CN102583841B - Diffusion and electrodialysis integrated treatment method and device for acid waste liquid containing metallic ion - Google Patents
Diffusion and electrodialysis integrated treatment method and device for acid waste liquid containing metallic ion Download PDFInfo
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Abstract
The invention discloses a diffusion dialysis and electrodialysis integrated treatment method and device for acid waste liquid containing metallic ion. The diffusion dialysis and electrodialysis integrated treatment device is characterized in that a diffusion dialysis device adopts a plate and frame type diffusion dialysis device or a spiral reeling type diffusion dialysis device; a buffer tank isadopted to connect the diffusion dialysis device and an electrodialysis device to form an integrated device for treating the acid waste liquid containing metallic ion; the concentration and dilution capability of the electrodialysis device is used for diluting the dialysate in the diffusion dialysis process, and then the diluted dialysate serves as receptor liquid in the diffusion dialysis process, so that the solution on the receptor liquid side of the diffusion dialysis device is reused and water consumption amount in the diffusion dialysis process is greatly reduced; and meanwhile, the operation time of the electrodialysis process can be prolonged, the concentration of recovered acid can achieve the direct use requirement, fresh acid liquid does not need to be added into recovered acidafter the continuous diffusion dialysis operation, and the acid obtained by recovery is fully utilized.
Description
Technical field
The invention belongs to technical field of waste water processing, be specifically related to the metal ion acid waste liquid is carried out the device and method of diffusion dialysis and the integrated processing of electrodialysis.
Background technology
According to China's " pollution prevention technique " magazine (2008,21:59-61) introduce, in industry such as titanium material, iron and steel, plating, wet type copper smelting, rare earth, usually adopt mineral acids such as hydrochloric acid, sulfuric acid, nitric acid and hydrofluoric acid to come clean metal surface or dissolving ore, the acid waste liquid that therefore has a large amount of metal ion produces.If suitably do not handle and directly discharging for these acid waste liquids, not only can environment be polluted, also wasted natural resources simultaneously.Though at present more existing methods for the treatment of this class waste liquid, comprising: dispensing neutralization, acidic and alkaline waste water neutralize, filter neutralization etc. mutually, but these methods can't reclaim available material fully effectively, and exist cost too high, be easy to generate secondary pollution problems.Diffusion dialysis is a kind of with the spontaneous membrane sepn process of concentration gradient as impellent, because it has advantages such as efficient height, installation and process cost are low, simple to operate, energy consumption is low, be successfully applied in the industries such as titanium dioxide processing, Iron and Steel Production, non-ferrous metal metallurgy, be used for handling the metal ion acid waste liquid and reclaim mineral acid.But diffusion dialysis also exists some shortcomings.At first, because what diffusion dialysis was mainly taked when industrial application is operate continuously, acid waste liquid and fresh water continuously enter the diffusion dialysis device and carry out mass transfer exchange, therefore need a large amount of fresh water to accept mineral acid from the acid waste liquid side as acceptable solution.Yet according to U.S.'s " science " magazine (Science; 302:1524-1528) introduce, the whole world all is faced with the water crisis in recent years, and nearly 5,000,000,000 people live in the area of short water supply or olighydria; it is more and more nervous that water resources has become, can further limit the widespread use of diffusion dialysis thus.In addition, since lower through the recovery acid strength after the diffusion dialysis processing, do not reach the standard of direct use usually, need the fresh acid solution of mixing portion to come into operation again, therefore in the system of whole diffusion dialysis, must introduce extra acid solution.
" the 3rd membrane separation technique used the Conference Papers collection in metallurgical industry " (2009, introduced a kind of plate and frame diffusion dialysis device that afterwards fixedly forms with gripping unit that laminated successively by back up pad, gasket, ion-exchange membrane, gasket, runner filter, gasket, ion-exchange membrane, gasket and back up pad 51-55), but the huge heaviness of this device, difficult transportation, and install that inner packing density is low, circulation passage is narrow, result in blockage easily and mass transfer insufficient; When industrial application, plate and frame diffusion dialysis device needs acid waste liquid jar, fresh water jar, seepage remaining liquid jar and four tank bodies of dialysis flow container to hold solution usually, fresh water in acid waste liquid in the acid waste liquid jar and the fresh water jar continuously enters plate and frame diffusion dialysis device and carries out the mass transfer exchange, therefore need a large amount of fresh water as acceptable solution, and the recovery acid strength in the dialysis flow container is lower.So far do not see relevant report plate and frame diffusion dialysis device is integrated with electrodialysis unit or that be coupled together and use as yet.
The Chinese patent application number 201010144042.4 a kind of spiral wound diffusion dialysis devices that propose, it is the runner filter that between two pipe cores side by side, sandwiches an ion-exchange membrane and film both sides, be close to mutually around pipe core by same direction one roll set, and become cylinder in the axial edge adhesive seal; The ion-exchange membrane end forms the tangential direction runner opening of two radial symmetry in the cylinder outer rim, adhering and sealing is fixed a lateral flow tubes respectively, to comprise that with plastics film the whole cylinder of lateral flow tubes takes up sealing and fixing again, form the film core, the film core is packed in the cylindrical housing, two ends is fixing with the tackiness agent casting, constitutes with two pairs and imports and exports the spiral wound diffusion dialysis device of taking over.This spiral wound diffusion dialysis device that forms that rolled by pipe core, ion-exchange membrane, runner filter, lateral flow tubes is compared with plate and frame diffusion dialysis device, have volume little, in light weight, be convenient to transportation and assembling, conserve space, radially for spirally flowing, promote turbulent flow, be convenient to reinforcing mass transfer and alleviate advantage such as concentration polarization.But the same acid waste liquid jar, fresh water jar, seepage remaining liquid jar and four tank bodies of dialysis flow container of needing with plate and frame diffusion dialysis device of this spiral wound diffusion dialysis device hold solution, fresh water in waste liquid in the acid waste liquid jar and the fresh water jar continuously enters spiral wound diffusion dialysis device and carries out the mass transfer exchange, therefore need a large amount of fresh water as acceptable solution equally, and it is also very low to reclaim the acid strength that obtains.So far do not see relevant report spiral wound diffusion dialysis device is integrated with electrodialysis unit or that be coupled together and use yet.
Summary of the invention
The objective of the invention is to propose a kind of for the apparatus and method that the metal ion acid waste liquid is carried out diffusion dialysis and the integrated processing of electrodialysis, to overcome the above-mentioned defective of prior art.
Of the present invention for the device that the metal ion acid waste liquid is carried out diffusion dialysis and the integrated processing of electrodialysis, combined as follows by diffusion dialysis device and electrodialysis unit:
Described diffusion dialysis device adopt two side by side pipe core 35A and 35B between sandwich the runner filter of an ion-exchange membrane and these film both sides, be close to mutually around pipe core 35A and 35B and roll together by same direction, the limit crimping is in the axial edge coated with adhesive adhesive seal of ion-exchange membrane and runner filter, form the tangential direction runner opening of two radial symmetry in the cylinder outer rim to the ion-exchange membrane end, the lateral flow tubes that is adhesively fixed respectively 36 and 37, and become cylinder in the axial edge adhesive seal, to comprise that with plastics film the whole cylinder of lateral flow tubes takes up sealing and fixing again, form the film core, the film core is packed in the cylindrical housing, two ends is fixing with the tackiness agent casting, formation from two pipe core 35A and 35B respectively through ion-exchange membrane, two side runner filter to two lateral flow tubes 36 and two runners of 37, connect two pairs and import and export the spiral wound diffusion dialysis device of taking over 1, interface 28 with pipe 35B centered by the import of a runner in two runners of this device, be connected to acid waste liquid jar 4 inside with silicone rubber tube, the outlet of this runner is the interface 31 of lateral flow tubes 37, be connected to seepage remaining liquid jar 5 inside by silicone rubber tube and through seepage remaining liquid peristaltic pump 3, as the acid waste liquid runner;
Or, described diffusion dialysis device adopts the membrane stack 40 that is overrided to form successively by back up pad, gasket, ion-exchange membrane, gasket, runner filter, gasket, ion-exchange membrane, gasket and back up pad, the plate and frame diffusion dialysis device 1 ' that fixedly forms by front clamp plate 38 and back clamping piece 39, the import 43 of a runner in two runners of this device is connected to acid waste liquid jar 4 inside by silicone rubber tube, the outlet 42 of this runner is connected to seepage remaining liquid jar 5 inside by silicone rubber tube and through seepage remaining liquid peristaltic pump 3, and this runner is as the acid waste liquid runner;
Described electrodialysis unit 2 adds membrane stack 34 and negative electrode 19 and the positive electrode 18 that subsidiary material such as upper runner filter and gasket are formed after alternately being laminated by anion-exchange membrane and cationic exchange membrane, by front splint 32 and rear plate 33 fixing formations, its inner anolyte compartment that forms, cathode compartment, four compartments of concentration compartments and diluting compartment, its anolyte compartment's import 20, outlet 22, cathode compartment import 24, outlet 27 and concentration compartments's import 25, outlet 23 is connected to corresponding anolyte compartment's jar 6 by emulsion tube respectively, the inside of cathode compartment jar 8 and concentration compartments's jar 7, these three tank bodies are built-in with respectively and corresponding anolyte compartment jar 6, the anode submersible pump 12 that cathode compartment jar 8 links to each other with import emulsion tube in concentration compartments's jar 7, negative electrode submersible pump 14 and concentrated submersible pump 13, form anolyte compartment's circulation loop, three of cathode compartment circulation loop and concentration compartments's circulation loops be circulation loop independently separately, and the negative electrode 19 of this electrodialysis unit 2 is connected with negative pole 17 with the positive pole 16 of supporting direct supply by lead respectively with positive electrode 18;
It is characterized in that:
With another runner of spiral wound diffusion dialysis device 1 import--the interface 29 of lateral flow tubes 36 is connected to surge tank 9 inside by silicone rubber tube, the interface 30 of the outlet of this runner--pipe core 35A is connected to surge tank 9 inside by silicone rubber tube and through acceptable solution peristaltic pump 11, and this runner is as the acceptable solution runner;
Or the import 44 of another runner of plate and frame diffusion dialysis device 1 ' is connected to surge tank 9 inside by silicone rubber tube, and the outlet 41 of this runner is connected to surge tank 9 inside by silicone rubber tube and through acceptable solution peristaltic pump 11, and this runner is as the acceptable solution runner;
Diluting compartment import 21 in the described electrodialysis unit 2, outlet 26 are connected to the inside of surge tank 9 by emulsion tube, and in surge tank 9, settle buffering submersible pump 15 to link to each other with the import emulsion tube of electrodialysis unit 2 diluting compartments.
By surge tank 9 spiral wound diffusion dialysis device 1 or plate and frame diffusion dialysis device 1 ' are connected with electrodialysis unit 2 like this, form a device that can carry out integrated processing to the metal ion acid waste liquid.
The method that the present invention utilizes the device of above-mentioned integrated processing the metal ion acid waste liquid to be carried out diffusion dialysis and the integrated processing of electrodialysis, it is characterized in that: in surge tank 9, pour into fresh water to the buffering submersible pump 15 that floods in the jar respectively earlier, the perfusion acid concentration is 1-10mol/L in the acid waste liquid jar 4, concentration of metal ions is that the metal ion acid waste liquid of 0.1-10mol/L is to the 10-90% that accounts for the tank body volume, receive the acid waste liquid of handling through diffusion dialysis with seepage remaining liquid jar 5, in concentration compartments's jar 7 perfusion concentration be 0.1-2mol/L and with acid waste liquid in mineral acid be solution with a kind of acid to the concentrated submersible pump 13 that floods in the tank body, in anolyte compartment's jar 6 and cathode compartment jar 8, pour into the strong electrolyte solution of 0.01-2mol/L respectively to the anode submersible pump 12 that floods in the jar, negative electrode submersible pump 14; Wash the acceptable solution runner of diffusion dialysis device to get rid of two bubbles in the runner with the acid waste liquid runner of acid waste liquid flushing diffusion dialysis device with fresh water respectively, open seepage remaining liquid peristaltic pump 3 then, regulate a selected flow velocity as the flow velocity of seepage remaining liquid, and keep seepage remaining liquid peristaltic pump 3 in whole integrated treating processes, to move with this flow velocity all the time; Keep solution in the Peak Flow Rate circular buffering jar 9 that acceptable solution peristaltic pump 11 can reach with this peristaltic pump all the time to guarantee carrying out abundant mass transfer with acid waste liquid simultaneously; Elder generation's isolated operation diffusion dialysis device, and in the operation of diffusion dialysis device, start four submersible pumps respectively the solution in antianode chamber jar 6, cathode compartment jar 8, concentration compartments's jar 7, the surge tank 9 circulate to get rid of the bubble of electrodialysis unit 2 inside; After diffusion dialysis device isolated operation at least ten minutes, open direct supply 10 operation electrodialysis units again, keep diffusion dialysis device and electrodialysis unit to move together afterwards.
Can realize constant currents or constant voltage operation by regulating 10 pairs of electrodialysis units of direct supply, the processing power of regulating electrodialysis unit by the curtage size of regulating direct supply 10.
The processing power that can regulate the diffusion dialysis device by the flow velocity size of regulating seepage remaining liquid peristaltic pump 3.
It is sodium hydroxide, sulfuric acid, potassium hydroxide or the metabisulfite solution of 0.01-2mol/L that described strong electrolyte solution can be selected concentration for use; Preferred concentration is the metabisulfite solution of 0.1-1mol/L.
Because the treatment unit of metal ion acid waste liquid of the present invention and treatment process are utilized the dialyzate of the concentrated dilution capacity desalination diffusion dialysis process of electrodialysis unit, again with the dialyzate of desalination as the acceptable solution of diffusion dialysis process, the acceptable solution one side solution of diffusion dialysis device is recycled, compare with the continuous water inlet of existing diffusion dialysis process, significantly reduced the consumption of water in the diffusion dialysis process; Can prolong simultaneously the operating time of electrodialysis process, make and reclaim the requirement that the acid concentration that obtains can reach direct use, add fresh acid solution thereby removed from the recovered acid after diffusion dialysis is operated continuously, therefore the acid that recovery is obtained is fully used.
Description of drawings
Fig. 1 is existing spiral wound diffusion dialysis device synoptic diagram.
Fig. 2 is existing electrodialysis unit synoptic diagram.
Fig. 3 is the process flow sheet that changes into paper tinsel waste water by the integrated treatment unit of spiral wound diffusion dialysis device and electrodialysis unit and treatment of simulated thereof of the present invention.
Fig. 4 is existing plate and frame diffusion dialysis device synoptic diagram.
Fig. 5 is of the present invention by the integrated treatment unit of plate and frame diffusion dialysis device and electrodialysis unit and the process flow sheet for the treatment of of simulated steel wastewater thereof.
Embodiment
Further describe treatment unit and the treatment process that the present invention handles the metal ion acid waste liquid below in conjunction with embodiment.
Embodiment 1: adopt and change into paper tinsel waste water by spiral wound diffusion dialysis device and the integrated treatment unit treatment of simulated of electrodialysis unit
The spiral wound diffusion dialysis device synoptic diagram of Fig. 1 for adopting in the present embodiment.This spiral wound diffusion dialysis device 1 is to assemble according to the mode of introducing in the Chinese patent application numbers 201010144042.4: two side by side pipe core 35A and 35B between sandwich DF-120 anion-exchange membrane that sky, Shandong dimension membrane technique company limited provides and the runner filter of these film both sides, be close to mutually to roll together by same direction around pipe core 35A and 35B and form, the limit crimping is in the axial edge coated with adhesive adhesive seal of ion-exchange membrane and runner filter, form the tangential direction runner opening of two radial symmetry in the cylinder outer rim to the ion-exchange membrane end, the lateral flow tubes that is adhesively fixed respectively 36 and 37, and become cylinder in the axial edge adhesive seal, to comprise that with plastics film the whole cylinder of lateral flow tubes takes up sealing and fixing again, form the film core, the film core is packed in the cylindrical housing, two ends is fixing with the tackiness agent casting, formation from two pipe core 35A and 35B respectively through ion-exchange membrane, two side runner filter to two lateral flow tubes 36 and two runners of 37, and connect two pairs in the import and export of two runners and import and export and take over.The effective film area of this spiral wound diffusion dialysis device 1 is about 1.0m
2With a runner of this device import--the interface 28 of pipe core 35B is connected to acid waste liquid jar 4 inside by silicone rubber tube, the interface 31 of the outlet of this runner--lateral flow tubes 37 is connected to seepage remaining liquid jar 5 inside by silicone rubber tube and through seepage remaining liquid peristaltic pump 3, as the acid waste liquid runner; The interface 29 of the import of another runner--lateral flow tubes 36 is connected to the inside of fresh water jar 47 by silicone rubber tube, the interface 30 of the outlet of this runner--pipe core 35A is connected to the inside of dialysis flow container 48 by silicone rubber tube and through acceptable solution peristaltic pump 11, and this runner is as the acceptable solution runner;
The existing electrodialysis unit synoptic diagram of Fig. 2 for adopting in the present embodiment.This electrodialysis unit is to assemble according to the mode of introducing in the dynamo-electric market conditions net: adopt the anion-exchange membrane that provided by the court of a feudal ruler, Beijing profit membrane technique development corporation, Ltd. and cationic exchange membrane alternately to stack subsidiary material such as adding gasket and runner filter and be formed with the membrane stack 34 that seven pairs of yin, yang ion-exchange membrane repeating units constitute, the useful area of every film is about 0.78 * 1.03dm
2And be separately positioned on the anodic-cathodic 19 at membrane stack two ends, 18 and be placed in the front splint 32 at electrode two ends and rear plate 33 clamps the electrodialysis unit 2 that forms by bolt, its anolyte compartment's import 20, outlet 22, cathode compartment import 24, outlet 27, concentration compartments's import 25, outlet 23 and diluting compartment import 21, outlet 26 is connected to corresponding anolyte compartment's jar 6 by emulsion tube respectively, cathode compartment jar 8, the inside of concentration compartments's jar 7 and diluting compartment jar 46, these four tank bodies are built-in with respectively and corresponding anolyte compartment jar 6, cathode compartment jar 8, the anode submersible pump 12 that concentration compartments's jar 7 links to each other with import emulsion tube in the diluting compartment jar 46, negative electrode submersible pump 14, concentrate submersible pump 13 and desalination submersible pump 45, form from anolyte compartment's jar 6 and begin to export the 22 anode circulation loops of getting back to anolyte compartment's jar 6 at last through anode submersible pump 12 again to the anolyte compartment to anolyte compartment's import 20, begin to get back to the cathode recycle loop of cathode compartment jar 8 at last to cathode compartment outlet 27 through negative electrode submersible pump 14 again to cathode compartment import 24 from cathode compartment jar 8, begin to export 23 again to the concentration compartments to concentration compartments's import 25 and get back to the concentrated circulation loop of concentration compartments's jar 7 at last and these four of desalination circulation loops beginning to get back to diluting compartment jar 46 at last to diluting compartment outlet 26 through desalination submersible pump 45 again to diluting compartment import 21 from diluting compartment jar 46 circulation loop independently separately through concentrating submersible pump 13 from concentration compartments's jar 7.The negative electrode 19 of this electrodialysis unit 2 is connected with negative pole 17 with the positive pole 16 of supporting direct supply by lead respectively with positive electrode 18.
Above-mentioned existing spiral wound diffusion dialysis device and electrodialysis unit carry out the process flow sheet that integrated treatment unit and treatment of simulated thereof change into paper tinsel waste water to Fig. 3 for present embodiment utilizes.
The integrating device of present embodiment is on the basis of above-mentioned existing spiral wound diffusion dialysis device 1 and electrodialysis unit 2, the import and export silicone rubber tube of the acceptable solution runner of this spiral wound diffusion dialysis device 1 is placed surge tank 9, import and export emulsion tube in the electrodialysis unit 2 diluting compartment jars 46 places surge tank 9, and in surge tank 9, settle buffering submersible pump 15 to link to each other with the import emulsion tube of electrodialysis unit 2 diluting compartments, namely use surge tank 9 to substitute the fresh water jar 47 of spiral wound diffusion dialysis device 1, the diluting compartment jar 46 of dialysis flow container 48 and electrodialysis unit 2 so connects the integrating device that the processing of metal ion acid waste liquid is carried out in one of formation by surge tank 9 with spiral wound diffusion dialysis device 1 and electrodialysis unit 2.
Utilize the above-mentioned acid waste liquid integrated treating device that assembles to carry out the metal ion acid waste liquid and handle when operating, in surge tank 9, pour into 2L fresh water to 2/3 of tank body capacity earlier; Perfusion 2-3L consists of 0.15mol/LAlCl in the acid waste liquid jar 4
3Change into paper tinsel waste water with the simulation of 1.35mol/L HCl, account for the 70-90% of tank body; Receive through the acid waste liquid after the diffusion dialysis processing with seepage remaining liquid jar 5; Perfusion 1L concentration is the hydrochloric acid soln of 0.24mol/L in concentration compartments's jar 7, accounts for 90% of tank body volume; Pour into the metabisulfite solution that 0.5L concentration is 0.5mol/L respectively for 8 li toward anolyte compartment's jar 6 and cathode compartment jar, account for 50% of tank body volume; Respectively with the acid waste liquid runner of acid waste liquid flushing spiral wound diffusion dialysis device 1 and with the acceptable solution runner of fresh water flushing spiral wound diffusion dialysis device 1 to get rid of the bubble in the runner, open seepage remaining liquid peristaltic pump 3 power supplys then, regulate a flow velocity as the seepage remaining liquid flow velocity, and keep seepage remaining liquid peristaltic pump 3 in whole integrated treating processes, to move with this flow velocity all the time.Regulate the flow velocity Q of seepage remaining liquid in the present embodiment
fBe respectively 0.24,0.36,0.48,0.60,0.72L/h.Keep solution in the Peak Flow Rate 10.2L/h circular buffering jar 9 that acceptable solution peristaltic pump 11 can reach with this peristaltic pump all the time to guarantee carrying out abundant mass transfer with acid waste liquid simultaneously; In the process of spiral wound diffusion dialysis device 1 isolated operation, start four submersible pumps 12,14,13 and 15 respectively the solution in circulating anode chamber jars 6, cathode compartment jar 8, concentration compartments's jar 7, the surge tank 9 to get rid of the bubble of electrodialysis unit 2 inside; After at least ten minutes, the time T of diffusion dialysis device isolated operation is set in the present embodiment in 1 isolated operation of spiral wound diffusion dialysis device
1Be respectively 10,20,30,40,50min, open direct supply 10 operation electrodialysis units 2, in the present embodiment electric current I be set to 1,1.5,2 respectively, 2.5A, keep spiral wound diffusion dialysis device 1 and electrodialysis unit 2 to move 180min together afterwards.
In the integrated processing operating process of above-mentioned metal ion acid waste liquid, the pending 0.15mol/LAlCl that consists of
3Change into paper tinsel waste water with the simulation of 1.35mol/L HCl and enter into the pipe core 35B of the spiral wound diffusion dialysis device 1 of integrated treating device of the present invention by silicone rubber tube from the acid waste liquid jar, enter the acid waste liquid runner then, carry out abundant mass transfer exchange with the acceptable solution of acceptable solution runner, flow out by silicone rubber tube and through the seepage remaining liquid peristaltic pump 3 final seepage remaining liquid jars 5 that arrive from lateral flow tubes 37 then, wherein in the process of mass transfer exchange, the hydrochloric acid that simulation changes in the paper tinsel waste water sees through DF-120 anion-exchange membrane arrival acceptable solution runner, also namely simulates the hydrochloric acid that changes in the paper tinsel waste water and has obtained recovery.The lateral flow tubes 36 that solution in the surge tank 9 enters the spiral wound diffusion dialysis device 1 in the integrated treating device of the present invention by silicone rubber tube on one side, enter the acceptable solution runner then, change into paper tinsel waste water with the simulation of acid waste liquid runner and carry out abundant mass transfer exchange, accept the hydrochloric acid from the acid waste liquid runner simultaneously, flow out by silicone rubber tube and through acceptable solution peristaltic pump 11 from pipe core 35A at last and arrive surge tank 9, on one side again by buffering submersible pump 15 and enter into the diluting compartment of electrodialysis unit 2 through emulsion tube, utilize the solution in the concentrated dilution capacity desalination surge tank 9 of electrodialysis unit 2, solution after the desalination is got back in the surge tank 9 by emulsion tube then, so, strength of solution in the surge tank remains lower, and the strength of solution in concentration compartments's jar is more and more higher.Therefore, the present invention is the dialyzate that utilizes the concentrated dilution capacity desalination diffusion dialysis process of electrodialysis unit in the integrated treating device, with the dialyzate of the desalination acceptable solution as the diffusion dialysis process, makes the acceptable solution of diffusion dialysis device obtain circulation again.Simultaneously, can prolong the operating time makes the concentration of hydrochloric acid solution of concentration compartments of the electrodialysis unit in the integrated treating device of the present invention can reach the requirement of direct use.
By above-mentioned processing operating process, the partial results that obtains is put in order as table 1.
Table 1 spiral wound diffusion dialysis device and electrodialysis unit treatment of simulated change into the partial results of paper tinsel waste water
As can be seen from Table 1: along with Q
fIncrease, acid recovering rate and recovered acid concentration increase to some extent, and the aluminium leakage rate descends, energy consumption is reduced; Along with T
1Increase, acid recovering rate, aluminium leakage rate and energy consumption all decrease, and acid recovery concentration increases; Along with the increase of I, acid recovering rate, aluminium leakage rate, recovered acid concentration and energy consumption increase to some extent; In addition, it can also be seen that from table 1 energy consumption of integrating device is lower.For integrating device, not only need to investigate acid recovering rate and aluminium leakage rate, energy consumption also is an important index, so when selecting each operating parameters, answer the influence of integrated survey each side.Data and U.S.'s " membrane science technology " magazine (2011 with table 1,384:219-225) Bao Dao data are compared as can be known: compare with single diffusion dialysis device, the water yield of integrated film device consumption significantly reduces, and particularly under the situation of long operational time, this advantage is more remarkable; Owing to introduced electrodialysis unit, can make that the concentration of recovered acid is enough high by prolonging working time simultaneously, reach the standard of direct use, the adding of saving fresh acid solution.
Utilizing liquid waste disposal integrating device of the present invention to carry out the metal ion acid waste liquid handles in the said process of operation, owing to utilize the dialyzate of the concentrated dilution capacity desalination diffusion dialysis process of electrodialysis unit, again with the dialyzate of desalination as the acceptable solution of diffusion dialysis process, so make the solution of acceptable solution one side obtain recycling, compare with the continuous water inlet of existing diffusion dialysis process, greatly reduce the consumption of water in the diffusion dialysis process; Can prolong simultaneously the operating time of electrodialysis process, make the concentration that reclaims the acid that obtains to reach the requirement of direct use, add fresh acid solution thereby removed from the recovered acid after diffusion dialysis is operated continuously, therefore the acid that recovery is obtained is fully used.
Embodiment 2: adopt by plate and frame diffusion dialysis device and integrated treatment unit and the treatment of simulated steel wastewater thereof of electrodialysis unit
Fig. 4 carries out the synoptic diagram of diffusion dialysis operation for the existing plate and frame diffusion dialysis device that adopts in the present embodiment.This plate and frame diffusion dialysis device 1 ' is the membrane stack 40 that is overrided to form successively by back up pad, gasket, ion-exchange membrane, gasket, runner filter, gasket, ion-exchange membrane, gasket and back up pad, fixedly forms by front clamp plate 38 and back clamping piece 39.What adopt in this device is the DF-120 anion-exchange membrane that is provided by sky, Shandong dimension membrane technique company limited, and total effective film area of this device is about 21cm
2The import 43 of a runner in two runners of this device is connected to acid waste liquid jar 4 inside by silicone rubber tube, and the outlet 42 of this runner is connected to seepage remaining liquid jar 5 inside by silicone rubber tube and through seepage remaining liquid peristaltic pump 3, and this runner is as the acid waste liquid runner; The import 44 of another runner is connected to fresh water jar 47 inside by silicone rubber tube, and the outlet 41 of this runner is connected to dialysis flow container 48 inside by silicone rubber tube and through acceptable solution peristaltic pump 11, and this runner is as the acceptable solution runner.
The electrodialysis unit that adopts in the present embodiment is similar to the electrodialysis unit 2 among the embodiment 1, and is just smaller relatively on the size, this device use be to be about 7cm by individual film useful area that Japanese Astom company provides
2The membrane stack that constitutes of the two pairs of yin, yang ion-exchange membrane repeating units.
Above-mentioned existing plate and frame diffusion dialysis device 1 ' shown in Figure 4 reaches the process flow sheet that the simulation steel wastewater is handled with electrodialysis unit 2 integrated treatment unit shown in Figure 2 to Fig. 5 for present embodiment utilizes.Step among the number of assembling steps of this integrating device and the embodiment 1 is similar: the import and export silicone rubber tube of the acceptable solution runner of this plate and frame diffusion dialysis device 1 ' is placed surge tank 9, import and export emulsion tube in the electrodialysis unit 2 diluting compartment jars 46 places surge tank 9, and in surge tank 9, settle buffering submersible pump 15 to link to each other with the import emulsion tube of electrodialysis unit 2 diluting compartments, namely use the fresh water jar 47 of surge tank 9 replacing plate frame diffusion dialysis devices 1 ', the diluting compartment jar 46 of dialysis flow container 48 and electrodialysis unit 2 so connects the integrating device that the processing of metal ion acid waste liquid is carried out in one of formation by surge tank 9 with plate and frame diffusion dialysis device 1 ' and electrodialysis unit 2.
Utilize when the above-mentioned acid waste liquid integrated treating device that assembles carries out metal ion acid waste liquid processing operation in the present embodiment, in surge tank 9, pour into 0.3L fresh water to 1/3 of tank body capacity; Perfusion 0.5-1L consists of 0.48mol/L FeCl in the acid waste liquid jar 4
2With the simulation steel wastewater of 2.54mol/L HCl, account for the 40-70% of tank body; Receive through the acid waste liquid after the diffusion dialysis processing with seepage remaining liquid jar 5; Pouring into the 0.5L concentration toward concentration compartments's jar 7 is the hydrochloric acid soln of 0.12mol/L, accounts for 50% of tank body volume; Pour into the metabisulfite solution that 0.25L concentration is 0.3mol/L respectively for 8 li toward anolyte compartment's jar 6 and cathode compartment jar, account for 50% of tank body volume; Respectively with the acid waste liquid runner of acid waste liquid flushing plate and frame diffusion dialysis device 1 ' and with the acceptable solution runner of fresh water flushing plate and frame diffusion dialysis device 1 ' to get rid of the bubble in the runner, open the power supply of seepage remaining liquid peristaltic pump 3 then, regulate a flow velocity as the seepage remaining liquid flow velocity, and keep seepage remaining liquid peristaltic pump 3 to move with this flow velocity all the time in whole integrated treating processes, present embodiment is regulated the flow velocity Q of seepage remaining liquid
fBe respectively 0.033,0.053L/h, keep solution in the Peak Flow Rate 10.2L/h circular buffering jar 9 that acceptable solution peristaltic pump 11 can reach with this peristaltic pump all the time to guarantee carrying out abundant mass transfer with acid waste liquid simultaneously; In the process of plate and frame diffusion dialysis device 1 ' isolated operation, start four submersible pumps 12,14,13 and 15 respectively the solution in circulating anode chamber jars 6, cathode compartment jar 8, concentration compartments's jar 7, the surge tank 9 to get rid of the bubble in the electrodialysis unit 2, after at least ten minutes, plate and frame diffusion dialysis device 1 ' isolated operation time T is set in the 1 ' isolated operation of plate and frame diffusion dialysis device
1Be respectively 10,20min, open direct supply 10 operation electrodialysis units, electric current I is set to 0.07 respectively, 0.14A, holding plate frame diffusion dialysis device 1 ' and electrodialysis unit 2 move 180min together afterwards.
In the integrated processing operating process of above-mentioned metal ion acid waste liquid, the pending 0.48mol/LFeCl that consists of
2Enter into the acid waste liquid runner of the plate and frame diffusion dialysis device 1 ' of integrated treating device of the present invention with the simulation steel wastewater of 2.54mol/L HCl by silicone rubber tube from the acid waste liquid jar, carry out abundant mass transfer exchange with the acceptable solution of acceptable solution runner, then by silicone rubber tube and through the seepage remaining liquid peristaltic pump 3 final seepage remaining liquid jars 5 that arrive, wherein in the process of mass transfer exchange, hydrochloric acid in the simulation steel wastewater sees through anion-exchange membrane and arrives the acceptable solution runner, and also the hydrochloric acid of namely simulating in the steel wastewater has obtained recovery.Solution in the surge tank 9 enters the acceptable solution runner of the plate and frame diffusion dialysis device 1 ' in the integrated treating device of the present invention on one side by silicone rubber tube, carry out abundant mass transfer exchange with the simulation steel wastewater of acid waste liquid runner, accept the hydrochloric acid from the acid waste liquid runner simultaneously, arrive surge tank 9 by silicone rubber tube and through acceptable solution peristaltic pump 11 at last, on one side again by buffering submersible pump 15 and enter into the diluting compartment of electrodialysis unit 2 through emulsion tube, utilize the solution in the concentrated dilution capacity desalination surge tank 9 of electrodialysis unit 2, solution after the desalination is got back in the surge tank 9 by emulsion tube then, so, strength of solution in the surge tank remains lower, and the strength of solution in concentration compartments's jar is more and more higher.Therefore, the present invention is the dialyzate that utilizes the concentrated dilution capacity desalination diffusion dialysis process of electrodialysis unit in the integrated treating device, with the dialyzate of the desalination acceptable solution as the diffusion dialysis process, makes the acceptable solution of diffusion dialysis device obtain circulation again.Simultaneously, can prolong the operating time makes the concentration of hydrochloric acid solution of concentration compartments of the electrodialysis unit in the integrated treating device of the present invention can reach the requirement of direct use.
By above-mentioned processing operating process, the partial results that obtains is put in order as table 2.
Table 2 plate and frame diffusion dialysis device and the integrated treatment of simulated steel wastewater of electrodialysis unit part of test results
As can be seen from Table 2: than single diffusion dialysis device, the acid recovering rate of integrating device obtains increasing, and aluminium recovery is reduced; Along with Q
fIncrease, acid recovering rate and aluminium leakage rate all descend to some extent, energy consumption is reduced, and recovered acid concentration increases; Along with T
1Increase, acid recovering rate, aluminium leakage rate and energy consumption all decrease, recovered acid concentration raises to some extent; Along with the increase of I, acid recovering rate, aluminium leakage rate, recovered acid concentration and energy consumption increase to some extent; In addition, be similar to table 1, it can also be seen that from table 2 integrated back energy consumption is lower.For integrated device, not only need to investigate acid recovering rate and aluminium leakage rate, and energy consumption also is an important index, so when selecting each operating parameters, answer the influence of integrated survey each side.In addition, because the solution in the surge tank of integrating device is recycling always, than the continuously water inlet of independent diffusion dialysis process, water loss greatly reduces, and especially under working time long situation, this advantage is particularly remarkable.Therefore, as known from Table 2: reducing the consumption of water, removing from and add fresh acid solution, consume under the prerequisite of small amount of electrical energy, the treatment effect of integrating device is better than single diffusion dialysis device.
Utilizing liquid waste disposal integrating device of the present invention to carry out the metal ion acid waste liquid handles in the said process of operation, owing to utilize the dialyzate of the concentrated dilution capacity desalination diffusion dialysis process of electrodialysis unit, again with the dialyzate of desalination as the acceptable solution of diffusion dialysis process, so make the solution of acceptable solution one side obtain recycling, compare with the continuous water inlet of existing diffusion dialysis process, greatly reduce the consumption of water in the diffusion dialysis process; Can prolong simultaneously the operating time of electrodialysis process, make the concentration that reclaims the acid that obtains to reach the requirement of direct use, add fresh acid solution thereby removed from the recovered acid after the diffusion dialysis operation continuously, make and reclaim the acid that obtains and be fully used.
Claims (5)
1. one kind is used for device that the metal ion acid waste liquid is carried out diffusion dialysis and the integrated processing of electrodialysis, is combined as follows by diffusion dialysis device and electrodialysis unit:
Described diffusion dialysis device adopts the runner filter that sandwiches an ion-exchange membrane and these film both sides between two pipe cores (35A and 35B) side by side, be close to mutually to roll together by same direction around pipe core (35A and 35B) and form, the limit crimping is in the axial edge coated with adhesive adhesive seal of ion-exchange membrane and runner filter, form the tangential direction runner opening of two radial symmetry in the cylinder outer rim to the ion-exchange membrane end, the lateral flow tubes that is adhesively fixed respectively (36 and 37), and become cylinder in the axial edge adhesive seal, to comprise that with plastics film the whole cylinder of lateral flow tubes takes up sealing and fixing again, form the film core, the film core is packed in the cylindrical housing, two ends is fixing with the tackiness agent casting, formation from two pipe cores (35A and 35B) respectively through ion-exchange membrane, two runners of two side runner filter to two lateral flow tubes (36 and 37), connect two pairs and import and export the spiral wound diffusion dialysis device of taking over (1), the interface (28) of pipe (35B) centered by the import of a runner in two runners of this device is connected to acid waste liquid jar (4) inside with silicone rubber tube, the outlet of this runner is that the interface (31) of lateral flow tubes (37) is connected to seepage remaining liquid jar (5) inside by silicone rubber tube and through seepage remaining liquid peristaltic pump (3), as the acid waste liquid runner;
Or, described diffusion dialysis device adopts by back up pad, gasket, ion-exchange membrane, gasket, the runner filter, gasket, ion-exchange membrane, the membrane stack that gasket and back up pad are overrided to form successively (40), by front clamp plate (38) and the plate and frame diffusion dialysis device (1 ') that fixedly forms of back clamping piece (39), the import (43) of a runner in two runners of this device is connected to acid waste liquid jar (4) inside by silicone rubber tube, the outlet of this runner (42) is connected to seepage remaining liquid jar (5) inside by silicone rubber tube and through seepage remaining liquid peristaltic pump (3), and this runner is as the acid waste liquid runner;
After alternately being laminated by anion-exchange membrane and cationic exchange membrane, described electrodialysis unit (2) adds membrane stack (34) and negative electrode (19) and positive electrode (18) that upper runner filter and gasket are formed, by front splint (32) and the fixing formation of rear plate (33), its inner anolyte compartment that forms, cathode compartment, four compartments of concentration compartments and diluting compartment, its anolyte compartment's import (20), anolyte compartment's outlet (22), cathode compartment import (24), cathode compartment outlet (27) and concentration compartments's import (25), concentration compartments's outlet (23) is connected to corresponding anolyte compartment's jar (6) by emulsion tube respectively, the inside of cathode compartment jar (8) and concentration compartments's jar (7), these three tank bodies are built-in with respectively and corresponding anolyte compartment jar (6), the anode submersible pump (12) that cathode compartment jar (8) links to each other with import emulsion tube in concentration compartments's jar (7), negative electrode submersible pump (14) and concentrated submersible pump (13), form anolyte compartment's circulation loop, three of cathode compartment circulation loop and concentration compartments's circulation loops be circulation loop independently separately, and the positive electrode (18) of this electrodialysis unit (2) is connected with negative pole (17) with the positive pole (16) of supporting direct supply by lead respectively with negative electrode (19);
It is characterized in that:
With another runner of spiral wound diffusion dialysis device (1) import--the interface (29) of lateral flow tubes (36) is connected to surge tank (9) inside by silicone rubber tube, the interface (30) of the outlet of this runner--pipe core (35A) is connected to surge tank (9) inside by silicone rubber tube and through acceptable solution peristaltic pump (11), and this runner is as the acceptable solution runner;
Or, the import (44) of another runner of plate and frame diffusion dialysis device (1 ') is connected to surge tank (9) inside by silicone rubber tube, the outlet of this runner (41) is connected to surge tank (9) inside by silicone rubber tube and through acceptable solution peristaltic pump (11), and this runner is as the acceptable solution runner; Diluting compartment import (21) in the described electrodialysis unit (2) and outlet (26) are connected to the inside of surge tank (9) by emulsion tube, and in surge tank (9), settle buffering submersible pump (15) to link to each other with the import emulsion tube of electrodialysis unit (2) diluting compartment.
2. utilize the device of the described integrated processing of claim 1 to carry out the method that the metal ion acid waste liquid is handled, it is characterized in that: in surge tank (9), pour into fresh water to the buffering submersible pump (15) that floods in the jar respectively; The perfusion acid concentration is that 1-10mol/L, concentration of metal ions are that the metal ion acid waste liquid of 0.1-10mol/L is to the 10-90% that accounts for the tank body volume in the acid waste liquid jar (4); Receive the acid waste liquid of handling through diffusion dialysis with seepage remaining liquid jar (5); In concentration compartments's jar (7) perfusion concentration be 0.1-2mol/L and with mineral acid in the acid waste liquid be that solution with a kind of acid is to the concentrated submersible pump (13) that floods in the tank body; In anolyte compartment's jar (6) and cathode compartment jar (8), pour into the strong electrolyte solution of 0.01-2mol/L respectively to the anode submersible pump (12), the negative electrode submersible pump (14) that flood in the jar; Wash the acceptable solution runner of diffusion dialysis device to get rid of two bubbles in the runner with the acid waste liquid runner of acid waste liquid flushing diffusion dialysis device with fresh water respectively, open seepage remaining liquid peristaltic pump (3) then, regulate a selected flow velocity as the flow velocity of seepage remaining liquid, and keep seepage remaining liquid peristaltic pump (3) in whole integrated treating processes, to move with this flow velocity all the time; Keep solution in the Peak Flow Rate circular buffering jar (9) that acceptable solution peristaltic pump (11) can reach with this peristaltic pump all the time to guarantee carrying out abundant mass transfer with acid waste liquid simultaneously; Elder generation's isolated operation diffusion dialysis device, and in the operation of diffusion dialysis device, the solution that starts in four submersible pumps difference antianode chamber jars (6), cathode compartment jar (8), concentration compartments's jar (7), the surge tank (9) circulates to get rid of the inner bubble of electrodialysis unit (2); After diffusion dialysis device isolated operation at least ten minutes, open direct supply (10) operation electrodialysis unit (2) again, keep diffusion dialysis device and electrodialysis unit to move together afterwards.
3. the device of integrated processing carries out the method that the metal ion acid waste liquid is handled as described in the claim 1 as utilizing as described in the claim 2, be characterised in that by regulating direct supply (10) electrodialysis unit is realized constant current or constant voltage operation, the processing power of regulating electrodialysis unit by the curtage size of regulating direct supply (10).
4. the device of integrated processing carries out the method that the metal ion acid waste liquid is handled as described in the claim 1 as utilizing as described in the claim 2, is characterised in that the processing power of regulating the diffusion dialysis device by the flow velocity size of regulating seepage remaining liquid peristaltic pump (3).
5. the device of integrated processing carries out the method that the metal ion acid waste liquid is handled as described in the claim 1 as utilizing as described in the claim 2, and be characterised in that: it is sodium hydroxide, sulfuric acid, potassium hydroxide or the metabisulfite solution of 0.01-2mol/L that described strong electrolyte solution is selected concentration for use.
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| CN103882431B (en) * | 2012-12-19 | 2016-08-10 | 温州大学 | The zero-emission recovery and treatment method of a kind of aluminium foil industry corrosion waste acid and system thereof |
| CN103058441B (en) * | 2013-01-25 | 2014-01-29 | 清华大学 | Method and equipment for treating acidic wastewater with high salinity |
| CN103349913B (en) * | 2013-07-24 | 2015-04-22 | 宜宾海丝特纤维有限责任公司 | Novel alkali recovery technology during viscose fiber production |
| CN103864249B (en) * | 2014-03-28 | 2015-06-24 | 中国科学技术大学 | Method for extracting lithium hydroxide by salt lake brine |
| CN103882468B (en) * | 2014-03-28 | 2016-03-02 | 中国科学技术大学 | A kind of electrolysis-bipolar membrane electrodialysis system and production method thereof of being produced lithium hydroxide by Quilonum Retard |
| CN105177619B (en) * | 2015-07-28 | 2017-12-08 | 合肥工业大学 | A kind of device and method for preparing potassium sulfate |
| CN105463505A (en) * | 2015-11-25 | 2016-04-06 | 合肥科佳高分子材料科技有限公司 | Device and method for conducting diffusion dialysis and electrolysis electrodialysis integrated treatment on vanadium-alkali feed liquid in alkali method vanadium extraction process |
| CN106277479A (en) * | 2016-08-11 | 2017-01-04 | 南京大学 | Integrated retracting device containing metal acid pickle and method |
| CN106630014A (en) * | 2016-12-23 | 2017-05-10 | 南京河海环境研究院有限公司 | Diffusive dialysis-electrodeposition combined treatment method for heavy metal-containing waste acid |
| CN106589099B (en) * | 2017-01-24 | 2023-05-12 | 军事科学院系统工程研究院卫勤保障技术研究所 | Desalination system and desalination method for soluble silk fibroin solution |
| CN108821398B (en) * | 2018-07-10 | 2022-02-01 | 佛山市云米电器科技有限公司 | EDR desalination system |
| CN109231556A (en) * | 2018-10-16 | 2019-01-18 | 合肥工业大学 | The diffusion dialysis processing unit and its processing method of acid/base waste liquid |
| CN114735860A (en) * | 2022-04-01 | 2022-07-12 | 清华大学 | Integrated membrane system and method for treating waste acid liquid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2764765Y (en) * | 2005-02-05 | 2006-03-15 | 浙江欧美环境工程有限公司 | Spiral wound type capacitive ion remover |
| CN101857315A (en) * | 2010-06-22 | 2010-10-13 | 赵胜利 | Noble metal waste liquor recovering and regenerating process by film integration-dialysis separation and concentration |
| CN202465427U (en) * | 2012-01-18 | 2012-10-03 | 中国科学技术大学 | Device for performing diffusion dialysis and electrodialysis integrated treatment on acid waste liquid containing metal ions |
-
2012
- 2012-01-18 CN CN 201210015221 patent/CN102583841B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2764765Y (en) * | 2005-02-05 | 2006-03-15 | 浙江欧美环境工程有限公司 | Spiral wound type capacitive ion remover |
| CN101857315A (en) * | 2010-06-22 | 2010-10-13 | 赵胜利 | Noble metal waste liquor recovering and regenerating process by film integration-dialysis separation and concentration |
| CN202465427U (en) * | 2012-01-18 | 2012-10-03 | 中国科学技术大学 | Device for performing diffusion dialysis and electrodialysis integrated treatment on acid waste liquid containing metal ions |
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