CN101830587B - Process and device for processing heavy metal wastewater - Google Patents
Process and device for processing heavy metal wastewater Download PDFInfo
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- CN101830587B CN101830587B CN2010101550034A CN201010155003A CN101830587B CN 101830587 B CN101830587 B CN 101830587B CN 2010101550034 A CN2010101550034 A CN 2010101550034A CN 201010155003 A CN201010155003 A CN 201010155003A CN 101830587 B CN101830587 B CN 101830587B
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Abstract
The invention provides a process and a device for processing heavy metal wastewater. The device mainly comprises a wastewater electroplating and rinsing pool, a concentrated liquid circulating pool, an inverse penetrating/nanofiltering device, a compound electroosmosis device and a compound EDI (Electronic Data Interchange) device. The invention provides the process and the device for processing heavy metal wastewater by using a compound membrane separation technique according to the characteristics of inverse penetration, electroosmosis and EDI, which can be used for effectively processing the processing heavy metal wastewater through experiment verification.
Description
Technical field
Field of waste water treatment of the present invention relates to a kind of technology and device of handling heavy metal wastewater thereby, is specifically related to a kind of technology and equipment of handling heavy metal-containing waste water with composite membrane technology.
Background technology
Fast development of modern industry has produced a lot of bazardous wastes, for example contains the waste water of heavy metal etc., if these discharge of wastewater can be caused serious destruction to ecology in environment, so must handle.The enterprise that produces heavy metal-containing waste water is a lot, like industries such as mine, smelting, plating, chemical industry, all might produce heavy metal wastewater thereby.With the plating is example; Generally can be divided into and contain chromium (Cr) waste water, nickeliferous (Ni) waste water, contain cadmium (Cd) waste water, cupric (Cu) waste water, contain zinc (Zn) waste water, contain gold (Au) waste water, argentiferous (Ag) waste water etc.; Waste water is acid generally speaking; Except that containing heavy metal, also have surfactant, brightener etc.; The processing of electroplating wastewater has chemical precipitation method, neutralization precipitation method, sulphide precipitation, the chelating precipitation method, chemical reduction method, ferrite process, biosorption process, biogenic sediment method, ion-exchange, membrane separation process etc., but existent method or disposal cost are high, and the processing cost of waste water per ton is far above running water; Waste water after handling can not reuse, can not satisfy the requirement of production.Using more method now is chemical precipitation method, and this method is discharged heavy metal after with the flocculant flocculating setting, and its sediment also produces secondary pollution in discharging landfill process, so studies the target that new electroplating effluent treatment method is a researcher always.
Existing technology (Lou Yongtong etc., the 1200m that adopts reverse osmosis membrane technology to handle and reclaim electroplating wastewater
3/ d electroplating wastewater embrane method recycling engineering, membrane science and technology, 2004; 24 (5): 43-46), 3 grades of counter-infiltrations of this process using can realize recycling of waste water; But the concentration of its condensed water is merely 20g/L, far below the concentration of electroplating bath, can not direct reuse in electroplating bath; Must after counter-infiltration, add vaporising device for this reason, invest bigger, troublesome poeration.Document: " the nickel-plating waste water embrane method concentrates reuse technology, and Chen Feng etc. electroplate and environmental protection 2007,27 (5): 36-37 ", adopt 3 grades of counter-infiltrations can only condensed water concentration be brought up to 12-16g/L, need evaporation and concentration equally.
The EdI technology is called the packed-bed electrodialysis technology again; Perhaps continuous electrodeionization is technological; Its key technology is in electrodialysis dilute chamber, to add ion exchange resin; Thereby improved the purity of electrodialytic stability and water outlet, a kind of separate assembling electric deionizer is provided like ZL03240411.5; Document " application of EDI technology in pure water is made " (Xu Haiying, Chinese water supply and drainage, 2005,21 (7): 95-97) introduced the application of EDI technology aspect the preparation ultra-pure water.Existing document is mentioned and is adopted EDI to handle electroplating wastewater; Like: electrodeionization desalting process and be used for removing the research of water copper ion; (Xu is noisy wealthy, University Of Tianjin's thesis, 2002); A kind of technology of Treatment of Copper electroplating wastewater is provided, but this technology because of making its practical application, problems such as life-span is affected.Document: " EDI reclaims the experimental study of acid copper-plating poaching wastewater " (Guan Shan etc., Tianjin University of Technology's journal, 2007,26 (6): 25-27) introduced the experimental result that EDI handles the test of acid copper-plating poaching wastewater, its condensed water Cu
2+Reach 1000mg/L, but have the CuO fouling of black to form near the female die surface of delivery port in second section enriched chamber of membrane stack, this be because: the OH that produces of water decomposition on the one hand
-See through cavity block and get into the enriched chamber, cause the OH of this position
-Concentration is higher, and on the other hand, because the existence of concentration difference diffusion layer, this position is again Cu
2+And OH
-The higher part of concentration, these zwitterions have the trend of combination, if the Cu of localized positions
2+With OH
-Ionic product greater than Cu (OH)
2Solubility product, will form Cu (OH)
2Deposition, local reaction heat causes Cu (OH)
2Further be decomposed into the CuO of black, finally cause the EDI membrane stack to lose efficacy.Be head it off, the document proposes to adopt the method for 2 EDI film pieces, but this certainly will increase investment and energy consumption, and is unreasonable economically.The document also points out to adopt Na
2SO
4Solution is made utmost point water can reduce operating voltage.Document " Electrodialytic regeneration of ion exchange resin " (Johann J, EigenbergerG, Chem Ing Tech, 1993,65 (1): 75～78) having provided employing sulfuric acid is utmost point water, handles to reclaim to contain Cu
2+The technology of waste water, " Electromembrane process, Part 2.Applications " (Kuppinger F F; NeubrandW, Rapp HJ, et al; Chem Ing Tech, 1995,67 (6): 731～739) also introduced a kind of device that reclaims copper; Or the like, document " progress of EDI technical finesse heavy metal wastewater thereby " (prints 2008 during chemical industry; 22 (3): 58-61) recent EDI technology is summarized, wherein also introduced Sung, prevented Cu (OH) effectively through within the specific limits with Current Control
2The generation of deposition and the reduction of metallic copper.At water inlet Cu
2+Mass concentration 5mg/L, current density 11mA/cm
2Under the condition, water outlet Cu
2+Mass concentration is lower than 0.4mg/L, concentrate Cu
2+Mass concentration is greater than 60mg/L.But this device influent concentration is lower, is merely 5mg/L, and the waste water more for metal ion must dilute in advance, perhaps does other preliminary treatment.
Through the analysis to existing EDI, the main obstacle that present EDI is used for heavy metal containing wastewater treatment is that the life-span is short, and the film surface is prone to fouling, and energy consumption is higher.In addition, we find that existing EDI device in order to improve cocnentration factor, adopts lower condensed water flow velocity usually; With this understanding, dense water is Laminar Flow in the enriched chamber, and experimental study is found; Even all under low pH condition, during like pH value 2-3, the enriched chamber still has the heavy metal hydroxide deposition for enriched chamber's water inlet and water outlet; Like Kocide SD, nickel hydroxide etc., according to the calculating of solubility product, under such pH value environment and corresponding metal ion concentration condition; Be can not produce precipitation of hydroxide, this explanation exists bigger concentration gradient in the enriched chamber, promptly in the surface near film higher pH is arranged; And lower in the most of regional pH value of enriched chamber, therefore only produce deposition on the film surface, cause the film fouling.EDI disassembles the back pH mensuration is carried out on the film surface, and highest point is about 10, obviously under such pH condition, can produce such as depositions such as Kocide SD, nickel hydroxides.The also normal fouling of same reason, the anode membrane of utmost point chamber.
Existing EDI device adopts Na more
2SO
4Be utmost point water, its advantage is a good conductivity, and voltage is low, but this method has been introduced new salt in the water body that needs are handled, and in condensed water, has concentrated Na simultaneously
+, and in maybe the entering system, all have a negative impact for the recovery of heavy metal and the reuse of fresh water.Existing EDI device can only be realized the removal of heavy metal, can't realize the recovery of heavy metal, and energy consumption is bigger, and cost is higher.In order to realize the recovery of heavy metal, (Xing Yunqing, Zhejiang University's thesis for the doctorate, 2007) have proposed EDI-ED technology with document " the EDI method is removed and the research of reclaiming Cr (VI) in the waste water ", but device technique makes energy consumption increase by 31%.Have the research report of electroplating wastewater directly being used electrodialysis process, but will concentration be brought up to electroplating bath concentration very big difficulty is arranged also, its cycles of concentration reaches 1000 times, possibly cause serious concentration polarization, and the film fouling is serious.
In sum, the methods of flocculating setting that adopt are handled heavy metal wastewater thereby more in the industry, and cost is very high, and easy generation of secondary pollution.The technology preferably or the device that also directly are not used at present heavy metal containing wastewater treatment.
Through analysis to existing heavy metal containing wastewater treatment device; Can find out that existing technology just is applied to a certain processing method separately the processing of heavy metal wastewater thereby separately; They are not combined,, when commercial Application, just run into a lot of difficult problems because these methods respectively have pluses and minuses.As: the advantage of using the reverse-osmosis treated electroplating wastewater separately is that energy consumption is low, but shortcoming has two: the one, its waste strength of handling still is higher than discharging standards, can only reuse, can not discharge; The 2nd, reverse osmosis concentrated liquid concentration is lower, even adopt three grades of counter-infiltrations, the concentration of concentrate also can only reach 12-20g/L, and the concentration of this and electroplating bath also differs also bigger, therefore can not direct reuse; In addition, the pressure of three grades of counter-infiltrations is very high, reaches 3.2MPa, and is very high to the requirement of equipment and film.Then energy consumption is bigger to adopt ED to handle electroplating wastewater for another example separately, and its fresh water water outlet does not reach discharge standard yet.The advantage of using EDI to handle low concentration wastewater separately is that treatment effect is good, and shortcoming is that energy consumption is bigger, the membrane stack bad adaptability.Therefore it all is defective that counter-infiltration, electrodialysis, EDI are used for electroplating wastewater processing separately, adopts electrodialysis or EDI also all can't waste strength be brought up to the concentration that electroplating bath needs separately.
Summary of the invention
For overcoming the above problems; The present invention has proposed the technology of composite membrane isolation technics processing heavy metal wastewater thereby according to the characteristics of counter-infiltration, electrodialysis and EDI; Made electroplating waste processing equipment, and under confidential state, verified through laboratory experiment and Electroplate Factory's industrial experiment.
Technical scheme of the present invention is achieved in that a kind of technology of handling heavy metal wastewater thereby, comprises following technical essential:
Waste water in A, the electroplate rinsing wastewater pond is handled through counter-infiltration/nanofiltration device earlier; Fresh water after counter-infiltration/nanofiltration device is handled can direct reuse in electroplating bath; Dense water after counter-infiltration/nanofiltration device is handled advances the composite electroosmosis analysis apparatus and analyses fresh water as composite electroosmosis, after the composite electroosmosis analysis apparatus is removed most of heavy metal, goes back to former electroplate rinsing wastewater pond;
Concentrate in B, the concentrate circulatory pool or the pure water that stores in advance deliver into the dense hydroecium of composite electroosmosis analysis apparatus through pump; Loop back the concentrate circulatory pool after having concentrated heavy metal ion; When heavy metal concentration reached requiring of electroplating bath in the concentrate circulatory pool, extraction partial concentration liquid went the electroplating bath reuse;
Fresh water or the former water of waste water after C, counter-infiltration/nanofiltration device is handled directly get into compound EDI device, and the fresh water qualified discharge after compound EDI apparatus processes, the dense water after compound EDI apparatus processes can be wired back and plated the poaching wastewater pond and further handle.
Foregoing technology, preferred scheme is that said composite electroosmosis analysis apparatus is secondary or multistage electrodialysis plant.When selecting the secondary electrodialysis plant for use; Concentrate circulatory pool in the middle of said composite electroosmosis analysis apparatus is established; Between the dense water and the dense water in the concentrate circulatory pool of the concentration of the heavy metal ion in the middle concentrate circulatory pool after counter-infiltration/nanofiltration device is handled, the advanced one-level electrodialysis cell of the dense water in the middle concentrate circulatory pool is advanced the secondary electrodialysis cell then as the dense water of electrodialysis cell; As the fresh water of secondary electrodialysis cell, concentrate circulatory pool in the middle of returning then.
Foregoing technology, preferred scheme is that said compound EDI device is made up of electrodialysis cell and EDI unit, and first half is an electrodialysis cell, and latter half is the EDI unit, is divided into secondary or multistage, and the dense water of previous stage is as the fresh water of back one-level.
Foregoing technology; Preferred scheme is, in said compound EDI device, becomes three the tunnel from fresh water or the former moisture of waste water after counter-infiltration/nanofiltration device processing; Get into the freshwater room of the electrodialysis cell of compound EDI device, dense hydroecium and anode chamber respectively; Advance the freshwater room of EDI unit, dense hydroecium and cathode chamber again, further handle in the fresh water qualified discharge after compound EDI apparatus processes, the dense water after the compound EDI apparatus processes plating poaching wastewater pond of can wiring back.
The present invention also provides the device of realizing aforementioned technology; Mainly constitute by electroplate rinsing wastewater pond, concentrate circulatory pool, counter-infiltration/nanofiltration device, composite electroosmosis analysis apparatus and compound EDI device; Said electroplate rinsing wastewater pond is connected with counter-infiltration/nanofiltration device through pump; The dense water out of said counter-infiltration/nanofiltration device is connected with the import of composite electroosmosis analysis apparatus fresh water, and the water outlet of said counter-infiltration/nanofiltration device is connected with compound EDI device.
The function of counter-infiltration/nanofiltration device is mainly used in removes the separation of the heavy metal in the heavy metal wastewater thereby, guarantees the requirement of recycle-water.After the composite electroosmosis analysis apparatus is mainly used in counter-infiltration/nanofiltration device is handled dense water in heavy metal further be concentrated into 100-200g/L, reach the requirement that is back to electroplating bath.Compound EDI device is mainly used in the waste water that needs are directly discharged and handles, and reaches the requirement of qualified discharge.
Before address, directly bringing up to electroplating bath concentration with electrodialytic method has very big difficulty with electroplating wastewater, its cycles of concentration reaches 1000 times; Possibly cause serious concentration polarization, the film fouling is serious, to this problem; The present invention proposes a kind of composite electroosmosis and analyse technology; Reduced the concentration difference of dense hydroecium and freshwater room, made it to satisfy the requirement that heavy metal ion concentrates, proved through certain Electroplate Factory's actual experiment; This device can be brought up to concentrate concentration more than the 100g/L, satisfies the reuse requirement of electroplating bath.
According to technological requirement of the present invention, composite electroosmosis is analysed and need the waste water about concentration 300mg/L be concentrated into 200～300g/L, 300 to 1000 times of cycles of concentration; As adopt the common electrical dialysis then because dense chamber and both sides, light chamber concentration difference are bigger, concentration polarization is serious, causes the film surface scale; The present invention utilizes the composite electroosmosis analysis apparatus for this reason; With reference to accompanying drawing 2, from the dense water of counter-infiltration/nanofiltration as 1 grade of electrodialytic fresh water, through the plating poaching wastewater pond of wiring back after the electrodialysis process; Concentrate circulatory pool in the middle of composite electroosmosis is analysed and established, the advanced 1 grade of electrodialysis of the dense water of middle concentrate circulatory pool is advanced 2 grades of electrodialysis then as 1 grade of electrodialytic dense water, as 2 grades of electrodialytic fresh water, concentrate circulatory pool in the middle of returning then; The dense water of concentrate circulatory pool advances 2 grades of electrodialytic dense hydroeciums, after concentrating, returns the concentrate circulatory pool.Concentrate circulatory pool in the middle of composite electroosmosis is analysed and established; Wherein the concentration of heavy metal ion is in dense water of counter-infiltration/nanofiltration and concentrate circulatory pool between the dense water; Reduced the concentration difference between the dense hydroecium and freshwater room in the electrodialysis; Prevented electrodialysis because of the concentration polarization fouling, made the electrodialysis can stable operation.
The present invention adopts compound EDI technology that the waste water that needs directly discharge is handled, and has proposed a kind of compound EDI device.Compound EDI is made up of electrodialysis and EDI two parts, and first half is electrodialysis, and latter half is EDI.Be divided into three the tunnel from the fresh water of counter-infiltration/nanofiltration or the electroplating wastewater of electroplating workshop, get into freshwater room, dense hydroecium and the anode chamber of the electrodialysis part of compound EDI respectively; Advance freshwater room, dense hydroecium and the cathode chamber of the EDI part of compound EDI again, the fresh water after handling through compound EDI can reach that discharge standard is discharged or reuse, and dense water and utmost point water can return the electroplating wastewater pond.
The present invention installs electrodialysis spacer before EDI, through electrodialysis the concentration of former water is reduced to the condition that is fit to the EDI operation, like this; Can guarantee the treatment effect of EDI; Can not produce the pollution of film again, because for light chamber, precipitation of hydroxide is mainly that concentration polarization causes.The anode membrane surface is because Ni in light chamber
2+Transmission speed is slower, and the hydrolysis of part hydrone produces H
+And OH
-, H
+Transmission speed is fast, replaces Ni
2+Played the effect of delivered current, and OH
-Ion has little time to transmit and Ni
2+Be combined into nickel hydroxide precipitate.The concentration polarization phenomenon takes place more greatly in current density more easily.Experimental study shows that the condition that the light chamber of EDI device film produces precipitation of hydroxide has two: enough big voltage and sufficiently high concentration.If the light chamber of EDI inlet concentration is lower, then deposited phenomenon can not take place; Before EDI, increase the electrodialysis part and can reduce the waste strength that gets into EDI, prevent the fouling of light chamber.
For preventing the fouling of utmost point chamber, the present invention adopts bigger utmost point water flow velocity, and installs the dividing plate net additional in EDI utmost point chamber, makes dense hydroecium and utmost point chamber be in turbulence state and flows, and therefore can not have OH on the anode membrane surface
-The boundary layer that concentration is higher can not produce precipitation of hydroxide yet, thereby improves the life-span of film.
It is utmost point water that the present invention adopts former water or condensed water, has saved the trouble of preparation utmost point water, and has avoided Xiang Shuizhong to introduce the problem of new salt, has prevented Na
+Appear in fresh water or the dense water, and Na
+Reuse and the adverse effect that discharging produces to water have realized the recovery of heavy metal simultaneously.
In order to realize the recovery of precious metal, compound EDI plate designs is an easily detachable, when the precious metal that electrolysis goes out can in time be changed recovery more for a long time.
Composite electroosmosis is analysed with compound EDI also can be designed to one-level, secondary or multi-stag; Can be according to the concentration design electrodialysis dividing plate number partly of heavy metal in the former water that is processed; The greatly then electrodialytic number of plies of concentration of heavy metal ion is many in the former water, and the little then electrodialytic number of plies of concentration of heavy metal ion is few in the former water.
Technology of the present invention can be used for the processing of the waste water of heavy metals such as cupric, nickel, zinc, cadmium, lead, chromium.
Description of drawings
Fig. 1 is technological process of the present invention (structural representation) figure.
Fig. 2 is the structural representation of composite electroosmosis analysis apparatus.
Fig. 3 is the structural representation of compound EDI device.
Wherein: 1-electroplate rinsing wastewater pond, 2-concentrate circulatory pool, 3-counter-infiltration/nanofiltration device, the dense water trend after 4-counter-infiltration/nanofiltration device is handled; Fresh water trend after 5-counter-infiltration/nanofiltration device is handled, 6-composite electroosmosis analysis apparatus, the compound EDI device of 7-, the dense water trend after 8-composite electroosmosis analysis apparatus is handled; Fresh water trend after 9-composite electroosmosis analysis apparatus is handled, the dense hydromining after 10-composite electroosmosis analysis apparatus is handled goes out (removing electroplating bath), the fresh water (directly effluxing) after the compound EDI apparatus processes of 11-, the dense water trend after the compound EDI apparatus processes of 12-; The 13-pure water replenishes, 14-one-level electrodialysis cell, concentrate circulatory pool in the middle of the 15-, 16-secondary electrodialysis cell; The dense hydroecium of 17-one-level electrodialysis cell, 18-one-level electrodialysis cell freshwater room, 19-transition chamber, 20-secondary electrodialysis cell freshwater room; The dense hydroecium of 21-secondary electrodialysis cell, 22-cathode chamber, 23-anode membrane, 24-cavity block; The 25-anode chamber, 26-mixed bed ion exchanger resin, 27-EDI unit freshwater room; The dense hydroecium in 28-EDI unit, the compound EDI electrodialysis cell of 29-, 30-EDI unit.
The specific embodiment
Below in conjunction with embodiment and accompanying drawing, specify technical scheme of the present invention, but protection domain is not limited thereto.
Embodiment 1:
Fig. 1 is technological process of the present invention (structural representation) figure; Figure can find out thus; The present invention handles the device of heavy metal wastewater thereby; Mainly constitute by electroplate rinsing wastewater pond 1, concentrate circulatory pool 2, counter-infiltration/nanofiltration device 3, composite electroosmosis analysis apparatus 6 and compound EDI device 7; Said electroplate rinsing wastewater pond 1 is connected with counter-infiltration/nanofiltration device 3 through pump, and the dense water out of said counter-infiltration/nanofiltration device 3 is connected with the 6 fresh water imports of composite electroosmosis analysis apparatus, and the water outlet of said counter-infiltration/nanofiltration device 3 is connected with compound EDI device 7.
Fig. 2 is the structural representation of composite electroosmosis analysis apparatus 6; Figure can find out that said composite electroosmosis analysis apparatus 6 is made up of one-level electrodialysis cell, secondary electrodialysis cell, middle concentrate circulatory pool, the dense hydroecium of one-level electrodialysis cell, one-level electrodialysis cell freshwater room, transition chamber, secondary electrodialysis cell freshwater room, the dense hydroecium of secondary electrodialysis cell, cathode chamber, anode chamber etc. thus.Composite electroosmosis analysis apparatus 6 is made as secondary (also can be made as one or more levels according to actual needs certainly).Structure that composite electroosmosis is analysed and conventional electrodialysis are similar, and composite electroosmosis is analysed equally and is made up of amberplex, dividing plate, pole plate and clamping plate, can (Zhang Gensheng etc. write with reference to " electrodialytic water treatment technology "; Science Press, 1981, the 1st edition); Film, dividing plate, clamping plate, pole plate all are conventional; Structure is also similar, and different is, and composite electroosmosis of the present invention analyses is divided into the two poles of the earth or multistage, and the dense water of previous stage is as the fresh water of back one-level; Such structure can reduce the concentration difference of dense chamber and light chamber, prevents concentration polarization.
Fig. 3 is the structural representation of compound EDI device 7, and figure can find out that said compound EDI device 7 is made up of EDI unit freshwater room, the dense hydroecium in EDI unit, compound EDI electrodialysis cell, EDI unit etc. thus.Compound EDI pole plate, dividing plate, the amberplex of electrodialysis part similar with the electrodialysis of routine, can (Zhang Gensheng etc. write, Science Press with reference to " electrodialytic water treatment technology "; 1981, the 1st edition), the EDI part is also similar with the EDI of routine; Can reclaim the experimental study of acid copper-plating poaching wastewater with reference to EDI " (Guan Shan etc.; Tianjin University of Technology's journal, 2007,26 (6): 25-27).
Embodiment 2: utilization embodiment 1 said device is handled the technology of heavy metal wastewater thereby:
Waste water in A, the electroplate rinsing wastewater pond 1 is handled through counter-infiltration/nanofiltration device 3 earlier; Fresh water after counter-infiltration/nanofiltration device 3 is handled can direct reuse in electroplating bath; Dense water after counter-infiltration/nanofiltration device 3 is handled advances composite electroosmosis analysis apparatus 6 and analyses fresh water as composite electroosmosis, after composite electroosmosis analysis apparatus 6 is removed most of heavy metal, goes back to former electroplate rinsing wastewater pond 1;
Concentrate in B, the concentrate circulatory pool 2 or the pure water that stores in advance deliver into the dense hydroecium of composite electroosmosis analysis apparatus 6 through pump; Loop back concentrate circulatory pool 2 after having concentrated heavy metal ion; When heavy metal concentration reached requiring of electroplating bath in the concentrate circulatory pool 2, extraction partial concentration liquid went the electroplating bath reuse;
Fresh water or the former water of waste water after C, counter-infiltration/nanofiltration device 3 are handled directly get into compound EDI device 7, and the fresh water qualified discharge after compound EDI device 7 is handled, the dense water after compound EDI device 7 is handled can be wired back and plated further processing of poaching wastewater pond 1.
Concentrate circulatory pool 15 in the middle of said composite electroosmosis analysis apparatus 6 is established; Between the dense water and the dense water in the concentrate circulatory pool 2 of the concentration of the heavy metal ion in the middle concentrate circulatory pool 15 after counter-infiltration/nanofiltration device 3 is handled; The advanced one-level electrodialysis cell 14 of dense water in the middle concentrate circulatory pool 15 is as the dense water of electrodialysis cell 14; Advance secondary electrodialysis cell 16 then, as the fresh water of secondary electrodialysis cell 16, concentrate circulatory pool 15 in the middle of returning then.
(compound EDI plate designs is an easily detachable to said compound EDI device; Install the dividing plate net additional in EDI utmost point chamber; Making dense hydroecium and utmost point chamber be in turbulence state flows) 7 to form by electrodialysis cell 29 and EDI unit 30, first half is an electrodialysis cell 29, latter half is EDI unit 30.In said compound EDI device 7; Fresh water or the former moisture of waste water from after 3 processing of counter-infiltration/nanofiltration device become three the tunnel; Get into freshwater room 18, dense hydroecium 17 and the anode chamber 25 of the electrodialysis cell 29 of compound EDI device 7 respectively; Advance freshwater room 27, dense hydroecium 28 and the cathode chamber 22 of EDI unit 30 again, the fresh water qualified discharge after compound EDI device 7 is handled, the dense water after compound EDI device 7 is handled can be wired back and plated further processing of poaching wastewater pond 1.
Adopt the treatment effect of this technology, see table 1 the nickel-containing waste water charging.
Table 1 nickel-containing waste water treatment effect
Can be found out by table 1: concentration is that the concentration of dense water can reach 105.6g/L after the process of the 375mg/L apparatus processes of the present invention; And EDI fresh water concentration is lower than the permission concentration of emission of national regulation; And reverse osmosis freshwater concentration 3.3mg/L can satisfy the requirement of reuse.
Should be pointed out that the specific embodiment is the more representational example of the present invention, obvious technical scheme of the present invention is not limited to the foregoing description.A lot of distortion can also be arranged.Those of ordinary skill in the art from then on disclosedly in the file mentions or associates, and all should think the claimed scope of this patent.
Claims (8)
1. a technology of handling heavy metal wastewater thereby is characterized in that,
Waste water in A, electroplate rinsing wastewater pond (1) is handled through counter-infiltration/nanofiltration device (3) earlier; Fresh water direct reuse after counter-infiltration/nanofiltration device (3) is handled is in electroplating bath; Dense water after counter-infiltration/nanofiltration device (3) is handled advances composite electroosmosis analysis apparatus (6) and analyses fresh water as composite electroosmosis, the plating poaching wastewater pond (1) of after composite electroosmosis analysis apparatus (6) is removed most of heavy metal, wiring back;
Concentrate in B, the concentrate circulatory pool (2) or the pure water that stores in advance deliver into the dense hydroecium of composite electroosmosis analysis apparatus (6) through pump; Loop back concentrate circulatory pool (2) after having concentrated heavy metal ion; When heavy metal concentration reached requiring of electroplating bath in the concentrate circulatory pool (2), extraction partial concentration liquid went the electroplating bath reuse;
C, the former water of waste water directly get into compound EDI device (7), and the fresh water qualified discharge after compound EDI device (7) is handled, the dense water after compound EDI device (7) is handled are wired back, and plating poaching wastewater pond (1) is further handles;
Concentrate circulatory pool (15) in the middle of said composite electroosmosis analysis apparatus (6) is established; Between the dense water and the dense water in the concentrate circulatory pool (2) of the concentration of the heavy metal ion in the middle concentrate circulatory pool (15) after counter-infiltration/nanofiltration device (3) is handled; The advanced one-level electrodialysis cell of dense water (14) in the middle concentrate circulatory pool (15) is as the dense water of one-level electrodialysis cell (14); Advance secondary electrodialysis cell (16) then; As the fresh water of secondary electrodialysis cell (16), concentrate circulatory pool (15) in the middle of returning then; In said compound EDI device (7); The former moisture of waste water becomes three the tunnel; Get into freshwater room (18), dense hydroecium (17) and anode chamber (25) of the electrodialysis cell (29) of compound EDI device (7) respectively; Advance the freshwater room (27) of EDI unit (30), dense hydroecium (28) and cathode chamber (22) again, the fresh water qualified discharge after compound EDI device (7) is handled, the dense water after compound EDI device (7) is handled are wired back, and plating poaching wastewater pond (1) is further handles.
2. the described technology of claim 1 is characterized in that, said composite electroosmosis analysis apparatus (6) is secondary or multistage electrodialysis plant, and the dense water of previous stage is as the fresh water of back one-level.
3. the arbitrary described technology of claim 1-2 is characterized in that, adopting former water or condensed water is utmost point water, the part heavy metal ion at cathode chamber by electrolytic recovery.
4. the arbitrary described technology of claim 1-2 is characterized in that, said heavy metal is copper, nickel, zinc, cadmium, lead or chromium.
5. realize the device of claim 1 or 2 said technologies; It is characterized in that; Mainly constitute by electroplate rinsing wastewater pond (1), concentrate circulatory pool (2), counter-infiltration/nanofiltration device (3), composite electroosmosis analysis apparatus (6) and compound EDI device (7); Said electroplate rinsing wastewater pond (1) is connected with counter-infiltration/nanofiltration device (3) through pump; The dense water out of said counter-infiltration/nanofiltration device (3) is connected with composite electroosmosis analysis apparatus (6) fresh water import, and the water outlet of said counter-infiltration/nanofiltration device (3) is connected with compound EDI device (7).
6. the described device of claim 5 is characterized in that, said compound EDI device (7) is made up of electrodialysis cell (29) and EDI unit (30); First half is electrodialysis cell (29); Latter half is EDI unit (30), is divided into secondary or multistage, and the dense water of previous stage is as the fresh water of back one-level.
7. the described device of claim 5 is characterized in that, said compound EDI device (7) plate designs is an easily detachable.
8. the described device of claim 5 is characterized in that, the water of dense hydroecium of compound EDI device (7) and utmost point chamber flows with turbulence state.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101550034A CN101830587B (en) | 2010-04-26 | 2010-04-26 | Process and device for processing heavy metal wastewater |
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| CN2010101550034A CN101830587B (en) | 2010-04-26 | 2010-04-26 | Process and device for processing heavy metal wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103359854A (en) * | 2012-04-06 | 2013-10-23 | 王明亚 | Method and device for treating inorganic ammonium salt wastewater by using integrated membrane |
| CN103708668B (en) * | 2013-12-27 | 2016-01-13 | 苏州华辰净化股份有限公司 | A kind for the treatment of process of mother solution of pure terephthalic acid waste water |
| CN106145457A (en) * | 2015-03-27 | 2016-11-23 | 苏州卓融水处理科技有限公司 | A kind of waste water resource recycles processing method entirely |
| CN106698759B (en) * | 2015-11-18 | 2019-08-13 | 建德蓝忻环境科技有限公司 | A kind for the treatment of method of chemical nickel-plating wastewater |
| CN105271581A (en) * | 2015-11-21 | 2016-01-27 | 青岛海大北方节能有限公司 | Boiler feed water treatment system high in water yield |
| CN105502756B (en) * | 2015-11-27 | 2018-01-23 | 中国科学院青岛生物能源与过程研究所 | A kind of water-soluble liquid treating system and its processing method of the easy scale-forming ion containing concentration |
| CN105906111B (en) * | 2016-05-11 | 2018-11-06 | 合肥科佳高分子材料科技有限公司 | A method of salt is detached from coal chemical industrial waste water by electrodialytic technique |
| CN106219830A (en) * | 2016-06-01 | 2016-12-14 | 东莞汇金环境科技有限公司 | A kind of electroplated heavy metals wastewater zero discharge system and method |
| CN114075003A (en) * | 2020-08-18 | 2022-02-22 | 中石化南京化工研究院有限公司 | Method for recycling copper and zinc in catalyst production wastewater |
| CN113292194A (en) * | 2021-06-08 | 2021-08-24 | 苏州融和福天宝环保科技有限责任公司 | Method for treating electroplating comprehensive wastewater |
| CN114275945B (en) * | 2021-12-28 | 2023-07-21 | 安徽铜冠铜箔集团股份有限公司 | Copper recovery device and process |
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| WO2008079362A1 (en) * | 2006-12-22 | 2008-07-03 | Siemens Water Technologies Corp. | Systems and methods for process stream treatment |
| CN101402497A (en) * | 2008-09-16 | 2009-04-08 | 王方 | Electric ion removing method and device for recycling inorganic ammonia nitrogen wastewater |
| CN101543730B (en) * | 2009-02-16 | 2012-09-12 | 浙江东洋环境工程有限公司 | Organic liquid desalinisation process and system capable of preventing scale formation |
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