CN1795147A - Electrochemical liquid treatment equipments - Google Patents
Electrochemical liquid treatment equipments Download PDFInfo
- Publication number
- CN1795147A CN1795147A CNA2004800147443A CN200480014744A CN1795147A CN 1795147 A CN1795147 A CN 1795147A CN A2004800147443 A CNA2004800147443 A CN A2004800147443A CN 200480014744 A CN200480014744 A CN 200480014744A CN 1795147 A CN1795147 A CN 1795147A
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- China
- Prior art keywords
- electrode
- ion
- anode
- exchange membrane
- liquid
- 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.)
- Pending
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- 239000007788 liquid Substances 0.000 title claims abstract description 90
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- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 35
- 239000012528 membrane Substances 0.000 claims abstract description 22
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- 239000000463 material Substances 0.000 claims description 45
- 238000005342 ion exchange Methods 0.000 claims description 36
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- 238000009296 electrodeionization Methods 0.000 claims description 22
- 125000002091 cationic group Chemical group 0.000 claims description 17
- 238000002242 deionisation method Methods 0.000 claims description 17
- 230000005855 radiation Effects 0.000 claims description 15
- 238000000909 electrodialysis Methods 0.000 claims description 14
- 238000010559 graft polymerization reaction Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
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- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- 238000006277 sulfonation reaction Methods 0.000 description 2
- 239000008400 supply water Substances 0.000 description 2
- 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 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 206010058490 Hyperoxia Diseases 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 238000007654 immersion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 150000007530 organic bases Chemical class 0.000 description 1
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- 230000036961 partial effect Effects 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- VBUNOIXRZNJNAD-UHFFFAOYSA-N ponazuril Chemical compound CC1=CC(N2C(N(C)C(=O)NC2=O)=O)=CC=C1OC1=CC=C(S(=O)(=O)C(F)(F)F)C=C1 VBUNOIXRZNJNAD-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 1
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000005200 wet scrubbing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
- C02F1/4695—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis electrodeionisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
- B01D61/48—Apparatus therefor having one or more compartments filled with ion-exchange material, e.g. electrodeionisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/52—Accessories; Auxiliary operation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/02—Column or bed processes
- B01J47/06—Column or bed processes during which the ion-exchange material is subjected to a physical treatment, e.g. heat, electric current, irradiation or vibration
- B01J47/08—Column or bed processes during which the ion-exchange material is subjected to a physical treatment, e.g. heat, electric current, irradiation or vibration subjected to a direct electric current
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46152—Electrodes characterised by the shape or form
- C02F2001/46157—Perforated or foraminous electrodes
- C02F2001/46161—Porous electrodes
- C02F2001/46166—Gas diffusion electrodes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/46115—Electrolytic cell with membranes or diaphragms
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Urology & Nephrology (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The present invention aims to provide electrode compartment structures in electrochemical liquid treatment equipments, which enable stable operation using pure water as an electrode compartment liquid requiring no concentration adjustment without adverse electrode reaction. The present invention relates an electrochemical liquid treatment equipment comprising ion exchange membranes between an anode and a cathode, which has an anode compartment defined by the anode and a cation exchange membrane and a cathode compartment defined by the cathode and an anion exchange membrane (12), each of the anode compartment and cathode compartment being packed with an ion exchanger (14) composed of a fibrous material, each of the anode and cathode (11) being formed from a liquid- and gas-permeable and electrically conductive material, and the equipment also having an electrode compartment liquid flowing chamber (15) which is formed behind each of the anode and cathode.
Description
Technical field
The present invention relates to the electrode vessel structure in for example electrodialysis of electrochemical liquid treatment equipments, electrolysis and the electrode ionization device.
Background technology
Be various by with during electric current is from the electrodes transfer to liquid with the processing of the material in electrolysis or this liquid of electrodialysis designed for example electrodialysis of electrochemical liquid treatment equipments, electrolysis and electrode ionization device in, the frequent zone partition that will contain each battery lead plate by ion-exchange membrane makes the liquid circulation that comes from treatment liq source in addition to be formed for the electrode vessel of wetting electrode in this electrode vessel.Round-robin liquid is called as electrode vessel liquid and is made of to guarantee electroconductibility the solution that contains electrolyte substance usually in this electrode vessel.Yet oxidation of using the solution contain such electrolyte substance to have to be produced by electrode reaction or reduzate are comprised in this electrode vessel liquid the problem of damaging ion-exchange membrane along with the operational cycle.Because when the concentration of electrolyte in the electrode vessel liquid reduced, the operating voltage of equipment increased along with the resistance of electrode vessel liquid, therefore must replenish the electrolytic solution in the electrode vessel liquid.And, the electrode reaction product enters effluent so that the downgrade of product, perhaps the pH of electrode vessel liquid changes with the material in the liquid of precipitation electrodes chamber, thus the interference means that need for example remove the electrolytic solution material in electrode reaction product or the additional electrode vessel liquid.
Thereby, become complicated and must use the ion-exchange membrane of expensive material as electrode materials and this electrode vessel of formation with high corrosion resistance about the design and the operation of electrode vessel.For example, marquis when the slightly salty deionization being produced tap water by electrodialysis (electrodialyzer), owing to produced chlorine and produced the free chlorine and the hypochlorous acid (HOCl) of hyperoxia voltinism at anode, so must use expensive fluorinated ionic exchange membrane as the ion-exchange membrane that forms this anolyte compartment with high antioxidant with the water reaction.
Having proposed a kind of bipolar membrane that uses replaces ion-exchange membrane as limiting the barrier film of anode and cathode compartment and be used for anode and the electrode vessel liquid of cathode compartment is the method for round-robin separately in electrodialysis appts.If forming the barrier film of electrode vessel is made of bipolar membrane, then because to such an extent as to bipolar membrane can penetrate hydrogen ion (cathode compartment) or hydroxide ion (anolyte compartment) the inflow electrode vessel that electrolytic solution material seldom only produces in bipolar membrane, and hydrogen ion is transformed into oxygen being transformed into hydrogen and hydroxide ion on the cathode surface on anode surface, thereby the material in electrode vessel liquid almost is not affected.Like this, use the method for bipolar membrane to make it possible to the successive electrodialysis, and replenish as the chemical solution of electrolytic solution for example acid or alkali without anode and cathode compartment in the course of the work.Yet this method has following problem: need two electrode vessel liquid-flow systems; Used expensive bipolar membrane; So become very huge owing to bipolar membrane under high current density is difficult to operation equipment; Be difficult in by the fluorizated oxidation-resistant material and form anionite zone in the bipolar membrane.
From useless TMAH solution, concentrating and reclaiming in the processing of TMAH (tetramethylammonium hydroxide) by electrodialysis, proposed to prevent that the impurity content from entering into the method for concentrated solution, comprise anode and cathode compartment supply TMAH solution, to reduce the TMAH solution that the impurity content enters into recovery, and TMAH solution is fed to the other liquid chamber that forms in the anolyte compartment, so that the impurity of the heavy amine flavor of the release that is produced by the TMAH oxygenolysis in the anolyte compartment can not penetrate ion-exchange membrane.Yet this method has following defective: the program complexity that is used to prepare the TMAH solution that is fed to other liquid chamber; The impurity that can not avoid counter electrode reaction to produce is to such an extent as to round-robin TMAH solution comprises impurity and can not be recovered and reuse in electrode vessel and other liquid chamber.
In the electrode ionization device, proposed a kind ofly to reclaim/utilize again the method for anolyte by handle the anolyte (anolyte compartment's liquid) contain the free chlorine that oxidizing substance for example emits from the anolyte compartment with active carbon adsorption column.Yet this method has following problem: because active carbon adsorption column and its post-filter are necessary, expensive thereby this equipment becomes; Owing to produced oxidizing substance in the anolyte compartment, the ion-exchange membrane that forms the anolyte compartment is not enough to prevent damage.
Handling by electrodeionization (electrodeionization agent electric deionizer) in the method for the water that contains hydrofluoric acid, a kind of method has been proposed, make electrode vessel fluid passage in each electrode vessel be full of the ionic conduction dividing plate of diagonal screen form, to such an extent as to the effluent by the electrode ionization device that contains the electrolytic solution material hardly can be used as electrode vessel liquid, and by using this electrode vessel to prevent that as the deionization chamber counter electrode from reacting the chamber doping electrolytic solution material that prevents from contiguous.Structure by the electrode vessel that this quadrat method proposed is shown among Fig. 1.In the electrode vessel structure of routine shown in Figure 1, electrode vessel is to be limited by electrode 2 and ion-exchange membrane 3, ionic conduction dividing plate 5 with ionic conductivity is filled in the electrode vessel 4, and electrode vessel liquid inlet 6 and electrode vessel liquid exit 7 are connected on the electrode vessel 4.The treating water that is equivalent to pure water by 6 supplies that enter the mouth is as electrode vessel liquid, and it emitted by the effect ionic conduction of ionic conduction dividing plate 5 time by exporting 7.Be supplied to electrode vessel because be equivalent to the treating water of pure water, the method with ionic conduction dividing plate filling electrode vessel like this helps avoiding the counter electrode reaction, but owing to consider the necessity of guaranteeing the liquid-flow in the electrode vessel, so it is not enough to reduce operating voltage as the dividing plate that is filled in electrode vessel must to use the diagonal screen with certain mesh, this means between electrode surface and the ionic conduction dividing plate and little contact area between ionic conduction dividing plate and the ion-exchange membrane, thereby in little area, ionic conduction takes place.Bubble is caught and developed into to the another one problem by the gaseous constituent that electrode reaction produces by the net of dividing plate, and its surface that adheres to electrode has increased the pressure drop in the electrode vessel.Like this, need big discharge come from electrode vessel, to remove bubble and must guarantee that big passage to reduce voltage loss, has caused the increase of cost thus by the ionic conduction dividing plate of filling mass expensive.Because these problems, the top method with ionic conduction diagonal screen dividing plate filling electrode vessel has related to high operating voltage and narrow available current density, for example, this method can be applied to electrode ionization and is used at low working current density 0.02-0.2A/dm for example
2Under produce pure water, but almost can not be applied at high working current 1-20A/dm for example
2Under electrodialysis.
Such as described above, still do not solve in the problem relevant with the electrode vessel liquid in the electrode vessel of for example electrolysis of electrochemical liquid treatment equipments (electrolyzer), electrodialysis and electrode ionization device.In common electrode for electrodialysis chamber, guarantee the passage of water by the filled plastics dividing plate, if but because pure water is an isolator pure water is fed to electrode vessel then does not have electric current.Like this, in conventional equipment, must supply electrolyte solution to electrode vessel.
Yet, if the solution that for example uses fluoride ion is as electrode vessel liquid, this electrode is the stability of electrode and economy is endangered and be diffused into the fluid of processing from electrode dissolved metal ion by hydrofluoric acid institute Corrosion results, and is included in wherein as impurity.If the solution that uses chloride ion-containing as electrode vessel liquid, produce at the anode place free chlorine by oxidation damage ion-exchange membrane, thereby must use expensive resistance to oxidation destructive fluorinated film as the ion-exchange membrane that forms the anolyte compartment.If use the solution contain organic bases, then as described abovely produced deleterious oxidative breakdown product by electrode reaction like that as electrode vessel liquid.
Owing to these reasons, usually use for example sodium hydroxide of the inorganic alkaline aqueous solution, acidic aqueous solution for example sulfuric acid or salt the aqueous solution for example sodium sulfate as the electrolytic solution material of electrode vessel liquid, but because electrode vessel is in the course of the work as deionization chamber or concentration compartments, thereby the concentration of electrode vessel liquid changes.Like this, need some for example to interfere with electrolytic solution material continuous supplementation round-robin electrode vessel liquid or extracting section and dilution electrode vessel liquid, and complicated program is for example adjusted in the process of operation and the control electrode chamber in the concentration of electrolytic solution material.The another one problem is that then it is comprised in the circulating fluid as impurity if use the electrolytic solution that is different from the composition that is reclaimed by electrochemical liquid treatment equipments as electrode vessel liquid.
The objective of the invention is to solve the problems of the prior art as described above and be provided at electrode vessel structure in the electrochemical processing apparatus, this structure makes it possible to realize using the pure water that does not need concentration adjustment as the operation of electrode vessel liquid stabilising and there is not the counter electrode reaction.
Summary of the invention
In order to solve problem described above, the invention provides a kind of electrochemical liquid treatment equipments, it is included in the ion-exchange membrane between anode and the negative electrode, it has anolyte compartment that is limited by anode and cationic exchange membrane and the cathode compartment that is limited by negative electrode and anion-exchange membrane, in anolyte compartment and the cathode compartment each has all been filled the ion-exchanger that is made of filamentary material, in anode and the negative electrode each all is that the material by liquid permeable and gas and conduction forms, and this equipment also has in anode and each electrode vessel liquid-flow chamber that forms later of negative electrode.
Description of drawings
Fig. 1 is the synoptic diagram that has shown an example of the electrode vessel structure in the conventional electrochemical liquid treatment equipments.
Fig. 2 is the synoptic diagram that has shown the structure of an embodiment in the electrochemical liquid treatment equipments of the present invention.
Fig. 3 is the synoptic diagram of employed water treatment system in embodiments of the invention and the Comparative Examples.
Embodiment
Explain according to electrochemical liquid treatment equipments of the present invention below with reference to appended accompanying drawing
Specific embodiments.
Fig. 2 is the synoptic diagram that has shown according to the electrode vessel structure in the electrochemical liquid treatment equipments of one embodiment of the invention.Electrode vessel structure 10 in electrochemical liquid treatment equipments A comprises the electrode vessel 14 that is limited by electrode 11 and cationic exchange membrane 12; Electrode vessel liquid-flow chamber 15 with electrode 11 back.Electrochemical liquid treatment equipments A comprises that another electrode vessel structure relative with the electrode vessel structure 10 shown in Fig. 2 (that is to say, reverse counterpart on the right side of the electrode vessel structure 10 among Fig. 2, its ion-exchange membrane 12 is in the left side), and ion-exchange membrane suitably is placed between two electrode vessel structures.For example, be under the situation of electrode ionization device at electrochemical liquid treatment equipments, cationic exchange membrane and anion-exchange membrane to small part alternately is arranged between the electrode of opposite cell structure to form a deionization chamber and a concentration compartments.At another electrochemical liquid treatment equipments is to be used to reclaim under the situation of electrodialysis appts of bronsted lowry acids and bases bronsted lowry, and cationic exchange membrane and anion-exchange membrane to small part alternately is arranged between this electrode of opposite cell structure to form sour chamber, ionization chamber, alkali chamber and water-splitting chamber.
The statement of employed in this article " in the electrode back " means from the vision of the electrode of opposite side to be seen " back " and can be understood as that " outside " of the liquid treatment equipment that is made of two comparative electrodes.
Electrode vessel liquid inlet 16 links to each other with electrode vessel liquid-flow chamber 15 with electrode vessel liquid exit 17.If desired, can form the ventilation opening 18 that is connected to electrode vessel liquid exit 17.This electrode vessel 14 has been filled the ion-exchanger 13 that is made of filamentary material.This ion-exchanger can be made of the filamentary material of the form of textile fabric or nonwoven fabric etc.
Electrode 11 be by can permeation liquid and the material of gas and conduction form, can be used for this purpose can permeation liquid and the material of gas and conduction comprise, for example, wire netting, metal diagonal screen material, grid metal material, eyelet metallic substance, foam metal material and sintered metal fiber plate.Particularly, can will buy the wire netting material of commodity Hi-Expand Metal by name from Fukuzawa Wire Net Mfg. or be used for electrode 11 from the foam metal material that Mitsubishi MaterialsCorporation buys.
Each chamber to the electrochemical liquid treatment equipments with such configuration provides supply water, and supplies pure water by electrode vessel liquid inlet 16 to the electrode vessel liquid-flow chamber 15 of electrode vessel structure.The pure water that electrode 11 by water permeable will be fed to electrode vessel liquid-flow chamber 15 is incorporated in the electrode vessel 14 ion-exchanger 13 that is made of filamentary material that is filled in the electrode vessel 14 to soak into.The existence of electrode vessel intermediate ion exchanger 13 makes the pure water that uses isolator have good electroconductibility as electrode vessel liquid.In addition, own at electrode vessel 14 with the interior electrode vessel liquid flow that do not need, to such an extent as to compare with the ionic conduction dividing plate of the forms such as diagonal screen of routine, this electrode vessel can be full of by the ion-exchanger that the filamentary material of more intensive structure example such as textile fabric or non-textile fabric form constitutes.Like this, compare with the ionic conduction dividing plate of routine, the contact area of ion-exchanger and electrode surface can increase, thereby resistance descends and operating voltage can be further reduced.Especially when current density is high,, therefore can solve the problem of the damage of the ion-exchanger that causes by heat owing to can reduce the local pyrexia that causes by electric current.Filled the ion-exchanger that constitutes by such filamentary material if having the electrode vessel of conventional structure as shown in Figure 1, for example the mobile bubble that has been subjected to too big obstruction and can not have avoided producing on flow resistance increase and the described below electrode surface of electrode vessel liquid is restricted and is retained in the filamentary material, thereby has greatly increased operating voltage.
Can also eliminate because the defective that gas caused that electrode reaction produced as top electrode vessel structure of constructing.
On the surface of electrode, in galvanization by electrode reaction generation electrolysis.When pure water the time as the electrode vessel liquid-flow, the electrolytic reaction below having taken place.
Reaction below anode takes place.
These reactions are represented by a following reaction formula:
On the other hand, the reaction below negative electrode takes place.
These reactions are represented by a following reaction formula:
That is to say, produce oxygen simultaneously and hydrogen ion on the anodic surface, and produce hydrogen and hydroxide ion simultaneously on the surface of negative electrode.In the electrode vessel structure of as shown in Figure 1 routine, for example, in electrode vessel, produced oxygen and hydrogen having formed bubble, thereby the surface resistivity of electrode vessel liquid increases to lure that operating voltage increases into.
Yet, in electrode vessel structure according to the present invention, oxygen that produces on electrode surface and hydrogen unlikely enter in the ion exchange fiber material that contains water, but thereby permeate easily in the electrode vessel liquid-flow chamber 15 that this gas-permeable electrode moves to its back easily, and they rise through mobile electrode vessel liquid (pure water) in this chamber as bubble 20.The problem that the caused operating voltage of bubbling during this has solved in the electrode vessel structure of routine by electrode vessel increases.If it is formed on electrode vessel liquid exit 17, then the bubble that rises from electrode vessel liquid is discharged to the outside of this equipment by venting hole 18.
In the present invention, need electrode to have three following functions.
The first, it should be to be made by the corrosion resistant material that allows good electrode reaction takes place.That is to say, cause that by energising or electrolysis the material of oxidation damage is not preferred easily.The second, as the structure unit that is used for ion exchange fiber material is pressed onto ion-exchange membrane, it should be enough firm.For example, if use fibrous carbon material or metallic substance as electrode separately, it has very low intensity so that need strongthener, and this may cause complicated structure.The 3rd, most important and topmost requirement is that the pure water that electrolysis consumes should be fed to (water permeability) the electrode vessel by electrode from the electrode vessel liquid-flow chamber of electrode back, and the gas that is produced in electrode vessel should move in the electrode vessel liquid-flow chamber of electrode back (gas-permeable) by this electrode.Satisfy preferably top mentioned wire netting, metal diagonal screen material, stereotype metallic substance, mesh metallic substance, foam metal material and the sintered metal fiber plate form of electrode materials of these functions, this is because their macropore and gratifying water permeability and gas permeability.On the contrary, not too preferably have the smooth plate material of big metering-orifice, perforated metal for example, this is because the gas that is produced on the interface between ion exchange fiber material and the electrode materials unlikely permeates this electrode and may increase this electrolysis voltage.Preferred materials used is stainless steel, nickel and platinized titanium for example.
The electrode materials of above-mentioned requirements preferably has 2mm or the bigger initial little electrolysis bubble that produces of pore size permeates them easily to such an extent as to satisfy.It is on 1mm or the littler hole that bubble trends towards adhering to pore size, and can not easily to pass the aperture be 0.5mm or littler hole.Therefore, this electrode materials preferably has 1mm or bigger, more preferably 2mm or bigger aperture.Yet owing to reduce with the contact area of ion exchange fiber material and the current density inhomogeneous local ion migration that caused that becomes, the hole that institute's ether is big is not preferred.Therefore, for the purpose of putting into practice, this electrode materials preferably has 1mm-20mm, more preferably the pore size of 2mm-10mm.Owing to wish that electrode materials has enough support ion exchange fiber materials and unbending intensity, therefore electrode materials preferably has certain thickness and contact with the ion-exchange film close to allow ion exchange fiber material, still too big thickness for processing be inconvenience and caused blocked up electrode vessel.Consider these aspects, electrode materials preferably has the thickness of about 0.6mm-1.2mm.
In electrode vessel structure according to the present invention, the ion exchange fiber material that is filled in the electrode vessel has following function.The first, it can reduce from electrode surface to the ion migration resistance of ion-exchange membrane to prevent the increase of operating voltage.Second, the filamentary material that is made by fine-fibered is for example weaved or the whole surface of non-textile fabric contacts with the ion-exchange film close so that iontophoretic injection is gone into the whole surface of ion-exchange membrane, thereby has reduced the resistance of ion-exchange membrane and reduced because the power loss that heating is produced.The 3rd, its interface between electrode and ion-exchange membrane is as buffering.Wire netting material and metal diagonal screen material have very big hole, to such an extent as to when electrode directly is pressed onto on the ion-exchange membrane, applying on the ion-exchange membrane that thereby uneven pressure has increased the probability of film breaks and the ionic current that produces is crossed interface with ion-exchange membrane on electrode surface, thereby local current flows through the life-span that ion-exchange membrane has shortened ion-exchange membrane.According to the present invention, these problems can be solved by using the ion-exchanger that is made of filamentary material to fill the electrode vessel that is limited by electrode and ion-exchange membrane.
Particularly preferred can be the graft polymerization that causes by radiation as the ion-exchanger of the filamentary material form of the packing material in the electrode vessel of the present invention with ion-exchange group be incorporated into the polymer fiber base material, for example obtain on weaving or the nonwoven fabric those.
The graft polymerization that radiation causes is to form free radical and make this free radical and monomer reaction is guided to suprabasil technology with monomer by the irradiated polymer substrate.
The polymer fiber substrate that can be used to prepare the ion-exchanger that is filled in electrode vessel of the present invention can be by polymkeric substance for example polyolefin polymer, the single fiber that forms as polyethylene or polypropylene or the conjugated fibre that is formed by different cores and shell polymeric.The example of suitable conjugated fibre comprise have shell be by polyolefin polymer for example polyethylene form and core be by those of the core-shell structure that forms of polypropylene for example of the polymkeric substance except being used for shell.
Can be used for the radiation of radiation initiation grafting polymeric and comprise β ray, gamma-rays, electron beam etc., wherein preferably use gamma-rays and electron beam in the present invention.The polymerization of radiation initiation grafting comprises the pre-irradiation grafting polymerization that relates to radiation grafting substrate in advance and it is contacted with the grafted monomer that is used to react, with relate to radiation substrate simultaneously and monomeric while radiation grafting polymerization, and wherein any method can be used for the present invention.The graft polymerization that radiation causes comprises the way of contact between a variety of monomers and the substrate, for example substrate is immersed in the liquid-phase grafting polymerization of carrying out in the monomer solution; The gas phase graft polymerization that substrate is contacted with monomer vapours and carry out; Perhaps, then it is taken out the immersion gas phase graft polymerization that is used in gas phase, reacting from monomer solution by substrate is immersed in the monomer solution; And any method can be used among the present invention.
Do not have concrete qualification to being incorporated into the ion-exchange group that is used for preparing as the polymer fiber substrate of the ion-exchanger of the packing material of electrode vessel of the present invention, but can use various ion-exchange groups.For example, suitable cation exchange group comprises for example sulfo group of strong-acid cation cation exchange groups; Moderate acidic cation cation exchange groups is phosphate for example; With Subacidity cation cation exchange groups for example carboxyl and phenolic hydroxyl group; And suitable anion exchange groups comprise the weak base anion cation exchange groups for example uncle to uncle amino and strong base anion cation exchange groups quaternary ammonium group for example.In addition, can also use and have the ion-exchanger of positively charged ion and anion exchange groups as described above.
These ion-exchange groups can be by graft polymerization, the graft polymerization that preferred radiation causes, use has the monomer of these ion-exchange groups or use and has and can be converted into one of these ion-exchange groups, then described group is transformed into can being incorporated in the polymer fiber substrate by the polymeric monomer of ion-exchange group.The monomer that this purpose has ion-exchange group be can be used for and vinylformic acid (AAc), methacrylic acid, Sodium styrene sulfonate (SSS), sodium methallyl sulfonate, sodium allyl sulfonate, sodium vinyl sulfonate, monobutyltin trichloride vinyl benzene methyl trimethoxy base ammonium (VBTAC), aminoethyl methacrylic diethyl phthalate, dimethyl aminopropyl acrylamide etc. comprised.For example, can use graft polymerization that Sodium styrene sulfonate causes by radiation as monomer directly with strong-acid cation exchange groups for example sulfo group be incorporated into polymeric substrates, perhaps can use graft polymerization that ethylene chloride base phenmethyl trimethyl ammonium causes by radiation as monomer directly with the strongly basic anion cation exchange groups for example quaternary ammonium group be incorporated into polymeric substrates.Monomer with the group that can be transformed into ion-exchange group comprises vinyl cyanide, propenal, vinyl pyridine, vinylbenzene, 1-chloro-4-methyl-benzene, glycidyl methacrylate (GMA) etc.For example, can glycidyl methacrylate be incorporated in the substrate by the graft polymerization that radiation causes, then itself and sulphonating agent for example the S-WAT reaction and with strong-acid cation exchange groups for example sulfo group be incorporated into the polymer fiber substrate, perhaps can 1-chloro-4-methyl-benzene be incorporated in the substrate by the graft polymerization that radiation causes, then it is immersed in the water-based Trimethylamine solution with quaternary ammonium group functionalized and with the strongly basic anion cation exchange groups for example quaternary ammonium group be incorporated in the polymeric substrates.
Preferably,, introduce sulfo group at least, perhaps if, introduce quaternary ammonium group at least with the introducing of the moon cation exchange groups if cation exchange group is incorporated into fibrous substrate.This is because if the ion-exchange group that exists is not sulfo group or the quaternary ammonium group that is free on as the pure water in the neutral pH scope of electrode vessel liquid, and operating voltage will raise and will be difficult to the performance that obtains to wish.Should be appreciated that for example carboxyl of Subacidity cation cation exchange groups, or the weakly-basic anion cation exchange groups for example uncle is amino or more weak group can coexist as in the ion exchange fiber material, but sulfo group or quaternary ammonium group preferably exist with the scope that is expressed as division salt ability 0.5-3.0meq/g.Can increase or reduce ion-exchange capacity by changing the grafting degree, and the ability of ion-exchange increases along with the grafting degree.
In electrochemical liquid treatment equipments according to the present invention, preferably fill the anolyte compartment with cationite respectively, and fill cathode compartment with anionite.When these ion-exchangers are filled in separately the electrode vessel, because the hydrogen ion H that in the anolyte compartment, produces
+With the hydroxide ion OH that in cathode compartment, produces
-Respectively along cationite and anionite migration, so only need very little potential difference to be used for ion migration.Hydrogen ion that moves in the anolyte compartment and the hydroxide ion that moves in cathode compartment pass cationic exchange membrane that limits the anolyte compartment and the anion-exchange membrane that limits cathode compartment respectively, thereby move in the adjacent chamber.
Such as explained above, because electrode vessel has been filled the ion-exchanger of filamentary material form, so pure water can be used as according to the electrode vessel liquid in the electrode vessel structure of the present invention.In this case, be provided to the water that adds that minimum water in the electrode vessel is the water that decomposes of electrode reaction.Yet, iff the pure water that replenishes institute's consumption, because a spot of electrolytic solution permeates ion-exchange membrane by the concentration diffusion from the chamber adjacent to electrode vessel, so the concentration of electrolyte in electrode vessel liquid increases gradually.Like this, wish by prevent the increase of concentration of electrolyte to electrode vessel pure water without interruption.Because the electrolytic solution that covers in the electrode vessel liquid by concentration diffusion changes along with the kind and the other factors of electrolytic solution, the amount that is fed to the pure water of electrode vessel can be by the rule of thumb suitable control of those skilled in the art.
In order to save the amount of employed pure water, a certain amount of water can be fed in the electrode vessel liquid, and when on the circulation path, removing electrolytic solution, under electrode vessel liquid circulation condition, operate by filter core ion exchange resin.
In electrochemical liquid treatment equipments according to the present invention, the thickness of electrode vessel depends in part on the size of other chamber, but is usually located at preferred 2.0-10mm, more preferably in the scope of 2.5-3.5mm.The various tests that are positioned at the ion exchange fiber material that is filled in electrode vessel of this size range of a lot of uses show, for that obtain and stable outflow quality, the most preferred ion exchange fiber material that is filled in electrode vessel is that thickness is 0.1-1.0mm, and surface density is 10-100g/m
2, porosity is that 50-98% and Fibre diameter are the nonwoven fabric substrate of 10-70pm.
In electrochemical liquid treatment equipments according to the present invention, consider operability, process easily and good geometrical stability, the case material that can be used for forming electrode vessel and other chamber preferably includes, for example, inflexible vinylchlorid, polypropylene, polyethylene, EPDM etc., but it specifically is not confined to top listed those and can uses be used for electrodialysis in this area, any material of electrolysis and electrode ionization device housing.
According to electrochemical liquid treatment equipments of the present invention can specifically be forms such as electrodialysis as explained above, electrolysis and electrode ionization device.For example, electrode ionization device form can be according to electrochemical liquid treatment equipments of the present invention by two electrode vessel structures shown in Figure 2 according to the present invention relatively are set, and ion-exchange membrane is in the inboard, and is arranged alternately cationic exchange membrane at least in part and anion-exchange membrane forms the deionization chamber and the concentration compartments forms between them.In this case, the ion-exchanger of the various suitable forms that proposed has preferably been filled by deionization chamber and concentration compartments in this technology.
Embodiment
By the following examples, more specifically explained the present invention.The following examples are the embodiments that are used for explaining the technology of the present invention notion, rather than the present invention is defined in this.
The preparation of ion-exchange nonwoven fabric and ionic conduction dividing plate
Table 1 has shown the specification of the nonwoven fabric that is used for preparing in an embodiment the substrate of ion-exchange nonwoven fabric.This nonwoven fabric is to comprise the core that formed by polypropylene and the conjugated fibre of the shell that formed by polyethylene obtains by thermal caking.
Table 1
| Core/shell is formed | Polypropylene (core)/polyethylene (shell) |
| Surface density | 50g/m 2 |
| Thickness | 0.55mm |
| Fibre diameter | 15-40μm |
| The preparation method of nonwoven fabric | Thermal caking |
| Porosity | 91％ |
Table 2 has shown the specification of the diagonal screen of the substrate that is used as preparation ionic conduction dividing plate in these embodiments.
Table 2
| Form | Polyethylene |
| Structure | Diagonal screen |
| Thickness | 0.8mm |
| Width of mesh | 6mm×3mm |
With gamma-rays nonwoven fabric shown in the radiometer 1 under nitrogen atmosphere, then it is immersed in glycidyl methacrylate (GMA) solution, and make its reaction to produce 175% grafting degree.Then, by this grafted nonwoven fabric of sulfonation in the mixing solutions that immerses S-WAT/isopropanol.The ion-exchange capacity of determining formed ion-exchange nonwoven fabric demonstrates and obtained the salt cracking ability is the strong-acid cation exchange nonwoven fabric of 2.82meq/g.
Respectively, immerse in 1-chloro-4-methyl-benzene (CMS) solution with gamma-rays radiating nonwoven fabric, and make its reaction to provide 148% grafting degree with top.Make this grafted nonwoven fabric functionalized by it being immersed 10% water-based Trimethylamine solution with quaternary ammonium group.Formed ion-exchange nonwoven fabric is to have the strongly basic anion exchange nonwoven fabric that the salt cracking ability is 2.49meq/g.
With gamma-rays at N
2Diagonal screen substrate under the atmosphere shown in the radiometer 2 is immersed it in mixing solutions of glycidyl methacrylate (GMA)/dimethyl formamide (DMF) then, and makes its reaction to provide 53% grafting degree.Come this grafted net of sulfonation by the mixing solutions that immerses S-WAT/isopropanol, to produce the strong-acid cation conductive separator plate that the salt cracking ability is 0.62meq/g.
With with the diagonal screen shown in the identical mode radiometer 2 described above, it is immersed in the mixing solutions of ethylene chloride base phenmethyl trimethyl ammonium (VBTAC)/DMAA (DMAA)/water then, and reaction is to provide 36% grafting degree.This dividing plate is to have the strongly-acid anionic electroconductive dividing plate that the salt cracking ability is 0.44meq/g.
Embodiment 1
The ion-exchange membrane that can buy on the ion-exchange nonwoven fabric that is obtained above using and ionic conduction dividing plate and the market forms the electrode ionization device.(trade(brand)name: cationic exchange membrane C66-10F) is with (trade(brand)name: anion-exchange membrane AMH) forms the electrode ionization device with 11 parallel deionization chambers from Tokuyama Corp. from TokuyamaCorp. in use.Fill each deionization chamber with cationic exchange nonwoven fabric that as top, is obtained and anionresin nonwoven fabric, meeting the boundary with cationic exchange membrane and anion-exchange membrane respectively, and fill each deionization chamber with a slice at the cationic electroconductive dividing plate that as top, obtains and the anionic electroconductive dividing plate of a slice on anionresin nonwoven fabric side of cationic exchange nonwoven fabric side respectively.Fill each concentration compartments with a slice less than that handle and polyethylene diagonal screen nonionic electroconductibility.With from Fukuzawa Wire Net Mfg. (trade(brand)name: Hi-Expand Metal; Width of mesh 4.0 * 8.0mm, thickness 0.8mm) wire netting material is used in combination the electrode vessel with the structure shown in Fig. 2, and the cationic exchange nonwoven fabric that is as above obtained with a slice is filled by the anolyte compartment that anode and cationic exchange membrane limited respectively, and the cathode compartment that the anionresin nonwoven fabric is filled and negative electrode and anion-exchange membrane limited that is as above obtained with a slice.Each chamber has the size of 400mm * 600mm.
The electrode ionization device that use has this structure comes the water treatment system shown in the pie graph 3.To be stored in the raw water basin 52 from the waste water (raw water of recovery) of wet scrubbing method, and by flowing into pipeline 61 feed, the effect by service pump 55 makes it be sent in the deionization chamber of electrode ionization device 54 through active carbon filter core 58 and strainer 59 then.
The supply water of the concentration compartments in the electrode ionization device 54 is to be sent to the raw water that concentrates the recovery the circulation basin 53 by service pump 56 from raw water basin 52.Effect by service pump 57 will be stored in the raw water that concentrates the recovery in the basin 53 and be fed in the concentration compartments in the electrode ionization device 54 through concentrating pipeline 67.To be recycled in the concentrated solution circulation basin 53 from the effluent (concentrated solution) of concentration compartments by concentration compartments's escape route 68.Conductometer 60 is placed on concentration compartments's escape route 68 measuring the electric conductivity of concentrated solution, thus the ionic concn of monitoring concentrated solution.In case the ionic concn of concentrated solution surpasses the level of 2-4mS/m, just opens valve 72 by concentrated solution escape route 69 water is discharged in the water shoot 70.Effect by service pump 56 is fed to raw water 51 and remedies in the concentrated solution circulation basin 53 because the circulation loss that this discharge causes.
By deionization chamber export pipeline 63 being branched into electrode feed pipeline 64 and being connected to two electrode vessels and two electrode vessel supply parts in electrode ionization device 54 come from the effluent (deionized water) of deionization chamber.The effluent that comes from each electrode vessel is turned back in the raw water basin 52 by anolyte compartment's export pipeline 65 and cathode compartment export pipeline 66.
When use equipment described above and at constant current practice (0.05A/dm
2) under with 1m
3It is the hydrofluoric acid solution of 0.7-0.8mg/L in the time of 1000 hours that the flow rate of/hr is supplied with concentration, has stably guaranteed 16MOcm or bigger ratio resistance in this treating water (effluent that comes from the outlet of deionization chamber) 63.By determining pressure drop in each electrode vessel with being inserted in platinum line measuring voltage between electrode surface and the ion-exchange nonwoven fabric and between ion-exchange nonwoven fabric and the ion-exchange membrane.What the pressure drop in two electrode vessels was stable is 0.6V in the anolyte compartment, and is 0.9V in cathode compartment.
After supplying with water, the damage of the corrosion of evaluate electrode and ion-exchange membrane and ion-exchanger, demonstrating does not have practical problems.
Comparative Examples 1
Except the electrode vessel in the electrode ionization device has conventional structure as shown in fig. 1 and fills the anolyte compartment with the cationic electroconductive dividing plate that as above obtained, and fill cathode compartment with the anionic electroconductive dividing plate that is as above obtained, form the electrode ionization device in the mode identical, and use this deionizater to constitute water treatment system shown in Figure 3 with embodiment 1.
In this system of use and with 1m
3The flow velocity of/hr is at constant current operation (0.05A/dm
2) to supply with down concentration be the hydrofluoric acid solution of 0.7-0.8mg/L in the time of 1000 hours, stably guaranteed 15MOcm or bigger ratio resistance in this treating water (effluent that comes from the outlet of deionization chamber) 63.Pressure drop in the electrode vessel is about 2.4V in the anolyte compartment and is about 2.8V in cathode compartment, and have the change of pact ± 0.2V in operational process.
After supplying with water, not unusual to demonstrate with the damage of the corrosion of the mode evaluate electrode identical and ion-exchange membrane and ion-exchanger with embodiment 1.
Embodiment 2
When using the equipment identical and with 1m with embodiment 1
3The flow velocity of/hr is at constant current operation (2.5A/dm
2) supply with down concentration and be the hydrofluoric acid solution of about 100mg/L in the time of 200 hours, in this treating water (coming from the effluent that the deionization chamber exports) 63, stably guaranteed 2MOcm or bigger ratio resistance.By determining pressure drop in each electrode vessel with being inserted in platinum line measuring voltage between electrode surface and the ion-exchange nonwoven fabric and between ion-exchange nonwoven fabric and the ion-exchange membrane.Pressure drop in two electrode vessels is stable is 2.8V in the anolyte compartment and is 4.7V in cathode compartment.
Comparative Examples 2
When using the equipment identical and with 1m with Comparative Examples 1
3The flow velocity of/hr is at constant current operation (2.5A/dm
2) under to supply with concentration in the mode identical with embodiment 2 be the hydrofluoric acid solution of about 100mg/L in the time of 50 hours, in this treating water (effluent that comes from the outlet of deionization chamber) 63, stably guaranteed 1.5-2MOcm or bigger ratio resistance.Pressure drop in the electrode vessel when bringing into operation about 7V of anolyte compartment and at about 12V of cathode compartment along with the cycle of operation is increased to 13V the anolyte compartment after 50 hours and the about 25V in cathode compartment gradually.After supplying with water, the assessment that the ionic conduction dividing plate is damaged demonstrates, along with at the interface on ionic conduction dividing plate and motor surface and the interface between the lamellated ionic conduction dividing plate turn brown and damage.This may be caused by the heating that partial big electric current causes.Electrode and ion-exchange membrane do not show abnormality.
Advantage of the present invention
The electrochemical liquid treatment equipments that has according to electrode vessel structure of the present invention makes water treatment carry out under stable operating voltage, and without any the caused defective of electrode vessel structure by routine.
Claims (8)
1, a kind of electrochemical liquid treatment equipments, it is included in the ion-exchange membrane between anode and the negative electrode, have anolyte compartment that limits by anode and cationic exchange membrane and the cathode compartment that limits by negative electrode and anion-exchange membrane, in anolyte compartment and the cathode compartment each has all been filled the ion-exchanger that is made of filamentary material, in anode and the negative electrode each all is that the material by liquid permeable and gas and conduction forms, and this equipment also has the electrode vessel liquid-flow chamber that is formed at anode and each back of negative electrode.
2, electrochemical liquid treatment equipments according to claim 1, the material of wherein said liquid permeable and gas and conduction are selected from wire netting, metal diagonal screen, grid metal, netted metallic substance, foam metal material and sintered metal fibers sheet.
3, electrochemical liquid treatment equipments according to claim 1 and 2, wherein the ion-exchanger that is made of filamentary material is ion-exchange yarn fabric or the nonwoven fabric that is prepared by the graft polymerization that radiation causes.
4, according to each described electrochemical liquid treatment equipments of claim 1-3, wherein fill with cationite the anolyte compartment, and cathode compartment is filled with anionite.
5,, wherein one of at least provide pure water or ultrapure water in anode chamber and the cathode compartment as electrode vessel liquid according to each described electrochemical liquid treatment equipments of claim 1-4.
6, according to each described electrochemical liquid treatment equipments of claim 1-5, wherein said electrode vessel liquid-flow chamber has ventilation hole.
7, according to each described electrochemical liquid treatment equipments of claim 1-6, it is to be included between anode and the negative electrode cationic exchange membrane alternately arranged to small part and anion-exchange membrane to form the electrode ionization device of deionization chamber and concentration compartments.
8, according to each described electrochemical liquid treatment equipments of claim 1-6, it is to be included between anode and the negative electrode cationic exchange membrane alternately arranged to small part and anion-exchange membrane to form the electrodialysis appts of sour chamber, ionization chamber, alkali chamber and water-splitting chamber.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP151971/2003 | 2003-05-29 | ||
| JP2003151971A JP4384444B2 (en) | 2003-05-29 | 2003-05-29 | Electric demineralizer and electrodialyzer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1795147A true CN1795147A (en) | 2006-06-28 |
Family
ID=33487245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004800147443A Pending CN1795147A (en) | 2003-05-29 | 2004-05-25 | Electrochemical liquid treatment equipments |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20070056847A1 (en) |
| JP (1) | JP4384444B2 (en) |
| CN (1) | CN1795147A (en) |
| WO (1) | WO2004106243A1 (en) |
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| CN105668726A (en) * | 2016-03-23 | 2016-06-15 | 东北大学 | Waste PCB (printed circuit board) etchant and ink liquid treatment method and apparatus |
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| CN108927005A (en) * | 2012-11-19 | 2018-12-04 | 懿华水处理技术有限责任公司 | electrochemical separation device |
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| US7083733B2 (en) | 2003-11-13 | 2006-08-01 | Usfilter Corporation | Water treatment system and method |
| US8377279B2 (en) | 2003-11-13 | 2013-02-19 | Siemens Industry, Inc. | Water treatment system and method |
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| US5198086A (en) * | 1990-12-21 | 1993-03-30 | Allied-Signal | Electrodialysis of salts of weak acids and/or weak bases |
| DE69204187T2 (en) * | 1991-03-13 | 1996-01-25 | Ebara Corp | Electrically regenerable demineralization device. |
| US5376240A (en) * | 1991-11-04 | 1994-12-27 | Olin Corporation | Process for the removal of oxynitrogen species for aqueous solutions |
| SE511003C2 (en) * | 1992-03-16 | 1999-07-19 | Eka Chemicals Ab | Process and apparatus for producing sulfuric acid and alkali metal hydroxide |
| DE4415678A1 (en) * | 1994-05-04 | 1995-11-09 | Hoechst Ag | Electrochemical cell |
| DE4418812C2 (en) * | 1994-05-30 | 1999-03-25 | Forschungszentrum Juelich Gmbh | Single and multiple electrolysis cells and arrangements thereof for the deionization of aqueous media |
| JP3801821B2 (en) * | 1999-10-29 | 2006-07-26 | 株式会社荏原製作所 | Electric desalination equipment |
| US6607647B2 (en) * | 2001-04-25 | 2003-08-19 | United States Filter Corporation | Electrodeionization apparatus with expanded conductive mesh electrode and method |
-
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- 2003-05-29 JP JP2003151971A patent/JP4384444B2/en not_active Expired - Lifetime
-
2004
- 2004-05-25 WO PCT/JP2004/007633 patent/WO2004106243A1/en active Application Filing
- 2004-05-25 US US10/556,057 patent/US20070056847A1/en not_active Abandoned
- 2004-05-25 CN CNA2004800147443A patent/CN1795147A/en active Pending
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Also Published As
| Publication number | Publication date |
|---|---|
| US20070056847A1 (en) | 2007-03-15 |
| WO2004106243A1 (en) | 2004-12-09 |
| JP4384444B2 (en) | 2009-12-16 |
| JP2004351317A (en) | 2004-12-16 |
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