CN105236527B - A kind of three-diemsnional electrode device and method of the synchronous continuous desalination removal organic polluter of waste water - Google Patents
A kind of three-diemsnional electrode device and method of the synchronous continuous desalination removal organic polluter of waste water Download PDFInfo
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Abstract
The invention discloses a kind of three-diemsnional electrode device of the synchronous continuous desalination removal organic polluter of waste water and Green Electrochemical processing method.The device includes cationic ion-exchange resin unit, anion exchange resin unit, pole room unit and several OFR electro-catalysis units；Sodium sulphate is put into pole room unit as pole room circulation fluid；Ion exchange resin unit is equipped with ion exchange resin filler, and anion-exchange membrane is placed in cathodic region, and cation-exchange membrane is placed in anode region；OFR electro-catalysis unit is equipped with OFR filler specials；Formation and collecting region of the OFR electro-catalysis unit for concentrated water in the middle part of device；Waste water sequentially passes through OFR electro-catalysis unit, cationic ion-exchange resin unit, OFR electro-catalysis unit, anion exchange resin unit, and last discharger realizes the purpose that organic matter is removed with one-step desalting.The present invention realizes the synchronous desalination of high-efficiency and continuous and removes the purpose of organic wastewater, and runs this into low, automaticity is high, environmental protection.
Description
Technical field
The invention belongs to technical field of sewage.Continuously taken off using electrochemical method waste water more particularly, to one kind
The green water process electrochemical method and its three-diemsnional electrode device (DSROTDE) of salt removal organic polluter.
Background technology
Based on Three-dimensional Electrode Method (Three-dimensional electrodes, abbreviation TDE) is that a kind of conventional processing is organic
Method for waste water, the method is on the basis of traditional two dimension feed pole plate, to add a kind of particle with low-impedance electric conductivity
Derivation is into three-diemsnional electrode (E.Fockedey, 2002；Jiang Hui etc., 2014), and the particle being polarized in the presence of electric field just by
Serve as the 3rd pole, by occurring electrochemical oxidation reactions on the surface of electrode particle, the oxide for producing strong oxidation is gone
Organic target thing is attacked, so as to reach the effect for the organic pollution for removing difficult for biological degradation.This conductive particle of above-mentioned addition
Son, on the one hand increases considerably the surface area of electrode reaction, on the other hand can act on the voltage of the feeding electrode of script and extend
Into the main body of solution, this is equivalent to the electric field distance for shortening two-plate so that target processed material is being run on pole plate
Distance also greatly shortens.
The early-stage Study of the present inventor achieves Patent No. ZL02114740.X three-diemsnional electrode catalytic oxidation processing
Organic wastewater technology, when the technology is used for the processing of organic wastewater, with broad spectrum activity, efficiently, quickly, sludge quantity is few, does not produce
Raw secondary pollution, while having the functions such as deodoring and disinfecting, it has a extensive future；But, the granule electrode that the technology is used is urged
Agent filler has that cost of material is too high, and mechanical strength is poor, wherein not strong etc. enough defect of the cooperative effect between each composition.This
The particle electrode catalyst that inventor obtains a kind of three-diemsnional electrode of Patent No. 200410077704.5 in follow-up study is filled out
Material and preparation method thereof, this conducting particles has a very high specific surface area, and with very huge very intensive absorption duct,
These ducts are exactly the significant points that granule electrode plays a role, exactly because the also presence in this duct, is greatly added
The response area of electrode reaction, is several orders of magnitude of traditional two-dimentional feeding electrode response area, is removing difficult for biological degradation
Important function has been played in organic pollution.But, above-mentioned this method processing contain organic wastewater high in salt when, by
Processing procedure energy consumption is set to increase in the presence of salt side reaction, while also significantly decline there is also organic matter treatment effeciency
Problem.
Electrodeionization technology (Eleetrodeionization, abbreviation EDI) is also known as continuous deionization technology
(Continuous Deionization, CEDI), early stage is also referred to as packed-bed electrodialysis.EDI technologies have merged electricity well
Osmotic technique and ion exchange technique, are that mixed-bed resin is filled between amberplex by one kind, under DC electric field effect
The new method for treating water of continuous desalination is realized, is also after the intermembranous filling ion-exchange resin of electrodialysis plant, in direct current
In the presence of electric field, a kind of new separation technology (K E Bouhidel etc., 2006 of continuous deionising process can be achieved；Sun Xian
Deng 2011).Electroosmose process (Electro Dialysis, abbreviation ED) is to utilize amberplex, including anion-exchange membrane
(Anion exchange membrane, AEM), cation-exchange membrane (Cation exchange membrane, CEM), relies on
Amberplex in the presence of applying direct current electric field, is realized electrolyte concentration or desalinated to the selective penetrated property of anions and canons
Technology.Electroosmose process is because aquifer yield is small, power consumption big and film is easily polluted by organic matter and fails, and method is used for small-sized
Water desalination station.Ion-exchange (Ion-exchange process, abbreviation IEX) includes anion using Solid-state Ion-exchange agent
Exchanger resin (Anion exchange resin, AER) and cationic ion-exchange resin (Cation exchange resin,
CER), swapped by the ion in the ion and Solid-state Ion-exchange agent in solution, so as to reach removal or extract solution
In some ions purpose.Generally, the absorption of ion exchange resin and exchange capacity are very strong, and pollutant removal is preferable, but
Be, it is desirable to regenerative elution technique it is cumbersome, investment and maintenance cost it is higher, resin is vulnerable to Organic Pollution and failed in addition.
The design of system, operation, manage all cumbersome, it is necessary to professional and technical personnel, so being typically only used for the advanced treating of waste water
In.
In EDI devices, electric conductivity two to three numbers higher than the aqueous conductive contacted of ion exchange resin
Magnitude, ion permeable film surface almost all is the effect of ion exchange resin, i.e., the raising of intermembranous electric conductivity is significantly enhanced
The migration of ion, the problem of solving the poor phenomenon of ion and the big resistance in film surface concentration retention layer, and occur in electrode chamber
Water decomposition effect produce hydrogen ion and hydroxide ion can regenerating resin can also loading section electric current.Therefore, EDI devices energy
The regeneration of resin, ion exchange, deionization is set to occur simultaneously, the desalination of its existing electrodialysis plant has ion again
The ion exchange of exchanger resin, it is to avoid harmful effect and the ion exchange resin regeneration of electrodialysis concentration polarization and cause
Environmental pollution the shortcomings of.
Effect of traditional EDI devices when producing ultra-pure water or pure water is preferable, but applied to heavy metal containing wastewater treatment
In, when water inlet contains compared with metal ions such as high contents of calcium and magnesium, often because the hydroxyl formation hydroxide precipitation that hydrolysis is produced, is caused
Make easily occur scale problems on film and resin during continuous operation, largely limit the application of method.To prevent fouling,
Current EDI methods generally use down the operation such as pole, acid adding or antisludging agent to maintain the stable operation of whole device, but this obviously increases
The complexity of system, declines efficiency, cost increase.Further, since ion exchange resin and electrodialysis-ion exchange film
Itself easily influenceed and failed by organic pollution, therefore be difficult to be applied in the processing of saliferous organic wastewater.
The content of the invention
The technical problem to be solved in the present invention is to overcome electrodeionization technology (EDI) and Based on Three-dimensional Electrode Method in the prior art
(TDE) it is difficult to the defect and deficiency for being applied to processing saliferous organic wastewater, in the patent of invention of the present inventor's early stage
《ZL200410077704.5, a kind of particle electrode catalyst filling of three-diemsnional electrode and preparation method thereof》On the basis of, to EDI
Carry out technology bridge joint transformation, enables two kinds of ingenious fusions of technical advantage, and research has manufactured a kind of continuous desalination of waste water except organic
The three-diemsnional electrode device (abbreviation DSROTDE) of pollutant.
It is an object of the invention to provide a kind of three-diemsnional electrode device of the synchronous continuous desalination removal organic polluter of waste water.
Another object of the present invention is to provide a kind of green water process electrification of the synchronous continuous desalination removal organic polluter of waste water
Method.
Above-mentioned purpose of the present invention is achieved through the following technical solutions：
A kind of three-diemsnional electrode device (abbreviation DSROTDE) of the synchronous continuous desalination removal organic polluter of waste water, the device by
Anode region, cathodic region and several functional areas units are constituted, including cationic ion-exchange resin unit, anion exchange resin list
First (cationic ion-exchange resin, anion exchange resin are respectively provided with inside it), pole room unit and several OFR electro-catalysis units
(its internal dress has OFR filler specials)；Device produces soda acid technology, the online desalination skill of ion exchange resin by pole room unit
Art, suppression resin and the easy fouling technology in amberplex surface, electro-catalysis three-diemsnional electrode handle the ingenious combination of organic matter technology
Design, realizes the desalination simultaneously of saliferous organic wastewater except the purpose of the continuous operation of the function of organic matter.
Specifically, the device is by tactic anode region (1), cation exchange area (2), the first organic matter successively
Manage area (3), concentrated water area (4), the second organic matter treating area (5), anion exchange area (6) and cathodic region (7) composition；Anode region
(1), between cation exchange area (2), the first organic matter treating area (3) and concentrated water area (4) by cation-exchange membrane (8) every
Open, anion exchange is passed through between concentrated water area (4), the second organic matter treating area (5), anion exchange area (6) and cathodic region (7)
Film (9) is separated；Wherein, between the first organic matter treating area (3) and cation exchange area (2), cation exchange area (2) and second
Pass through connecting tube respectively between organic matter treating area (5), between the second organic matter treating area (5) and anion exchange area (6)
(10) connect；Waterwater entrance (11), anion exchange area are respectively arranged with first organic matter treating area (3) and concentrated water area (4)
(6) processing water outlet (12) is provided with, concentrated water outlet (13) is provided with concentrated water area (4).
Concentrated water area (4) is an OFR area for being located at the positive middle part of device, and it is only one by cation-exchange membrane 1 and the moon
The functional areas that amberplex 6 is separated, inside is covered with the concentrated water area collector unit that OFR Special electrics catalytic filler grain 3 is constituted.
Preferably, the device is supported by support (14).
Further, OFR Special electrics catalytic filler grain (OFR, i.e. patent are covered with the anode region (1)
200410077704.5 the filler provided) it is used as Chan Suan areas.
It is covered with OFR Special electrics catalytic filler grain inside cathodic region (7) as Chan Jian areas.
First organic matter treating area (3), concentrated water area (4) and the second organic matter treating area (5) inside are covered with OFR Special electrics and urged
Change filler grain (OFR).
It is covered with cationic ion-exchange resin filler grain (CER) inside cation exchange area (2).
It is covered with anion exchange resin filler grain (AER) inside anion exchange area (6).
Preferably, the cationic ion-exchange resin filler grain is D001 macropore strong acid polystyrene cation exchange trees
Fat, the anion exchange resin filler grain is the dilute series anion exchange resin of D201 macroporous strong basic benzene second.
It is highly preferred that above-mentioned ion exchange resin using be preceding both needed to by pretreatment.
Specifically, the preprocess method of cationic ion-exchange resin：Soaked with appropriate pure water, filtering, be soaked in saturation food
18~30h in salt solution, is then soaked in 3~6h in twice of 3%~5%NaOH solution of resin volume, is finally soaked in tree
5~10h in 3%~5%HCl solution of twice of fat volume, then soaks stand-by in deionized water always.Wherein, preferably
Ground, is soaked in 20h in saturated aqueous common salt.Preferably, the concentration of NaOH solution is 3%.Preferably, it is soaked in 3%NaOH solution
Middle 4h.Preferably, the concentration of HCl solution is 5%.Preferably, it is soaked in 8h in 5%HCl solution.
Specifically, the preprocess method of anion exchange resin：Soaked with appropriate pure water, filtering, be soaked in saturation food
18~30h in salt solution, is then soaked in 3~6h in twice of 3%~5%HCl solution of resin volume, is finally soaked in resin
5~10h in 3%~5%NaOH solution of twice of volume, then soaks stand-by in deionized water always.Wherein, preferably
Ground, is soaked in 20h in saturated aqueous common salt.Preferably, the concentration of HCl solution is 5%.Preferably, it is soaked in 5%HCl solution
4h.Preferably, the concentration of NaOH solution is 3%.Preferably, it is soaked in 8h in 3%NaOH solution.
Furthermore it is preferred that above-mentioned OFR Special electrics catalytic filler first carries out dipping pretreatment, every 20 before using pure water
~30h (being preferably 24h) changes 1 st pure water, totally 3~6 times (being preferably 5 times), so as to remove the impurity that the inside is included.
It is further preferred that the anode region (1) of above-mentioned three-diemsnional electrode device, cation exchange area (2), at the first organic matter
Manage area (3), concentrated water area (4), the second organic matter treating area (5), cation exchange area (6) and cathodic region (7) inside cloth full water with
Infiltrate filler.
As a kind of preferable scheme, the anode region (1) of above-mentioned three-diemsnional electrode device, cation exchange area (2), first
Organic matter treating area (3), concentrated water area (4), the second organic matter treating area (5), cation exchange area (6) and cathodic region (7) it is upper
Bottom is respectively equipped with the gateway of water, so as in these functional areas cloth full water to infiltrate filler；Preferably, and each area's water can be ensured
Position balance.
In addition, being put into pole room circulation fluid to produce soda acid in the anode region (1) and cathodic region (7) of above-mentioned three-diemsnional electrode device
Acid-base condition is maintained, the pole room circulation fluid is metabisulfite solution.
Preferably, the pole room circulation fluid is 3~150mg/L sodium sulphate.
Device, which is often run, replaces once a week pole room circulation fluid.The pole room circulation fluid changed can as low concentration acid
Or alkali is recycled.
Preferably, the anode material of anode region (1) is graphite electrode plate, and the cathode material of cathodic region (7) is stainless steel electricity
Pole.
The above-mentioned three-diemsnional electrode device of the present invention is in terms of processing brine waste, organic wastewater or high salt organic wastewater
Using also within protection scope of the present invention.
The method of concrete application, namely a kind of synchronous continuous desalination removal organic polluter of waste water green water process electrochemistry
Method, comprises the following steps：
S1. waste water carries out pre-exposure gas disposal；
S2. above-mentioned three-diemsnional electrode device DSROTDE processing is utilized
S21. the waste water after pre-exposure gas disposal respectively enters the first organic matter treating area (3) and concentrated water by waterwater entrance (11)
In area (4)；
S22. the waste water entered by the first organic matter treating area (3), configured some connecting tubes (10), in DC electric field
In the presence of sequentially pass through the first organic matter treating area (3), cation exchange area (2), the second organic matter treating area (5), it is cloudy from
Sub- exchange area (6), most complete the synchronous desalination of waste water and except organic matter through handling water outlet (12) discharger afterwards；By
The waste water that concentrated water area (4) enters gradually continuously turns into concentrated water, passes through concentrated water outlet during whole wastewater treatment
(13) discharge.
Preferably, waste water described in step S1 first passes through pre-exposure gas disposal 30min.In processing saliferous organic wastewater process
In, waste water first passes around pre-exposure gas disposal, makes to contain after enough dissolved oxygens in waste water, waste water enters dress under the thrust of pump again
In putting, in the presence of DC electric field, waste water is respectively through OFR areas, resin cation area and resin anion (R.A.) area and to going out
Mouth of a river direction is flowed, finally, and waste water after processing is by outside continually by delivery port discharger, so as to realize synchronous desalination
Except the purpose of organic matter.
Preferably, it is ensured that enter the water flow velocity or water of the first organic matter treating area (3) and concentrated water area (4) in step S21
Amount is identical；Or ensure that discharge processing water is identical with the speed or amount of discharge concentrated water in step S22.
Preferably, the intensity of DC electric field described in step S22 is 0.4~1.5V/cm.
It is highly preferred that the intensity of DC electric field is 0.6V/cm in processing procedure.
Preferably, treatment temperature is 25~35 DEG C in processing procedure.
Specifically, waste water described in step S1 is high salt organic wastewater.Three-diemsnional electrode device provided by the present invention is especially
Suitable for the processing of high salt organic wastewater, continuously synchronous desalination organic matter can be removed.And it is useless simultaneously for common saliferous
Water or organic wastewater equally have good treatment effect.
Present invention three-diemsnional electrode device (DSROTDE) disclosed above draws by numerous studies and exploring, for
Electrodeionization technology (EDI) and Based on Three-dimensional Electrode Method (TDE) are difficult to the defect for being applied to processing saliferous organic wastewater, at this
The patent of invention of inventor's early stage《A kind of particle electrode catalyst filling of three-diemsnional electrode and preparation method thereof
ZL200410077704.5》On the basis of, technology bridge joint transformation is carried out to EDI, cleverly by two kinds of technical advantages of EDI and TDE
Mutually fusion, is maximized favourable factors and minimized unfavourable ones, and organic pollution is removed using OFR electro-catalysis unit, and pole room unit produces soda acid, to ensure
The online desalination of ion exchange resin, so as to realize that DSROTDE device continuous synchronizations desalination removes the purpose of organic matter.The specific dress
Put and include ion exchange resin unit (it is internal equipped with ion exchange resin), pole room unit and OFR electro-catalysis units (in it
Portion's dress has OFR filler specials).
The operation principle and core of the technology are to be put into the sodium sulphate of Sq (preferably in the pole room unit of device first
For 3.0~150.0mg/L) as pole room circulation fluid, in the presence of DC electric field, on the one hand can be produced in pole room area acid or
Alkali, can pass through amberplex, both ensured ion exchange resin can desalination online, the on-line automatic of ion exchange resin is met again
Recover, another aspect pole room circulation fluid electrical conductivity is moderate, energy consumption is too high (i.e. when can prevent OFR electro-catalysis cell processing organic matters
The energy consumption that effectively reduction Based on Three-dimensional Electrode Method is run), energy self-cleaning circulating unimpeded purpose when reaching work；Next to that in device
Zhong Ge ion exchange resin area is equipped with studying the ion exchange resin filler filtered out, while again by negative and positive film traditional EDI
It is staggered and is changed to cavity block, anode membrane arranged in parallel (i.e. cavity block is placed in negative pole area, anode membrane and is placed in positive polar region arrangement), hands over cation
The process of changing is remained and carried out in acid condition, so as to effectively suppress the problem of resin and the easy fouling of female die surface,
It ensure that the lasting stability of online desalination；3rd is that device Zhong Ge nonionic exchange resins area is equipped with OFR filler specials, when
Saliferous organic wastewater is at each OFR electro-catalysis area by device, the organic dirt of difficult for biological degradation in the waste water that can decompose
The effect of thing is contaminated, and it is that can both ensure difficulty that each nonionic exchange resin area, which is equipped with the purpose that OFR filler specials so design,
The removal of biodegradable organic pollution, the migration rate of ion can be accelerated simultaneously again so that in waste water salt ion accelerate to
Concentrated water area direction is moved, and outside final discharger.
In practical application, the saliferous organic wastewater of inflow device is in the presence of DC electric field, continuously respectively through
OFR areas, resin cation area and resin anion (R.A.) area, and finally discharge in outside device, so that it may reach same one-step desalting except organic
The purpose of thing；In addition, the formation of concentrated water and collecting region unit are located at the OFR areas in the middle part of device, the purpose so designed is abundant
It make use of under the tractive force effect of DC electric field, can accelerate to make the salt ion in waste water complete by ion exchange resin area rapidly
Into exchange interaction, and through after amberplex, it finally can all come together in the concentrated water area of device.
The invention has the advantages that：
The present invention produces soda acid technology, the online desalting technology of ion exchange resin by pole room unit, suppress resin and from
The easy fouling technology in proton exchange surface, electro-catalysis three-diemsnional electrode handle the ingehious design of organic matter technology, overcome EDI and three-dimensional
Electrode method is difficult to the defect being applied in saliferous organic wastewater, realizes the synchronous desalination of high-efficiency and continuous and removes organic wastewater
Purpose, a kind of new treatment technology and device are provided for the processing of saliferous organic wastewater, to high salt organic wastewater
Processing has great importance.
Moreover, the synchronous desalination of the high-efficiency and continuous of the present invention is except the green water process electrochemical method of organic wastewater, with into
This is low, environmental protection the characteristics of, wastewater treatment run this into it is low, only need to consume a small amount of electric energy just can realize the synchronous desalination of waste water
Except organic matter, it is easy to which Automated condtrol, automaticity be high, without personal management, without any chemical reagent in operation,
Secondary pollution is not likely to produce, its whole operation process realizes saliferous organic wastewater desalination simultaneously under conditions of environmental protection
Except the continuous operation of the function of organic matter.
Brief description of the drawings
Fig. 1 is three-diemsnional electrode device (DSROTDE) schematic diagram of the continuous desalination removal organic polluter of waste water.
Fig. 2 is the live dynamic test results (COD) of the continuous desalination removal organic polluter of DSROTDE devices.
Fig. 3 is the live dynamic test results (salt rejection rate) of the continuous desalination removal organic polluter of DSROTDE devices.
Fig. 4 is the contrast of DSROTDE thinkings device Yu EDI thinking devices of the invention in comparative example experimental study, wherein,
A is DSROTDE thinkings device (film symmetric arrays of the invention：Anion-exchange membrane is placed in cathodic region, and cation-exchange membrane is placed in
Anode region), B is that (film is staggered separated type EDI thinkings device:Each functional areas be by anion-exchange membrane and cation from
Proton exchange is constituted).
Fig. 5 is the live dynamic test knot of DSROTDE thinkings device and the continuous desalination removal organic polluter of EDI thinking devices
Really (COD) is contrasted.
Fig. 6 is the live dynamic test knot of DSROTDE thinkings device and the continuous desalination removal organic polluter of EDI thinking devices
Really (salt rejection rate) is contrasted.
Fig. 7 is the electron-microscope scanning figure before and after cationic ion-exchange resin fails.
Fig. 8 is the electron-microscope scanning figure before and after anion exchange resin fails.
Embodiment
The present invention is further illustrated below in conjunction with Figure of description and specific embodiment, but embodiment is not to the present invention
Limit in any form.Unless stated otherwise, the reagent of the invention used, method and apparatus routinely try for the art
Agent, method and apparatus.
Unless stated otherwise, following examples agents useful for same and material are purchased in market.
The DSROTDE devices of embodiment 1
A kind of three-diemsnional electrode device (abbreviation DSROTDE) of the synchronous continuous desalination removal organic polluter of waste water, DSROTDE dresses
Put and its operation principle signal is as shown in Figure 1.
The device is by tactic anode region (1), cation exchange area (2), the first organic matter treating area successively
(3), concentrated water area (4), the second organic matter treating area (5), anion exchange area (6) and cathodic region (7) are constituted；Anode region (1), sun
Separated between ion-exchange area (2), the first organic matter treating area (3) and concentrated water area (4) by cation-exchange membrane (8), concentrated water
Between area (4), the second organic matter treating area (5), anion exchange area (6) and cathodic region (7) by anion-exchange membrane (9) every
Open；Wherein, between the first organic matter treating area (3) and cation exchange area (2), cation exchange area (2) and the second organic matter
Pass through connecting tube (10) between treatment region (5), between the second organic matter treating area (5) and anion exchange area (6) respectively to connect；
It is respectively arranged with waterwater entrance (11), anion exchange area (6) and sets on first organic matter treating area (3) and concentrated water area (4)
There is processing water outlet (12), concentrated water outlet (13) is provided with concentrated water area (4).The device is supported by support (14).
Further, the anode region (1), the first organic matter treating area (3), concentrated water area (4), the second organic matter treating area
(5) and inside cathodic region (7) being covered with OFR Special electrics catalytic filler grain respectively, (OFR, i.e. patent 200410077704.5 are provided
Filler)；It is covered with cationic ion-exchange resin filler grain (CER) inside cation exchange area (2)；Anion exchange area (6) is internal
It is covered with anion exchange resin filler grain (AER).
In addition further, the anode region (1) of above-mentioned three-diemsnional electrode device, cation exchange area (2), at the first organic matter
Manage the top and the bottom difference of area (3), concentrated water area (4), the second organic matter treating area (5), cation exchange area (6) and cathodic region (7)
Gateway provided with water, so that cloth full water, to infiltrate filler, and can ensure each area's water level balance in these functional areas.
In addition, being put into pole room circulation fluid to produce soda acid in the anode region (1) and cathodic region (7) of above-mentioned three-diemsnional electrode device
Acid-base condition is maintained, the pole room circulation fluid is 3~150mg/L sodium sulphate, and often operation is replaced once a week.Change
Pole room circulation fluid can be recycled as the acid or alkali of low concentration.
The anode material of the anode region (1) is graphite electrode plate, and the cathode material of cathodic region (7) is stainless steel electrode.
The synchronization desalination of the high-efficiency and continuous of embodiment 2 is except the green water process electrochemical method of the waste water of organic matter
1st, saliferous organic wastewater is handled using the DSROTDE devices described in embodiment 1
(1) in practical application, each filler is loaded into each functional areas before needing processing waste water.Each filler is in use, need elder generation
It can be just loaded in DSROTDE devices after being pre-processed.
Cationic ion-exchange resin filler grain is D001 large hole strong acid styrene system cation exchange resins used in this experiment,
Anion exchange resin filler grain used is the dilute series anion exchange resin of D201 macroporous strong basic benzene second.Because resin is in processing
Often containing a small amount of oligomer and the base matter for being not engaged in reacting when production, while can also remain a part without electromechanics
Solve matter ion, such as Fe3+、Pb2+、Cu2+Deng foreign ion.So need to pre-process resin in the early stage that resin is used, will
Resin is soaked with appropriate pure water, filtering, it is to avoid because influenceing desalting effect the reason for resin.
Specifically, the cationic ion-exchange resin is using preceding needing to be pre-processed：Soaked with appropriate pure water, filtering,
20h in saturated aqueous common salt is soaked in, 4h in twice of 3%NaOH solution of resin volume is then soaked in, is finally soaked in tree
8h in the 5%HCl solution of twice of fat volume, then soaks stand-by in deionized water always.
The anion exchange resin is using preceding needing to be pre-processed：Soaked with appropriate pure water, filtering is soaked in full
With 20h in saline solution, 4h in twice of 5%HCl solution of resin volume is then soaked in, the two of resin volume are finally soaked in
8h in 3%NaOH solution again, then soaks stand-by in deionized water always.
Above-mentioned OFR Special electrics catalytic filler first carries out dipping pretreatment before using pure water, changes once pure per 24h
Water, totally 5 times, so as to remove the impurity that the inside is included.
(2) in this experiment, anode material is graphite electrode plate, and cathode material is stainless steel electrode.Electrode solution is used
10.0mg/L Na2S04Solution is circulated.
2nd, wastewater treatment process
(1) waste water first passes around preaeration 30min processing, makes to contain after enough dissolved oxygens in waste water, waste water is again by pump
Thrust under enter device in；
(2) waste water after pre-exposure gas disposal respectively enters the first organic matter treating area (3) and concentrated water by waterwater entrance (11)
In area (4)；Ensure identical with the water flow velocity or water of concentrated water area (4) into the first organic matter treating area (3).
The waste water entered by the first organic matter treating area (3), configured some connecting tubes (10), in the work of DC electric field
The first organic matter treating area (3), cation exchange area (2), the second organic matter treating area (5), anion friendship are sequentially passed through under
Area (6) is changed, the waste water after finally handling complete the synchronization of waste water by continually by processing water outlet (12) discharger
Desalination and except organic matter；
The waste water entered by concentrated water area (4) gradually continuously turns into concentrated water, by dense during whole wastewater treatment
Water outlet (13) is discharged.
Likewise, in processing procedure, keeping discharge processing water identical with the speed or amount of discharge concentrated water.
In addition, treatment temperature is 25~35 DEG C in whole processing procedure, the intensity of step (2) described DC electric field is 0.4
~1.5V/cm.
The rich field chemical plant wastewater processing experiment of embodiment 3
Using the DSROTDE devices of the present invention in the biochemical live lab scale of qualified discharge mouthful water intaking in rich field chemical plant, experiment is former
Water COD100 ± 10mg/L, 1500 ± 100us/cm of electrical conductivity.
Even electric-field intensity 0.6V/cm is being controlled, temperature is 25.0~35.0 DEG C, wastewater treatment capacity 10L/hr, hydraulic retention
40 minutes time, draining and concentrated water draining ratio are 1 after processing：Under conditions of 1, by 3 months continuously run, device was never
There is the phenomenon of ion exchange resin and amberplex surface scale, asking for treatment effeciency decline also never occurred
Topic, with very high stability.
As a result such as Fig. 2 and Fig. 3, shown by data results, the operating cost only 0.3 degree/m of power consumption of device3Waste water,
The organic removal rate (COD ＜ 60mg/L) of waste water is above more than 45.0%, salt rejection rate (the electrical conductivity ＜ 300us/ of waste water
Cm more than 83.0%) is above, manufacturer's recycle-water requirement is met.
Comparative example 1
1st, DSROTDE devices and water technology of the invention are that the present inventor is directed to electrodeionization technology (EDI) and three
Dimension electrode method (TDE) is difficult to the defect for being applied to processing saliferous organic wastewater, in the patent of invention of the present inventor's early stage
《A kind of particle electrode catalyst filling of three-diemsnional electrode and preparation method thereof ZL200410077704.5》On the basis of, to EDI
Two kinds of technical advantages of EDI and TDE are cleverly mutually merged what is drawn, in the course of the study, gone out by carry out technology bridge joint transformation
Show and much made the unexpected difficulties and problems of inventor, inventor have passed through substantial amounts of research and explore to be overcome one by one, is obtained
The DSROTDE devices and water technology of the present invention are gone out.
2nd, found during research and development desalination simultaneously removes organic matter device, pattern of rows and columns of anion and cation exchange membrane is to dress
Putting the effect of processing waste water has vital influence.The device of contrast test is as described in accompanying drawing 4, A and B dresses in Fig. 4
The pattern of rows and columns for the anion and cation exchange membrane put is different.Wherein, A devices are the DSROTDE thinking devices of the present invention, the dress
The negative and positive film symmetric arrays put：I.e. anion-exchange membrane is placed in cathodic region, and cation-exchange membrane is placed in anode region；B devices are film
It is staggered：I.e. each functional areas are to constitute (separated type EDI thinkings dress by anion-exchange membrane and cation ion-exchange membrane
Put).
Here illustrate a bit, the DSROTDE devices of embodiment 1 are the device of Unit seven, are also optimal embodiment；And
Unit seven can not possibly carry out contrast experiment in contrast test, therefore in order to adapt to contrast test, employ five modular contrasts
Device series, only in this way, is only possible to carry out contrast experiment's research with the conditions of.
3rd, by the development test of be the same as Example 3, as a result as shown in Figure 5 and Figure 6.The result of contrast experiment shows：With
Under the same experimental conditions of be the same as Example 3, the desalinations of A devices is all highly stable except the effect of organic matter, is significantly better than B devices
(especially salt rejection rate).The undesirable main cause of B device treatment effects is that regeneration of ion-exchange resin needs frequently pole-reversing,
Without continuous desalination function, the situation in Fig. 6 such as will be produced using continuous de-salting operation, ion exchange resin is ultimately resulted in
Fouling and failure, salt rejection rate persistently decline to a great extent.
State before and after our failures of the cationic ion-exchange resin and anion exchange resin to B devices is studied.
As a result as shown in Figure 7 and Figure 8.Fig. 7 is the electron-microscope scanning figure before and after cationic ion-exchange resin fails, and wherein a is cation exchange
Electron-microscope scanning figure before efficiency lost resin, b is the electron-microscope scanning figure after cationic ion-exchange resin fails, and Fig. 8 is anion exchange tree
Electron-microscope scanning figure before and after fat failure, wherein a is the electron-microscope scanning figure before anion exchange resin fails, and b is anion exchange
Electron-microscope scanning figure after efficiency lost resin.
It is can be seen that from the electron-microscope scanning figure before and after ion exchange resin failure on cationic ion-exchange resin surface or in the moon
Ion exchange resin surface coats (mainly hydroxide precipitation foulant) by layer of substance to some extent, and this is illustrated
With the increase of B device processing times, the material that the surface of anion and cation exchange membrane is depended on has completely cut off resin and swapped
Passage, the exchange capacity of resin can be reduced gradually, and then lose its exchange capacity.
Claims (5)
1. a kind of three-diemsnional electrode device of the synchronous continuous desalination removal organic polluter of waste water, the device by anode region, cathodic region with
And some functional areas units are constituted, including cationic ion-exchange resin unit, anion exchange resin unit, pole room unit and some
Individual OFR electro-catalysis unit；Sodium sulphate is put into pole room unit as pole room circulation fluid；Ion exchange resin unit is handed over equipped with ion
Resin extender is changed, anion-exchange membrane is placed in cathodic region, and cation-exchange membrane is placed in anode region；OFR electro-catalysis unit is equipped with OFR
Filler special；Formation and concentrated water collecting region of the OFR electro-catalysis unit for concentrated water in the middle part of device；Waste water is successively continuously across OFR
Electro-catalysis unit, cationic ion-exchange resin unit, OFR electro-catalysis unit, anion exchange resin unit, are finally discharged in device
Outside, realize and remove organic matter with one-step desalting.
2. three-diemsnional electrode device described in claim 1 is in terms of processing brine waste, organic wastewater or high salt organic wastewater
Application.
3. a kind of green water process electrochemical method of the synchronous continuous desalination removal organic polluter of waste water, it is characterised in that including
Following steps：
S1. waste water carries out pre-exposure gas disposal；
S2. handled using three-diemsnional electrode device described in claim 1；
S21. the waste water after pre-exposure gas disposal is by waterwater entrance（11）Respectively enter organic matter treating area（3）With concentrated water area（4）In；
S22. by organic matter treating area（3）The waste water of entrance, configured some connecting tubes（10）, in the presence of DC electric field
Sequentially pass through organic matter treating area（3）, cation exchange area（2）, organic matter treating area（5）, anion exchange area（6）, finally
Through handling water outlet（12）Discharge, that is, complete the synchronous desalination of waste water and except organic matter；Concentrated water area（4）In concentrated water pass through it is dense
Water outlet（13）Discharge；
Wherein, specifically, the structure of three-diemsnional electrode device is as follows described in step S2：
The device is by tactic anode region successively（1）, cation exchange area（2）, organic matter treating area（3）, concentrated water area
（4）, organic matter treating area（5）, anion exchange area（6）And cathodic region（7）Composition；Anode region（1）, cation exchange area（2）、
Organic matter treating area（3）With concentrated water area（4）Between pass through cation-exchange membrane（8）Separate, concentrated water area（4）, organic matter treating area
（5）, anion exchange area（6）And cathodic region（7）Between pass through anion-exchange membrane（9）Separate；Wherein, organic matter treating area
（3）With cation exchange area（2）Between, cation exchange area（2）And organic matter treating area（5）Between, organic matter treating area（5）
With anion exchange area（6）Between pass through connecting tube respectively（10）Connection；Organic matter treating area（3）With concentrated water area（4）Upper difference
It is provided with waterwater entrance（11）, anion exchange area（6）On be provided with processing water outlet（12）, concentrated water area（4）On be provided with
Concentrated water outlet（13）；
The anode region（1）, organic matter treating area（3）, concentrated water area（4）, organic matter treating area（5）And cathodic region（7）Interior part
It is not covered with OFR Special electrics catalytic filler grain；Cation exchange area（2）Inside is covered with cationic ion-exchange resin filler grain；Anion
Exchange area（6）Inside is covered with anion exchange resin filler grain；
The anode region（1）, cation exchange area（2）, organic matter treating area（3）, concentrated water area（4）, organic matter treating area（5）、
Cation exchange area（6）And cathodic region（7）Top and the bottom cloth full water is respectively equipped with the gateway of water, these functional areas to infiltrate
Filler.
4. green water process electrochemical method according to claim 3, it is characterised in that ensure to enter organic in step S21
Thing treatment region（3）With concentrated water area（4）Water flow velocity or water it is identical；And/or ensure that discharge processing water and discharge are dense in step S22
The speed of water is measured identical.
5. green water process electrochemical method according to claim 3, it is characterised in that DC electric field described in step S22
Intensity is 0.4~1.5V/cm.
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| CN111762852A (en) * | 2020-08-03 | 2020-10-13 | 苏州聚智同创环保科技有限公司 | Electrocatalytic oxidation reactor for treating high-hardness high-organic matter high-salt wastewater |
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