CN105236527A - Three-dimensional electrode device and method for synchronously continuously removing salt and organic pollutants from wastewater - Google Patents
Three-dimensional electrode device and method for synchronously continuously removing salt and organic pollutants from wastewater Download PDFInfo
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Abstract
The invention discloses a three-dimensional electrode device and a green electrochemical treatment method for synchronously continuously removing salt and organic pollutants from wastewater. The device comprises a cation exchange resin unit, an anion exchange resin unit, a pole chamber unit and a plurality of OFR electro-catalytic units. Sodium sulfate is placed in the pole chamber unit and serves as pole chamber circulation liquid. An ion exchange resin filling material is arranged in the ion exchange resin units. An anion exchange membrane is arranged in an anion zone, and a cation exchange membrane is arranged in a cation zone. An OFR special-purposed filling material is arranged in the OFR electro-catalytic units. The OFR electro-catalytic unit at the middle part of the device forms a concentrated water formation and collection zone. With the device, wastewater sequentially passes the OFR electro-catalytic unit, the cation exchange resin unit, the OFR electro-catalytic unit and the anion exchange resin unit, and is discharged from the device. Therefore, salt and organic matters are removed synchronously. With the device and the method, salt and organic matters are continuously and synchronously removed from wastewater with high efficiency; the operation cost is low; automation degree is high; and the method and the device are green and environment-friendly.
Description
Technical field
The invention belongs to technical field of sewage.More specifically, a kind of the Green Water process electrochemical method and the three-diemsnional electrode device (DSROTDE) thereof that adopt the continuous desalination removal organic polluter of electrochemical method waste water is related to.
Background technology
Based on Three-dimensional Electrode Method (Three-dimensionalelectrodes, be called for short TDE) be a kind of conventional process organic waste water method, this method is on the basis of traditional two-dimentional feed pole plate, adds a kind of particle derivation with low-impedance electroconductibility and becomes three-diemsnional electrode (E.Fockedey, 2002; Jiang Hui etc., 2014), and particle polarized under the effect of electric field to be just as be the 3rd pole, by there is electrochemical oxidation reactions on the surface of electrode particle, the oxide compound producing strong oxidation goes to attack organic target thing, thus reaches the effect of the organic pollutant removing difficult for biological degradation.The above-mentioned this conducting particles added, increase considerably the surface-area of electrode reaction on the one hand, can the voltage effect of feeding electrode originally be extended in the main body of solution on the other hand, this is equivalent to the electric field distance shortening two-plate, and target processing thing is also shortened greatly running to the distance on pole plate.
The early-stage Study of the present inventor achieves the three-diemsnional electrode catalytic oxidation process organic waste water technology that the patent No. is ZL02114740.X, when this technology is used for the process of organic waste water, there is broad spectrum, efficiently, fast, sludge quantity is few, does not produce secondary pollution, have the functions such as deodoring and disinfecting, it has a extensive future simultaneously; But it is too high to there is raw materials cost in the particle electrode catalyst filling that this technology adopts, the defects such as physical strength is poor, and the synergistic effect wherein between each composition is strong not.It is particle electrode catalyst filling of a kind of three-diemsnional electrode of 200410077704.5 and preparation method thereof that the present inventor obtains the patent No. in follow-up study, this conducting particles has very high specific surface area, and there is very huge very intensive absorption duct, these ducts are exactly the significant points that granule electrode plays a role, exactly because the also existence in this duct, add the reaction area of electrode reaction greatly, be several orders of magnitude of traditional two-dimentional feeding electrode reaction area, in removal difficult for biological degradation organic pollutant, played vital role.But above-mentioned this method, when processing containing organic wastewater high in salt, makes treating processes energy consumption increase due to the existence of salt side reaction, also there is the problem that organism processing efficiency also significantly declines simultaneously.
Electrodeionization technology (Eleetrodeionization is called for short EDI), also known as continuous deionization technology (ContinuousDeionization, CEDI), is also called as packed-bed electrodialysis in early days.EDI technology has merged electrodialytic technique and ion exchange technique well, that mixed-bed resin is filled between ion-exchange membrane by one, the new type water treatment process of continuous desalination is realized under DC electric field effect, also be after the intermembranous filling ion-exchange resin of electrodialysis unit, under the effect of DC electric field, a kind of new separation technology (KEBouhidel etc., 2006 of continuous deionising process can be realized; Sun Xian etc., 2011).Electroosmose process (ElectroDialysis, be called for short ED) be utilize ion-exchange membrane, comprise anion-exchange membrane (Anionexchangemembrane, AEM), cationic exchange membrane (Cationexchangemembrane, CEM), by means of the selective penetrated property of ion-exchange membrane to anions and canons, under the effect of applying direct current electric field, realize the technology that ionogen concentrates or desalinates.Electroosmose process is because water production rate is little, current consumption large and film is subject to Organic pollutants and lost efficacy, and method is used for miniature water desalination station.Ion exchange method (Ion-exchangeprocess, be called for short IEX) utilize Solid-state Ion-exchange agent to comprise anionite-exchange resin (Anionexchangeresin, and Zeo-karb (Cationexchangeresin AER), CER), exchange by means of the ion in the ion in solution and Solid-state Ion-exchange agent, thus reach the object removed or extract some ion in solution.Usually, the absorption of ion exchange resin and exchange capacity are very strong, and pollutant removal is better, but the regenerative elution technique of requirement is loaded down with trivial details, investment and maintenance cost higher, resin is vulnerable to Organic pollutants and lost efficacy in addition.The design of system, operation, management are all cumbersome, need professional and technical personnel, so general only in the advanced treatment of waste water.
In EDI device, electroconductibility two to three orders of magnitude higher than the aqueous conductive contacted with it of ion exchange resin, ion permeable film surface is all almost the effect of ion exchange resin, namely the raising of intermembranous electroconductibility significantly enhances the migration of ion, solve the poor phenomenon of ion in face concentration retention layer and the large problem of resistance, and occur in electrode vessel hydrogen ion that water decomposition effect produces and hydroxide ion can regenerating resin can also loading section electric current.Therefore, EDI device can make the regeneration of resin, ion-exchange, deionization occur simultaneously, the desalting of its existing electrodialysis unit, there is again the ion exchange of ion exchange resin, avoid the detrimentally affect of electrodialysis concentration polarization and ion exchange resin regeneration and the shortcoming such as environmental pollution caused.
The effect of traditional E DI device when producing ultrapure water or pure water is better, but be applied in heavy metal containing wastewater treatment, when intaking containing metal ions such as comparatively high contents of calcium and magnesium, often because the hydroxide radical that hydrolysis produces forms precipitation of hydroxide, cause when running continuously and easily on film and resin, occur scale problems, limit the application of method largely.For preventing fouling, current EDI method adopts down the operations such as pole, acid adding or Scale inhibitors with the steady running maintaining whole device usually, but this obviously increases the complexity of system, makes decrease in efficiency, cost increase.In addition, lost efficacy because ion exchange resin and electrodialysis-ion exchange film itself are subject to organic pollutant impact, therefore be difficult to be applied in the process of saliferous organic wastewater.
Summary of the invention
The technical problem to be solved in the present invention overcomes defect and the deficiency that electrodeionization technology (EDI) and Based on Three-dimensional Electrode Method (TDE) in prior art be all difficult to be applied to process saliferous organic wastewater, at the patent of invention " ZL200410077704.5 in the present inventor's early stage, particle electrode catalyst filling of a kind of three-diemsnional electrode and preparation method thereof " basis on, the transformation of technology bridge joint is carried out to EDI, make two kinds of technical superioritys be able to ingenious fusion, research has manufactured the three-diemsnional electrode device (being called for short DSROTDE) of the continuous desalination removal organic polluter of a kind of waste water.
The object of this invention is to provide the three-diemsnional electrode device of the synchronous desalination removal organic polluter continuously of a kind of waste water.
Another object of the present invention is to provide the Green Water process electrochemical method of the synchronous desalination removal organic polluter continuously of a kind of waste water.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
The three-diemsnional electrode device (being called for short DSROTDE) of the synchronous desalination removal organic polluter continuously of a kind of waste water, this device is made up of positive column, cathodic area and several functional zone unit, comprise Zeo-karb unit, anionite-exchange resin unit (its inside is equipped with Zeo-karb, anionite-exchange resin respectively), pole chamber unit and several OFR electrocatalysis unit (its inner dress has OFR filler special); Device produces the ingenious combination design of soda acid technology, the online desalting technology of ion exchange resin, the easy fouling technology of suppression resin and ion-exchange membrane surface, electrocatalysis three-diemsnional electrode process organism technology by pole chamber unit, achieves the object of the continuous operation of the function of saliferous organic wastewater desalination simultaneously organic matter removal.
Particularly, this device is by tactic positive column (1), cationic exchange district (2), organic matter treating area (3), dense pool (4), organic matter treating area (5), anionresin district (6) and cathodic area (7) form successively; Positive column (1), cationic exchange district (2), separated by cationic exchange membrane (8) between organic matter treating area (3) and dense pool (4), dense pool (4), organic matter treating area (5), pass through anion-exchange membrane (9) between anionresin district (6) and cathodic area (7) and separate; Wherein, be communicated with respectively by pipe connecting (10) between organic matter treating area (3) and cationic exchange district (2), between cationic exchange district (2) and organic matter treating area (5), between organic matter treating area (5) and anionresin district (6); Organic matter treating area (3) and dense pool (4) are respectively arranged with waterwater entrance (11), anionresin district (6) are provided with process water relief outlet (12), dense pool (4) are provided with concentrated water drainage outlet (13).
Dense pool (4) is the OFR district being positioned at the positive middle part of device, and it is unique functional zone separated by cationic exchange membrane 1 and anion-exchange membrane 6, and inside is covered with the dense pool collector unit that OFR Special electric catalytic filler grain 3 is formed.
Preferably, this device is supported by support (14).
Further, OFR Special electric catalytic filler grain (OFR, the i.e. filler that provides of patent 200410077704.5) is covered with in described positive column (1) as Chan Suan district.
Cathodic area (7) inside is covered with OFR Special electric catalytic filler grain as Chan Jian district.
Organic matter treating area (3), dense pool (4) and organic matter treating area (5) inside are covered with OFR Special electric catalytic filler grain (OFR).
Cationic exchange district (2) inside is covered with Zeo-karb filler grain (CER).
Anionresin district (6) inside is covered with anionite-exchange resin filler grain (AER).
Preferably, described Zeo-karb filler grain is D001 large hole strong acid styrene system cation exchange resin, and described anionite-exchange resin filler grain is the rare series anion exchange resin of D201 macroporous strong basic benzene second.
More preferably, above-mentioned ion exchange resin all needs to pass through pre-treatment before use.
Particularly, the pretreatment process of Zeo-karb: soak with appropriate pure water, filter, be soaked in 18 ~ 30h in saturated aqueous common salt, then 3 ~ 6h in 3% ~ 5%NaOH solution of the twice of resin volume is soaked in, finally be soaked in 5 ~ 10h in 3% ~ 5%HCl solution of the twice of resin volume, then soak stand-by in deionized water always.Wherein, preferably, 20h in saturated aqueous common salt is soaked in.Preferably, the concentration of NaOH solution is 3%.Preferably, 4h in 3%NaOH solution is soaked in.Preferably, the concentration of HCl solution is 5%.Preferably, 8h in 5%HCl solution is soaked in.
Particularly, the pretreatment process of anionite-exchange resin: soak with appropriate pure water, filter, be soaked in 18 ~ 30h in saturated aqueous common salt, then 3 ~ 6h in 3% ~ 5%HCl solution of the twice of resin volume is soaked in, finally be soaked in 5 ~ 10h in 3% ~ 5%NaOH solution of the twice of resin volume, then soak stand-by in deionized water always.Wherein, preferably, 20h in saturated aqueous common salt is soaked in.Preferably, the concentration of HCl solution is 5%.Preferably, 4h in 5%HCl solution is soaked in.Preferably, the concentration of NaOH solution is 3%.Preferably, 8h in 3%NaOH solution is soaked in.
In addition, preferably, above-mentioned OFR Special electric catalytic filler first adopts pure water to carry out dipping pretreatment before using, and every 20 ~ 30h(is preferably 24h) change 1 st pure water, totally 3 ~ 6 times (being preferably 5 times), thus the impurity comprised inside removing.
Further preferably, the positive column (1) of above-mentioned three-diemsnional electrode device, cationic exchange district (2), organic matter treating area (3), dense pool (4), organic matter treating area (5), cationic exchange district (6) and cathodic area (7) inner cloth full water are to infiltrate filler.
Can preferred scheme as one, the top and the bottom of the positive column (1) of above-mentioned three-diemsnional electrode device, cationic exchange district (2), organic matter treating area (3), dense pool (4), organic matter treating area (5), cationic exchange district (6) and cathodic area (7) are respectively equipped with the gangway of water, so that cloth full water is to infiltrate filler in these functional zone; Preferably, and each district water level balance can be ensured.
In addition, put into room, pole circulation fluid to produce soda acid maintenance acid-base condition in the positive column (1) of above-mentioned three-diemsnional electrode device and cathodic area (7), room, described pole circulation fluid is metabisulfite solution.
Preferably, room, described pole circulation fluid is the sodium sulfate of 3 ~ 150mg/L.
Device often runs one week and changes once room, pole circulation fluid.Room, the pole circulation fluid changed can be used as the acid of lower concentration or alkali is recycled.
Preferably, the anode material of positive column (1) is graphite electrode plate, and the cathode material of cathodic area (7) is stainless steel electrode.
The application of the present invention's above-mentioned three-diemsnional electrode device in process brine waste, organic wastewater or high salt organic wastewater, also within protection scope of the present invention.
The method of embody rule, is also the Green Water process electrochemical method of the synchronous desalination removal organic polluter continuously of a kind of waste water, comprises the steps:
S1. waste water carries out preaeration process;
S2. above-mentioned three-diemsnional electrode device DSROTDE process is utilized
S21. the waste water after preaeration process enters in organic matter treating area (3) and dense pool (4) by waterwater entrance (11) respectively;
S22. the waste water entered by organic matter treating area (3), through the some pipe connectings (10) arranged, successively through organic matter treating area (3), cationic exchange district (2), organic matter treating area (5), anionresin district (6) under the effect of DC electric field, finally by process water relief outlet (12) discharger, namely complete synchronous desalination and the organic matter removal of waste water; The waste water entered by dense pool (4), in the process of whole wastewater treatment, becomes dense water gradually continuously, is discharged by concentrated water drainage outlet (13).
Preferably, waste water described in step S1 is first through preaeration process 30min.In process saliferous organic wastewater process, waste water is first through preaeration process, make in waste water containing after enough dissolved oxygens, waste water is again by access to plant under the thrust of pump, under the effect of DC electric field, waste water respectively through OFR district, resin cation (R.C.) district and resin anion(R.A) district and to water outlet direction flowing, finally, waste water after treatment by continually by outside water outlet discharger, thus realizes the object of synchronous desalination organic matter removal.
Preferably, water flow velocity or the water yield that ensure to enter in step S21 organic matter treating area (3) and dense pool (4) are identical; Or ensure discharge process water in step S22 and discharge the speed of dense water or measure identical.
Preferably, the intensity of DC electric field described in step S22 is 0.4 ~ 1.5V/cm.
More preferably, in treating processes, the intensity of DC electric field is 0.6V/cm.
Preferably, in treating processes, treatment temp is 25 ~ 35 DEG C.
Particularly, waste water described in step S1 is high salt organic wastewater.Three-diemsnional electrode device provided by the present invention is particularly useful for the process of high salt organic wastewater, can the synchronous desalination organic matter removal of continuous print.And simultaneously, for common brine waste or organic wastewater, there is good treatment effect equally.
The present invention above-mentioned disclosed three-diemsnional electrode device (DSROTDE) is through large quantity research and explores and draws, the defect being applied to process saliferous organic wastewater is difficult to for electrodeionization technology (EDI) and Based on Three-dimensional Electrode Method (TDE), on the basis of the present inventor's patent of invention " particle electrode catalyst filling of a kind of three-diemsnional electrode and preparation method thereof ZL200410077704.5 " in earlier stage, the transformation of technology bridge joint is carried out to EDI, cleverly EDI and TDE two kinds of technical superioritys are merged mutually, maximize favourable factors and minimize unfavourable ones, adopt OFR electrocatalysis unit removing organic pollutant, and pole chamber unit produces soda acid, ensure the online desalination of ion exchange resin, thus realize the object of DSROTDE device continuous synchronization desalination organic matter removal.This device concrete includes ion exchange resin unit (ion exchange resin is equipped with in its inside), pole chamber unit and OFR electrocatalysis unit (its inner dress has OFR filler special).
First the principle of work of this technology and core are in the pole chamber unit of device, put into the sodium sulphate of sufficient quantity (being preferably 3.0 ~ 150.0mg/L) as room, pole circulation fluid, under the effect of DC electric field, acid or alkali can be produced on the one hand in Ji Shi district, can pass through ion-exchange membrane, both ensured that ion exchange resin can desalination online, meet again the on-line automatic recovery of ion exchange resin, room, pole circulation fluid specific conductivity is moderate on the other hand, energy consumption too high (effectively reducing the energy consumption that Based on Three-dimensional Electrode Method runs) when can prevent OFR electrocatalysis cell processing organism, can the unimpeded object of self-cleaning circulating when reaching work, next is that the ion exchange resin filler studied and filter out all is equipped with in each ion exchange resin district in a device, again negative and positive film traditional for EDI is staggered simultaneously and changes cavity block, anode membrane arranged in parallel (namely cavity block is placed in negative pole district, anode membrane is placed in positive polar region and arranges) into, base exchange process is remained carry out in acid condition, thus effectively can suppress a difficult problem for resin and the easy fouling of female die surface, ensure that the lasting stability of online desalination, 3rd is that OFR filler special is all equipped with in device Zhong Ge nonionic exchange resin district, when saliferous organic wastewater is in each OFR electrocatalysis district by device, all can there is the effect of difficult for biological degradation organic pollutant in Decomposition Wastewater, and the object that OFR filler special designs so is all housed is the removal that both can ensure difficult for biological degradation organic pollutant in each nonionic exchange resin district, the rate of migration of ion can be accelerated again simultaneously, salt ion in waste water is made to accelerate to move to direction, dense pool, and outside final discharger.
When practical application, the saliferous organic wastewater of inflow device, under the effect of DC electric field, continuously respectively through OFR district, resin cation (R.C.) district and resin anion(R.A) district, and is finally discharged outside device, just can reach the object of same one-step desalting organic matter removal; In addition, the formation of dense water and collecting region unit are positioned at the OFR district in the middle part of device, the object of such design takes full advantage of under the tractive force effect of DC electric field, can accelerate to make the salt ion in waste water complete exchange interaction through ion exchange resin district rapidly, and through after ion-exchange membrane, the dense pool of device finally all can be come together in.
The present invention has following beneficial effect:
The present invention produces the ingehious design of soda acid technology, the online desalting technology of ion exchange resin, the easy fouling technology of suppression resin and ion-exchange membrane surface, electrocatalysis three-diemsnional electrode process organism technology by pole chamber unit, overcome EDI and Based on Three-dimensional Electrode Method is difficult to be applied to the defect in saliferous organic wastewater, achieve the object of high-efficiency and continuous synchronous desalination organic matter removal waste water, process for saliferous organic wastewater provides a kind of new treatment technology and device, has great importance to the process of high salt organic wastewater.
And, high-efficiency and continuous of the present invention synchronous desalination organic matter removal waste water Green Water process electrochemical method, have that cost is low, the feature of environmental protection, wastewater treatment run this one-tenth low, only need consume the synchronous desalination organic matter removal that a small amount of electric energy just can realize waste water, be easy to Automated condtrol, level of automation high, need not personal management, any chemical reagent is not added in operation, also not easily secondary pollution is produced, its whole operating process, under the condition of environmental protection, realizes the continuous operation of the saliferous organic wastewater simultaneously function of desalination organic matter removal.
Accompanying drawing explanation
Fig. 1 is three-diemsnional electrode device (DSROTDE) schematic diagram of the continuous desalination removal organic polluter of waste water.
Fig. 2 is the on-the-spot dynamic test results (COD) of DSROTDE device continuous desalination removal organic polluter.
Fig. 3 is the on-the-spot dynamic test results (ratio of desalinization) of DSROTDE device continuous desalination removal organic polluter.
Fig. 4 is the contrast of DSROTDE thinking device of the present invention and EDI thinking device in comparative example experimental study, wherein, A is DSROTDE thinking device (film symmetric offset spread: anion-exchange membrane is placed in cathodic area of the present invention, cationic exchange membrane is placed in positive column), B is separated type EDI thinking device (film is staggered: each functional zone are all be made up of anion-exchange membrane and cation ion-exchange membrane).
Fig. 5 is that the on-the-spot dynamic test results (COD) of DSROTDE thinking device and EDI thinking device continuous desalination removal organic polluter contrasts.
Fig. 6 is that the on-the-spot dynamic test results (ratio of desalinization) of DSROTDE thinking device and EDI thinking device continuous desalination removal organic polluter contrasts.
Fig. 7 is the electron-microscope scanning figure before and after Zeo-karb lost efficacy.
Fig. 8 is the electron-microscope scanning figure before and after anionite-exchange resin lost efficacy.
Embodiment
Further illustrate the present invention below in conjunction with Figure of description and specific embodiment, but embodiment does not limit in any form to the present invention.Unless stated otherwise, the present invention adopts reagent, method and apparatus are the art conventional reagent, method and apparatus.
Unless stated otherwise, following examples agents useful for same and material are commercial.
embodiment 1DSROTDE device
The three-diemsnional electrode device (being called for short DSROTDE) of the synchronous desalination removal organic polluter continuously of a kind of waste water, DSROTDE device and principle of work signal thereof are as shown in Figure 1.
This device is by tactic positive column (1), cationic exchange district (2), organic matter treating area (3), dense pool (4), organic matter treating area (5), anionresin district (6) and cathodic area (7) form successively; Positive column (1), cationic exchange district (2), separated by cationic exchange membrane (8) between organic matter treating area (3) and dense pool (4), dense pool (4), organic matter treating area (5), pass through anion-exchange membrane (9) between anionresin district (6) and cathodic area (7) and separate; Wherein, be communicated with respectively by pipe connecting (10) between organic matter treating area (3) and cationic exchange district (2), between cationic exchange district (2) and organic matter treating area (5), between organic matter treating area (5) and anionresin district (6); Organic matter treating area (3) and dense pool (4) are respectively arranged with waterwater entrance (11), anionresin district (6) are provided with process water relief outlet (12), dense pool (4) are provided with concentrated water drainage outlet (13).This device is supported by support (14).
Further, described positive column (1), organic matter treating area (3), dense pool (4), organic matter treating area (5) and cathodic area (7) inside are covered with OFR Special electric catalytic filler grain (OFR, the i.e. filler that provides of patent 200410077704.5) respectively; Cationic exchange district (2) inside is covered with Zeo-karb filler grain (CER); Anionresin district (6) inside is covered with anionite-exchange resin filler grain (AER).
In addition further, the top and the bottom of the positive column (1) of above-mentioned three-diemsnional electrode device, cationic exchange district (2), organic matter treating area (3), dense pool (4), organic matter treating area (5), cationic exchange district (6) and cathodic area (7) are respectively equipped with the gangway of water, so that cloth full water is to infiltrate filler in these functional zone, and each district water level balance can be ensured.
In addition, put into room, pole circulation fluid to produce soda acid maintenance acid-base condition in the positive column (1) of above-mentioned three-diemsnional electrode device and cathodic area (7), room, described pole circulation fluid is the sodium sulfate of 3 ~ 150mg/L, often runs one week and changes once.Room, the pole circulation fluid changed can be used as the acid of lower concentration or alkali is recycled.
The anode material of described positive column (1) is graphite electrode plate, and the cathode material of cathodic area (7) is stainless steel electrode.
the waste water Green Water process electrochemical method of the synchronous desalination organic matter removal of embodiment 2 high-efficiency and continuous
1, the DSROTDE device process saliferous organic wastewater described in embodiment 1 is utilized
(1) when practical application, before needing process waste water, each filler is loaded each functional zone.When each filler uses, just can fill in DSROTDE device after first need carrying out pre-treatment.
This tests Zeo-karb filler grain used is D001 large hole strong acid styrene system cation exchange resin, and anionite-exchange resin filler grain used is the rare series anion exchange resin of D201 macroporous strong basic benzene second.Because resin often containing a small amount of oligopolymer and the base matter not participating in reaction, also can remain a part of inorganic electrolyte ion, as Fe when processing simultaneously
3+, Pb
2+, Cu
2+deng foreign ion.So need to carry out pre-treatment to resin in the early stage that resin uses, the appropriate pure water of resin is soaked, filters, avoid because the cause influence desalting effect of resin.
Particularly, described Zeo-karb needs to carry out pre-treatment before use: soak with appropriate pure water, filter, be soaked in 20h in saturated aqueous common salt, then 4h in the 3%NaOH solution of the twice of resin volume is soaked in, finally be soaked in 8h in the 5%HCl solution of the twice of resin volume, then soak stand-by in deionized water always.
Described anionite-exchange resin needs to carry out pre-treatment before use: soak with appropriate pure water, filter, be soaked in 20h in saturated aqueous common salt, then 4h in the 5%HCl solution of the twice of resin volume is soaked in, finally be soaked in 8h in the 3%NaOH solution of the twice of resin volume, then soak stand-by in deionized water always.
Above-mentioned OFR Special electric catalytic filler first adopts pure water to carry out dipping pretreatment before using, and every 24h changes 1 st pure water, totally 5 times, thus the impurity comprised inside removing.
(2) in this experiment, anode material is graphite electrode plate, and cathode material is stainless steel electrode.That electrode solution Bian is 10.0mg/LNa
2s0
4solution circulates.
2, wastewater treatment process
(1) waste water is first through preaeration 30min process, and make containing after enough dissolved oxygens in waste water, waste water is again by access to plant under the thrust of pump;
(2) waste water after preaeration process enters in organic matter treating area (3) and dense pool (4) by waterwater entrance (11) respectively; Guarantee enter the water flow velocity of organic matter treating area (3) and dense pool (4) or the water yield identical.
The waste water entered by organic matter treating area (3), through the some pipe connectings (10) arranged, successively through organic matter treating area (3), cationic exchange district (2), organic matter treating area (5), anionresin district (6) under the effect of DC electric field, waste water finally after process by continually by process water relief outlet (12) discharger, namely completes synchronous desalination and the organic matter removal of waste water;
The waste water entered by dense pool (4), in the process of whole wastewater treatment, becomes dense water gradually continuously, is discharged by concentrated water drainage outlet (13).
Same, in treating processes, keep discharging process water and discharging the speed of dense water or measure identical.
In addition, in whole treating processes, treatment temp is 25 ~ 35 DEG C, and the intensity of step (2) described DC electric field is 0.4 ~ 1.5V/cm.
the chemical plant wastewater process test of embodiment 3 rich field
Utilize DSROTDE device of the present invention in chemical plant, rich field biochemical qualified discharge mouth to fetch water on-the-spot lab scale, test former water COD100 ± 10mg/L, specific conductivity 1500 ± 100us/cm.
At the even strength of electric field 0.6V/cm of control, temperature is 25.0 ~ 35.0 DEG C, wastewater treatment capacity 10L/hr, hydraulic detention time 40 minutes, after process, draining and concentrated water drainage water ratio are under the condition of 1:1, and by the continuous running of 3 months, the phenomenon of ion exchange resin and ion-exchange membrane surface scale never appearred in device, also never there is the problem that processing efficiency declines, there is very high stability.
Result, as Fig. 2 and Fig. 3, is shown by data results, the working cost only power consumption 0.3 degree/m of device
3waste water, the organic removal rate (COD < 60mg/L) of waste water is all higher than more than 45.0%, and the ratio of desalinization (specific conductivity < 300us/cm) of waste water, all higher than more than 83.0%, meets manufacturer's reuse water requirement.
comparative example 1
1, DSROTDE device of the present invention and water technology are the defects that the present inventor is difficult to for electrodeionization technology (EDI) and Based on Three-dimensional Electrode Method (TDE) be applied to process saliferous organic wastewater, on the basis of the present inventor's patent of invention " particle electrode catalyst filling of a kind of three-diemsnional electrode and preparation method thereof ZL200410077704.5 " in earlier stage, the transformation of technology bridge joint is carried out to EDI, cleverly EDI and TDE two kinds of technical superioritys to be merged mutually and draw, in the process of research, occur much making the beyond thought problem of contriver, contriver have passed through large quantifier elimination and explores and overcomes one by one, DSROTDE device of the present invention and water technology are drawn.
2, find in the process of research and development desalination simultaneously organic matter removal device, the effect of pattern of rows and columns on device process waste water of anion and cation exchange membrane has vital impact.The device of simultaneous test is as described in accompanying drawing 4, and pattern of rows and columns of the anion and cation exchange membrane of A and the B device in Fig. 4 is different.Wherein, A device is the negative and positive film symmetric offset spread of DSROTDE thinking device of the present invention, this device: namely anion-exchange membrane is placed in cathodic area, and cationic exchange membrane is placed in positive column; B device is that film is staggered: namely each functional zone are all be made up of (separated type EDI thinking device) anion-exchange membrane and cation ion-exchange membrane.
Here illustrate a bit, the DSROTDE device of embodiment 1 is the device of Unit seven, is also best embodiment; And Unit seven can not carry out contrast experiment in simultaneous test, therefore in order to adapt to simultaneous test, have employed five modular compare device's series, only in this way, just the contrast experiment's research under same condition may be carried out.
3, through the research trial with embodiment 3, result as shown in Figure 5 and Figure 6.The result of contrast experiment shows: with under the same experimental conditions of same embodiment 3, and the effect of the desalination organic matter removal of A device is all highly stable, is all significantly better than B device (especially ratio of desalinization).The undesirable major cause of B device treatment effect is that regeneration of ion-exchange resin needs frequently pole-reversing, not there is continuous desalination function, as adopted continuous de-salting operation will produce situation in Fig. 6, finally cause ion exchange resin fouling and inefficacy, ratio of desalinization continues to decline to a great extent.
We are studied the state before and after the Zeo-karb of B device and anionite-exchange resin inefficacy.Result as shown in Figure 7 and Figure 8.Fig. 7 is the electron-microscope scanning figure before and after Zeo-karb lost efficacy, wherein a is the electron-microscope scanning figure before Zeo-karb lost efficacy, b is the electron-microscope scanning figure after Zeo-karb lost efficacy, Fig. 8 is the electron-microscope scanning figure before and after anionite-exchange resin lost efficacy, wherein a is the electron-microscope scanning figure before anionite-exchange resin inefficacy, b is the electron-microscope scanning figure after anionite-exchange resin lost efficacy.
Electron-microscope scanning figure before and after losing efficacy as can be seen from ion exchange resin, Zeo-karb surface or on anionite-exchange resin surface all to some extent by layer of substance coated (mainly precipitation of hydroxide foulant), which illustrate the increase along with the B device treatment time, the surface of anion and cation exchange membrane has all been completely cut off by the material depended on the passage that resin carries out exchanging, the exchange capacity of resin can reduction gradually, and then loses its exchange capacity.
Claims (10)
1. the three-diemsnional electrode device of the synchronous desalination removal organic polluter continuously of waste water, this device is made up of positive column, cathodic area and some functional zone unit, comprises Zeo-karb unit, anionite-exchange resin unit, pole chamber unit and several OFR electrocatalysis unit; Sodium sulphate is put into as room, pole circulation fluid in the chamber unit of pole; Ion exchange resin unit is equipped with ion exchange resin filler, and anion-exchange membrane is placed in cathodic area, and cationic exchange membrane is placed in positive column; OFR electrocatalysis unit is equipped with OFR filler special; OFR electrocatalysis unit in the middle part of device is the formation of dense water and dense water collecting region; Waste water continuously across OFR electrocatalysis unit, Zeo-karb unit, OFR electrocatalysis unit, anionite-exchange resin unit, is finally discharged outside device successively, realizes same one-step desalting organic matter removal.
2. the three-diemsnional electrode device of the synchronous desalination removal organic polluter continuously of waste water according to claim 1, it is characterized in that, this device is by tactic positive column (1), cationic exchange district (2), organic matter treating area (3), dense pool (4), organic matter treating area (5), anionresin district (6) and cathodic area (7) form successively; Positive column (1), cationic exchange district (2), separated by cationic exchange membrane (8) between organic matter treating area (3) and dense pool (4), dense pool (4), organic matter treating area (5), pass through anion-exchange membrane (9) between anionresin district (6) and cathodic area (7) and separate; Wherein, be communicated with respectively by pipe connecting (10) between organic matter treating area (3) and cationic exchange district (2), between cationic exchange district (2) and organic matter treating area (5), between organic matter treating area (5) and anionresin district (6); Organic matter treating area (3) and dense pool (4) are respectively arranged with waterwater entrance (11), anionresin district (6) are provided with process water relief outlet (12), dense pool (4) are provided with concentrated water drainage outlet (13).
3. three-diemsnional electrode device according to claim 2, it is characterized in that, described positive column (1), organic matter treating area (3), dense pool (4), organic matter treating area (5) and cathodic area (7) inside are covered with OFR Special electric catalytic filler grain respectively; Cationic exchange district (2) inside is covered with Zeo-karb filler grain; Anionresin district (6) inside is covered with anionite-exchange resin filler grain.
4. three-diemsnional electrode device according to claim 3, it is characterized in that, the top and the bottom of described positive column (1), cationic exchange district (2), organic matter treating area (3), dense pool (4), organic matter treating area (5), cationic exchange district (6) and cathodic area (7) are respectively equipped with the gangway of water, and in these functional zone, cloth full water is to infiltrate filler.
5. three-diemsnional electrode device according to claim 3, it is characterized in that, described Zeo-karb filler grain is D001 large hole strong acid styrene system cation exchange resin; Described anionite-exchange resin filler grain is the rare series anion exchange resin of D201 macroporous strong basic benzene second.
6. three-diemsnional electrode device according to claim 2, is characterized in that, put into room, pole circulation fluid in positive column (1) and cathodic area (7) and maintain acid-base condition to produce soda acid, room, described pole circulation fluid is metabisulfite solution.
7. the application of the arbitrary described three-diemsnional electrode device of claim 1 ~ 6 in process brine waste, organic wastewater or high salt organic wastewater.
8. a Green Water process electrochemical method for the synchronous desalination removal organic polluter continuously of waste water, is characterized in that, comprise the steps:
S1. waste water carries out preaeration process;
S2. the arbitrary described three-diemsnional electrode device of claim 1 ~ 6 is utilized to process
S21. the waste water after preaeration process enters in organic matter treating area (3) and dense pool (4) by waterwater entrance (11) respectively;
S22. the waste water entered by organic matter treating area (3), through the some pipe connectings (10) arranged, successively through organic matter treating area (3), cationic exchange district (2), organic matter treating area (5), anionresin district (6) under the effect of DC electric field, discharge finally by process water relief outlet (12), namely complete synchronous desalination and the organic matter removal of waste water; Dense water in dense pool (4) is discharged by concentrated water drainage outlet (13).
9. Green Water process electrochemical method according to claim 8, is characterized in that, the water flow velocity or the water yield that ensure to enter in step S21 organic matter treating area (3) and dense pool (4) are identical; And/or ensure discharge process water in step S22 and discharge the speed of dense water or measure identical.
10. Green Water process electrochemical method according to claim 8, it is characterized in that, the intensity of DC electric field described in step S22 is 0.4 ~ 1.5V/cm.
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