CN100581640C - Electro-deionization method and device for synchronously concentrating and purifying heavy metal wastewater - Google Patents
Electro-deionization method and device for synchronously concentrating and purifying heavy metal wastewater Download PDFInfo
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- CN100581640C CN100581640C CN200710151171A CN200710151171A CN100581640C CN 100581640 C CN100581640 C CN 100581640C CN 200710151171 A CN200710151171 A CN 200710151171A CN 200710151171 A CN200710151171 A CN 200710151171A CN 100581640 C CN100581640 C CN 100581640C
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Abstract
The invention relates to an electro-deionization method and device for concentrating and purifying heavy metal wastewater synchronously, belonging to a wastewater treatment technique, which adopts first-stage two-section or first-stage multi-section electro-deionization device, wherein the inner sides of the positive and negative poles are arranged with corresponding pole protection chambers, the desalting chamber is filled with large-hole strong-acid strong-base mixed bed resin with narrow particles distributed; cation exchange film is adopted as the direction-turning film, after direction-turning, two adjacent concentration chambers are arranged continuously, both are separated by cation exchange film, simultaneously after direction-turning, the first concentration chamber is filled with large-hole mixed bed resin with the volume of cathode resin more than 50 percent, the heavy metal wastewater to be treated enters the desalting chamber and the concentration chamber in two paths, the heavy metal ion and cathode in the desalted water flow are transferred into the concentration chamber so as to obtain the desalted water, the concentrated water flow is partially circulated or closely circulated so as to obtain the concentrated liquid of metal wastewater, thereby recycling valence metals and pure water resources synchronously and realizing zero emission and resource treatment of wastewater. Compared with the prior art, the wastewater treatment process has higher separation efficiency, more reliable operation, more convenient operation, continuous process operation and no secondary pollution.
Description
Technical field
The present invention relates to a kind of processing method and device of heavy metal wastewater thereby, especially a kind of electrodeionization concentrates the processing method with purifying heavy metal wastewater, belongs to wastewater processing technology.
Background technology
Electroplating wastewater is the main source of heavy metal wastewater thereby.The annual electroplating wastewater that produces of domestic electroplating industry surpasses 4,000,000,000 m
3, wherein accounting for and be the electroplating rinse water of low concentration more than 80%, the typical concentration of contained heavy metal ion generally is no more than 100mgL
-1
Existing process for treating heavy-metal waste water has evaporation concentration method, chemical method, bioanalysis, ion-exchange, film separation (electrodialysis, counter-infiltration) etc.Therefore evaporation and concentration and chemical method (comprising chemical precipitation and electrolysis) mainly are applicable to the processing that contains the higher concentration effluent containing heavy metal ions, go out very low that water concentration can not fall, to being that the low concentration heavy metal water of representative is almost powerless with the electroplating rinse water.The chemical precipitation method water outlet need be carried out the pH adjusting, also produces a large amount of sludge containing heavy metals, is difficult to handle, and easily causes secondary pollution; Also there are the defective that investment is big, energy consumption is high in evaporation and concentration and electrolysis.
Bioanalysis mainly refers to bioflocculation and biological absorption.Though these two kinds of technology can be used for the low concentration heavy metal containing wastewater treatment, but when commercial Application, generally needing to build 2 is used alternatingly with the baterial cultivation pool of wastewater disposal basin with volume, keeping every day about 40 ℃ of conditions to carry out function bacterium cultivates, consume a large amount of culture mediums, need to use more chemical agent simultaneously, therefore the cost of handling is higher, and floor space is big; Water outlet after the processing still contains more residual microbial, can not direct reuse, also need make further purified treatment.In addition, bioanalysis is handled heavy metal wastewater thereby and is generally all had selectivity, can only draw or adsorb one or more metals, can causing when concentration of heavy metal ion is higher of having poisons, and the treatment effect when having the competitive Adsorption of coexisting ion that has can be subjected to very big the influence.
The open CN1557999A of patent of invention has then described a kind of " biochemical process is administered electroplating wastewater technology ".This technology is characterised in that utilizing BM function cenobium that electroplating sewerage is carried out Two-Stage Biochemical handles: add the BM function bacterium earlier in wastewater equalization pond, carry out the one-level biological respinse; And then add NaOH or add the BM function bacterium simultaneously, carry out the secondary biochemical reaction precipitation and filter.This with the combine method of processing electroplating wastewater of bioanalysis and chemical method, focus on the purification qualified discharge of waste water, but do not exempt bioanalysis and chemical Treatment heavy metal wastewater thereby defective separately, and still have the after-treatment problem of sludge containing heavy metal.
Ion-exchange is a kind of low-concentration heavy metal ion waste water treatment technology that always is widely adopted, and effluent quality is better, often can reuse; Defective is system complex, invest higher, complex operation; Especially institute's spent ion exchange resin needs the frequent soda acid chemical agent regeneration of using, and produces secondary pollution, and has the handling problem of regenerative elution liquid.
That the open CN1403385A of patent of invention has described is a kind of " cyanogen system and contain two methods that reclaim circulation of heavy metal-containing electroplating effluent ".This technology is the retracting device of electroplating wastewater by making with ion exchange resin with cyanogen mainly, makes poisonous cyanide heavy metal substance be adsorbed in resin fully; The water that purified through ion exchange resin returns a last technology as the required washings of electroplating process; With anion regeneration agent (alkali lye), the toxic cyanide heavy metal substance is broken away from from resin, resin is recycling again, and the cyanide heavy metal substance that breaks away from is again with the electrolysis of positive and negative electricity.Though said process energy reclaiming clean water and heavy metal substance do not solve periodic running, complex operation, chemical regeneration, secondary pollution problems.
In addition, the processing method that also has some to adopt evaporation and concentration to combine with ion-exchange or chemical method, as the open CN1456713A of patent of invention, " a kind of new technology of the electroplating wastewater circulating and recovering with acid coppering, cyanide electroplating, nickel plating, chromium plating " described.This technology is at first with collected electroplating wastewater evaporation concentrator concentration, purify with ion-exchange or chemical cleaning method or back-electrolysis again and be for further processing, the liquid that finally obtains suitably adds new reagent by electroplating requirement, is mixed with the additional liquid of plating and returns electroplating system.This method focuses on the concentrated recovery of heavy metal substance, but same long, with high investment, the secondary pollution problems of system complex, flow process of giving prominence to that exists.
For the processing of heavy metal wastewater thereby, in the said method, what at present commercial Application was more relatively is chemical precipitation method and ion-exchange, or integrated based on the kinds of processes of these two kinds of methods.These two kinds of methods all are a kind of pollution transportation in essence, and the heavy metal that is about in the waste water is converted into precipitation or more tractable other forms, but all can't directly realize closed cycle at the scene, can not effectively reclaim valuable metal and water resource.
Film separates as one of chemical separation technology of contemporary novel advanced person, have characteristics such as efficient, energy-conservation, pollution-free, easy and simple to handle, of many uses, wherein membrane technology such as electrodialysis and counter-infiltration has significant application value in heavy metal containing wastewater treatment, but main also heavy metal containing wastewater treatment that is used for higher ion more.For concentration is tens of mgL
-1The low concentration heavy metal water of level then is difficult to application because of technology such as concentration polarization and restriction economically.
For this reason, at the processing of low concentration heavy metal wastewater thereby, some membrane technologies have been produced again and the conventional process technology is integrated, the integrated treatment process of perhaps multiple membrane technology.As utility model patent CN2670349Y a kind of " electroplating waste processing equipment " described.This device comprises broken cyanide reaction tank, reduction reaction pond, comprehensive wastewater pond, sedimentation basin and reverse osmosis membrane separation device.Waste water is after a series of chemical treatments, again through reverse osmosis advanced processing.The open CN1590322A of patent of invention has then set forth a kind of " membrane separating method of electroplating wastewater processing zero-emission ".This technology has adopted " preliminary treatment/nanofiltration/bitter counter-infiltration/seawater high pressure counter-infiltration " flow scheme design, and wherein pretreatment process is finished the removing of impurity, organic matter and fine suspension; The one-level NF membrane is separated makes waste water concentrate 10 times perhaps, and the rejection of heavy metal ion is greater than 97%; Secondary bitter reverse osmosis membrane separation makes the waste water concentrate concentrate 5 times again and is permitted, and the divalent ion rejection is higher than 98%; Three grades of last seawater reverse osmosis membranes separate waste water concentrated more than 2 times or 2 times, and the rejection of inorganic ions is higher than 99.5%; After concentrating, the desalination water of three grades of film separation further is recovered as the rinsing process water through the ion-exchange process desalination.This technology has realized the recovery of water and valuable metal preferably, but the technological process complexity, cost is very high, and system needs frequent on-line cleaning and pH to adjust.In addition, the decay of film permeation flux is obvious, and the film replacement cycle is too short.
The open CN100999368A of patent of invention has described a kind of " reclaiming electric deionizing method and device that heavy metal wastewater thereby is used ".This technology adopts the electrodeionization process to handle heavy metal wastewater thereby, is characterised in that the clean room, promptly is divided into two parts up and down in the diluting compartment of potting resin, and positive resin is filled on top, and yin and yang resin is filled in bottom then layering.For the electrodeionization process, when only filling single positive resin or negative resin, can only from water, remove corresponding cation or anion, and the anion of oppositely charged/cationic migration is subjected to the obstruction of institute's potting resin in the part of diluting compartment.This obstruction can cause the reversed electric field opposite with external electrical field in the part, thereby influences effluent quality, and desalination water can not directly reach the pure water standard.On the other hand, only fill the as easy as rolling off a log violent water decomposition in part that causes of filling Strategy of single electrical resin, produce fouling then.Especially in the part of only filling positive resin, because anionic migration is hindered on the contrary, therefore violent concentration polarization and water decomposition can take place in the surface of anion-exchange membrane in this section, thereby make one of water decomposition product, OH
-Ion combines with heavy metal ion rapidly, causes fouling to generate.In addition, this technology lacks the effective protection measure to concentrated stream, utmost point current in electrodeionization internal water flow process, still easily produce the precipitation of hydroxide of heavy metal ion in enriched chamber and electrode chamber, thereby the process that makes can't be stablized and carries out.In the enriched chamber, though because desalination water is opposite with the condensed water water (flow) direction, can make the heavy metal ion in the freshet move out of membrane stack as early as possible to a certain extent, yet, because in actual the use, the concentrated stream water inlet mostly is the former moisture stream of heavy metal, itself just contains heavy metal ion, therefore no matter dense water and fresh water are reverse counterflow or following current in the same way, all can not guarantee not take place fouling.The control of water decomposition degree in the process, prevent water decomposition product OH as far as possible
-Ion combines with heavy metal ion, and can eliminate fouling automatically and be only prior.Moreover, by the disclosed accompanying drawing 2,3 of CN100999368A as seen, the fishbolt of electric deionizer has not only passed the clamping plate and the positive-negative electrode plate of membrane stack both sides, and passed whole enriched chambers, diluting compartment and anion and cation exchange membrane, promptly two ends up and down and the periphery at amberplex all offers the corresponding bolts hole.This design very easily causes contacting of metal bolts and amberplex, thereby causes electric leakage and even short circuit risk.
Therefore, for the processing of low concentration heavy metal water, need further efficient, reliable, convenient, low-cost, the eco-friendly treatment technology of exploitation, technical process can steady in a long-term be moved; Not only thoroughly eliminate the discharge of wastewater that contains heavy metal ion, heavy metal ion and the effective recycling of pure water resource can be reached wastewater zero discharge and resource simultaneously.
Summary of the invention
Purpose of the present invention is the defective at existing low concentration heavy metal water treatment technology, provide a kind of efficient, electrodeionization concentrates and the treatment process of purifying heavy metal wastewater synchronously reliably, heavy metal wastewater therebies such as electroplating rinse water are carried out are on the spot directly handled.On the one hand, by the optimization to the in-built improvement of electrodeionization membrane stack design and institute's spent ion exchange resin, elimination membrane stack scaling inside hidden danger makes process stable operation reliably and with long-term; On the other hand, process has higher separation and thickening efficiency, and technological process obtains simplifying, reduce investment outlay, Operation and Maintenance is more easy, thereby utilizes the single technology of electrodeionization to reclaim valuable metal and pure water resource synchronously, realizes that the resource of waste water under the non-secondary pollution condition is recycling.
The objective of the invention is to realize by the following technical solutions:
A kind of concentrating synchronously and the electric deionizing method of purifying heavy metal wastewater; adopt the electric deionizer of two sections of one-levels or one-level multistage; wherein the electrodeionization membrane stack includes the positive and negative electrode chamber of both sides; its inboard is respectively two electrode chamber protection chambers; and constitute by anion and cation exchange membrane, enriched chamber's dividing plate, diluting compartment dividing plate; replace enriched chamber and the diluting compartment arranged, and in diluting compartment, be filled with the mixed bed ion exchanger resin.Pending heavy metal wastewater thereby enters diluting compartment and enriched chamber respectively by the different flow ratio, centrifugation at the driving harmonizing yinyang amberplex of DC electric field, and under the promotion transfer function of institute's potting resin, heavy metal ion and anion transport in the diluting compartment current enter the enriched chamber, thereby obtain freshet; Current in the enriched chamber are through part circulation or closed cycle, and its concentration constantly increases, and finally obtains the concentrate of heavy metal wastewater thereby.The desalination water of handling gained reaches the pure water standard and reuse, and condensed water then can be returned electroplating bath again, or obtains crystal and reclaim through vacuum distillation, thereby realizes continuously, the heavy metal wastewater thereby recycling treatment of cleaning.
The electric deionizing method of above-mentioned concentrated synchronously and purifying heavy metal wastewater has following feature:
1, to the negative pole direction cation-exchange membrane and an anion-exchange membrane are set by positive pole in the cathode chamber inboard continuously, and corresponding water flow partition board, constitute positive electrode chamber and anodal protection chamber;
2, to positive extreme direction a cation-exchange membrane and an anion-exchange membrane are set by negative pole in the anode chamber inboard continuously, and corresponding water flow partition board, constitute negative electrode chamber and negative pole protection chamber;
3, the electrode water of preparation is entered by the bottom of positive electrode chamber and anodal protection chamber earlier separately, after the top delivery port is derived, enter by the bottom of negative electrode chamber and negative pole protection chamber again through the membrane stack external pipe, finally derive, constitute independently utmost point water lines at negative side upper electrode water delivery port;
4, evenly fill the macropore negative and positive mixed bed ion exchanger resin that narrow particle diameter distributes in diluting compartment, the resin particle diameter is 0.5-0.9mm;
5, middle part or other relevant positions at membrane stack adopt cation-exchange membrane to be the commutation film, promptly this commutation film only has dense at the one end, the fresh water hole, the other end is not then offered, thereby make the current commutation, make the membrane stack internal structure become two sections of one-levels or one-level multistage form, and from import to the outlet along water (flow) direction, after the commutation cation-exchange membrane, two adjacent enriched chambers are set continuously, separate with a cation-exchange membrane between these two enriched chambers, and the shared volume ratio of filling negative resin is the mixed bed ion exchanger resin of 50-100% in first enriched chamber after commutation.
Among the present invention, electrode water is to prepare separately, does not contain heavy metal cation and the easy strong electrolyte solution that generates the metal hydroxides fouling, as Na
2SO
4Or K
2SO
4Solution, mass concentration more than 0.2% to keep the satisfactory electrical conductivity of electrode chamber.Electrode water enters from side of the positive electrode, is discharged by negative side, enters the outer electrode water pot, can be recycled behind the gas of getting rid of the electrode reaction generation.In the normal course of operation, because of electrode reaction, cause the positive electrode chamber current to be acid, negative electrode chamber current then are alkalescence.Electrode water imports anode chamber by cathode chamber, can eliminate the issuable fouling in negative electrode chamber because of neutralization.
The setting of anodal protection chamber can prevent the diffusion mobility of electrode reaction product to first diluting compartment that is adjacent, and Cl
2Deng the oxidation destruction of pernicious gas to the diluting compartment amberplex; The setting of negative pole protection chamber can stop the reduction of heavy metal cation at negative electrode surface, and one of electrode reaction product OH
-Ion moves to first enriched chamber of cathode side, thereby causes fouling hidden danger.
Among the present invention, in diluting compartment, evenly fill macropore mixed bed ion exchanger resin, avoided under lower operating voltage, promptly producing violent water decomposition.The relative gel resin of macroreticular resin inside has stable and more for the hole of ion migration, and not with changing transition of resin, thereby help the transmission of heavy metal and high valence ion.Adopt the resin of particle size range 0.5-0.9mm, the resin that distributes than 0.3-1.2mm standard particle diameter has lower resistance to water-flow and better hydrodynamic characteristic, and separation process can reach stable fast.
Among the present invention, the internal water flow process of electrodeionization membrane stack is two sections of one-levels or one-level multistage form, owing to realized the mixing again and the secondary/repeated dispensing of membrane stack water flow inside, therefore the one section form separative efficiency of one-level that adopts than prior art is significantly improved.For the form of two sections of the one-levels of routine, in first enriched chamber after the current commutation, the OH that the heavy metal ion of film both sides and possible water decomposition because of to a certain degree produce
-The concentration of ion is the membrane stack inner maximum, the easiliest the most relatively causes fouling.After the commutation cation-exchange membrane, two adjacent enriched chambers are set continuously among the present invention, separate with a cation-exchange membrane therebetween, and fill the mixed-bed resin that negative resin surpasses 50% volume in first enriched chamber after commutation, thereby can stop these two kinds of combinations that cause the zwitterion of fouling at this place, the process that makes is able to safe operation.
For the present invention, by adopting the enriched chamber and the diluting compartment dividing plate of different area specification, and the number that increases or reduce enriched chamber, diluting compartment in the electric deionizer, can handle the heavy metal wastewater thereby of different flow.Condensed water is taked part circulation or closed cycle flow process, can regulate the flow and the pressure that concentrate current neatly, makes process operation operating mode the best.
Concentrate synchronously and the electric deionizing method of purifying heavy metal wastewater according to above-mentioned, realize that the electric deionizer of this method is achieved through the following technical solutions.Electric deionizer comprises membrane stack, electrode assembly, clamping bracing or strutting arrangement and clamping device four parts.Clamping device is made up of two clamping plates, turnbuckle and nuts; In the inboard of two clamping plates is respectively the positive and negative electrode device that positive and negative electrode chamber and battery lead plate are formed; Adjacent with the positive and negative electrode chamber is respectively protection chamber, positive and negative electrode chamber; It between positive and negative electrode chamber protection chamber the clamping bracing or strutting arrangement that the rectangular hollow support edge deckle board by some constitutes; In the hollow cavity of hollow support lateral frame board, be membrane stack.The elementary cell of membrane stack is that film is right, each film is to being made up of each one of cation-exchange membrane, enriched chamber's dividing plate, anion-exchange membrane, diluting compartment dividing plate successively, and fills the large porous strong acid strong basicity mixed bed ion exchanger resin of 0.5-0.9mm particle diameter in the diluting compartment dividing plate.Appropriate location in membrane stack, adopt cation-exchange membrane to be the commutation film, making membrane stack water flow inside mode is two sections of one-levels or one-level multistage, and from import to outlet by water (flow) direction, two adjacent enriched chambers are set after commutation continuously, and fill mixed-bed resin in first enriched chamber after commutation, wherein the shared volume ratio of negative resin is 50-100%.
Of the present invention concentrating synchronously and the electric deionizing method and the device of purifying heavy metal wastewater, its running possesses following effect:
(1) utilize the single process of electrodeionization to realize the continuous concentration and the purifying of heavy metal wastewater thereby synchronously, what obtain high concentration contains the heavy metal ion concentrate for recycling, desalination product water then directly reaches the pure water standard, can be used as process water reuses such as high-quality rinse water, thereby reach the zero-emission and the resource of waste water;
(2) the internal water flow process of two sections of one-levels or one-level multistage has realized the secondary of electric deionizer water flow inside or repeatedly mixing and reallocation again, can significantly improve separative efficiency;
(3) in diluting compartment, fill even mixed-bed resin and can avoid under lower operating voltage, just taking place significant concentration polarization and water decomposition; Protection chamber, both positive and negative polarity chamber and the design that two adjacent enriched chambers are set after the commutation film continuously can ensure the operation steady in a long-term of electrodeionization process, do not produce the heavy metal hydroxide fouling;
(4) compare with prior aries such as ion-exchange and chemical precipitations, processing procedure does not consume any soda acid medicament, does not discharge any environmental hazard pollutant, does not produce sludge containing heavy metal, and process can the high-efficiency and continuous operation, realizes on-the-spot directly processing;
(5) compare with " nanofiltration ", " counter-infiltration " equal pressure drive membrane process and integrated prior art thereof, technical process is more simple, but the fresh water water outlet need not be through ion-exchange and direct reuse, and separative efficiency is higher, and system's investment is saved; Compare with the existing electric drive membrane process of " electrodialysis ", " pole-reversing electroosmosis ", electrodeionization process freshwater product water can directly reach the pure water standard, and the cycles of concentration of condensed water then significantly improves.
Description of drawings
Fig. 1 is provided by the present invention concentrating synchronously and the internal structure schematic diagram of two sections electric deionizing methods of one-level of purifying heavy metal wastewater;
Fig. 2 is in the described electrodeionization internal structure of Fig. 1, ion principle of displacement schematic diagram in each diluting compartment and the enriched chamber before and after the current commutation;
Fig. 3 is provided by the present invention concentrating synchronously and the internal water flow process schematic diagram of two sections electric deionizers of one-level of purifying heavy metal wastewater, and wherein every section has 2 diluting compartments;
Fig. 4 is provided by the present invention concentrating synchronously and the generalized section of two sections electric deionizers of one-level of purifying heavy metal wastewater, and wherein every section contains 2 diluting compartments;
Fig. 5 is two sections electric deionizer sections of the described one-level of Fig. 4 decomposing schematic representation, and wherein 6 hollow support lateral frame boards illustrate 1, and 5 do not mark in addition;
Fig. 6 is the idiographic flow structure chart of a kind of embodiment device provided by the present invention;
Among the above figure:
The 1-cation-exchange membrane; The 2-anion-exchange membrane; The 3-cation-exchange membrane that commutates; The 4-film is right; The 5-cationic ion-exchange resin; 6-anion exchange resin; The 7-cathode chamber; The 8-anode chamber; The anodal protection of 9-chamber; 10-negative pole protection chamber; The 11-diluting compartment; The 12-enriched chamber; The 13-positive electrode; The 14-negative electrode; The water inlet of 15-fresh water; The dense water water inlet of 16-; The anodal water inlet of 17-; The anodal water outlet of 18-; The water inlet of 19-negative pole; The water outlet of 20-negative pole; The 21-desalination water; The 22-condensed water; 23-side of the positive electrode clamping plate; 24-negative side clamping plate; The 25-positive electrode plate; The 26-negative electrode plate; 27-hollow support lateral frame board; The 28-turnbuckle; The 29-nut; 30-fresh water raw water box; The 31-stop valve; The 32-fresh water pump; The dense water-circulating pump of 33-; 34-utmost point water pump; The 35-Pressure gauge; The 36-spinner flowmeter; The dense water circulating tank of 37-; 38-utmost point water pot; The 39-electric deionizer.
The specific embodiment
Below in conjunction with drawings and Examples the present invention is further described.
According to Fig. 1 and Fig. 3; anion-exchange membrane 2 between anodal protection chamber 9 and the 1st enriched chamber; the cation transport that has prevented electrode water in the anodal protection chamber 9 enters concentrated current; thereby can additionally not increase the cation type in the condensed water; also reduced the fouling tendency in the enriched chamber adjacent to a certain extent with positive pole protection chamber; make that condensed water 22 can direct reuse, and improved operation stability.Cation-exchange membrane 1 between anode chamber 8 and the negative pole protection chamber 10 can stop negative reaction product OH
-Ion precipitates thereby can not produce corresponding heavy metal hydroxide in this enriched chamber towards the migration of negative pole protection chamber 10 and adjacent with it enriched chamber 11.Electrode water water (flow) direction in cathode chamber and anode chamber all is from bottom to top, and this gas that helps the electrode reaction generation is in time discharged electric deionizer.Anodal water outlet 18 links to each other on the water route with negative pole water inlet 19, rather than passes through in membrane stack inside, thereby constitutes the independent poles water lines.Anodal water outlet 18 is acid, thereby can eliminate possible fouling in anode chamber 8 and the negative pole protection chamber 10 because of neutralization.
According to Fig. 1 and Fig. 2,, before commutation cation-exchange membrane 3, be diluting compartment 11 by water (flow) direction, then be two continuous enriched chambers 12 afterwards, the 1st enriched chamber's thickness increases after wherein adjacent with the diluting compartment commutation, and is filled with ion exchange resin, and the negative resin proportion surpasses 50%.Heavy metal ion in the fresh water water inlet is as Ni
2+Ion is in the 1st enriched chamber that sees through under the driving of DC electric field after commutation cation-exchange membrane 3 enters commutation.Heavy metal ion then is subjected to the retardation of anion exchange resin towards the migration of negative pole direction in this enriched chamber, and the increase of this enriched chamber's thickness also makes the lateral transfer stroke of heavy metal ion extend, thereby make it be difficult to arrive the surface of the cation-exchange membrane 1 of this enriched chamber's opposite side, or when no show still, be discharged from the electrodeionization membrane stack.On the other hand, in the 2nd section the freshwater room 11 near the position of delivery port, be in the whole current journey water decomposition reacting phase to the most violent, the OH of its generation
-Ion concentration is also the highest.OH
-Ion sees through anion-exchange membrane and enters the 2nd enriched chamber after the commutation film under electric field driven, can not enter the 1st enriched chamber after the commutation but it finally is subjected to the retardation of the place ahead cation-exchange membrane 1, can only be directly by concentrated current discharge membrane stack.Therefore, heavy metal ion and OH in whole membrane stack
-Ion concentration is the highest position, and these two kinds of ions can't mutually combine, thereby can not generate precipitation.
In the flow process that Fig. 6 provided, it is the fresh water water inlet that enters electric deionizer that the former water of fresh water is divided into 2 the tunnel, the one tunnel by fresh-water tank 30 through fresh water pump 32, and another road is the condensed water supplementing water that enters electric deionizer.Condensed water is taked the part circulation technology, be that partial concentration water carries out circular flow by dense water circulating tank 37 and dense water-circulating pump 33, quantity of circulating water and condensed water amount of makeup water sum are the concentrated water yield of real time execution in the electric deionizer, under the steady operational status, the water yield by the concentrated product water 22 of stop valve and spinner flowmeter control equates that with the condensed water amount of makeup water of being shunted by fresh water pump the water level in the dense water circulating tank 37 is kept constant.
At the initial stage of device start, close the discharging of concentrated product water, the dense water water outlet of electric deionizer all enters dense water circulating tank 37.After treating that condensed water goes out water concentration and reaches required standard, open the drain cut valve of concentrated product water 22 again, system enters steady operational status.
Among this embodiment, electric deionizer is two sections structures of one-level, and every section contains 2 diluting compartments, and its section is shown in accompanying drawing 4,5.Diluting compartment dividing plate specification is 100*300*3mm, and enriched chamber's dividing plate is 100*300*0.9mm, and the 1st enriched chamber's dividing plate specification of commutation back institute potting resin is similarly 100*300*3mm, effective film area 160cm
2Used amberplex is the special-purpose amberplex of out-phase hyposmosis electrodeionization, is produced by Zhejiang Qianqiu Environmental Water Treatment Co., Ltd.; Ion exchange resin is D072 and D296 large porous strong acid, basic resin, and the volume ratio of yin and yang resin is 1: 1 in the diluting compartment, and the volume ratio of the yin and yang resin of filling then is 9: 1 in the 1st enriched chamber after the current commutation.The particle size range of all resins is 0.5-0.9mm.
Pre-configured 50mgL in fresh water raw water box 30 and the condensed water circulating tank
-1Nickelous sulfate (NiSO
4) solution, use H
2SO
4Regulating fresh-water tank Central Plains water pH is 5.0, and dense water circulating tank Central Plains water pH is 3.2.Electrode water is the Na of mass concentration 0.3%
2SO
4Solution.The initial operating stage condensed water is carried out closed cycle earlier and is not effluxed, and is closed to the stop valve of condensed water pipeline shunting by fresh water pump, and the fresh water pump water outlet is entirely the fresh water water inlet of electric deionizer.The flow of desalination water, condensed water and electrode water is respectively 15Lh
-1, 4Lh
-1And 2.5Lh
-1, the membrane stack operating voltage is 15V.Surpass 2000 μ Scm when monitoring the condensed water electrical conductivity
-1The time, change condensed water into the part circulation process, be 0.36Lh by the condensed water supplementing water of fresh water shunting and the flow of the concentrated product water 22 that effluxes
-1, the membrane stack operating voltage remains unchanged.Continue operation until reaching stable thereafter.Water quality with online resistance rate instrument monitoring desalination water detects Ni in condensed water, the desalination water with the flame method atomic absorption spectrophotometry
2+The content of ion.The result shows, Ni in the desalination water
2+Be lower than 0.1mgL
-1, resistivity reaches 2.0-3.2M Ω cm, the Ni of concentrated product water
2+Ion concentration finally reaches 1560mgL
-1
Among this embodiment, the structure of electric deionizer, enriched chamber are all identical with embodiment 1 with diluting compartment dividing plate specification, internal water flow process, amberplex etc., institute's spent ion exchange resin also is D72 and D296 large porous strong acid, basic resin, but the resin particle size range is standard particle diameter, i.e. 0.3-1.25mm.
Same pre-configured 50mgL in fresh water raw water box 30 and the condensed water circulating tank
-1Nickelous sulfate (NiSO
4) solution, and use H
2SO
4Regulating fresh-water tank Central Plains water pH is 5.1, and dense water circulating tank Central Plains water pH is 3.16.Electrode water is the Na of mass concentration 0.3%
2SO
4Solution.The initial operating stage condensed water is carried out closed cycle earlier, and the fresh water pump water outlet is entirely the fresh water water inlet of electric deionizer.The flow of desalination water, condensed water and electrode water is identical with embodiment 1, is respectively 15Lh
-1, 4Lh
-1And 2.5Lh
-1, the membrane stack operating voltage also is 15V.Surpass 2000 μ Scm when monitoring the condensed water electrical conductivity
-1The time, change condensed water into the part circulation process, be 0.36Lh equally by the condensed water supplementing water of fresh water shunting and the flow of the concentrated product water 22 that effluxes
-1, the membrane stack operating voltage remains unchanged.Get relevant water sample detection after reaching steady operational status, the water quality with online resistance rate instrument monitoring desalination water detects Ni in condensed water, the desalination water with the flame method atomic absorption spectrophotometry
2+The content of ion.The result shows, Ni in the desalination water
2+Be lower than 0.1mgL
-1, resistivity is 1.0-1.2M Ω cm, the Ni of concentrated product water
2+Ion concentration finally reaches 1280mgL
-1The narrow particle diameter distribution resin of particle size range 0.5-0.9mm is adopted in this explanation, adopts the standard particle diameter distribution resin of 0.3-1.25mm, and process has higher separative efficiency.
Among the embodiment, the rejection of heavy metal ion surpasses 99.8% in the desalination water, and resistivity all more than 1.0-1.2M Ω cm, reaches the pure water water standard, and the cycles of concentration of condensed water then can be higher than 30.Embodiment shows, utilizes the single process of electrodeionization, can be easy and concentrate synchronously efficiently and purifying heavy metal wastewater, additionally not increasing in the condensed water under the cationic kind condition, realize the zero-emission and resource recovery of water resource and valuable metal.
Claims (5)
1, a kind of concentrating synchronously and the electric deionizing method of purifying heavy metal wastewater, with the electric deionizer of two sections of one-levels or one-level multistage heavy metal wastewater thereby is carried out concentrating synchronously and purification process, it is characterized in that simultaneously the design below the termination electrode place of electric deionizer and current commutation place have been adopted:
(1) to the negative pole direction 1 cation-exchange membrane and 1 anion-exchange membrane are set by positive pole in the cathode chamber inboard continuously, and corresponding water flow partition board, constitute positive electrode chamber and anodal protection chamber;
(2) to positive extreme direction 1 cation-exchange membrane and 1 anion-exchange membrane are set by negative pole in the anode chamber inboard continuously, and corresponding water flow partition board, constitute negative electrode chamber and negative pole protection chamber;
(3) adopt cation-exchange membrane to be the commutation film, making electrodeionization membrane stack internal water flow process is two sections of one-levels or one-level multisection type, and from import to the outlet along water (flow) direction, after the commutation cation-exchange membrane, two adjacent enriched chambers are set continuously, separate with 1 cation-exchange membrane therebetween, and the shared volume ratio of filling negative resin is the macropore mixed-bed resin of 50-100% in the 1st enriched chamber after commutation.
2, according to claim 1 concentrating synchronously and the electric deionizing method of purifying heavy metal wastewater, it is Na that its feature also is to adopt institute's cation
+Or K
+The strong electrolyte solution of ion is electrode water; and enter cathode chamber and anodal protection chamber by the side of the positive electrode bottom earlier, and derive on top, enter anode chamber and negative pole protection chamber through the membrane stack exterior line by the negative side bottom again; finally discharge, constitute the independent poles water lines on negative side top.
3, according to claim 1 concentrating synchronously and the electric deionizing method of purifying heavy metal wastewater, its feature also are the macropore mixed bed ion exchanger resin of filling in diluting compartment, its resin particle diameter is 0.5-0.9mm.
4, a kind of concentrating synchronously and the electric deionizer of purifying heavy metal wastewater, comprise membrane stack, electrode assembly, clamping bracing or strutting arrangement and clamping device four parts, adopt cation-exchange membrane to be the commutation film, the internal water flow process is two sections of one-levels or one-level multisection type, it is characterized in that electric deionizer inside has following structure simultaneously:
(1) is provided with the 1st enriched chamber of 1 cation-exchange membrane, anodal protection chamber, 1 anion-exchange membrane, membrane stack successively continuously towards the negative pole direction in the cathode chamber inboard;
(2) be provided with last 1 enriched chamber of 1 cation-exchange membrane, negative pole protection chamber, 1 anion-exchange membrane, membrane stack successively continuously towards positive extreme direction in the anode chamber inboard;
(3) along current from the import to the Way out, be provided with two adjacent enriched chambers in commutation continuously after the cation-exchange membrane, and the film that is provided with between these 2 enriched chambers is a cation-exchange membrane;
(4) be filled with the macropore mixed-bed resin in the 1st enriched chamber after the commutation cation-exchange membrane.
5, according to claim 4 concentrating synchronously and the electric deionizer of purifying heavy metal wastewater, its feature also is in current commutate latter two adjacent enriched chamber, is filled in the 1st mixed-bed resin in the enriched chamber and contains the negative resin that volume ratio is 50-100%.
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| CN200710151171A CN100581640C (en) | 2007-12-21 | 2007-12-21 | Electro-deionization method and device for synchronously concentrating and purifying heavy metal wastewater |
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