and second desalting chamber or the anolyte compartment anion-exchange membrane is arranged, between second desalting chamber and first desalting chamber Bipolar Membrane is arranged, the cavity block side anode of Bipolar Membrane, the anode membrane side of Bipolar Membrane has cationic exchange membrane to negative electrode between first desalting chamber and concentration compartments or the cathode compartment; In first desalting chamber, fill strongly acidic cation exchanger; In second desalting chamber He in the concentration compartments, fill strongly basic anionite respectively.
2, a kind of Bipolar Membrane electrodeionization is produced the method for ultrapure water, it is characterized in that: adopt the electric deion equipment described in the claim 1, logical direct current on cathode and anode, electrode water flow through anolyte compartment and cathode compartment successively and directly discharge or the part pump around circuit to the anolyte compartment, the feed liquor of the concentration compartments concentration compartments that flows through, flow through successively first desalting chamber and second desalting chamber's electrodeionization of former water produces ultrapure water.
3, produce the method for ultrapure water according to the Bipolar Membrane electrodeionization described in the claim 2, it is characterized in that the solution countercurrent flow in the concentration compartments and second desalting chamber.
4, produce the method for ultrapure water according to the Bipolar Membrane electrodeionization described in the claim 2, the feed liquor that it is characterized in that the concentration compartments is the lower aqueous solution of specific conductivity, and its conductivity range is 0.0055～30 μ S/cm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100321484A CN100345615C (en) | 2005-09-12 | 2005-09-12 | Electric deionisation method and apparatus for producing superpure water using bipolar membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100321484A CN100345615C (en) | 2005-09-12 | 2005-09-12 | Electric deionisation method and apparatus for producing superpure water using bipolar membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1769192A true CN1769192A (en) | 2006-05-10 |
| CN100345615C CN100345615C (en) | 2007-10-31 |
Family
ID=36750789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100321484A Expired - Fee Related CN100345615C (en) | 2005-09-12 | 2005-09-12 | Electric deionisation method and apparatus for producing superpure water using bipolar membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100345615C (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101694007B (en) * | 2009-10-09 | 2011-08-03 | 南开大学 | A kind of treatment method of electroplating rinsing wastewater |
| CN102186781B (en) * | 2008-10-17 | 2013-11-27 | 有限会社春天 | Apparatus for producing hydrogen-dissolved drinking water and process for producing dissolved drinking water |
| CN104888870A (en) * | 2014-03-06 | 2015-09-09 | 苏州华清水处理技术有限公司 | Apparatus for electrically regenerating mixed bed ion exchange resin through bipolar membrane method |
| CN110487851A (en) * | 2019-09-10 | 2019-11-22 | 华能国际电力股份有限公司 | A kind of measuring system and method for the hydrogen conductivity that deaerates |
| CN110508139A (en) * | 2019-08-28 | 2019-11-29 | 华东理工大学 | An electrodialysis micropump |
| CN111615497A (en) * | 2018-01-19 | 2020-09-01 | 奥加诺株式会社 | Electric deionizing device for producing deionized water |
| CN111763952A (en) * | 2020-07-01 | 2020-10-13 | 辽宁黄花沟田园综合体开发有限公司 | A kind of desalination method and device for producing ultra-high-purity hypochlorous acid aqueous solution using table salt as raw material |
| CN114014415A (en) * | 2021-10-27 | 2022-02-08 | 杨晓刚 | Continuous regeneration deionization cation exchanger and anion exchanger system by using direct-current power supply |
| CN114084941A (en) * | 2021-11-30 | 2022-02-25 | 中科精仪吉林省科技有限公司 | Dialysis water purification equipment and water purification method based on bipolar ion membrane |
| CN114105379A (en) * | 2021-12-09 | 2022-03-01 | 中科精仪吉林省科技有限公司 | A dialysis pure water treatment process based on LINX system |
| CN114291959A (en) * | 2022-03-09 | 2022-04-08 | 中国电子工程设计院有限公司 | Preparation method of ultrapure water capable of effectively removing total organic carbon and weakly ionized impurities |
| CN115432773A (en) * | 2021-06-03 | 2022-12-06 | 广东栗子科技有限公司 | Method for regenerating bipolar membrane electric auxiliary deionization device and bipolar membrane electric auxiliary deionization device |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2397102Y (en) * | 1997-07-22 | 2000-09-20 | 王方 | Equal gap packed bed electric dialyzer |
| JP3726449B2 (en) * | 1997-09-30 | 2005-12-14 | オルガノ株式会社 | Electric deionized 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 |
| JP4403621B2 (en) * | 2000-01-20 | 2010-01-27 | 栗田工業株式会社 | Electrodeionization equipment |
| JP2003117557A (en) * | 2001-10-17 | 2003-04-22 | Japan Organo Co Ltd | Electric deionized water manufacturing device and pure water manufacturing device |
| JP3729349B2 (en) * | 2002-05-13 | 2005-12-21 | 株式会社荏原製作所 | Electric regenerative desalination equipment |
| CN1140353C (en) * | 2002-06-18 | 2004-03-03 | 北京国电龙源环保工程有限公司 | Method and apparatus for regenerating ion exchange resin by bipolar membrane hydrolytic dissociation |
| CN2567203Y (en) * | 2002-08-29 | 2003-08-20 | 王建友 | First-level multi-section electric deion device of water concentration partition plate inserted film pair structure |
-
2005
- 2005-09-12 CN CNB2005100321484A patent/CN100345615C/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102186781B (en) * | 2008-10-17 | 2013-11-27 | 有限会社春天 | Apparatus for producing hydrogen-dissolved drinking water and process for producing dissolved drinking water |
| CN101694007B (en) * | 2009-10-09 | 2011-08-03 | 南开大学 | A kind of treatment method of electroplating rinsing wastewater |
| CN104888870A (en) * | 2014-03-06 | 2015-09-09 | 苏州华清水处理技术有限公司 | Apparatus for electrically regenerating mixed bed ion exchange resin through bipolar membrane method |
| CN104888870B (en) * | 2014-03-06 | 2017-04-12 | 苏州华清水处理技术有限公司 | Apparatus for electrically regenerating mixed bed ion exchange resin through bipolar membrane method |
| CN111615497A (en) * | 2018-01-19 | 2020-09-01 | 奥加诺株式会社 | Electric deionizing device for producing deionized water |
| CN111615497B (en) * | 2018-01-19 | 2022-05-31 | 奥加诺株式会社 | Electric deionizing device for producing deionized water |
| CN110508139B (en) * | 2019-08-28 | 2021-08-03 | 华东理工大学 | Electrodialysis micropump |
| CN110508139A (en) * | 2019-08-28 | 2019-11-29 | 华东理工大学 | An electrodialysis micropump |
| CN110487851A (en) * | 2019-09-10 | 2019-11-22 | 华能国际电力股份有限公司 | A kind of measuring system and method for the hydrogen conductivity that deaerates |
| CN111763952A (en) * | 2020-07-01 | 2020-10-13 | 辽宁黄花沟田园综合体开发有限公司 | A kind of desalination method and device for producing ultra-high-purity hypochlorous acid aqueous solution using table salt as raw material |
| CN115432773A (en) * | 2021-06-03 | 2022-12-06 | 广东栗子科技有限公司 | Method for regenerating bipolar membrane electric auxiliary deionization device and bipolar membrane electric auxiliary deionization device |
| CN115432773B (en) * | 2021-06-03 | 2024-01-23 | 佛山市云米电器科技有限公司 | Regeneration method of bipolar membrane electric auxiliary deionization device and bipolar membrane electric auxiliary deionization device |
| CN114014415A (en) * | 2021-10-27 | 2022-02-08 | 杨晓刚 | Continuous regeneration deionization cation exchanger and anion exchanger system by using direct-current power supply |
| CN114084941A (en) * | 2021-11-30 | 2022-02-25 | 中科精仪吉林省科技有限公司 | Dialysis water purification equipment and water purification method based on bipolar ion membrane |
| CN114105379A (en) * | 2021-12-09 | 2022-03-01 | 中科精仪吉林省科技有限公司 | A dialysis pure water treatment process based on LINX system |
| CN114291959A (en) * | 2022-03-09 | 2022-04-08 | 中国电子工程设计院有限公司 | Preparation method of ultrapure water capable of effectively removing total organic carbon and weakly ionized impurities |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100345615C (en) | 2007-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5316637A (en) | Electrodeionization apparatus | |
| KR100426669B1 (en) | Electrodeionization apparatus and pure water producing apparatus | |
| JP6078074B2 (en) | Desalination system and method | |
| CN1278947C (en) | Equipment for electrodeionization of water | |
| CN103508521A (en) | Recycling treatment method for salt-containing wastewater | |
| CN1537078A (en) | Electric demineralizer | |
| CN1323279A (en) | Method and apparatus for preventing scaling in electrodeionization units | |
| JP2001113281A (en) | Electrodeionization equipment and pure water production equipment | |
| CN1294564A (en) | Electric desalting appts. | |
| CN101648738A (en) | Electro-deionization method and electro-deionization device for recycling ammonia nitrogen waste water | |
| CN100345615C (en) | Electric deionisation method and apparatus for producing superpure water using bipolar membrane | |
| WO1997046492A1 (en) | Process for producing deionized water by electrical deionization technique | |
| CN101694007B (en) | A kind of treatment method of electroplating rinsing wastewater | |
| CN101723491A (en) | Electrodeionization method and device for basic working unit containing three compartments | |
| SG177777A1 (en) | Super advanced sewage treatment method and device | |
| CN119053558A (en) | Operation method of deionized water manufacturing system and deionized water manufacturing system | |
| JP4403621B2 (en) | Electrodeionization equipment | |
| JP4250922B2 (en) | Ultrapure water production system | |
| CN101060021A (en) | A method for thickening the low level radioactive wastewater | |
| US20080023334A1 (en) | Liquid Treatment Apparatus | |
| CN1117034C (en) | acid/alkali electrolytic separation device | |
| CN100335419C (en) | Electric deionisation method and apparatus for producing superpure water using separation bed | |
| JP3952127B2 (en) | Electrodeionization treatment method | |
| CN105236527A (en) | Three-dimensional electrode device and method for synchronously continuously removing salt and organic pollutants from wastewater | |
| CN114014415A (en) | Continuous regeneration deionization cation exchanger and anion exchanger system by using direct-current power supply |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20071031 Termination date: 20140912 |
|
| EXPY | Termination of patent right or utility model |