CN101193823A

CN101193823A - Electrodialyzer, waste water treatment method, and fluorine treatment system

Info

Publication number: CN101193823A
Application number: CNA2006800204784A
Authority: CN
Inventors: 赤堀晶二; 中川创太; 佐佐木悠二
Original assignee: Ebara Corp
Current assignee: Ebara Corp
Priority date: 2005-06-09
Filing date: 2006-06-02
Publication date: 2008-06-04

Abstract

This invention provides an electrodialyzer comprising an anode chamber (10) having an anode (2) and a cathode chamber (50) having a cathode (3). The electrodialyzer further comprises a desalination chamber (40) for removing fluorine ions from fed waste water to produce treated water, a concentration chamber (30) for concentrating fluorine ions contained in the waste water moved from the desalination chamber (40) to produce concentrated water, and a buffer chamber (20) for blocking the fluorine ions in the waste water so that the fluorine ions in the waste water does not flow from the concentration chamber (30) directly into the anode chamber (10). The electrodialyzer further comprises a path for feeding pure water into the anode chamber (10) and a path for feeding water discharged from the anode chamber (10) into the buffer chamber (20).

Description

Electrodialysis device, drainage processing method and fluorine treatment system

Technical field

The present invention relates to the electrodialysis device, particularly contain the electrodialysis device of the liquid of fluorine as process object below for example: (1) is from relevant semi-conductor manufacturing, the draining after the pre-treatment has maybe been carried out this draining in the draining of the device of liquid crystal manufacturing or electronic unit manufacturing, (2) will be in the semi-conductor manufacturing, the gas that the PFC gas that uses in liquid crystal manufacturing or the electronic unit manufacturing generates with removing the evil the device decomposition cleans the draining that produces by water or buck and maybe this draining has been carried out the draining after the pre-treatment, (3) not Lyons class is destroyed in the industry with Lyons class not and is destroyed that facility decomposes Lyons not and the gas that generates cleans the draining that produces by water or buck and maybe this draining carried out the draining after the pre-treatment, (4) as with the fluorine in the aqueous solution as Calcium Fluoride (Fluorspan) (CaF ₂) draining for the treatment of water of the fluorine renewable resources device that reclaims maybe carried out this draining the draining after the pre-treatment etc.In addition, the present invention relates to use the drainage processing method of this electrodialysis device.And then, the present invention relates to use this electrodialysis device to handle the fluorine treatment system of fluorine.

Background technology

The carrying capacity of environment that neutral salt, spent acid, the salkali waste that contains in the draining that exploitation can reduce from various operations to discharge as by product or waste brings and can be bigger problem in the various factories with the technology of the useful component recycling in by product or the waste.In addition, if can will utilize in factory removing the treating water that obtains when bringing the material of load to environment from draining, it is preferred that yes again.

For example, produce tens to hundreds of mg-F/L thin fluorine-containing draining in large quantities from the manufacturing process of semi-conductor, liquid crystal or electronic unit.This thin fluorine-containing draining is up to the present by using calcium hydroxide (Ca (OH) ₂) coagulating sedimentation handle.But,, the problem that produces the relatively poor mud of the property handled is in large quantities arranged according to this coagulating sedimentation.Owing to this origin increases in the increase along with the draining water yield of the mud generation of fluorine, thus the appearanceization that subtracts of thin fluorine-containing draining studied always, but up to the present also do not have effective spissated technology.The mud that produces does not utilize fluorine again and by landfill disposal, treating water so utilize difficulty again, is discharged to the outside also owing to contain Ca in large quantities usually.

Water for cleaning as the exhaust washing unit, use process water or the more cheap and more use of municipal water, so in the draining that the gas that generates PFC gas is decomposed with the device of removing the evil carries out producing when water cleans, contain the Ca that in process water and municipal water, originally contains especially.Ca is the Calcium Fluoride (Fluorspan) (CaF of generation insoluble with the fluorine reaction easily ₂) and sedimentation or in the aqueous solution of alkalescence, form oxyhydroxide and precipitate.Therefore, be difficult to will in above-mentioned draining, contain fluorine separate or concentrate.

If the common water technology that will use in the concentration operation of the aqueous solution is applied in the processing of fluorine-containing draining, then known have a variety of issue.For example, under wanting to handle the spissated situation of fluorine-containing draining by the RO film because the film perviousness of hydrogen hydrofluoric acid (HF) is higher, thus have the HF that leaks into film permeate water side more, can not concentrate efficiently and treating water in fluorine concentration problem of higher.

In addition, evaporation concentration method is being wanted 10, is effective means when above dense draining further concentrates about 000mg/L, even but want to be applied in the thin draining, because the energy expenditure of relevant water evaporation becomes big, so the problem that is difficult to use is arranged.In addition, owing in distilled water, also carry fluorion,, be difficult to the shortcoming of directly utilizing again so also there is the fluorine concentration of distilled water higher.

With respect to these methods, the electrodialysis method is for being from 1 with ionic concn, 000mg/L to 10, the draining of the concentration about 000mg/L concentrates or desalination is good method, as the concentration technique of recovery, the salt of the manufacturing of carrying out sweet water from buck, acid practicability.But the electrodialysis method is owing to the desalination that can not carry out height, so residual morely in treating water have ion, so if want to be applied in the draining processing, the situation that need carry out the secondary treatment for the treatment of water is arranged then.

In addition, in the processing of the sour draining that contains the metal ion that forms metal hydroxides, use under the situation of electrodialysis method, need take some countermeasures so that in the electrodialysis groove, can not generate metal hydroxides.In addition, if be applied in the processing of the draining that contains fluorine, the electrode that the electrodialysis groove is then arranged is by fluorine corrosive problem.

In addition, fluorion is the object material of draining restriction as the objectionable impurities of the harm of the health that might produce relevant people, in Japan, be set at below the 8mg/L in the time of in the commons waters beyond being discharged to the marine site, be set at when being discharged in the marine site below the 15mg/L as general draining benchmark.In addition, be set at 0.8mg/L in the environmental criteria that with the health of protecting the people is purpose, the fluorine concentration in the treating water after fluorine-containing draining is handled not only will satisfy general draining benchmark, and wishes to approach as much as possible environmental criteria.

But, in the processing of fluorine-containing draining, use under the situation of coagulating sedimentation, if want to make the fluorine concentration in the treating water to approach environmental criteria, the problem that then have the usage quantity of the needed chemical reagent of coagulative precipitation to increase sharp, the generation of mud increases significantly.

In addition, under the situation that realizes utilizing again as the former water of pure water manufacturing usefulness etc. from fluorine-containing draining, fluorine being removed, wish to reduce fluorine concentration, preferably be reduced to below the 1mg/L.This be because, surpass under the situation of 1mg/L in fluorine concentration, mix and form under the situation of pure water manufacturing with former water containing Ca water, can generate Calcium Fluoride (Fluorspan) Water Purifiers is stopped up because of the separate impurities in the pure water manufacturing processed, concentration operation with for example underground water or tap water etc.

Conventional art as using the fluorine-containing draining of electrodialysis technical finesse etc. has technology shown below.

Open in the clear 54-20196 communique the spy, disclose in the electrodialysis groove that uses cationic exchange membrane and anion-exchange membrane and will contain fluorion (F ^-) and calcium ion (Ca ²⁺) the electrodialysis treatment process of aqueous electrolyte liquid desalination and concentration.In the method, use the electrodialysis groove alternately dispose desalting chamber and concentration compartments to turn round with the current density below 1/2 of limit current density, make than the more difficult fluorion that in anion-exchange membrane, moves of other negatively charged ion to remain in the desalting chamber, suppress the CaF in the concentration compartments ₂Incrustation scale is separated out, and carries out desalting treatment thus.

In No. 2726657 communique of special permission, disclose from the mixing salt that contains at least two kinds of different sorts negatively charged ion comprising fluorion and at least two kinds of salt utilize electrodialysis formula water decomposition device to reclaim the method for mixing acid the aqueous solution (stainless steel acid-washing waste liquid), described device is based on the 3 Room methods of having used known Bipolar Membrane.In the method, the waste liquid that contains heavy metal ion is added alkaline solution (being preferably KOH) in advance and makes its precipitation, by making the suspension liquid that obtains by filtering unit and with sedimentation and filtration, form thus the solubility mixing salt solution, by with this solubility mixing salt solution supply in the desalting chamber of electrodialysis formula water decomposition device, mixing acid is reclaimed.

In the fair 7-112558 communique of spy, the regeneration treating method of the nitre fluoric acid waste liquid that contains metal ion is disclosed.In the method, in containing the nitre fluoric acid waste liquid of metal ion, add hydrofluoric acid and improved F with formation for the organic efficiency of the nitric acid that improves electrodialysis operation ^-/ NO ^3-Behind the waste liquid of mol ratio, utilize acid recovery to handle (recovery nitric acid) with the depickling of dialysing of ion-exchange membrane electrodialysis groove.Then, add alkali, the metal ion that contains in treating water is removed as precipitation of hydroxide.Then, be separated into nitre fluorine bronsted lowry acids and bases bronsted lowry, reclaim by the ion-exchange membrane electrodialysis device that combines by Bipolar Membrane and anion-exchange membrane cationic exchange membrane.

In the fair 7-112559 communique of spy, the treatment process of the alkaline fluorochemical waste liquid that contains metal ion and oils is disclosed.In the method, the fluorochemical waste liquid that contains the alkalescence of metal ion and oils is carried out neutralizing treatment by the interpolation of hydrofluoric acid, carried out oils remove processing after, processing is removed in the absorption that utilizes resin to carry out metal ion, then be separated into alkali and hydrofluoric acid by the ion-exchange membrane electrodialysis device that combines by Bipolar Membrane and anion-exchange membrane cationic exchange membrane, and the recovery of regenerating.

In No. 3364308 communique of special permission, the treatment process of the draining that contains fluorine is disclosed.In the method, generation is removed treating water behind the fluorine from the draining that contains fluorine by the fluorine sorbent material, and will be from the elution of fluorine sorbent material the liquid of fluorine carry out electrodialysis and be separated into fluorine condensed water and the thin water of fluorine, generate and removed the treating water behind the fluorine by the fluorine sorbent material once more from the thin water of fluorine that obtains.

Open in the flat 9-262588 communique the spy, disclose from the aqueous solution that contains fluorine and ammonia of the BHF solution of mainly discharging etc. and separated, make the fluorine that obtains with calcium carbonate reaction and with the method for fluorine recovery in fluorine from semiconductor factory.In the method, use the electrodialysis groove that alternately is arranged with anion-exchange membrane and cationic exchange membrane, the draining that contains fluorine and ammonium is carried out draining and handled by draining and mineral acid are alternately supplied with every a Room, fluorion is as the liquids recovery that is concentrated to the concentration of the processing that is suitable for the lime carbonate grain, ammonium ion reclaims with the form of inorganic acid salt, and fluorion and ammonium ion all are lowered to the concentration range in the secondary treatment operation that can flow to resin absorption etc. of 50～100mg/L in the treating water.

In No. 3555732 communique of special permission, disclose and utilized electric to break away from sub-device is handled the lean mixture acid effluent that contains hydrofluoric acid and mineral acid that produces in the manufacturing process of semiconductor devices method.In the method, the thin sour water that contains mineral acid and hydrofluoric acid is added alkali up to the hydrofluoric acid dissociative pH value as weak electrolyte, utilization has the desalting chamber that is filled with ion exchange resin, ion-exchange fiber plasma permutoid and the electric of the concentration compartments that is separated by ion-exchange membrane of being situated between breaks away from sub-device (EDI) and handles the treating water of the hydrofluoric acid that has been removed thus.In addition, the condensed water after obtaining salt and concentrating.

Open in the 2000-176457 communique the spy, disclose in semiconductor fabrication factory the liquid waste treating apparatus that the waste liquid that produces when semi-conductor made is handled.In this liquid waste treating apparatus, use at the indoor electrodialysis device that is filled with ion exchange resin of the waste liquid of electrodialysis device, the fluorine in the waste liquid that will produce when semi-conductor is made reclaims as hydrogen fluoride.In addition, metal ion is recovered in the cathode compartment.Become following structure: see through anion-exchange membrane from the waste liquid chamber and move to F the acid recovery chamber ^-Composition is difficult to arrive the anolyte compartment owing to cationic exchange membrane is stayed in the acid recovery chamber.Metal cation component sees through to negative electrode side pole liquid chamber from the waste liquid chamber via cationic exchange membrane, the metal that precipitate into the cathode side electrode becomes opposite polarity at short notice by the polarity that makes electrode, make the metal reignition that precipitate into the cathode side electrode, shift to negative electrode side pole liquid case, as concentrating the back precipitation of hydroxide, become the formation that metal ingredient also reclaims thus.

Open in the 2000-229289 communique the spy, disclose the method for handling fluorinated water by electric desalting apparatus.This method is the relation that supplies to the long-pending water rate of recovery with electric desalting apparatus of the concentration of the calcium concn of the water in the electric desalting apparatus and fluorine concentration by restriction, prevents the generation of the Calcium Fluoride (Fluorspan) incrustation scale in the concentration compartments.

The spy opens the 2001-121152 communique and discloses the electrodialysis device that is used for carrying out the recovery of fluorine-containing thin acid effluent, utilizes.In this device, between two positive and negative electrodes,, cationic exchange membrane and anion-exchange membrane to small part formed desalting chamber and concentration compartments by alternately being arranged, in desalting chamber and utmost point chamber, be filled with ion exchanger at least.By using treating water from desalting chamber as the supply water to electrode vessel, the liquid that has reduced hydrofluoric acid is supplied with in the counter electrode chamber, so can not corrosion target and carry out desalting treatment.In addition, open in the 2001-121152 communique this spy, the electrode solution of having put down in writing after will using sends back in the raw water box, and with processed water blended technology.

Open in the 2001-145819 communique the spy, disclose the deflated treatment process that makes obnoxious flavour innoxious.In the method, to contain hydrofluoric sour gas carries out gas-to-liquid contact with (alkaline aqueous solution) absorption liquid, decomposes absorption in wet scrubber, the discharge opeing that generates delivered in the electrodialysis device with negatively charged ion permselective membrane carry out dialysis treatment, with absorb anionic part or all be discharged to outside the system, (alkaline aqueous solution) treatment solution that obtains is delivered in the wet scrubber once more as absorption liquid is circulated.

Open in the 2002-119974 communique the spy, disclose and fluorion is contained water electricity consumption regenerative broken away from sub-device and break away from the method that son is made pure water.In the method, after the condensed water of electric regenerative desalting plant handled with Zeo-karb, by add fluorinion concentration be below the 1mg/L water, add salt brine solution as required, coming the modulation electric conductivity is that the inlet pH of above water of 10 μ S/cm or anolyte compartment is the water more than 8, and as utmost point liquid and logical liquid prevents the corrosion of electrode thus.

Open in the 2003-126863 communique the spy, even disclose stronger ionic processed water such as the corrodibility that contains fluorion, also can not make electrode corrosion, break away from the device that son is handled by the sub-device of electric disengaging.In this device, by using on the surface of the substrate of electroconductibility film forming the positive plate and the negative plate of the CVD diamond thin of the boron that mixed are arranged, prevent the corrosion that hydrofluoric acid brings.

Open in the 2003-159593 communique the spy, disclose the method that the waste liquid that uses etc. contains the waste liquid of metal and fluorion of handling in stainless pickling.In the method, the waste liquid that at first will contain metal and fluorion neutralizes with alkaline solution, then filter, be separated into not the metal hydroxides mud and the neutralizer that contains fluorion of fluoride ion, the neutralizer that then will contain fluorion carries out soda acid by the Bipolar Membrane electrodialysis to be separated, thereby be separated into the acid solution and the alkaline solution that contain fluorion, use the solution separating that multistage Steam rectification tower will contain fluorion to be fluorion concentrated solution and thin acid solution then.Open in the 2003-159593 communique this spy, put down in writing and separated the spissated fluorinion concentration that contains the acid solution of fluorion by bipolar electrodialysis device and be for example 20g/L (2%), and the recycling fluorinion concentration that contains the concentrated solution of fluorion after concentrated is about 130g/L (13%) by multistage Steam rectification tower.

Open in the 2004-174439 communique the spy, disclose the treatment process of fluorine-containing draining.This method possesses fluorine-containing draining desalination and spissated electrodialysis operation, with desalting treatment liquid as supplementary feed regeneration to the generation source of fluorine-containing draining, with hydrofluoric acid concentrated solution electrodialysis to hydrofluoric acid solution regenerated degree as available concentration.In the electrodialysis operation, use to possess with the negative pole portion of opposed shape configuration and the electrodialysis mechanism of anodal portion.Negative pole portion and central part in this electrodialysis mechanism alternately dispose cationic exchange membrane and anion-exchange membrane, near anodal portion, dispose the multi-disc cationic exchange membrane continuously.Supply with desalting treatment water, desalting treatment liquid is also supplied with near the configuration position of the cationic exchange membrane the anodal portion (partition chamber) by anticathode portion and anodal portion, suppress electrode circulation fluid and the hydrofluoric acid concentration that cuts off liquid lower, prevent the anodal corrosion.In addition, the part of processed water becomes concentrated solution, by with the concentrated solution circulation, improves concentration rate.In addition, fluorinion concentration and/or electrolyte concentration in the instrumentation hydrofluoric acid concentrated solution are controlled concentration rate according to the change of this concentration.

According to above-mentioned electrodialysis device in the past because the fluorine perviousness of ion-exchange membrane is higher, so fluorion flow in the utmost point chamber with electrode corrosion, so the problem of running that can not be continual and steady is arranged.In addition, will contain under the situation of thin hydrofluoric acid draining as process object of calcium, owing to Calcium Fluoride (Fluorspan) precipitate in the concentration compartments, so the problem of running that can not be continual and steady is arranged.And then, contain ammonium ion fluorine-containing draining the fluorine renewable resources the difficulty.In addition, in electrodialysis device in the past, can not obtaining the recycling treating water that fluorine concentration is lower than 1mg/L from thin fluorine-containing draining when, the fluorine concentration the condensed water be increased to the degree that can supply in the fluorine renewable resources device.

And then, open in the described method of clear 54-20196 communique the spy, still residual in treating water have a fluorion, and the problem that need carry out the processing of residual fluorine is arranged.In addition, open in the clear 54-20196 communique this spy, the avoiding method of the electrode corrosion that brings for fluorine is without any open.

Speciallyying permit No. 2726657 described method of communique is to add alkali as pre-treatment, with mixing salt the heavy metal ion in the aqueous solution remove as precipitation of hydroxide, prevent to form in the electrodialysis groove method of oxyhydroxide thus, but owing to need settler and sedimentary filtration unit, so there is device to become big and the operation complicated problems that also becomes.In addition, the purpose of this method is a recovered acid from dense acid-washing stainless steel solution, owing to also residual in a large number in treating water fluorine is arranged, so the problem that no matter how can not directly utilize is again arranged.In addition, the described method of special fair 7-112558 communique has and No. 2726657 same problem of communique of special permission.

The described method of special fair 7-112558 communique is with the method for this special waste liquid of the alkaline fluorochemical waste liquid that contains oil content that produces from organic chemistry factory as object.In the method, after the neutralizing treatment of having carried out adding hydrofluoric acid and oil content are removed processing, metal ion is removed with resin, by the electrodialysis device that uses bipolar embrane method hydrofluoric acid and alkali are reclaimed then.In the fair 7-112558 communique of this spy, not open for the method for the electrode corrosion of avoiding fluorine to bring.

Speciallyying permit No. 3364308 described method of communique is from fluorine sorbent material elution fluorine, this eluant is carried out electrodialysis and is separated into fluorine condensed water and the thin water of fluorine, the method of the treating water after obtaining by above-mentioned fluorine sorbent material fluorine being removed from the thin water of above-mentioned fluorine, but, because the part of fluorine circulates in sorbent material and electrodialysis groove, so the relatively poor problem of the efficient of processing is arranged.In addition, in this speciallys permit No. 3364308 communique, not open for the method for the electrode corrosion of avoiding fluorine to bring.

The described method of Te Kaiping 9-262588 communique is will use the electrodialysis groove to reduce ammonia concentration and method that the condensed water that improved fluorine concentration reclaims as the liquid of the concentration of the lime carbonate grain that is suitable for being used for carrying out the fluorine recovery, but because the fluorine concentration in the treating water is higher and can not directly utilize again, so the secondary treatment of the treating water that need be undertaken by resin.In addition, open in the flat 9-262588 communique this spy, not open for the method for the electrode corrosion of avoiding fluorine to bring.

Speciallyying permit No. 3555732 described method of communique is to handle by the mixing sour water that contains hydrofluoric acid is added alkali and breaks away from sub-device with electric, the method for the treatment of water of hydrofluoric acid has been removed, but because fluorine is concentrated with the form of salt, so and is not suitable for the recovery of hydrofluoric acid or fluorine and utilizes again.In addition, because condensed water is supplied with in utmost point chamber, the problem of the electrode corrosion that can not avoid the fluorine generation is arranged.

Open in the described device of 2000-176457 communique the spy, precipitateing into the dissolving metal on the negative electrode and when being made as opposite polarity in order to make, need be with separating out the needed magnitude of current equal dissolution current amount, in addition, because fluorine and metal ion can leak in the treating water, so the problem that need carry out the secondary treatment for the treatment of water is arranged.

Open in the described method of 2000-229289 communique the spy, because the concentration range of calcium that can turn round and fluorine is narrower, so the fluorinated water spent ion exchange resin need be handled so that remove the fluorion or the calcium ion of composition of scale in advance as pre-treatment.In addition, open in the 2000-229289 communique this spy, not open for the method for avoiding electrode corrosion.

The spy opens the described device of 2001-121152 communique owing to be not the structure that is provided with surge chamber, if so the fluorine concentration in the concentration compartments is improved significantly, then begin to have from the concentration compartments leakage to the fluorine of utmost point chamber, so reduce fluorine concentration for dilution, need to increase the treating water flow that supplies to the electric chamber desalting plant in the electrode vessel, the problem of the recovery after the fluorine concentration that can not improve the concentration compartments is arranged.In addition, comprise in thin acid effluent under the Ca ionic situation, Ca ion and fluorion all are concentrated in the concentration compartments, because CaF ₂Separate out, so can not use.

Opening the spy has following problems in the described method of 2002-119974 communique: suppress lowlyer for the fluorine concentration of utmost point liquid is removed by anionite-exchange resin, and keep the electric conductivity of utmost point liquid higher, need add complicated management such as salt brine solution.

Open in the described device of 2003-126863 communique the spy, the problem that needs expensive large-scale CVD device in electrode is made is arranged.

In addition, open in the described method of 2003-159593 communique, need to use alkali that metal ion is separated in advance as pre-treatment the spy.In addition, open in the 2003-159593 communique this spy, not open for the method for the electrode corrosion of avoiding Bipolar Membrane electrodialysis device.

It is to import to by the de-salted water after electrodialysis is handled to cut off the method that prevents electrode corrosion in chamber and the electrode vessel that the spy opens the described method of 2004-174439 communique, but owing to do not take to suppress to be accompanied by the countermeasure of supplying with the running voltage rising that de-salted water produced, so the problem that has running voltage to uprise.In addition, because fluorine can leak in the partition chamber adjacent with the spissated concentration compartments of high magnification, become fluorinated water, the problem of the aftertreatment that generation need be removed fluorine or reclaim so cut off the chamber circulation fluid.In addition, because electrode circulation fluid and the fluorine concentration of cutting off liquid exist with ... the water quality of de-salted water, so under the situation that the fluorine concentration of de-salted water is uprised, the possible corrosive problem of electrode is arranged.

Owing to there is above problem, so wish to have effectively and the technology of stably handling with fluorine-containing draining.In addition, hope has from the concentrated fluorine of fluorine-containing draining and is made for the technology of utilizing again and simultaneously fluorine is removed the technology that can utilize this degree for the treatment of water again that goes to.

Summary of the invention

The present invention makes in view of the problem points of such conventional art, and the 1st purpose provides a kind of electrodialysis device that does not bring electrode corrosion, the fluorine-containing draining of electrodialysis stably.

In addition, the 2nd purpose provides a kind of fluorine concentration that can make the treating water of fluorine-containing draining behind electrodialysis and is low to moderate and is lower than 1mg/L, can utilize the electrodialysis device for the treatment of water again.

In addition, the 3rd purpose provides that a kind of electrodialysis contains the fluorine-containing draining of ammonium ion and the electrodialysis device that can access the fluorine condensed water after ammonium ion separated.

In addition, the 4th purpose provides a kind ofly carries out under the electrodialytic situation in the fluorine-containing draining that will contain the metal ion that forms metal hydroxides mud, can not form metal hydroxides mud and obtains electrodialysis device with the fluorine condensed water after the separation of metal ions.

In addition, the 5th purpose provide a kind of by with electrodialysis the fluorine condensed water after the fluorine-containing draining supply in the fluorine renewable resources device, thereby can be as Calcium Fluoride (Fluorspan) (CaF ₂) the electrodialysis device that reclaims.

In addition, the 6th purpose provides and a kind ofly the fluorine renewable resources become be easy to the fluorine condensed water and supply to the fluorine renewable resources device by separating ammonium ion from the fluorine-containing draining that contains ammonium ion, thereby can be as Calcium Fluoride (Fluorspan) (CaF ₂) the electrodialysis device that reclaims.

In addition, the 7th purpose provides and a kind ofly uses above-mentioned electrodialysis device to handle the fluorine treatment system of fluorine effectively.

According to the 1st technical scheme of the present invention, provide a kind of electrodialysis device that possesses the cathode compartment that has the anodic anolyte compartment and have negative electrode.This electrodialysis device possesses: desalting chamber, and from the processed water that is supplied to, remove the object ion, thereby generate the treating water that has reduced this object ionic concentration; The concentration compartments will concentrate from the object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the condensed water that has improved this object ionic concentration.In addition, at least a portion with the outflow water that pure water is supplied to the path in the above-mentioned anolyte compartment and will come out from above-mentioned anolyte compartment of electrodialysis device supplies to the path the above-mentioned concentration compartments.

According to the 2nd technical scheme of the present invention, provide a kind of electrodialysis device that possesses the cathode compartment that has the anodic anolyte compartment and have negative electrode.This electrodialysis device possesses: desalting chamber, and from the processed water that is supplied to, remove the object ion, thereby generate the treating water that has reduced this object ionic concentration; The concentration compartments will concentrate from the object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the condensed water that has improved this object ionic concentration; Surge chamber cuts off, so that the object ion in the above-mentioned processed water can not be fed directly to the above-mentioned anolyte compartment from above-mentioned concentration compartments.In addition, at least a portion with the outflow water that pure water is supplied to the path in the above-mentioned anolyte compartment and will come out from above-mentioned anolyte compartment of electrodialysis device supplies to the path the above-mentioned concentration compartments.

According to the 3rd technical scheme of the present invention, provide a kind of electrodialysis device that possesses the cathode compartment that has the anodic anolyte compartment and have negative electrode.This electrodialysis device possesses: desalting chamber, and from the processed water that is supplied to, remove the object ion, thereby generate the treating water that has reduced this object ionic concentration; The concentration compartments will concentrate from the object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the condensed water that has improved this object ionic concentration; Surge chamber cuts off, so that the object ion in the above-mentioned processed water can not be fed directly to the above-mentioned anolyte compartment from above-mentioned concentration compartments.In addition, at least a portion with the outflow water that pure water is supplied to the path in the above-mentioned anolyte compartment and will come out from above-mentioned anolyte compartment of electrodialysis device supplies to the path the above-mentioned surge chamber.

According to the 4th technical scheme of the present invention, provide a kind of electrodialysis device that possesses the cathode compartment that has the anodic anolyte compartment and have negative electrode.This electrodialysis device possesses: desalting chamber, and from the processed water that is supplied to, remove the object ion, thereby generate the treating water that has reduced this object ionic concentration; The concentration compartments will concentrate from the object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the condensed water that has improved this object ionic concentration; Surge chamber cuts off, so that the object ion in the above-mentioned processed water can not be fed directly to the above-mentioned anolyte compartment from above-mentioned concentration compartments.In addition, at least a portion with the outflow water that pure water is supplied to the path in the above-mentioned anolyte compartment and will come out from above-mentioned anolyte compartment of electrodialysis device supplies to path the above-mentioned concentration compartments via above-mentioned surge chamber.

According to the 5th technical scheme of the present invention, provide a kind of electrodialysis device that possesses the cathode compartment that has the anodic anolyte compartment and have negative electrode.This electrodialysis device possesses: desalting chamber, and from the processed water that is supplied to, remove the 1st object ion and the 2nd object ion, thereby generate the treating water that has reduced above-mentioned the 1st object ion and above-mentioned the 2nd object ionic concentration; The 1st concentration compartments will concentrate from the 1st object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the 1st condensed water that has improved the 1st object ionic concentration; The 2nd concentration compartments will concentrate from the 2nd object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the 2nd condensed water that has improved the 2nd object ionic concentration; The ion supply chamber will have the polar ion opposite with the 2nd object ion in the above-mentioned processed water and supply in above-mentioned the 2nd concentration compartments.In addition, at least a portion with the outflow water that pure water is supplied to the path in the above-mentioned anolyte compartment and will come out from above-mentioned anolyte compartment of electrodialysis device supplies to the path above-mentioned the 1st concentration compartments.

According to the 6th technical scheme of the present invention, provide a kind of electrodialysis device that possesses the cathode compartment that has the anodic anolyte compartment and have negative electrode.This electrodialysis device possesses: desalting chamber, and from the processed water that is supplied to, remove the 1st object ion and the 2nd object ion, thereby generate the treating water that has reduced above-mentioned the 1st object ion and above-mentioned the 2nd object ionic concentration; The 1st concentration compartments will concentrate from the 1st object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the 1st condensed water that has improved the 1st object ionic concentration; Surge chamber cuts off, so that the 1st object ion in the above-mentioned processed water can not be fed directly to the above-mentioned anolyte compartment from above-mentioned the 1st concentration compartments.In addition, the electrodialysis device also possesses: the 2nd concentration compartments will concentrate from the 2nd object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the 2nd condensed water that has improved the 2nd object ionic concentration; The ion supply chamber will have the polar ion opposite with the 2nd object ion in the above-mentioned processed water and supply in above-mentioned the 2nd concentration compartments.And then at least a portion that the electrodialysis device has the outflow water that pure water is supplied to the path in the above-mentioned anolyte compartment and will come out from above-mentioned anolyte compartment supplies to the path the above-mentioned surge chamber.

According to the 7th technical scheme of the present invention, provide a kind of electrodialysis device that possesses the cathode compartment that has the anodic anolyte compartment and have negative electrode.This electrodialysis device possesses: desalting chamber, and from the processed water that is supplied to, remove the 1st object ion and the 2nd object ion, thereby generate the treating water that has reduced above-mentioned the 1st object ion and above-mentioned the 2nd object ionic concentration; The 1st concentration compartments will concentrate from the 1st object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the 1st condensed water that has improved the 1st object ionic concentration; Surge chamber cuts off, so that the 1st object ion in the above-mentioned processed water can not be fed directly to the above-mentioned anolyte compartment from above-mentioned the 1st concentration compartments.In addition, the electrodialysis device also possesses: the 2nd concentration compartments will concentrate from the 2nd object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the 2nd condensed water that has improved the 2nd object ionic concentration; The ion supply chamber will have the polar ion opposite with the 2nd object ion in the above-mentioned processed water and supply in above-mentioned the 2nd concentration compartments.In addition, at least a portion with the outflow water that pure water is supplied to the path in the above-mentioned anolyte compartment and will come out from above-mentioned anolyte compartment of electrodialysis device supplies to the path above-mentioned the 1st concentration compartments.

According to the 8th technical scheme of the present invention, provide a kind of electrodialysis device that possesses the cathode compartment that has the anodic anolyte compartment and have negative electrode.This electrodialysis device possesses: desalting chamber, and from the processed water that is supplied to, remove the 1st object ion and the 2nd object ion, thereby generate the treating water that has reduced above-mentioned the 1st object ion and above-mentioned the 2nd object ionic concentration; The 1st concentration compartments will concentrate from the 1st object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the 1st condensed water that has improved the 1st object ionic concentration; Surge chamber cuts off, so that the 1st object ion in the above-mentioned processed water can not be fed directly to the above-mentioned anolyte compartment from above-mentioned the 1st concentration compartments.In addition, the electrodialysis device also possesses: the 2nd concentration compartments will concentrate from the 2nd object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the 2nd condensed water that has improved the 2nd object ionic concentration; The ion supply chamber will have the polar ion opposite with the 2nd object ion in the above-mentioned processed water and supply in above-mentioned the 2nd concentration compartments.And then at least a portion that the electrodialysis device has the outflow water that pure water is supplied to the path in the above-mentioned anolyte compartment and will come out from above-mentioned anolyte compartment supplies to path above-mentioned the 1st concentration compartments via above-mentioned surge chamber.

According to the 9th technical scheme of the present invention, provide a kind of electrodialysis device that possesses the cathode compartment that has the anodic anolyte compartment and have negative electrode.This electrodialysis device possesses: desalting chamber, and from the processed water that is supplied to, remove the 1st object ion and the 2nd object ion, thereby generate the treating water that has reduced above-mentioned the 1st object ion and above-mentioned the 2nd object ionic concentration; The 1st concentration compartments will concentrate from the 1st object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the 1st condensed water that has improved the 1st object ionic concentration; The 2nd concentration compartments will concentrate from the 2nd object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the 2nd condensed water that has improved the 2nd object ionic concentration.In addition, at least a portion with the outflow water that pure water is supplied to the path in the above-mentioned anolyte compartment and will come out from above-mentioned anolyte compartment of electrodialysis device supplies to the path above-mentioned the 1st concentration compartments.

According to the 10th technical scheme of the present invention, provide a kind of electrodialysis device that possesses the cathode compartment that has the anodic anolyte compartment and have negative electrode.This electrodialysis device possesses: desalting chamber, and from the processed water that is supplied to, remove the 1st object ion and the 2nd object ion, thereby generate the treating water that has reduced above-mentioned the 1st object ion and above-mentioned the 2nd object ionic concentration; The 1st concentration compartments will concentrate from the 1st object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the 1st condensed water that has improved the 1st object ionic concentration; Surge chamber cuts off, so that the 1st object ion in the above-mentioned processed water can not be fed directly to the above-mentioned anolyte compartment from above-mentioned the 1st concentration compartments; The 2nd concentration compartments will concentrate from the 2nd object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the 2nd condensed water that has improved the 2nd object ionic concentration.In addition, at least a portion with the outflow water that pure water is supplied to the path in the above-mentioned anolyte compartment and will come out from above-mentioned anolyte compartment of electrodialysis device supplies to the path the above-mentioned surge chamber.

According to the 11st technical scheme of the present invention, provide a kind of electrodialysis device that possesses the cathode compartment that has the anodic anolyte compartment and have negative electrode.This electrodialysis device possesses: desalting chamber, and from the processed water that is supplied to, remove the 1st object ion and the 2nd object ion, thereby generate the treating water that has reduced above-mentioned the 1st object ion and above-mentioned the 2nd object ionic concentration; The 1st concentration compartments will concentrate from the 1st object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the 1st condensed water that has improved the 1st object ionic concentration; Surge chamber cuts off, so that the 1st object ion in the above-mentioned processed water can not be fed directly to the above-mentioned anolyte compartment from above-mentioned the 1st concentration compartments; The 2nd concentration compartments will concentrate from the 2nd object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the 2nd condensed water that has improved the 2nd object ionic concentration.In addition, at least a portion with the outflow water that pure water is supplied to the path in the above-mentioned anolyte compartment and will come out from above-mentioned anolyte compartment of electrodialysis device supplies to the path above-mentioned the 1st concentration compartments.

According to the 12nd technical scheme of the present invention, provide a kind of electrodialysis device that possesses the cathode compartment that has the anodic anolyte compartment and have negative electrode.This electrodialysis device possesses: desalting chamber, and from the processed water that is supplied to, remove the 1st object ion and the 2nd object ion, thereby generate the treating water that has reduced above-mentioned the 1st object ion and above-mentioned the 2nd object ionic concentration; The 1st concentration compartments will concentrate from the 1st object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the 1st condensed water that has improved the 1st object ionic concentration; Surge chamber cuts off, so that the 1st object ion in the above-mentioned processed water can not be fed directly to the above-mentioned anolyte compartment from above-mentioned the 1st concentration compartments; The 2nd concentration compartments will concentrate from the 2nd object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the 2nd condensed water that has improved the 2nd object ionic concentration.In addition, at least a portion with the outflow water that pure water is supplied to the path in the above-mentioned anolyte compartment and will come out from above-mentioned anolyte compartment of electrodialysis device supplies to path above-mentioned the 1st concentration compartments via above-mentioned surge chamber.

According to the 13rd technical scheme of the present invention, provide a kind of electrodialysis device that possesses the cathode compartment that has the anodic anolyte compartment and have negative electrode.This electrodialysis device possesses: desalting chamber, and from the processed water that is supplied to, remove the object ion, thereby generate the treating water that has reduced this object ionic concentration; The concentration compartments will concentrate from the object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the condensed water that has improved this object ionic concentration; Surge chamber cuts off, so that the object ion in the above-mentioned processed water can not be fed directly to the above-mentioned anolyte compartment from above-mentioned concentration compartments.In addition, at least a portion with the outflow water that pure water is supplied to the path in the above-mentioned surge chamber and will come out from above-mentioned surge chamber of electrodialysis device supplies to the path the above-mentioned concentration compartments.

At least a portion that above-mentioned electrodialysis device also can also possess the outflow water that will come out from above-mentioned surge chamber is mixed into the path above-mentioned processed water or the above-mentioned treating water.

According to the 14th technical scheme of the present invention, provide a kind of electrodialysis device that possesses the cathode compartment that has the anodic anolyte compartment and have negative electrode.This electrodialysis device possesses: desalting chamber, and from the processed water that is supplied to, remove the 1st object ion and the 2nd object ion, thereby generate the treating water that has reduced above-mentioned the 1st object ion and above-mentioned the 2nd object ionic concentration; The 1st concentration compartments will concentrate from the 1st object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the 1st condensed water that has improved the 1st object ionic concentration; Surge chamber cuts off, so that the 1st object ion in the above-mentioned processed water can not be fed directly to the above-mentioned anolyte compartment from above-mentioned the 1st concentration compartments.In addition, the electrodialysis device also possesses: the 2nd concentration compartments will concentrate from the 2nd object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the 2nd condensed water that has improved the 2nd object ionic concentration.And then the electrodialysis device has: the 1st cationic exchange membrane is located between above-mentioned anolyte compartment and the above-mentioned surge chamber; The 1st anion-exchange membrane is located between above-mentioned cathode compartment and above-mentioned the 2nd concentration compartments; The 2nd cationic exchange membrane is located between above-mentioned surge chamber and above-mentioned the 1st concentration compartments; The 2nd anion-exchange membrane is located between above-mentioned the 1st concentration compartments and the above-mentioned desalting chamber; The 3rd cationic exchange membrane is located between above-mentioned desalting chamber and above-mentioned the 2nd concentration compartments.

According to the 15th technical scheme of the present invention, provide a kind of electrodialysis device that possesses the cathode compartment that has the anodic anolyte compartment and have negative electrode.This electrodialysis device possesses: desalting chamber, and from the processed water that is supplied to, remove the 1st object ion and the 2nd object ion, thereby generate the treating water that has reduced above-mentioned the 1st object ion and above-mentioned the 2nd object ionic concentration; The 1st concentration compartments will concentrate from the 1st object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the 1st condensed water that has improved the 1st object ionic concentration; Surge chamber cuts off, so that the 1st object ion in the above-mentioned processed water can not be fed directly to the above-mentioned anolyte compartment from above-mentioned the 1st concentration compartments.In addition, the electrodialysis device also possesses: the 2nd concentration compartments will concentrate from the 2nd object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the 2nd condensed water that has improved the 2nd object ionic concentration; The ion supply chamber will have the polar ion opposite with the 2nd object ion in the above-mentioned processed water and supply in above-mentioned the 2nd concentration compartments.And then the electrodialysis device has: the 1st cationic exchange membrane is located between above-mentioned anolyte compartment and the above-mentioned surge chamber; The 1st anion-exchange membrane is located between above-mentioned cathode compartment and the above-mentioned ion supply chamber; The 2nd cationic exchange membrane is located between above-mentioned surge chamber and above-mentioned the 1st concentration compartments; The 2nd anion-exchange membrane is located between above-mentioned the 1st concentration compartments and the above-mentioned desalting chamber; The 3rd cationic exchange membrane is located between above-mentioned desalting chamber and above-mentioned the 2nd concentration compartments; The 3rd anion-exchange membrane is located between above-mentioned the 2nd concentration compartments and the above-mentioned ion supply chamber.

According to the 16th technical scheme of the present invention, provide a kind of electrodialysis device that possesses the cathode compartment that has the anodic anolyte compartment and have negative electrode.This electrodialysis device possesses: a plurality of chambers structure, and it is made of a plurality of chambers; At least 1 multipole chamber with electrode; The 1st cationic exchange membrane is located between the structure of above-mentioned anolyte compartment and above-mentioned chamber; The 1st anion-exchange membrane is located between the structure of above-mentioned cathode compartment and above-mentioned chamber; The 2nd anion-exchange membrane is located at the above-mentioned anode side of above-mentioned multipole chamber; The 2nd cationic exchange membrane is located at the above-mentioned cathode side of above-mentioned multipole chamber.Above-mentioned multipole chamber is configured between the structure of above-mentioned a plurality of chambers, and is filled with ion exchanger.Above-mentioned chamber structure possesses: desalting chamber, and from the processed water that is supplied to, remove the 1st object ion and the 2nd object ion, thereby generate the treating water that has reduced above-mentioned the 1st object ion and above-mentioned the 2nd object ionic concentration; The 1st concentration compartments will concentrate from the 1st object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the 1st condensed water that has improved the 1st object ionic concentration; Surge chamber cuts off, so that the 1st object ion in the above-mentioned processed water can not be fed directly to above-mentioned anolyte compartment or the above-mentioned multipole chamber from above-mentioned the 1st concentration compartments.In addition, the chamber structure also possesses: the 2nd concentration compartments will concentrate from the 2nd object ion the above-mentioned processed water that above-mentioned desalting chamber shifts, thereby generates the 2nd condensed water that has improved the 2nd object ionic concentration; The ion supply chamber will have the polar ion opposite with the 2nd object ion in the above-mentioned processed water and supply in above-mentioned the 2nd concentration compartments.In addition, the electrodialysis device possesses pure water is supplied to path in above-mentioned anolyte compartment and the above-mentioned multipole chamber.And then the chamber structure has: the 3rd cationic exchange membrane is located between above-mentioned surge chamber and above-mentioned the 1st concentration compartments; The 3rd anion-exchange membrane is located between above-mentioned the 1st concentration compartments and the above-mentioned desalting chamber; The 4th cationic exchange membrane is located between above-mentioned desalting chamber and above-mentioned the 2nd concentration compartments; The 4th anion-exchange membrane is located between above-mentioned the 2nd concentration compartments and the above-mentioned ion supply chamber.

Above-mentioned processed water preferably contains the draining of fluorine.In addition, preferred regulate the water yield that supplies to the pure water in above-mentioned anolyte compartment or the above-mentioned cathode compartment so that from above-mentioned anolyte compartment or the fluorine concentration of the outflow water that comes out of above-mentioned cathode compartment be below the 1mg-F/L.

Preferably in above-mentioned anolyte compartment and above-mentioned cathode compartment, be filled with ion exchanger.In addition, preferably in each chamber, be filled with cation exchange fibre material that contacts with above-mentioned cationic exchange membrane or the anion exchanging fiber material that contacts with above-mentioned anion-exchange membrane.

According to the 17th technical scheme of the present invention, provide a kind of drainage processing method that utilizes the electrodialysis device to handle the draining that contains ammonium ion and fluorine at least.Thus, from above-mentioned draining, remove ammonium ion and fluorine, thereby generate the treating water of the concentration that has reduced ammonium ion and fluorine, generate the 1st condensed water and the 2nd condensed water that has improved the concentration of ammonium ion of the concentration that has improved fluorine simultaneously.

According to the 18th technical scheme of the present invention, provide a kind of drainage processing method that utilizes the electrodialysis device to handle to contain at least the draining of the metal ion that forms metal hydroxides mud and fluorine.Thus, from above-mentioned draining, remove above-mentioned metal ion and fluorine, thereby generate the treating water of the concentration that has reduced above-mentioned metal ion and fluorine, generate the 1st condensed water and the 2nd condensed water that has improved the concentration of above-mentioned metal ion of the concentration that has improved fluorine simultaneously.

Here, also the draining that contains hydrogen peroxide and fluorine at least can be carried out hydrogen peroxide decomposition and handle, and the draining after the above-mentioned hydrogen peroxide decomposition processing is supplied in the above-mentioned electrodialysis device.In addition, the fluorine concentration of above-mentioned draining is preferably above 1mg/L but 10, below the 000mg/L.And then the fluorine concentration of above-mentioned treating water is preferably and is lower than 1mg/L.In addition, also at least a portion of above-mentioned the 1st condensed water can be supplied in the fluorine renewable resources device, with the fluorine in the above-mentioned draining as Calcium Fluoride (Fluorspan) (CaF ₂) reclaim.

In addition, according to the importing purpose of electrodialysis device, the fluorine concentration that also can make treating water is more than the 1mg/L.Be discharged under the outside situation no longer utilizing treating water, as long as be made as below the 8mg/L that discharges benchmark just passable.Therefore, the fluorine concentration for the treatment of water can be maintained about 5mg/L, become than fluorine concentration is maintained and be lower than 1mg/L and turn round more energy-conservation method of operation by the revolution electric current of regulating the electrodialysis groove.

In addition,, can the fluorine condensed water not supplied in the fluorine renewable resources device yet, and supply in the coagulative precipitation equipment of processing mode in the past according to the other importing purpose of electrodialysis device.Even if in this case, and will directly carry out coagulative precipitation as the fluorine-containing draining of processed water and handle and to compare, the usage quantity that needed chemical reagent is handled in coagulative precipitation also can reduce, thereby has the advantage that the amount of the mud that is produced reduces.In addition, reduce owing to being concentrated the wastewater flow rate that makes process object, so also have the advantage that the scale of sewage treatment equipment can be less.For example, by the fluorine-containing draining simmer down to 1000mg/L with 10mg/L, water displacement becomes 1/100th, and it is about 1/100th that the requirement of the needed flocculation agent of coagulative precipitation that injects corresponding to water displacement becomes, and the result can significantly reduce the amount of the mud of generation.

In addition, also can obtain ammonium ion and fluorion all are concentrated in fluorine condensed water the identical liquid from the fluorine-containing draining that contains ammonium ion.This be because, general when carrying out the renewable resources of fluorine, if in the fluorine condensed water, contain ammonium ion, then can hinder the reaction that is used for carrying out the fluorine renewable resources, reaction efficiency reduces, but when the fluorine condensed water being carried out the coagulative precipitation processing, even exist ammonium ion also can not bring influence to reaction efficiency.

According to the 19th technical scheme of the present invention, a kind of fluorine treatment system is provided, it possesses: above-mentioned electrodialysis device; Fluorine renewable resources device, the fluorine condensed water that is used for obtaining from above-mentioned electrodialysis device reclaims as Calcium Fluoride (Fluorspan).

According to the 20th technical scheme of the present invention, a kind of fluorine treatment system is provided, it possesses: above-mentioned electrodialysis device; Cyclator, the water that is used for comprising at least a portion of the fluorine condensed water that is obtained by above-mentioned electrodialysis device carries out the coagulative precipitation processing.

According to the 21st technical scheme of the present invention, a kind of water circulation system is provided, it possesses: above-mentioned electrodialysis device; Water Purifiers is that former water is made pure water with the treating water that obtains from above-mentioned electrodialysis device.

According to the 22nd technical scheme of the present invention, a kind of water circulation system is provided, it possesses: above-mentioned electrodialysis device; The device of removing the evil; The draining of the above-mentioned device of removing the evil is supplied to path in the above-mentioned electrodialysis device; The part of the treating water that will be obtained by above-mentioned electrodialysis device supplies to the path in the above-mentioned device of removing the evil.

According to the 23rd technical scheme of the present invention, a kind of fluorine treatment system is provided, it possesses: above-mentioned electrodialysis device; Solid-liquid separation mechanism is used to contain at least the solid-liquid separation of the draining of fluorine; To carry out the draining after the solid-liquid separation by above-mentioned solid-liquid separation mechanism and supply to path in the above-mentioned electrodialysis device.

According to the 24th technical scheme of the present invention, a kind of fluorine treatment system is provided, it possesses: above-mentioned electrodialysis device; Separating organic matters mechanism is used to contain at least the separating organic matters of the draining of fluorine; To carry out the draining after the separating organic matters by above-mentioned separating organic matters mechanism and supply to path in the above-mentioned electrodialysis device.

Preferred embodiment as an example, contrasting explanation by the following stated with illustrated accompanying drawing with of the present invention, above-mentioned purpose of the present invention and other purposes and effect can become clear.

Description of drawings

Fig. 1 is the synoptic diagram of structure of the electrodialysis device of expression the 1st embodiment of the present invention.

Fig. 2 is the synoptic diagram of the electrodialysis groove of presentation graphs 1.

Fig. 3 is the synoptic diagram of structure of the electrodialysis device of expression the 2nd embodiment of the present invention.

Fig. 4 is the synoptic diagram of structure of the electrodialysis device of expression the 3rd embodiment of the present invention.

Fig. 5 is the synoptic diagram of structure of the electrodialysis device of expression the 4th embodiment of the present invention.

Fig. 6 is the synoptic diagram of the electrodialysis groove of presentation graphs 5.

Fig. 7 is the synoptic diagram of structure of the electrodialysis device of expression the 5th embodiment of the present invention.

Fig. 8 is the synoptic diagram of the electrodialysis groove of presentation graphs 7.

Fig. 9 is the synoptic diagram of structure of the electrodialysis device of expression the 6th embodiment of the present invention.

Figure 10 is the synoptic diagram of the electrodialysis groove of presentation graphs 9.

Figure 11 is the synoptic diagram of structure of the electrodialysis device of expression the 7th embodiment of the present invention.

Figure 12 is the synoptic diagram of the electrodialysis groove of expression Figure 11.

Figure 13 is the synoptic diagram of electrodialysis groove of the electrodialysis device of expression the 8th embodiment of the present invention.

Figure 14 is the concept map of representing an example of the fluorine treatment system after electrodialysis device of the present invention and the combination of fluorine renewable resources device.

Figure 15 is that expression is with electrodialysis device of the present invention and CaF ₂The concept map of one example of the fluorine treatment system after the displacement apparatus combination.

Figure 16 is that expression is with electrodialysis device of the present invention and CaF ₂The concept map of one example of the fluorine treatment system after the crystallization apparatus combination.

Figure 17 is the concept map of representing an example of the fluorine treatment system after electrodialysis device of the present invention and the cyclator combination.

Figure 18 is the concept map of an example of the fluorine treatment system after the electrodialysis device of the present invention and the device of removing the evil are made up in expression.

Figure 19 is the concept map of representing an example of the fluorine treatment system after electrodialysis device of the present invention and the activated carbon adsorption layer combination.

Figure 20 is the concept map of representing an example of the fluorine treatment system after electrodialysis device of the present invention and the vacuum distillation apparatus combination.

Embodiment

Below, referring to figs. 1 through Figure 20 the embodiment of electrodialysis device of the present invention is explained.In addition, in Figure 20, give identical label and the repetitive description thereof will be omitted at Fig. 1 for identical or suitable textural element.

Fig. 1 is the synoptic diagram of structure of the electrodialysis device of expression the 1st embodiment of the present invention.As shown in Figure 1, this electrodialysis device possess and have anolyte compartment 10, the electrodialysis groove 1 of surge chamber 20, concentration compartments 30, desalting chamber 40, concentration compartments 21, cathode compartment 50.In addition, the electrodialysis device possesses: via pump 70 pure water is supplied to utmost point liquid case 71 in anolyte compartment 10 and the cathode compartment 50, via pump 72 buffered water supplied to the buffer tank 73 in surge chamber 20 and the concentration compartments 21 and via pump 74 condensed water supplied to concentrated water tank 75 in the concentration compartments 30.

10 internal configuration has anode 2 in the anolyte compartment, in the internal configuration of cathode compartment 50 negative electrode 3 is arranged.Desalting chamber 40 removes fluorion and generates the treating water that has reduced fluorine concentration from the former water (processed water) that contains fluorine.In addition, surge chamber 20 cuts off so that the fluorion in the former water (object ion) can not be fed directly to the anolyte compartment 10 from concentration compartments 30.And then concentration compartments 30 will generation have improved the condensed water of fluorinion concentration from the fluorion the former water that desalting chamber 40 shifts is concentrated.

Fig. 2 is the synoptic diagram of the electrodialysis groove 1 of presentation graphs 1.As shown in Figure 2, separate anolyte compartment 10 and a kind of cationic exchange membrane CM1 that surge chamber 20 is used as ion-exchange membrane, and surge chamber 20 is separated with a kind of cationic exchange membrane CM2 that concentration compartments 30 is used as ion-exchange membrane.In addition, separate concentration compartments 30 and a kind of anion-exchange membrane AM1 that desalting chamber 40 is used as ion-exchange membrane, and separate concentration compartments 21 and a kind of cationic exchange membrane CM3 that desalting chamber 40 is used as ion-exchange membrane.In addition, cathode compartment 50 is separated with a kind of anion-exchange membrane AM2 that concentration compartments 21 is used as ion-exchange membrane.In addition, in Fig. 2, the diagram of sealing member that is positioned at the both sides of ion-exchange membrane is omitted.

In anolyte compartment 10, be filled with a kind of cationic exchange non-woven fabrics CF1 as ion exchanger.In surge chamber 20, be filled with a kind of cationic exchange non-woven fabrics CF2, as a kind of cationic exchange dividing plate (spacer) CS1 of ion exchanger, as a kind of cationic exchange non-woven fabrics CF3 of ion exchanger as ion exchanger.The ion-exchange non-woven fabrics is owing to be by the thin and ion exchanger of the non-woven fabrics shape that the bigger fiber of surface-area constitutes densely, though, have the pressure-losses to become big problem under the situation in being filled in the electrodialysis groove so ionic capturing ability and transmissibility are higher.On the other hand, the ion-exchange dividing plate is to import ion exchanging function on the surface of normally used netted dividing plate in electrodialysis groove in the past to form, the favorable dispersity of water, and the pressure-losses is lower, but the lower problem of ionic capturing ability is arranged.In the electrodialysis groove 1 of present embodiment, fill ion-exchange non-woven fabrics and ion-exchange dividing plate by combination, can be at the state decline low pressure loss of keeping ionic capturing ability and transmissibility higher.

In concentration compartments 30, be filled with a kind of cationic exchange non-woven fabrics CF4, as a kind of cationic exchange dividing plate CS2 of ion exchanger, as a kind of anionresin non-woven fabrics AF1 of ion exchanger as ion exchanger.In desalting chamber 40, be filled with a kind of anionresin non-woven fabrics AF2, as a kind of anionresin dividing plate AS1 of ion exchanger, as a kind of cationic exchange non-woven fabrics CF5 of ion exchanger as ion exchanger.

In concentration compartments 21, be filled with a kind of cationic exchange non-woven fabrics CF6, as a kind of cationic exchange dividing plate CS3 of ion exchanger with as a kind of anionresin non-woven fabrics AF3 of ion exchanger as ion exchanger.In cathode compartment 50, be filled with a kind of anionresin non-woven fabrics AF4 as ion exchanger.

To supply to as the pure water of utmost point liquid anolyte compartment 10 and the cathode compartment 50 from utmost point liquid case 71.The 10 outflow water that come out from the anolyte compartment will be because fluorinion concentration than pure water height, will all be measured so be not recycled in the present embodiment in the utmost point liquid case 71 supplies in the buffer tank 73.The outflow water that comes out from cathode compartment 50 is because fluorinion concentration is very thin usually, and experimental verification is the concentration level roughly the same with pure water, so, in the present embodiment, be recycled in the utmost point liquid case 71 for supply utmost point liquid.In addition, for the 10 outflow water that come out, also can make part or all amount is recycled to structure in the utmost point liquid case 71 from the anolyte compartment.In addition, also can make the outflow water supply of will come out to the structure that concentrates the water tank 75 from anolyte compartment 10.

In addition, from buffer tank 73 buffered water is supplied to surge chamber 20 and the concentration compartments 21.The outflow water that comes out from surge chamber 20 and concentration compartments 21 is fed into buffer tank 73 and the concentrated water tank 75.In addition, in the present embodiment, a part of having made the outflow water that will come out from surge chamber 20 and concentration compartments 21 supplies to the structure that concentrates the water tank 75, but the whole amounts with this outflows water also can made supply to the structure in the concentrated water tank 75.

In addition, from concentrating water tank 75 condensed water is supplied to the concentration compartments 30.The outflow water that comes out from concentration compartments 30 is except being removed as condensed water, and a part is fed into and concentrates in the water tank 75.

Supply with former water for desalting chamber 40, the outflow water that comes out from desalting chamber 40 is removed as treating water.

By such structure, the hydrogen ion that the electric decomposition reaction by water in anolyte compartment 10 generates carries out ionic conduction on cation exchange column CF1, CM1, CF2, CS1, CF3, CM2, CF4, CS2, can arrive concentration compartments 30 via surge chamber 20.Thereby, be applied to the ionic concn that voltage on anolyte compartment 10 and the surge chamber 20 does not exist with ... anolyte and buffered water, can keep lowlyer.

Contain under the situation of anionic water in the electrodialysis processing, the negatively charged ion in the former water is concentrated in the condensed water.Usually, cationic exchange membrane CM2, the CM1 that the negatively charged ion that is concentrated can see through anode 2 sides hardly for example leak in surge chamber 20 or the anolyte compartment 10, but under concentrating the situation that likes fluorion, the part that the fluorion in the condensed water takes place sometimes is arranged in than concentration compartments 30 more by the surge chamber 20 of anode 2 sides or the phenomenon of anolyte compartment 10 through concentration compartments 30 is arrived with the cationic exchange membrane CM2 of surge chamber 20 separations.

In the present embodiment, by said structure,, the fluorion that leaks into the anolyte compartment 10 from surge chamber 20 can be discharged to outside the anolyte compartment 10, thereby the fluorine concentration of anolyte compartment 10 is maintained very low value for anolyte compartment 10 supply pure water always.In addition, can suppress the electrode corrosion that fluorine brings.

In addition, for the fluorine concentration in the surge chamber 20, also can be by will be in the buffered water of buffer tank 73 and will leak into the outside that fluorion the surge chamber 20 is discharged to surge chamber 20 from concentration compartments 30 from the outflow water supply of anolyte compartment 10.Thus, though concentration ratio anolyte compartment 10 is high slightly, the fluorine concentration of surge chamber 20 can be maintained lower value.In addition, because by outflow water supply condensed water, so can reduce the amount of the supply pure water that concentrated water tank 75 is appended from surge chamber 20 and concentration compartments 21.

In addition, owing to use the supplementary feed of pure water, so the fluorine concentration in the supplementary feed can not change or improves because of operating condition as utmost point liquid.Therefore, no matter operating condition how, always the fluorine concentration of anolyte compartment 10 can both be maintained very low value.In addition, can prevent the corrosion of anode 2 more reliably.Here, be situation about being equal to pure water etc. in the water quality of the treating water of electrodialysis device, can replace pure water and use under the situation for the treatment of water, also can replace pure water and use treating water.

In addition, because by outflow water supply buffered water, be discharged to the amount of water of outside of device and the amount that is appended to the supply pure water the buffered water so can reduce from the anolyte compartment 10 from anolyte compartment 10.Particularly, if will supply in the buffer tank 73, then can make from the anolyte compartment 10 to be discharged to the amount of water of device outside and the amount vanishing that is appended to the supply pure water the buffered water from whole amounts of the outflow water of anolyte compartment 10.

In addition, because by outflow water supply condensed water, so can reduce the amount of the supply pure water that is appended in the condensed water and the amount that is discharged to the water of device outside from surge chamber 20 and concentration compartments 21 from surge chamber 20 and concentration compartments 21.Particularly, under the situation of using whole amounts of replenishing condensed water from the outflow water of surge chamber 20 and concentration compartments 21, can make the amount of the supply pure water that is appended in the condensed water and the amount vanishing that is discharged to the water of device outside from surge chamber 20 and concentration compartments 21.

Kind as the draining of discharging from electrodialysis groove 1, be under zero the situation in the amount of the water of the outside that is discharged to device from anolyte compartment 10 and the amount that is discharged to the water of device outside from surge chamber 20 and concentration compartments 21, become two systems that have only treating water and condensed water, it is complicated that piping system can not become.Balance fluorine concentration in anolyte compartment 10, surge chamber 20 and the concentration compartments 21 can by adjusting supply to the amount of the utmost point liquid in anolyte compartment 10 and the cathode compartment 50 and supply to surge chamber 20 and concentration compartments 21 in the amount of buffered water at random regulate.In addition, in embodiment shown in Figure 1, also at least a portion of utmost point liquid and/or buffered water can be mixed with former water or treating water.

Fig. 3 is the synoptic diagram of structure of the electrodialysis device of expression the 2nd embodiment of the present invention.The electrodialysis device of present embodiment has the structure same basically with the electrodialysis device of the 1st embodiment, but different with the electrodialysis device of the 1st embodiment in the following areas.

From buffer tank 73 buffered water is only supplied to the surge chamber 20, do not supply with for concentration compartments 21.Replace in this, the outflow water supply that will come out from cathode compartment 50 is to concentration compartments 21.In addition, the 21 outflow water that come out are fed into the utmost point liquid case 71 for supply utmost point liquid from the concentration compartments.

The positively charged ion that exists in the former water is concentrated in the concentration compartments 21 adjacent to cathode compartment 50, but is judging that the positively charged ion after concentrating can not bring to the handling property of electrodialysis device under the dysgenic situation, can use structure as shown in Figure 3.In addition, can certainly be to buffer tank 73 with the outflow water supply of coming out from concentration compartments 21.By such structure, also can bring into play effect of the present invention.

Fig. 4 is the synoptic diagram of structure of the electrodialysis device of expression the 3rd embodiment of the present invention.The electrodialysis device of present embodiment has the structure same basically with the electrodialysis device of the 1st embodiment, but different with the electrodialysis device of the 1st embodiment in the following areas.

From buffer tank 73 buffered water is only supplied to the surge chamber 20, do not supply with for concentration compartments 21.Replace in this, will supply to as the pure water of utmost point liquid anolyte compartment 10 and the concentration compartments 21 from utmost point liquid case 71.In addition, the outflow water that comes out from concentration compartments 21 is fed into the cathode compartment 50 adjacent to concentration compartments 21.By such structure, also can bring into play effect of the present invention.

Fig. 5 is the synoptic diagram of structure of the electrodialysis device of expression the 4th embodiment of the present invention.Fig. 6 is the synoptic diagram of the electrodialysis groove 101a of presentation graphs 5.The electrodialysis device of present embodiment has the structure same basically with the electrodialysis device of the 1st embodiment, but use adjacent to cathode compartment 50, be supplied to buffered water (Fig. 1), utmost point liquid (Fig. 3) or pure water (Fig. 4) concentration compartments 21 different with the electrodialysis device of the 1st embodiment on as concentration compartments's 31 this point that in Fig. 5, are supplied to condensed water.By such structure, also can bring into play effect of the present invention.

Fig. 7 is the synoptic diagram of structure of the electrodialysis device of expression the 5th embodiment of the present invention.Fig. 8 is the synoptic diagram of the electrodialysis groove 101b of presentation graphs 7.The electrodialysis device of present embodiment has the structure same basically with the electrodialysis device of the 1st embodiment, but has also appended on concentration compartments 30 and desalting chamber's 40 this point different with the electrodialysis device of the 1st embodiment between the desalting chamber 40 of Fig. 1 and concentration compartments 30.By such structure, also can bring into play effect of the present invention.In addition, also can be same with the situation of Fig. 5, will use as concentration compartments 31 adjacent to the concentration compartments 21 of cathode compartment 50, condensed water is supplied in this concentration compartments 31.

Fig. 9 is the synoptic diagram of structure of the electrodialysis device of expression the 6th embodiment of the present invention.This electrodialysis device and electrodialysis device shown in Figure 1 are same, can be prevented anodic corrosive effect, even and also hydrofluoric acid and metal ion can be concentrated individually under as the situation of object in the hydrofluoric acid draining that will contain metal ion.And, because metal ion is not to separate as the oxyhydroxide of separating out but as deliquescent muriate to concentrate, so can avoid fault such as separate out in the electrodialysis groove.

As shown in Figure 9, the electrodialysis device possess and have anolyte compartment 210, the electrodialysis groove 201 of surge chamber 220, sour concentration compartments 230, desalting chamber 240, alkali concentration compartments 231, sour supply chamber 260, multipole chamber 261, surge chamber 220, sour concentration compartments (the 1st concentration compartments) 230, desalting chamber 240, alkali concentration compartments (the 2nd concentration compartments) 231, sour supply chamber (ion supply chamber) 260, cathode compartment 250.Like this, in the present embodiment, clip multipole chamber 261 and be respectively equipped with surge chamber 220, sour concentration compartments 230, desalting chamber 240, alkali concentration compartments 231, sour supply chamber 260 in both sides.

In addition, as shown in Figure 9, the electrodialysis device possesses: via pump 270 pure water is supplied to utmost point liquid case 271 in anolyte compartment 210 and the cathode compartment 250, via pump 272 buffered water supplied to buffer tank 273 in the surge chamber 220, via pump 274 sour condensed water supplied to acid in the sour concentration compartments 230 and concentrate water tank 275, via pump 276 the alkali condensed water supplied to alkali in the alkali concentration compartments 231 and concentrate water tank 277 and via pump 278 water supply is supplied with in acid and supplied with water tank 279 to the acid in the sour supply chamber 260.

In addition, the electrodialysis device possesses and via pump 280 the sour stoste of HCl etc. is supplied to acid and supply with the sour stoste case 281 in the water tank 279 and measure the pH watch-dog 282 that the pH of water tank 279 is supplied with in acid.And then the electrodialysis device possesses via pump 283 raw water box 284 and will the remove the evil draining (processed water that contain fluorine) of former water supply in the desalting chamber 240 is supplied to pump 287 in the raw water box 284 via gac 285 and membrane cartridge formula strainer (cartridgefilter) 286.

210 internal configuration has anode 202 in the anolyte compartment, disposes negative electrode 203 in the inside of cathode compartment 250.In addition, the internal configuration in multipole chamber 261 has electrode 204.Desalting chamber 240 removes fluorion (the 1st object ion) and calcium ion (the 2nd object ion) and generates the treating water that has reduced fluorine concentration and calcium ion concn from former water (processed water).In addition, surge chamber 220 cuts off, so that the fluorion in the former water can not be fed directly to the anolyte compartment 210 from sour concentration compartments 230.And then sour concentration compartments 230 will generation have improved (the 1st) condensed water of fluorinion concentration from the fluorion the former water that desalting chamber 240 shifts is concentrated.In addition, alkali concentration compartments 231 will generation have improved (the 2nd) condensed water of calcium ion concn from the calcium ion the former water that desalting chamber 240 shifts is concentrated.Acid supply chamber 260 will have with draining in the ion of calcium ion opposite polarity supply in the alkali concentration compartments 231.

Figure 10 is the synoptic diagram of the electrodialysis groove 201 of presentation graphs 9.As shown in figure 10, a kind of cationic exchange membrane CM11 that anolyte compartment 210 and surge chamber 220 are used as ion-exchange membrane separates, and surge chamber 220 is separated with a kind of cationic exchange membrane CM12 that sour concentration compartments 230 is used as ion-exchange membrane.Separate acid concentration compartments 230 and a kind of anion-exchange membrane AM11 that desalting chamber 240 is used as ion-exchange membrane, and desalting chamber 240 and a kind of cationic exchange membrane CM13 that alkali concentration compartments 231 is used as ion-exchange membrane separate.A kind of anion-exchange membrane AM12 that is used as ion-exchange membrane between alkali concentration compartments 231 and the sour supply chamber 260 separates, and a kind of anion-exchange membrane AM13 that is used as ion-exchange membrane between sour supply chamber 260 and the multipole chamber 261 separates.In addition, in Figure 10, the diagram of sealing member that is positioned at the both sides of ion-exchange membrane is omitted.

In anolyte compartment 210, be filled with a kind of cationic exchange non-woven fabrics CF11 as ion exchanger.In surge chamber 220, be filled with a kind of cationic exchange non-woven fabrics CF12, as a kind of cationic exchange dividing plate CS11 of ion exchanger with as a kind of cationic exchange non-woven fabrics CF13 of ion exchanger as ion exchanger.

In sour concentration compartments 230, be filled with a kind of cationic exchange non-woven fabrics CF14, as a kind of cationic exchange dividing plate CS12 of ion exchanger, as a kind of anionresin non-woven fabrics AF11 of ion exchanger as ion exchanger.In desalting chamber 240, be filled with a kind of anionresin non-woven fabrics AF12, as a kind of anionresin dividing plate AS11 of ion exchanger, as a kind of cationic exchange non-woven fabrics CF15 of ion exchanger as ion exchanger.

In alkali concentration compartments 231, be filled with a kind of cationic exchange non-woven fabrics CF16, as a kind of cationic exchange dividing plate CS13 of ion exchanger, as a kind of anionresin non-woven fabrics AF13 of ion exchanger as ion exchanger.In sour supply chamber 260, be filled with a kind of anionresin non-woven fabrics AF14, as a kind of anionresin dividing plate AS12 of ion exchanger, as a kind of anionresin non-woven fabrics AF15 of ion exchanger as ion exchanger.

In multipole chamber 261, be filled with a kind of anionresin non-woven fabrics AF16 and cationic exchange non-woven fabrics CF11 as ion exchanger.Structure from the electrode 204 of multipole chamber 261 to the negative electrode 203 of cathode compartment 250 is because identical with above-mentioned structure from cationic exchange non-woven fabrics CF11 to anionresin non-woven fabrics AF16, so omit explanation here.

To supply to as the pure water of utmost point liquid anolyte compartment 210, multipole chamber 261 and the cathode compartment 250 from utmost point liquid case 271.From the anolyte compartment 210, the outflow water that comes out of multipole chamber 261 and cathode compartment 250 is recycled to the utmost point liquid case 271 for supply utmost point liquid.

In addition, from buffer tank 273 buffered water is supplied to the surge chamber 220.The outflow water that comes out from surge chamber 220 is fed into buffer tank 273 and the raw water box 284.The part of the outflow water that in addition, make from the anolyte compartment 210, multipole chamber 261 and cathode compartment 250 comes out is mixed with the outflow water that comes out from this surge chamber 220.

In addition, concentrating water tank 275 from acid supplies to sour condensed water the sour concentration compartments 230.The outflow water that comes out from sour concentration compartments 230 is except being used as the condensed water taking-up, and a part is fed into acid and concentrates in the water tank 275.In addition, concentrating water tank 277 from alkali supplies to the alkali condensed water the alkali concentration compartments 231.The outflow water that comes out from alkali concentration compartments 231 is fed into alkali and concentrates the water tank 277.

From raw water box 284 with former water supply to desalting chamber 240.The outflow water that comes out from desalting chamber 240 is removed as treating water.

Can flow into the multipole chamber 261 from surge chamber 220 owing to worry fluorine, so in the present embodiment,, similarly supply with pure water with anolyte compartment 210 for multipole chamber 261 adjacent to cathode compartment 250 sides of multipole chamber 261.In addition, for the outflow water that comes out from multipole chamber 261, also with from the anolyte compartment the 210 outflow water that come out same, use as the supplementary feed of buffer tank 273.

By such structure, acid and metal ion can be concentrated individually.In addition, form deliquescent salt, can prevent that metal hydroxides etc. from separating out by making metal ion and the negatively charged ion of supplying with by electrophoresis from sour supply chamber 260 from mineral acid.For example, using under the situation of hydrochloric acid as mineral acid, the calcium ion that contains in the former water is concentrated as the higher calcium chloride of solubleness.

Figure 11 is the synoptic diagram of structure of the electrodialysis device of expression the 7th embodiment of the present invention.Figure 12 is the synoptic diagram of the electrodialysis groove 301 of expression Figure 11.This electrodialysis groove 301 is structures of having omitted the sour supply chamber 260 of the negative electrode that is located at alkali concentration compartments 231 203 sides in the electrodialysis groove of above-mentioned the 6th embodiment.Though such structure can be alkalescence with ammonium ion etc. but using under the spissated situation of positively charged ion do not separated out.

Figure 13 is the synoptic diagram of electrodialysis groove 401 of the electrodialysis device of expression the 8th embodiment of the present invention.As shown in figure 13, this electrodialysis groove 401 possesses anolyte compartment 210, surge chamber 220, sour concentration compartments 230, desalting chamber 240, alkali concentration compartments 231, sour supply chamber 260, cathode compartment 250, is that in the electrodialysis groove 201 of above-mentioned the 6th embodiment multipole chamber 261 to be removed and make each chamber only be 1 structure.By such structure, also can bring into play effect of the present invention.

In the respective embodiments described above, the electrodialysis device preferably carries out deciding the electric current running or decides the voltage running, and current density is preferably 10A/dm ²Below, be preferably 3A/dm especially ²Below.The thickness of desalting chamber and concentration compartments is 1～10mm, be preferably 2～4mm.Under the situation of using flaky ion exchangers such as non-woven fabrics shape or dividing plate shape as ion exchanger, the filler piece number and the kind of each chamber can at random be set.Preferably, to each chamber feeding liquid, so that the fluorine concentration of anolyte compartment is to be lower than the fluorine concentration of 1mg/L, surge chamber for being lower than 10mg/L.

As the material of electrode, can use platinum, tantalum, niobium, diamond, SUS etc.In addition, can use on base materials such as titanium, nickel, Meng Naier alloy, Hasiteluoyi hastelloy, heat-resistant corrosion-resistant alloy of chrome-iron-nickel plating the material of platinum, gold, iridium oxide etc. as electrode.

The shape of electrode also can be a tabular, perhaps also can be that to have an iron wire of water-permeable and ventilation property netted etc.Be not particularly limited for the ionic concn in the condensed water, but positively charged ion or anionic concentration are preferably 100～100, in the scope of 000mg/L.Concentration for former water is not particularly limited, but positively charged ion or anionic concentration are preferably in the scope of 5～500mg/L.The concentration of the treating water that obtains in the case can be by setting the value that operating conditions such as current value are adjusted to hope.For example, can access positively charged ion or the treating water of anionic concentration in the scope of 0.01～10mg/L.

As the not special restriction of pure water that supplies in anolyte compartment, cathode compartment, the multipole chamber, can both use by the pure water of the normally used pure water production method manufacturing of those skilled in the art.For example, can use by technique known or its ultrapure waters that makes up the pure water of making or further improved the purity of this pure water such as RO (the anti-film that soaks into), ion exchange method, distillation method, electric desalination processs.In addition, the amount of the pure water that the anode chamber is supplied with most preferably is set at, and makes that the fluorine concentration in the anolyte compartment is lower than 1mg/L.

As the ion exchanger in the anolyte compartment that is filled into above-mentioned electrodialysis device, cathode compartment, multipole chamber, surge chamber, desalting chamber, the concentration compartments, preferably use ion-exchange group is imported to the material that forms in the macromolecular fibre base material by the graft polymerization method.The grafting base material that is made of macromolecular fibre can be a kind of ultimate fibre of polyolefins polymer, for example polyethylene or polypropylene etc. both, also can be the conjugated fibre that is made of the axle core polymer different with sheath portion.As the example of the conjugated fibre that can use, can list use the polyolefins polymer for example polyethylene as the sheath composition, use as the sheath composition use beyond polymer for example polypropylene as the conjugated fibre of the core sheath structure of core composition.Utilize radioactive rays graft polymerization method that ion-exchange group is imported in this complex fiber material and the material that obtains since ion-exchange capacity good, can be fabricated to homogeneous thickness, so be preferred as the example exchanging fiber material that uses with above-mentioned purpose.As the form of ion exchange fiber material, can list and weave cotton cloth and non-woven fabrics etc.

In addition, ion exchanger as the form of the partition component of oblique net etc., with polyolefins polymer system resin for example in the electrodialysis groove oblique net (reticulation) of widely used polyethylene system as base material, utilize radioactive rays graft polymerization method to give the material that ion exchanging function obtains because ion-exchange capacity is good, the favorable dispersity of processed water, so be preferred to it.

In addition, so-called radioactive rays graft polymerization method is to polymer base material irradiation radioactive rays and make it form free radical, monomer is imported to the method in the base material by making monomer and its reaction.Radioactive rays as using in radioactive rays graft polymerization method can list alpha-ray, β ray, gamma-rays, electron beam, ultraviolet ray etc., but preferably use gamma rays or electron beam.In radioactive rays graft polymerization method, the front irradiation graft polymerization method that has pair grafting base material to shine in advance it to be contacted behind the radioactive rays with grafted monomer and react and under base material and monomer coexistence irradiation graft polymerization method in the irradiation radioactive rays, use which kind of method can.

In addition, contact method according to monomer and base material, can list base material is impregnated under the state in the monomer solution carry out polymeric liquid-phase grafting polymerization, base material contacted with monomeric steam carry out polymeric gas phase graft polymerization method, base material is being impregnated into back in the monomer solution is taken out from monomer solution the impregnation gas phase graft polymerization method of in gas phase, reacting etc., use which kind of method can.

Ion-exchange group as importing in fiber base materials such as non-woven fabrics or the dividing plate base material is not particularly limited, and can use various cationic exchange bases or anionresin base etc.For example, as the cationic exchange base, can use Subacidity cation exchange groups such as middle acidic cation exchange group such as strong-acid cation exchange, phosphate, carboxyl such as sulfonic group, as the anionresin base, can use primary amino～strongly basic anion exchange groups such as weakly-basic anion exchange group, quaternary ammonium group such as uncle's amino.Perhaps, also can use and have above-mentioned cationic exchange base and both ion exchangers of anionresin base simultaneously.

In addition, also can use the ion exchanger that has following functional group etc. as the functional group: from imino-acetic acid and sodium salt deutero-functional group thereof, from each seed amino acid for example phenylalanine, Methionin, L-LEU, Xie Ansuan and proline(Pro) with and sodium salt deutero-functional group, from diethanolamine deutero-functional group etc.

As can listing vinylformic acid (AAc), methacrylic acid, Sodium styrene sulfonate (SSS), sodium methallyl sulfonate, sodium allyl sulfonate, sodium vinyl sulfonate, vinyl benzyl trimethyl ammonium chloride (VBTAC), methacrylic acid diethylin ethyl ester, diethylin propyl group acrylamide etc. with the monomer with ion-exchange group of above-mentioned purpose use.

For example, carry out the radioactive rays graft polymerization by using Sodium styrene sulfonate as monomer, can in base material, directly import sulfonic group as strong-acid cation exchange, in addition, by using the vinyl benzyl trimethyl ammonium chloride to carry out the radioactive rays graft polymerization, can in base material, directly import quaternary ammonium group as the strongly basic anion exchange group as monomer.

In addition, as monomer, can list vinyl cyanide, propenal, vinyl pyridine, vinylbenzene, 1-chloro-4-methyl-benzene, glycidyl methacrylate (GMA) etc. with the group that can be converted to ion-exchange group.For example, glycidyl methacrylate can be imported in the base material, then makes sulphonating agent such as S-WAT and its reaction come to import sulfonic group as strong-acid cation exchange in base material by the radioactive rays graft polymerization, perhaps after with the 1-chloro-4-methyl-benzene graft polymerization, base material is immersed in and carries out quaternizedly in the trimethylamine aqueous solution, the quaternary ammonium group as the strongly basic anion exchange group can be imported in the base material thus.

In addition,, make thioether reactant and after forming sulfonium salt, make the reaction of imino-acetic acid sodium, imino-acetic acid sodium base can be imported in the base material as the functional group by after to base material graft polymerization 1-chloro-4-methyl-benzene.Perhaps, at first in base material behind the graft polymerization 1-chloro-4-methyl-benzene, replace chloro with iodine, thereby then make the reaction of imino-acetic acid diethyl ester replace iodine with the imino-acetic acid diethyl-ester group, then make the sodium hydroxide reaction and ester group is transformed to sodium salt, imino-acetic acid sodium base can be imported in the base material as the functional group thus.

In the ion exchanger of above-mentioned various forms, the ion exchange fiber material of non-woven fabrics or form such as weave cotton cloth is particularly preferred.Weave cotton cloth and filamentary material such as non-woven fabrics is compared with the material of forms such as resin ball or oblique net, surface-area is very big, so the import volume of ion-exchange group is bigger, and can be as the resin ball in the micropore of ball inside or macropore, there be ion-exchange group, all ion-exchange groups all are configured on the surface of fiber, so the metal ion in the treating water easily is diffused near the ion-exchange group, is adsorbed by ion-exchange.Thereby, if use ion exchange fiber material, then can further improve removing and organic efficiency of metal ion.

In addition, beyond above-mentioned ion exchange fiber material etc., also can use known ion exchanger resin ball.For example, use with polystyrene with the ball of divinyl benzene crosslinked etc. as substrate resin, thereby it is handled with the such sulphonating agent of sulfuric acid or chlorsulfonic acid and carry out sulfonation sulfonic group is imported in the base material, can access the storng-acid cation exchange resin ball that can use in the respective embodiments described above thus.

Above-mentioned manufacture method is known, and, as the Zeo-karb ball of making by such method, can list the material of selling with the extensive stock name.In addition, also can use the resin ball that has following functional group etc. as the functional group: from imino-acetic acid and sodium salt deutero-functional group thereof, from each seed amino acid for example phenylalanine, Methionin, L-LEU, Xie Ansuan and proline(Pro) with and sodium salt deutero-functional group, from diethanolamine deutero-functional group etc.

Handle the draining that contains ammonium ion and fluorine at least if utilize the electrodialysis device of above-mentioned embodiment, then can from draining, remove ammonium ion and fluorine and generate the treating water of the concentration that has reduced ammonium ion and fluorine, can generate the 1st condensed water of the concentration that has improved fluorine simultaneously and improve the 2nd condensed water of the concentration of ammonium ion.Perhaps, at least contain the metal ion of formation metal hydroxides mud and the draining of fluorine if utilize the electrodialysis device of the respective embodiments described above to handle, then can from draining, remove above-mentioned metal ion and fluorine and generate the treating water of the concentration that has reduced metal ion and fluorine, can generate the 1st condensed water of the concentration that has improved fluorine simultaneously and improve the 2nd condensed water of the concentration of metal ion.

Contain in draining under the situation of hydrogen peroxide and fluorine, also draining can carried out the hydrogen peroxide decomposition treatment and supplied in the electrodialysis device.In addition, the fluorine concentration of draining is preferably above 1mg/L but 10, and below the 000mg/L, the fluorine concentration for the treatment of water is preferably and is lower than 1mg/L.

In addition, above-mentioned electrodialysis device can constitute fluorine treatment system with the combination of fluorine renewable resources device.For example, as shown in figure 14, fluorine-containing draining can be handled with above-mentioned electrodialysis device, will be supplied to by the fluorine condensed water that the electrodialysis device obtains in the fluorine renewable resources device 500, with the fluorine in the draining as Calcium Fluoride (Fluorspan) (CaF ₂) crystal reclaim.

Method of operation or control method as above-mentioned electrodialysis device have following method.At first, the fluorine measurement of concetration mechanism of the fluorine concentration by treating water, fluorine condensed water or former water that measurement obtains by electrodialysis device of the present invention are set (for example measure the Conductivity Meters of electric conductivity or measure the fluorine densitometer of fluorine concentration by the ion electrode method) can monitor handling property.In addition, by in former water line and/or treating water circuit, under meter being set, can carry out the supervision of fluorine load.

In addition, the fluorine concentration controlling organization of the fluorine concentration of control treating water preferably is set, as this fluorine concentration controlling organization, can be that the monitoring value of fluorine concentration, fluorine load or handling property according to former water, treating water or condensed water is automatically regulated to the energising amount of electrodialysis device or the mechanism that automatically regulates the flow of former water by flow control valve.Thus, can realize the automatic control of the fluorine concentration for the treatment of water.In addition, only also can make under the high situation of the value of the fluorine concentration ratio regulation for the treatment of water the structure of just water flowing automatically in the resinbed.In the case, can further improve the stability of water quality treatment.In addition, also can be reduced to the concentration that is lower than prescribed value or treating water by the concentration that the fluorine condensed water detects in fluorine measurement of concetration mechanism and be elevated to situation more than the prescribed value.Thus, breaking of the damage of electrodialysis groove inside, for example ion-exchange membrane etc. can be exported as signal error.

In addition, no matter (the fluorine renewable resources device (CaF for example of the secondary treatment mechanism of fluorine condensed water ₂Crystallization apparatus, make fluorine and calcium carbonate reaction and reclaim the CaF of fluorine ₂Displacement apparatus, cyclator, vacuum distillation apparatus) kind how, by the fluorine concentration of fluorine condensed water is supplied with as stable concentration, can both make the performance of the device that carries out these secondary treatments become stable.

Mechanism as the fluorine concentration of controlling the fluorine condensed water, can be based on the observed value of fluorine measurement of concetration mechanisms such as the Conductivity Meters that is installed on the circuit that the fluorine condensed water flows through or fluorine densitometer, regulate the water yield from the fluorine condensed water of the circuit of fluorine condensed water or concentrated water tank carrying-off (to the pushing quantity of the fluorine condensed water of the unit feeding that carries out secondary treatment) or the mechanism of the supply water yield supplied with to the circuit or the concentrated water tank of fluorine condensed water.In addition, also can be the mechanism that automatically regulates the flow of the energising amount of electrodialysis device and former water.

Here, for the operating condition of the device that makes the secondary treatment of carrying out the fluorine condensed water becomes suitable, for example can consider structure shown below.For example, as shown in figure 15, can with electrodialysis device of the present invention with as the CaF of fluorine renewable resources device ₂Displacement apparatus 501 combinations constitute the fluorine in the draining as CaF ₂The fluorine treatment system that crystal reclaims.The measuring mechanism of the pH value or the α value (value of acid degree) of the fluorine condensed water that is obtained by above-mentioned electrodialysis device can be set, be provided with and inject acid or alkali regulates so that pH value that this value becomes suitable or α value regulating mechanism 502.Thus, can prevent at CaF ₂The dissolving of the lime carbonate grain that uses in the displacement apparatus 501.In addition, the CaF that obtains ₂Crystalline purity improves.

Particularly, have and also mix the situation that has hydrochloric acid, sulfuric acid, nitric acid etc. in the draining of removing the evil except hydrofluoric acid, the acid beyond the hydrofluoric acid has the character of the dissolution of calcium carbonate of making.According to electrodialysis device of the present invention, these acid are arranged also with the spissated situation of hydrofluoric acid.Thereby, even be under the situation of object,, also can prevent the dissolving of lime carbonate by by above-mentioned pH value or α value regulating mechanism 502 pH being uprised or acid degree being reduced in for example fluorine condensed water with the device draining of removing the evil (draining of removing the evil).Be included in from CaF ₂Fluorine in the residual liquid that displacement apparatus 501 is discharged can separate as mud by cyclator 504 to be removed.

Electrodialysis device of the present invention is owing to setting operating condition so that the fluorine concentration for the treatment of water is lower than draining benchmark value 8mg-F/L, so do not need the further coagulative precipitation of this treating water.Thereby, not needing large-scale coagulative precipitation treatment facility, can discharge or Water reuse.For example, as shown in figure 15, the former water by will being utilized as Water Purifiers 505 from the treating water that the electrodialysis device is discharged again etc. can reduce the water usage quantity (the water amount of buying) of facility.

In addition, for example as shown in figure 16, can with electrodialysis device of the present invention with as the CaF of fluorine renewable resources device ₂Crystallization apparatus 506 combinations constitute the fluorine in the draining as CaF ₂The fluorine treatment system that crystal reclaims.In the case, can the fluorine condensed water be adjusted to by pH value or α value regulating mechanism 502 and be suitable for crystalline pH or acid degree.

And then, can be provided with and be adjusted in CaF ₂The calcium cpd addition regulating mechanism 507 of the addition of the calcium cpd (for example calcium chloride or calcium hydroxide) that adds in the crystallization apparatus 506 is regulated so that the addition of calcium cpd becomes suitable according to the observed value that the fluorine measurement of concetration mechanism by the fluorine condensed water obtains.Thus,, also can be adjusted to the addition of the calcium cpd that is adapted to it, can make the CaF that obtains even under the situation of the change of the fluorine concentration in the fluorine condensed water has taken place ₂Crystalline purity and particle diameter become the value of hope.Be included in from CaF ₂Fluorine in the residual liquid that crystallization apparatus 506 is discharged can separate as mud by cyclator 504 to be removed.

In addition, for example as shown in figure 17, electrodialysis device of the present invention and the water that will comprise at least a portion of fluorine condensed water are carried out cyclator 508 combinations that coagulative precipitation is handled, can be with the fluorine in the fluorine condensed water as containing CaF ₂Mud separate and to remove.In the case, even it is very low and be not suitable under the situation that coagulative precipitation handles in the fluorine concentration of fluorine-containing draining, also the concentration of fluorine can be brought up to and be suitable for the concentration that coagulative precipitation is handled, and, because the water yield of fluorine condensed water is lacked than the water yield of fluorine-containing draining, so compare with the situation of fluorine-containing draining directly being carried out the coagulative precipitation processing, can reduce the addition (for example per 1 day usage quantity) of flocculation agent, and can utilize small-scale treatment facility to carry out solid-liquid separation.For example, under situation, the processing water yield of cyclator 508 can be reduced to 1/10th with concentrated 10 times of the fluorine in the fluorine-containing draining.

Contain in fluorine-containing draining under the solid situations such as outstanding absurd creature matter or powder,, also can concentrate from the separation that fluorine is carried out in such draining by these solids are separated in advance.As the draining of removing the evil of the example of such draining.In the device of removing the evil, except PFC gas, also import the gas that contains silica, so produce silica powder in large quantities after the decomposing gas of the device of removing the evil is handled, it is blended in the draining.As the device of removing the evil, can list combustion-type, heating-type etc. and when work, produce the device of draining.

Under the situation of using such device of removing the evil, for example as shown in figure 18, be preferred with the fluorine treatment system that fluorine-containing draining imports in the electrodialysis device via solid-liquid separation mechanisms such as settlement separate grooves 550.In Figure 18, make the solid settlement that contains in the draining, separate as sludge blanket 552.In addition, will go up primary water 554 imports in the electrodialysis device.In the case, in last primary water 554, contain floatability solid situation owing to have, so can import in the electrodialysis device via security filter more micro-ly.In addition, contain under the organic situation in worrying draining, the ion-exchange membrane in the electrodialysis device pollutes because of organism, can import in the electrodialysis device via the activated carbon treatment layer again.

As solid-liquid separation mechanism, can use known all mechanisms, for example except settlement separate groove 550, can use known film (strainer) separation mechanism or centrifuge mechanism etc.The solid substance quantity that contains in draining is under a large amount of situation, preferably to use settlement separate groove 550 as solid-liquid separation mechanism.In addition, in Figure 18, be purpose to the outflow and the circuitous of current of back segment to prevent mud 552, be provided with a plurality of division plates 556.In addition, in the device inside of removing the evil, the situation of mechanism, for example solid-liquid separation tank or strainer that the solids be used for separating oversize particle is set is arranged also, but above-mentioned solid-liquid separation mechanism preferably is arranged on its rear section side in addition.

The treating water of electrodialysis device is reduced fully owing to fluorine concentration, so can also can realize the reduction of water usage quantity as the supply water cycle of the device 558 of removing the evil.In addition, by the part of the treating water of electrodialysis device is carried out draining, can realize that also micro substance accumulates to intrasystem.

Contain in fluorine-containing draining under the organic situation such as tensio-active agent,, also can concentrate from the separation that fluorine is carried out in such draining by these organism are separated in advance.As the example of such draining, can list and come from hydrofluoric acid or the buffered hydrofluoric acid (NH that contains tensio-active agent ₄F) draining and the draining that comes from the device of removing the evil that is supplied to the process water that contains micro-content organism.

Under these circumstances, for example as shown in figure 19, be preferred with the fluorine treatment system that fluorine-containing draining imports in the electrodialysis device via the separating organic matters mechanism of activated carbon adsorption layer 560 grades.As separating organic matters mechanism, except activated carbon adsorption layer, can use known separating organic matters mechanism, for example membrane sepn mechanism etc.In addition, can certainly use known organism to decompose mechanism etc.

In addition, as shown in figure 20, the fluorine condensed water that is obtained by electrodialysis device of the present invention can be improved fluorine concentration by mechanism such as evaporation such as vacuum distillation apparatus 562 water such as grade again.In the case, even be under the situation of 1000～10000mg/L in fluorine condensed water concentration, fluorine concentration also can easily further be brought up to more than 1～10%, so the acid-washing stainless steel purposes that can be used in the steel industry is medium, the purposes of utilizing enlarges again.

[embodiment 1]

Utilize electrodialysis device shown in Figure 1, carrying out with fluorine-containing draining (60mg-F/L) is the fluorine concentration test of object.The specification of electrodialysis device is as follows.

Dialysis area: 6dm ²

Cationic exchange membrane: アスト system corporate system ネオセプ CMB

Anion-exchange membrane: アスト system corporate system ネオセプ AHA

The cationic exchange non-woven fabrics: base material is a polyethylene system non-woven fabrics.The functional group is a sulfonic group.Make by the graft polymerization method.

The anionresin non-woven fabrics: base material is a polyethylene system non-woven fabrics.The functional group is a quaternary ammonium group.Make by the graft polymerization method.

The cationic exchange dividing plate: base material is a polyethylene system inclined hole net.The functional group is a sulfonic group.Make by the graft polymerization method.

The anionresin dividing plate: base material is a polyethylene system inclined hole net.The functional group is a quaternary ammonium group.Make by the graft polymerization method.

Anode: titanium has been implemented electrode behind the platinum coating.The wire netting shape.

Negative electrode: SUS304, the wire netting shape.

And the operating condition of electrodialysis device is as follows.

Current density: 1A/dm ²

The flow of former water: 500ml/min

The supply water yield of anolyte: 25ml/min

The quantity of circulating water of catholyte: 25ml/min

The quantity of circulating water of buffered water: 250ml/min

The buffered water supply water yield to the supply that concentrates water tank: 25ml/min

The quantity of circulating water of condensed water: 250ml/min

As a result, though the fluorine concentration in the concentration compartments is higher, be 1200mg-F/L, the concentration of surge chamber is 5～10mg-F/L, and the concentration of anolyte compartment is for being lower than 1mg-F/L, and the fluorine concentration of anolyte compartment is maintained very low value.Also can confirm not have the anodic corrosion.The fluorine concentration of cathode compartment is very low concentration also for being lower than 1mg-F/L.Also can confirm not have the corrosion of negative electrode.In addition, voltage across poles is about 10V.

[embodiment 2]

Utilize Fig. 3 to arrive electrodialysis device shown in Figure 5, carrying out with fluorine-containing draining (60mg-F/L) is the fluorine concentration test of object.The specification of electrodialysis device is as follows.

Dialysis area: 6dm ²

Cationic exchange membrane: アスト system corporate system ネオセプ CMB

Anion-exchange membrane: アスト system corporate system ネオセプ AHA

Negative electrode: SUS304, the wire netting shape.

In addition, the operating condition of electrodialysis device is as follows.

Current density: 1A/dm ²

The flow of former water: 500ml/min

The supply water yield of anolyte: 25ml/min

The quantity of circulating water of catholyte: 25ml/min

The quantity of circulating water of buffered water: 250ml/min

To concentrating the buffered water supply water yield that water tank is supplied with: 25ml/min

The quantity of circulating water of condensed water: 250ml/min

In these cases, though also be the higher 1200mg-F/L of being about of fluorine concentration in the concentration compartments, the concentration of surge chamber is 5～10mg-F/L, and the concentration of anolyte compartment is for being lower than 1mg-F/L, and the fluorine concentration of anolyte compartment is maintained very low value.The fluorine concentration of cathode compartment all for being lower than 1mg-F/L, is very low concentration in which electrodialysis device.Also can confirm both not had the anodic corrosion also not have the corrosion of negative electrode.

[embodiment 3]

Utilize electrodialysis device shown in Figure 9, the draining of carrying out with the organism (as total organic carbon) of the calcium ion that contains 10mg/L, 3mg/L of removing the evil (60mg-F/L) is the fluorine concentration test of object.The device of removing the evil is to contain the gas of silica and the structure that PFC gas is removed the evil by burn processing.Primary water on after the draining of removing the evil in the present embodiment uses the solid settlement that will contain in the draining of removing the evil by settlement separate groove to separate.In addition, in this experiment, made calcium ion has been carried out spissated structure as hydrochloride in the chamber different with hydrofluoric acid (alkali concentration compartments).In addition, be that two groups of electrodialysis unit are concentrated on 1 group of structure between the push plate, on the border, be provided with multipole chamber.Similarly supply with pure water for multipole chamber and anolyte compartment, the outflow water that comes out from multipole chamber uses as buffered water.Part from the outflow water of surge chamber is mixed with former water.The specification of electrodialysis device is as follows.

Dialysis area: 6dm ²

Cationic exchange membrane: アスト system corporate system ネオセプ CMB

Anion-exchange membrane: アスト system corporate system ネオセプ AHA

Negative electrode: SUS304, the wire netting shape.

Multipole: that titanium has been implemented electrode behind the platinum coating.The wire netting shape.

Membrane cartridge formula strainer: aperture 5 μ m

Gac: granular carbon packing layer

In addition, the operating condition of electrodialysis device is as follows.

Current density: 1A/dm ²

The flow of former water: 1000ml/min

The supply water yield of anolyte: 25ml/min

The supply water yield of multipole liquid: 25ml/min

The quantity of circulating water of catholyte: 25ml/min

The utmost point liquid supply water yield to the buffer tank supply: 50ml/min

The quantity of circulating water of buffered water: 500ml/min

The supply water yield of condensed water: 50ml/min

The quantity of circulating water of condensed water: 500ml/min

In these cases, though also be the higher 1200mg-F/L of being about of fluorine concentration in the sour concentration compartments, the concentration of surge chamber is lower, is 5～10mg-F/L.In addition, the concentration of anolyte compartment and multipole chamber is for being lower than 1mg-F/L, and the fluorine concentration of anolyte compartment and multipole chamber is maintained very low value.In addition, the concentration of cathode compartment is very low concentration for being lower than 1mg-F/L.Also can confirm not have the corrosion of the electrode of anode and multipole chamber, also can confirm not have the corrosion of negative electrode.

[embodiment 4]

Utilize electrodialysis device shown in Figure 11, the fluorine-containing draining of carrying out with the ammonium ion that contains 40mg/L (60mg-F/L) is the fluorine concentration test of object.In addition, in this experiment, made ammonium ion has been concentrated to structure in the chamber different with hydrofluoric acid (alkali concentration compartments).In addition, be that two groups of electrodialysis unit are concentrated on 1 group of structure between the push plate, on the border, be provided with multipole chamber.Similarly supply with pure water for multipole chamber and anolyte compartment, use as buffered water from the outflow water of multipole chamber.Being fed into acid from the part of the outflow water of surge chamber concentrates in the case.The specification of electrodialysis device is as follows.

Dialysis area: 6dm ²

Cationic exchange membrane: アスト system corporate system ネオセプ CMB

Anion-exchange membrane: アスト system corporate system ネオセプ AHA

The cationic exchange non-woven fabrics: base material is a polyethylene system non-woven fabrics.The functional group is a sulfo group.Make by the graft polymerization method.

The cationic exchange dividing plate: base material is a polyethylene system inclined hole net.The functional group is a sulfo group.Make by the graft polymerization method.

Negative electrode: SUS304, the wire netting shape.

In addition, the operating condition of electrodialysis device is as follows.

Current density: 1A/dm ²

The flow of former water: 1000ml/min

The supply water yield of anolyte: 25ml/min

The supply water yield of multipole liquid: 25ml/min

The quantity of circulating water of catholyte: 25ml/min

The utmost point liquid supply water yield to the buffer tank supply: 50ml/min

The quantity of circulating water of buffered water: 500ml/min

Concentrate the buffered water supply water yield that case is supplied with: 50ml/min to acid

The quantity of circulating water of acid or alkali condensed water: 500ml/min

In sour concentration compartments, fluorion is used as hydrofluoric acid and concentrates, and fluorine concentration is higher, be about 1200mg-F/L, but the concentration of surge chamber is lower, is 5～10mg-F/L.In addition, the concentration of anolyte compartment and multipole chamber is for being lower than 1mg-F/L, and the fluorine concentration of anolyte compartment and multipole chamber is maintained very low value.In addition, the concentration of cathode compartment is very low concentration for being lower than 1mg-F/L.In the alkali concentration compartments, it is concentrated with the concentration of about 1000mg/L that ammonium ion is used as ammoniacal liquor.Ammonium ion and fluorion can concentrate individually.Also can confirm not have the corrosion of the electrode of anode and multipole chamber, also can confirm not have the corrosion of negative electrode.

According to the present invention, can not bring electrode corrosion and the fluorine-containing draining of electrodialysis stably.In addition, the fluorine concentration of the treating water behind the fluorine-containing draining electrodialysis is lower, for being lower than 1mg/L, can utilize treating water again.And then, can will contain the fluorine-containing draining electrodialysis of ammonium ion and fluorine condensed water after obtaining ammonium ion separated.In addition, carry out under the electrodialytic situation, can not form metal hydroxides mud and obtain the fluorine condensed water after the separation of metal ions in the fluorine-containing draining that will contain the metal ion that forms metal hydroxides mud.And then, by with electrodialysis the fluorine condensed water after the fluorine-containing draining supply in the fluorine renewable resources device, can be as Calcium Fluoride (Fluorspan) (CaF ₂) reclaim.In addition, the fluorine renewable resources is become be easy to the hydrofluoric acid condensed water and supply to the fluorine renewable resources device by having separated ammonium ion from the fluorine-containing water vent that contains ammonium ion, can be as Calcium Fluoride (Fluorspan) (CaF ₂) reclaim.

In addition, with as with the fluorine in the aqueous solution as Calcium Fluoride (Fluorspan) (CaF ₂) the fluorine renewable resources device that reclaims treating water draining or the draining after the pre-treatment etc. has been carried out in this draining has been utilized under the situation that electrodialysis device of the present invention handles for process object, the fluorine renewable resources rate that can improve fluorine renewable resources device is promptly as the rate of recovery of calcium fluoride crystal.This be because, in fluorine renewable resources device, in the fluorine that obtains about about 10～20% is used as thin hydrofluoric acid draining and discharges, but concentrates with electrodialysis device of the present invention by the fluorine that will wherein contain, and can utilize once more as the former water of fluorine renewable resources device.This be because, fluorine renewable resources device is being under the situation of object with thin hydrofluoric acid draining, renewable resources, promptly as the recovery of calcium fluoride crystal difficulty is being under the situation of object with dense hydrofluoric acid draining, has the character of the sufficient performance of performance.

The present invention is applicable to that with liquid that contains fluorine etc. be the electrodialysis device of process object.

Claims

1. electrodialysis device, it possesses:

The anolyte compartment, it has anode;

Cathode compartment, it has negative electrode;

The object ion is removed by desalting chamber from the processed water that is supplied to, thereby generates the treating water that has reduced this object ionic concentration;

The concentration compartments will concentrate from the object ion the described processed water that described desalting chamber shifts, thereby generates the condensed water that has improved this object ionic concentration;

Pure water is supplied to path in the described anolyte compartment;

At least a portion of the outflow water that will come out from described anolyte compartment supplies to the path the described concentration compartments.

2. electrodialysis device, it possesses:

The anolyte compartment, it has anode;

Cathode compartment, it has negative electrode;

Surge chamber cuts off, so that the object ion in the described processed water can not be fed directly to the described anolyte compartment from described concentration compartments;

Pure water is supplied to path in the described anolyte compartment;

3. electrodialysis device, it possesses:

The anolyte compartment, it has anode;

Cathode compartment, it has negative electrode;

Pure water is supplied to path in the described anolyte compartment;

At least a portion of the outflow water that will come out from described anolyte compartment supplies to the path the described surge chamber.

4. electrodialysis device, it possesses:

The anolyte compartment, it has anode;

Cathode compartment, it has negative electrode;

Pure water is supplied to path in the described anolyte compartment;

At least a portion of the outflow water that will come out from described anolyte compartment supplies to path the described concentration compartments via described surge chamber.

5. electrodialysis device, it possesses:

The anolyte compartment, it has anode;

Cathode compartment, it has negative electrode;

The 1st object ion and the 2nd object ion are removed by desalting chamber from the processed water that is supplied to, thereby generate the treating water that has reduced described the 1st object ion and described the 2nd object ionic concentration;

The 1st concentration compartments will concentrate from the 1st object ion the described processed water that described desalting chamber shifts, thereby generates the 1st condensed water that has improved the 1st object ionic concentration;

The 2nd concentration compartments will concentrate from the 2nd object ion the described processed water that described desalting chamber shifts, thereby generates the 2nd condensed water that has improved the 2nd object ionic concentration;

The ion supply chamber will have the polar ion opposite with the 2nd object ion in the described processed water and supply in described the 2nd concentration compartments;

Pure water is supplied to path in the described anolyte compartment;

At least a portion of the outflow water that will come out from described anolyte compartment supplies to the path described the 1st concentration compartments.

6. electrodialysis device, it possesses:

The anolyte compartment, it has anode;

Cathode compartment, it has negative electrode;

Surge chamber cuts off, so that the 1st object ion in the described processed water can not be fed directly to the described anolyte compartment from described the 1st concentration compartments;

Pure water is supplied to path in the described anolyte compartment;

7. electrodialysis device, it possesses:

The anolyte compartment, it has anode;

Cathode compartment, it has negative electrode;

Pure water is supplied to path in the described anolyte compartment;

8. electrodialysis device, it possesses:

The anolyte compartment, it has anode;

Cathode compartment, it has negative electrode;

Pure water is supplied to path in the described anolyte compartment;

At least a portion of the outflow water that will come out from described anolyte compartment supplies to path described the 1st concentration compartments via described surge chamber.

9. electrodialysis device, it possesses:

The anolyte compartment, it has anode;

Cathode compartment, it has negative electrode;

Pure water is supplied to path in the described anolyte compartment;

10. electrodialysis device, it possesses:

The anolyte compartment, it has anode;

Cathode compartment, it has negative electrode;

Pure water is supplied to path in the described anolyte compartment;

11. an electrodialysis device, it possesses:

The anolyte compartment, it has anode;

Cathode compartment, it has negative electrode;

Pure water is supplied to path in the described anolyte compartment;

12. an electrodialysis device, it possesses:

The anolyte compartment, it has anode;

Cathode compartment, it has negative electrode;

Pure water is supplied to path in the described anolyte compartment;

13. an electrodialysis device, it possesses:

The anolyte compartment, it has anode;

Cathode compartment, it has negative electrode;

Pure water is supplied to path in the described surge chamber;

At least a portion of the outflow water that will come out from described surge chamber supplies to the path the described concentration compartments.

14. an electrodialysis device, it possesses:

The anolyte compartment, it has anode;

Cathode compartment, it has negative electrode;

The 1st cationic exchange membrane is located between described anolyte compartment and the described surge chamber;

The 1st anion-exchange membrane is located between described cathode compartment and described the 2nd concentration compartments;

The 2nd cationic exchange membrane is located between described surge chamber and described the 1st concentration compartments;

The 2nd anion-exchange membrane is located between described the 1st concentration compartments and the described desalting chamber;

The 3rd cationic exchange membrane is located between described desalting chamber and described the 2nd concentration compartments.

15. an electrodialysis device, it possesses:

The anolyte compartment, it has anode;

Cathode compartment, it has negative electrode;

The 1st anion-exchange membrane is located between described cathode compartment and the described ion supply chamber;

The 3rd cationic exchange membrane is located between described desalting chamber and described the 2nd concentration compartments;

The 3rd anion-exchange membrane is located between described the 2nd concentration compartments and the described ion supply chamber.

16. an electrodialysis device, it possesses:

The anolyte compartment, it has anode;

Cathode compartment, it has negative electrode;

A plurality of chambers structure is made of a plurality of chambers;

At least 1 multipole chamber, it has electrode, is configured between the structure of described a plurality of chambers, and is filled with ion exchanger;

The 1st cationic exchange membrane is located between the structure of described anolyte compartment and described chamber;

The 1st anion-exchange membrane is located between the structure of described cathode compartment and described chamber;

The 2nd anion-exchange membrane is located at the described anode side of described multipole chamber;

The 2nd cationic exchange membrane is located at the described cathode side of described multipole chamber;

Described chamber structure possesses:

Surge chamber cuts off, so that the 1st object ion in the described processed water can not be fed directly to described anolyte compartment or the described multipole chamber from described the 1st concentration compartments;

Pure water is supplied to path in described anolyte compartment and the described multipole chamber;

The 3rd cationic exchange membrane is located between described surge chamber and described the 1st concentration compartments;

The 3rd anion-exchange membrane is located between described the 1st concentration compartments and the described desalting chamber;

The 4th cationic exchange membrane is located between described desalting chamber and described the 2nd concentration compartments;

The 4th anion-exchange membrane is located between described the 2nd concentration compartments and the described ion supply chamber.

17. as each described electrodialysis device in the claim 1～13, its also possess with from described anolyte compartment or at least a portion of the outflow water that comes out of described surge chamber be mixed into path described processed water or the described treating water.

18. as each described electrodialysis device in the claim 1～16, wherein, described processed water is the draining that contains fluorine.

19. electrodialysis device as claimed in claim 18 wherein, is regulated the water yield supply to the pure water in described anolyte compartment and/or the described multipole chamber so that from described anolyte compartment and/or the fluorine concentration of the outflow water that comes out of described multipole chamber be below the 1mg-F/L.

20., wherein, at least one of described anolyte compartment, described cathode compartment and described multipole chamber, be filled with ion exchanger as each described electrodialysis device in the claim 1～16.

21., wherein, in each chamber, be filled with cation exchange fibre material that contacts with described cationic exchange membrane or the anion exchanging fiber material that contacts with described anion-exchange membrane as each described electrodialysis device in the claim 1～16.

22. as each described electrodialysis device in the claim 1～16, wherein, the treating water of supplying with the electrodialysis device to described anolyte compartment, described cathode compartment, described multipole chamber or described surge chamber is to replace pure water.

23. drainage processing method, wherein, by handle the draining that contains ammonium ion and fluorine at least by the electrodialysis device, from described draining, remove ammonium ion and fluorine, thereby generate the treating water of the concentration that has reduced ammonium ion and fluorine, generate the 1st condensed water and the 2nd condensed water that has improved the concentration of ammonium ion of the concentration that has improved fluorine simultaneously.

24. drainage processing method, wherein, at least contain the metal ion that forms metal hydroxides mud and the draining of fluorine by handling by the electrodialysis device, from described draining, remove described metal ion and fluorine, thereby generate the treating water of the concentration that has reduced described metal ion and fluorine, generate the 1st condensed water and the 2nd condensed water that has improved the concentration of described metal ion of the concentration that has improved fluorine simultaneously.

25. as claim 23 or 24 described drainage processing methods, wherein,

At least hydrogen peroxide decomposition is carried out in the draining that contains hydrogen peroxide and fluorine to be handled;

Draining after the described hydrogen peroxide decomposition processing is supplied in the described electrodialysis device.

26. as claim 23 or 24 described drainage processing methods, wherein, the fluorine concentration of described draining is for surpassing 1mg/L but 10, below the 000mg/L.

27., it is characterized in that the fluorine concentration of described treating water is for being lower than 1mg/L as claim 23 or 24 described drainage processing methods.

28. as claim 23 or 24 described drainage processing methods, wherein, at least a portion of described the 1st condensed water is supplied in the fluorine renewable resources device, with the fluorine in the described draining as Calcium Fluoride (Fluorspan) CaF ₂Reclaim.

29. a fluorine treatment system, it possesses:

Each described electrodialysis device is used to handle the draining that contains fluorine at least in the claim 1～12;

Fluorine renewable resources device, the fluorine condensed water that is used for obtaining from described electrodialysis device reclaims as Calcium Fluoride (Fluorspan).

30. a fluorine treatment system, it possesses:

Cyclator, the water that is used for comprising at least a portion of the fluorine condensed water that is obtained by described electrodialysis device carries out the coagulative precipitation processing.

31. a water circulation system, it possesses:

Each described electrodialysis device in the claim 1～12;

Water Purifiers is that former water is made pure water with the treating water that obtains from described electrodialysis device.

32. a water circulation system, it possesses:

Each described electrodialysis device in the claim 1～12;

The device of removing the evil;

The draining of the described device of removing the evil is supplied to path in the described electrodialysis device;

The part of the treating water that will be obtained by described electrodialysis device supplies to the path in the described device of removing the evil.

33. a fluorine treatment system, it possesses:

Each described electrodialysis device in the claim 1～12;

Solid-liquid separation mechanism is used to contain at least the solid-liquid separation of the draining of fluorine;

To carry out the draining after the solid-liquid separation by described solid-liquid separation mechanism and supply to path in the described electrodialysis device.

34. a fluorine treatment system, it possesses:

Each described electrodialysis device in the claim 1～12;

Separating organic matters mechanism is used to contain at least the separating organic matters of the draining of fluorine;

To carry out the draining after the separating organic matters by described separating organic matters mechanism and supply to path in the described electrodialysis device.