CN205635005U - Synchronous desalination in succession of waste water removes organic pollutant's three -dimensional electrode assembly - Google Patents
Synchronous desalination in succession of waste water removes organic pollutant's three -dimensional electrode assembly Download PDFInfo
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- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The utility model discloses a synchronous desalination in succession of waste water removes organic pollutant's three -dimensional electrode assembly. The device includes cation exchange resin unit, anion exchange resin unit, utmost point room unit and a plurality of OFR electricity catalysis unit, put into sodium sulphate conduct utmost point room circulation fluid in the unit of utmost point room, the duolite unit is equipped with duolite and packs, and anion exchange membrane arranges the cathodic region in, and cation exchange membrane arranges the anode region in, OFR electricity catalysis unit is equipped with the special filler of OFR, the OFR electricity catalysis unit at device middle part is the formation and the collecting region of dense water, waste water passes through OFR electricity catalysis unit, cation exchange resin unit, OFR electricity catalysis unit, anion exchange resin unit in proper order, and last eduction gear realizes synchronous desalination organic matter removal's purpose. The utility model discloses a purpose of high -efficient continuous synchronous desalination organic matter removal waste water moves moreover that this one -tenths hangs down, high, the green of degree of automation.
Description
Technical field
This utility model belongs to technical field of sewage.The three-diemsnional electrode device (DSROTDE) of continuous desalination removal organic polluter is synchronized more particularly, to a kind of waste water.
Background technology
Based on Three-dimensional Electrode Method (Three-dimensional electrodes, it is called for short TDE) it is a kind of conventional process organic wastewater method, this method is on the basis of traditional two dimension feed pole plate, add a kind of particle derivation with low-impedance electric conductivity become three-diemsnional electrode (E.Fockedey, 2002；Jiang Hui etc., 2014), and particle polarized under the effect of electric field is just as being the 3rd pole, by there is electrochemical oxidation reactions on the surface of electrode particle, the oxide producing strong oxidation removes to attack organic target thing, thus reaches to remove the effect of the organic pollution of difficult for biological degradation.This conducting particles of above-mentioned addition, on the one hand the surface area of electrode reaction is increased considerably, on the other hand the voltage effect of feeding electrode can be extended in the main body of solution originally, this electric field distance being equivalent to shorten two-plate so that target processed material the most greatly shortens in the distance run on pole plate.
The early-stage Study of the present inventor achieves the three-diemsnional electrode catalytic oxidation of Patent No. ZL02114740.X and processes organic wastewater technology, this technology is when the process of organic wastewater, there is broad spectrum activity, efficiently, quickly, sludge quantity is few, does not produce secondary pollution, having the functions such as deodoring and disinfecting, it has a extensive future simultaneously；But, the defects such as to there is cost of material the highest for the particle electrode catalyst filling that this technology uses, and mechanical strength is poor, and cooperative effect between the most each composition is the strongest.The present inventor is at follow-up study particle electrode catalyst filling of a kind of three-diemsnional electrode obtaining Patent No. 200410077704.5 and preparation method thereof, this conducting particles has the highest specific surface area, and there is the most intensive the hugest absorption duct, these ducts are exactly the significant points that granule electrode plays a role, exactly because the existence in the most this duct, greatly add the response area of electrode reaction, it is several orders of magnitude of traditional two-dimentional feeding electrode response area, in removing difficult for biological degradation organic pollution, has played important function.But, above-mentioned this method, when process contains organic wastewater high in salt, makes processing procedure energy consumption increase due to the existence of salt side reaction, there is also the problem that Organic substance treatment effeciency the most significantly declines simultaneously.
Electrodeionization technology (Eleetrodeionization is called for short EDI) is also referred to as packed-bed electrodialysis in early days also known as continuous deionization technology (Continuous Deionization, CEDI).EDI technology has merged electrodialytic technique and ion exchange technique well, it is that mixed-bed resin is filled between ion exchange membrane by one, the new type water processing method of continuous desalination is realized under DC electric field effect, also it is after the intermembranous filling ion-exchange resin of electrodialysis plant, under the effect of DC electric field, can realize continuous deionising process a kind of new separation technology (K E Bouhidel etc., 2006；Sun Xian etc., 2011).Electroosmose process (Electro Dialysis, it is called for short ED) it is to utilize ion exchange membrane, including anion exchange membrane (Anion exchange membrane, AEM), cation exchange membrane (Cation exchange membrane, CEM), by the ion exchange membrane selective penetrated property to anions and canons, under the effect of applying direct current electric field, it is achieved electrolyte concentrates or the technology of desalination.Electroosmose process lost efficacy because aquifer yield is little, power consumption big and film is the most polluted by organic matter, and method is used for miniature water desalination station.Ion exchange (Ion-exchange process, it is called for short IEX) utilize Solid-state Ion-exchange agent to include anion exchange resin (Anion exchange resin, and cation exchange resin (Cation exchange resin AER), CER), swap with the ion in Solid-state Ion-exchange agent by the ion in solution, thus reach to remove or extract the purpose of some ion in solution.Generally, the absorption of ion exchange resin and exchange capacity are very strong, and pollutant removal is preferable, but, it is desirable to regenerative elution technique loaded down with trivial details, investment and maintenance cost are higher, and resin is vulnerable to Organic Pollution and lost efficacy in addition.The design of system, operating, manage the most cumbersome, needing professional and technical personnel, so being typically only used in the advanced treating of waste water.
In EDI device, the electric conductivity of ion exchange resin is than aqueous conductive two to three orders of magnitude high contacted, ion permeable film surface almost all is the effect of ion exchange resin, the raising of the most intermembranous electric conductivity significantly enhances the migration of ion, solve the poor phenomenon of ion in face concentration retention layer and the big problem of resistance, and occur in electrode chamber hydrion 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 desalination of its existing electrodialysis plant, there is again the ion exchange of ion exchange resin, it is to avoid harmful effect and the ion exchange resin regeneration of electrodialysis concentration polarization and the shortcoming such as environmental pollution of causing.
The traditional E DI device effect when producing ultra-pure water or pure water is preferable, but in being applied to heavy metal containing wastewater treatment, when water inlet is containing metal ions such as relatively high contents of calcium and magnesium, often as the hydroxyl that hydrolysis produces forms hydroxide precipitation, cause and easily on film and resin, scale problems occurs when running continuously, limit the application of method largely.For preventing fouling, current EDI method generally uses down pole, acid adding or antisludging agent etc. to operate to maintain the stable operation of whole device, but this obviously increases the complexity of system, makes efficiency decline, cost increase.Additionally, due to ion exchange resin and electrodialysis-ion exchange film itself are easily affected by organic pollution and lost efficacy, therefore it is difficult to be applied in the process of saliferous organic wastewater.
Summary of the invention
The technical problems to be solved in the utility model is to overcome electrodeionization technology (EDI) and Based on Three-dimensional Electrode Method (TDE) in prior art to be all difficult to defect and the deficiency being applied to process saliferous organic wastewater, patent of invention " ZL200410077704.5 in the present inventor's early stage, a kind of particle electrode catalyst filling of three-diemsnional electrode and preparation method thereof " on the basis of, EDI is carried out technology bridge joint transformation, two kinds of technical advantages are made to be able to ingenious fusion, research has manufactured the three-diemsnional electrode device (being called for short DSROTDE) of a kind of waste water continuous desalination removal organic polluter.
The purpose of this utility model is to provide a kind of waste water and synchronizes the three-diemsnional electrode device of continuous desalination removal organic polluter.
This utility model above-mentioned purpose is achieved through the following technical solutions:
A kind of waste water synchronizes the three-diemsnional electrode device (being called for short DSROTDE) of continuous desalination removal organic polluter, this device is made up of anode region, cathode chamber and several functional areas unit, including cation exchange resin unit, anion exchange resin unit (being respectively provided with cation exchange resin and anion exchange resin inside it), pole chamber unit and several OFR electro-catalysis unit (its internal dress has OFR filler special)；Pole chamber unit is put into sodium sulfate as room, pole circulation fluid；Ion exchange resin unit is equipped with ion exchange resin filler, and anion exchange membrane is placed in cathode chamber, and cation exchange membrane is placed in anode region；OFR electro-catalysis unit is equipped with OFR filler special；Formation and collecting region that OFR electro-catalysis unit is dense water in the middle part of device；Device produces soda acid technology, the online desalting technology of ion exchange resin, suppression resin and the easy fouling in ion exchange membrane surface technology by pole chamber unit, the ingenious combination of electro-catalysis three-diemsnional electrode process Organic substance technology designs, it is achieved that the desalination simultaneously of saliferous organic wastewater is except the purpose of the continuous operation of organic function.
Specifically, this device is made up of the most tactic anode region (1), cation exchange area (2), organic matter treating area one (3), dense pool (4), organic matter treating area two (5), anion exchange district (6) and cathode chamber (7)；Anode region (1), cation exchange area (2), separated by cation exchange membrane (8) between organic matter treating area one (3) and dense pool (4), pass through anion exchange membrane (9) between dense pool (4), organic matter treating area two (5), anion exchange district (6) and cathode chamber (7) and separate；Wherein, between organic matter treating area one (3) and cation exchange area (2), connected by connecting tube (10) respectively between cation exchange area (2) and organic matter treating area two (5), between organic matter treating area two (5) and anion exchange district (6)；It is respectively arranged with waterwater entrance (11) on organic matter treating area one (3) and dense pool (4), it is provided with process water outlet (12) in anion exchange district (6), dense pool (4) are provided with concentrated water drainage outlet (13).
Dense pool (4) is in an OFR district at the positive middle part of device, and it is the functional areas that only one is separated by cation 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 constituted.
Preferably, this device is supported by support (14).
Further, OFR Special electric catalytic filler grain (OFR, the filler that i.e. patent 200410077704.5 is provided) it is covered with in described anode region (1) as Chan Suan district.
Cathode chamber (7) is internal is covered with OFR Special electric catalytic filler grain as Chan Jian district.
Organic matter treating area one (3), dense pool (4) and organic matter treating area two (5) are internal is covered with OFR Special electric catalytic filler grain (OFR).
Cation exchange area (2) is internal is covered with cation exchange resin filler grain (CER).
Anion exchange district (6) is internal is covered with anion exchange resin filler grain (AER).
Preferably, described cation exchange resin filler grain is D001 large hole strong acid styrene system cation exchange resin, and described anion exchange resin filler grain is the D201 macroporous strong basic dilute series anion exchange resin of benzene second.
It is highly preferred that above-mentioned ion exchange resin is both needed to pass through pretreatment before use.
Specifically, the preprocess method of cation exchange resin: soak with appropriate pure water, filter, it is soaked in saturated aqueous common salt 18～30h, in 3%～5%NaOH solution of the twice being then soaked in resin volume 3～6h, in 3%～5%HCl solution of the twice being finally soaked in resin volume 5～10h, soak the most stand-by the most always.Wherein it is preferred to, it is soaked in 20h in saturated aqueous common salt.Preferably, the concentration of NaOH solution is 3%.Preferably, 4h in 3%NaOH solution it is soaked in.Preferably, the concentration of HCl solution is 5%.Preferably, 8h in 5%HCl solution it is soaked in.
Specifically, the preprocess method of anion exchange resin: soak with appropriate pure water, filter, it is soaked in saturated aqueous common salt 18～30h, in 3%～5%HCl solution of the twice being then soaked in resin volume 3～6h, in 3%～5%NaOH solution of the twice being finally soaked in resin volume 5～10h, soak the most stand-by the most always.Wherein it is preferred to, it is soaked in 20h in saturated aqueous common salt.Preferably, the concentration of HCl solution is 5%.Preferably, 4h in 5%HCl solution it is soaked in.Preferably, the concentration of NaOH solution is 3%.Preferably, 8h in 3%NaOH solution it is soaked in.
Furthermore it is preferred that above-mentioned OFR Special electric catalytic filler first uses pure water to carry out dipping pretreatment before using, every 20～30h (preferably 24h) changes 1 st pure water, totally 3～6 times (preferably 5 times), thus removes the impurity that the inside comprises.
It is further preferred that the anode region (1) of above-mentioned three-diemsnional electrode device, cation exchange area (2), organic matter treating area one (3), dense pool (4), organic matter treating area two (5), cation exchange area (6) and cathode chamber (7) internal cloth full water are to infiltrate filler.
As a kind of preferable scheme, the anode region (1) of above-mentioned three-diemsnional electrode device, cation exchange area (2), organic matter treating area one (3), dense pool (4), organic matter treating area two (5), the top and the bottom of cation exchange area (6) and cathode chamber (7) are respectively equipped with the gateway of water, in order in these functional areas, cloth full water is to infiltrate filler；Preferably, and each district water level balance can be ensured.
It addition, put into room, pole circulation fluid in the anode region (1) of above-mentioned three-diemsnional electrode device and cathode chamber (7) to maintain acid-base condition to produce soda acid, 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 and replaces once a week room, pole circulation fluid.Room, the pole circulation fluid changed can be recycled as the acid of low concentration or alkali.
Preferably, the anode material of anode region (1) is graphite electrode plate, and the cathode material of cathode chamber (7) is stainless steel electrode.
Three-diemsnional electrode device described in the utility model can be used for the process aspect in terms of high salt organic wastewater, can synchronize to realize desalination and removal organic polluter the most continuously, have significant advantage in terms of high salt organic wastewater process.Same, it is possible to it is applied to the process of brine waste or organic wastewater.
Utilize this utility model to process high salt organic wastewater, i.e. achieve a kind of waste water and synchronize the Green Water process electrochemical method of continuous desalination removal organic polluter, comprise 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 processes is respectively enterd in organic matter treating area one (3) and dense pool (4) by waterwater entrance (11)；
S22. the waste water entered by organic matter treating area one (3), configured some connecting tubes (10), organic matter treating area one (3), cation exchange area (2), organic matter treating area two (5), anion exchange district (6) are sequentially passed through under the effect of DC electric field, last treated water outlet (12) discharger, i.e. completes the synchronization desalination of waste water and except Organic substance；The waste water entered by dense pool (4), during whole waste water processes, becomes dense water the most continuously, is discharged by concentrated water drainage outlet (13).
Preferably, waste water described in step S1 first passes through preaeration and processes 30min.During processing saliferous organic wastewater, waste water first passes around preaeration and processes, after making waste water contains enough dissolved oxygen, waste water is again by entering in device under the thrust of pump, under the effect of DC electric field, waste water flows, finally respectively through OFR district, cationic resin district and resin anion (R.A.) district and to outlet direction, waste water after treatment is by outside continually by outlet discharger, thus realizes synchronizing desalination except organic purpose.
Furthermore it is preferred that it is identical with the water flow velocity of dense pool (4) or the water yield to enter organic matter treating area one (3) in step S21 to be ensured；Or ensure that in step S22, discharge processes water and the speed discharging dense water or measures identical.
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, in processing procedure, treatment temperature is 25～35 DEG C.
Specifically, waste water described in step S1 is high salt organic wastewater.Three-diemsnional electrode device provided by the utility model is particularly suited for the process of high salt organic wastewater, it is possible to continuous print synchronizes desalination except Organic substance.And simultaneously for common brine waste or organic wastewater, there is good treatment effect equally.
This utility model three-diemsnional electrode device (DSROTDE) disclosed above draws through numerous studies and exploring, the defect being applied to process saliferous organic wastewater it is difficult to for electrodeionization technology (EDI) and Based on Three-dimensional Electrode Method (TDE), on the basis of the patent of invention " particle electrode catalyst filling of a kind of three-diemsnional electrode and preparation method thereof ZL200410077704.5 " of the present inventor's early stage, EDI is carried out technology bridge joint transformation, cleverly two kinds of technical advantages of EDI and TDE are mutually merged, maximize favourable factors and minimize unfavourable ones, OFR electro-catalysis unit is used to remove organic pollution, and pole chamber unit produces soda acid, ensure the online desalination of ion exchange resin, thus realize DSROTDE device continuous synchronization desalination except organic purpose.This device concrete includes ion exchange resin unit (equipped with ion exchange resin inside it), pole chamber unit and OFR electro-catalysis unit (its internal dress has OFR filler special).
First the operation principle of this technology and core are to put into the sodium sulfate of Sq (preferably 3.0～150.0mg/L) in the pole chamber unit of device as room, pole circulation fluid, under the effect of DC electric field, on the one hand acid or alkali can be produced 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, on the other hand room, pole circulation fluid electrical conductivity is moderate, energy consumption too high (effectively reducing the energy consumption that Based on Three-dimensional Electrode Method runs) when can prevent OFR electro-catalysis cell processing Organic substance, reach the purpose that during work, energy self-cleaning circulating is unimpeded；Next to that the most each ion exchange resin district is equipped with studying the ion exchange resin filler filtered out, again negative and positive film traditional for EDI is staggered simultaneously and changes cavity block, anode membrane arranged in parallel (i.e. cavity block is placed in negative pole district, anode membrane is placed in the arrangement of positive polar region) into, make base exchange process remain in acid condition to carry out, thus can effectively suppress resin and a difficult problem for the easy fouling of female die surface, it is ensured that the lasting stability of online desalination；3rd is that device Zhong Ge nonionic exchange resin district is equipped with OFR filler special, when saliferous organic wastewater is when by each OFR electro-catalysis district of device, all can decompose the effect of difficult for biological degradation organic pollution in waste water, and it is both to have ensured the removal of difficult for biological degradation organic pollution that each nonionic exchange resin district is equipped with the purpose that OFR filler special so designs, the migration rate 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 reality is applied, the saliferous organic wastewater of inflow device, under the effect of DC electric field, continuously respectively through OFR district, cationic resin district and resin anion (R.A.) district, and is finally discharged outside device, so that it may reach same one-step desalting except organic purpose；Additionally, the formation of dense water and collecting region unit are positioned at the OFR district in the middle part of device, so the purpose of design is to take full advantage of under the pull strength 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 the most all can be come together in.
This utility model has the advantages that
This utility model produces soda acid technology, the online desalting technology of ion exchange resin, suppression resin and the easy fouling in ion exchange membrane surface technology, the ingehious design of electro-catalysis three-diemsnional electrode process Organic substance technology by pole chamber unit, overcome EDI and Based on Three-dimensional Electrode Method is difficult to the defect that is applied in saliferous organic wastewater, achieve high-efficiency and continuous and synchronize desalination except the purpose of organic wastewater, process for saliferous organic wastewater provides a kind of new treatment technology and device, and the process to high salt organic wastewater has great importance.
And, this utility model has the feature of low cost, environmental protection, waste water process this one-tenth of operation is low, only need to consume a small amount of electric energy just can realize the synchronization desalination of waste water except Organic substance, it is prone to Automated condtrol, automaticity high, without personal management, without any chemical reagent in operation, being not easy to produce secondary pollution, its whole operating process is under conditions of environmental protection, it is achieved saliferous organic wastewater desalination simultaneously is except the continuous operation of organic function.
Accompanying drawing explanation
Fig. 1 is three-diemsnional electrode device (DSROTDE) schematic diagram of waste water continuous desalination removal organic polluter.
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 (salt rejection rate) of DSROTDE device continuous desalination removal organic polluter.
Fig. 4 is the DSROTDE thinking device (film symmetric arrays: anion exchange membrane is placed in cathode chamber, cation exchange membrane is placed in anode region) of the present invention in comparative example experimentation.
Fig. 5 is separated type EDI thinking device in comparative example experimentation (film is staggered: each functional areas are all to be made up of anion exchange membrane and cation ion-exchange membrane).
Fig. 6 is on-the-spot dynamic test results (COD) contrast of DSROTDE thinking device and EDI thinking device continuous desalination removal organic polluter.
Fig. 7 is on-the-spot dynamic test results (salt rejection rate) contrast of DSROTDE thinking device and EDI thinking device continuous desalination removal organic polluter.
Detailed description of the invention
Further illustrate this utility model below in conjunction with Figure of description and specific embodiment, but this utility model is not limited in any form by embodiment.
Unless stated otherwise, this utility model uses reagent, method and apparatus are the art conventional reagent, method and apparatus.
Unless stated otherwise, following example agents useful for same and material are commercial.
Embodiment 1 DSROTDE device
A kind of waste water synchronizes the three-diemsnional electrode device (being called for short DSROTDE) of continuous desalination removal organic polluter, and DSROTDE device and operation principle thereof are illustrated as shown in Figure 1.
This device is made up of the most tactic anode region (1), cation exchange area (2), organic matter treating area one (3), dense pool (4), organic matter treating area two (5), anion exchange district (6) and cathode chamber (7)；Anode region (1), cation exchange area (2), separated by cation exchange membrane (8) between organic matter treating area one (3) and dense pool (4), pass through anion exchange membrane (9) between dense pool (4), organic matter treating area two (5), anion exchange district (6) and cathode chamber (7) and separate；Wherein, between organic matter treating area one (3) and cation exchange area (2), connected by connecting tube (10) respectively between cation exchange area (2) and organic matter treating area two (5), between organic matter treating area two (5) and anion exchange district (6)；It is respectively arranged with waterwater entrance (11) on organic matter treating area one (3) and dense pool (4), it is provided with process water outlet (12) in anion exchange district (6), dense pool (4) are provided with concentrated water drainage outlet (13).This device is supported by support (14).
Further, described anode region (1), organic matter treating area one (3), dense pool (4), organic matter treating area two (5) and cathode chamber (7) inside are covered with OFR Special electric catalytic filler grain (OFR, the filler that i.e. patent 200410077704.5 is provided) respectively；Cation exchange area (2) is internal is covered with cation exchange resin filler grain (CER)；Anion exchange district (6) is internal is covered with anion exchange resin filler grain (AER).
The most further, the anode region (1) of above-mentioned three-diemsnional electrode device, cation exchange area (2), organic matter treating area one (3), dense pool (4), organic matter treating area two (5), the top and the bottom of cation exchange area (6) and cathode chamber (7) are respectively equipped with the gateway of water, so that in these functional areas, cloth full water is to infiltrate filler, and can ensure each district water level balance.
It addition, put into room, pole circulation fluid in the anode region (1) of above-mentioned three-diemsnional electrode device and cathode chamber (7) to maintain acid-base condition to produce soda acid, room, described pole circulation fluid is the sodium sulfate of 3～150mg/L, often runs and replaces once a week.Room, the pole circulation fluid changed can be recycled as the acid of low concentration or alkali.
The anode material of described anode region (1) is graphite electrode plate, and the cathode material of cathode chamber (7) is stainless steel electrode.
The application of embodiment 2 DSROTDE device
1, the DSROTDE device described in embodiment 1 is utilized to process saliferous organic wastewater
(1) when reality is applied, before needing to process waste water, each filler is loaded each functional areas.When each filler uses, just can fill in DSROTDE device after first need to carrying out pretreatment.
This experiment cation exchange resin filler grain used is D001 large hole strong acid styrene system cation exchange resin, and anion exchange resin filler grain used is the D201 macroporous strong basic dilute series anion exchange resin of benzene second.Because resin often contains a small amount of oligomer processing when and is not engaged in the base matter of reaction, a part of inorganic electrolyte ion the most also can be remained, such as Fe3+、Pb2+、Cu2+Deng foreign ion.So the early stage in resin use needs resin is carried out pretreatment, resin is soaked with appropriate pure water, filter, it is to avoid because the cause influence desalting effect of resin.
Specifically, described cation exchange resin needs to carry out pretreatment before use: soak with appropriate pure water, filter, it is soaked in 20h in saturated aqueous common salt, 4h in the 3%NaOH solution of the twice being then soaked in resin volume, 8h in the 5%HCl solution of the twice being finally soaked in resin volume, soaks the most stand-by the most always.
Described anion exchange resin needs to carry out pretreatment before use: soak with appropriate pure water, filter, it is soaked in 20h in saturated aqueous common salt, 4h in the 5%HCl solution of the twice being then soaked in resin volume, 8h in the 3%NaOH solution of the twice being finally soaked in resin volume, soaks the most stand-by the most always.
Above-mentioned OFR Special electric catalytic filler first uses 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.Electrode solution is 10.0mg/L Na2S04Solution is circulated.
2, wastewater treatment process
(1) waste water first passes around preaeration 30min process, and after making to contain enough dissolved oxygen in waste water, waste water is entered in device by under the thrust of pump again；
(2) waste water after preaeration processes is respectively enterd in organic matter treating area one (3) and dense pool (4) by waterwater entrance (11)；Ensure to enter organic matter treating area one (3) identical with the water flow velocity of dense pool (4) or the water yield.
The waste water entered by organic matter treating area one (3), configured some connecting tubes (10), organic matter treating area one (3), cation exchange area (2), organic matter treating area two (5), anion exchange district (6) are sequentially passed through under the effect of DC electric field, waste water after finally processing, by continually by processing water outlet (12) discharger, i.e. completes the synchronization desalination of waste water and except Organic substance；
The waste water entered by dense pool (4), during whole waste water processes, becomes dense water the most continuously, is discharged by concentrated water drainage outlet (13).
Same, in processing procedure, keep discharge process water and the speed discharging dense water or measure identical.
It 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.
Embodiment 3 rich field chemical plant wastewater processes test
Utilize DSROTDE device of the present utility model at the on-the-spot lab scale of rich chemical plant, field biochemistry qualified discharge mouth water intaking, test former water COD100 ± 10mg/L, electrical conductivity 1500 ± 100us/cm.
Controlling even electric field intensity 0.6V/cm, temperature is 25.0～35.0 DEG C, wastewater treatment capacity 10L/hr, hydraulic detention time 40 minutes, under conditions of after process, draining and concentrated water drainage water ratio are 1:1, by 3 months continuously run, never there is ion exchange resin and the phenomenon of ion exchange membrane surface scale in device, the problem that treatment effeciency declines the most never occurred, there is the highest stability.
Result such as Fig. 2 and Fig. 3, is shown by data results, the operating cost of device only 0.3 degree/m of power consumption3Waste water, the organic removal rate (COD ＜ 60mg/L) of waste water is above more than 45.0%, and the salt rejection rate (electrical conductivity ＜ 300us/cm) of waste water is above more than 83.0%, meets manufacturer's recycle-water requirement.
Comparative example 1
1, the 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 patent of invention " particle electrode catalyst filling of a kind of three-diemsnional electrode and preparation method thereof ZL200410077704.5 " of the present inventor's early stage, EDI is carried out technology bridge joint transformation, cleverly two kinds of technical advantages of EDI and TDE are mutually merged and to draw, during research, occur in that and much make the beyond thought difficulty of inventor and problem, inventor have passed through substantial amounts of research and exploration overcomes one by one, DSROTDE device and the water technology of the present invention are drawn.
2, finding during research and development desalination simultaneously is except Organic substance device, the effect that pattern of rows and columns of anion and cation exchange membrane processes waste water to device has vital impact.The device of contrast test is as described in accompanying drawing 4 and Fig. 5, and pattern of rows and columns of the anion and cation exchange membrane of A and B device in figures 4 and 5 is different.Wherein, A device is the DSROTDE thinking device of the present invention, the negative and positive film symmetric arrays of this device: i.e. anion exchange membrane is placed in cathode chamber, and cation exchange membrane is placed in anode region；B device is that film is staggered: the most each functional areas are all to be constituted (separated type EDI thinking device) by anion exchange membrane and cation ion-exchange membrane.
Here illustrating a bit, the device that DSROTDE device is Unit seven of embodiment 1, is also optimal embodiment；And Unit seven can not carry out contrast experiment in contrast test, therefore to adapt to contrast test, have employed five modular contrast devices series, only in this way, be only possible to the contrast experiment's research under the conditions of carrying out together.
3, through the development test with embodiment 3, result is as shown in Figure 6 and Figure 7.The result of contrast experiment shows: with under the same experimental conditions of same embodiment 3, the desalination of A device is the most highly stable except organic effect, is all significantly better than B device (especially salt rejection rate).The undesirable main cause of B device treatment effect is that regeneration of ion-exchange resin needs frequently pole-reversing, not there is continuous desalination function, as used continuous de-salting operation will produce the situation in Fig. 7, ultimately resulting in ion exchange resin fouling and inefficacy, salt rejection rate persistently declines to a great extent.
State before and after the cation exchange resin of B device and anion exchange resin were lost efficacy by we is studied.
Electron-microscope scanning figure before and after ion exchange resin lost efficacy can be seen that, it is coated with (mainly hydroxide precipitation foulant) by layer of substance the most to some extent on cation exchange resin surface or on anion exchange resin surface, this illustrates along with B device processes the increase of time, the material that the surface of anion and cation exchange membrane is all depended on has completely cut off the passage that resin swaps, the exchange capacity of resin can gradually reduce, and then loses its exchange capacity.
Claims (6)
1. the three-diemsnional electrode device of the waste water continuous desalination removal organic polluter of synchronization, this device is made up of anode region, cathode chamber and some functional areas unit, specifically includes cation exchange resin unit, anion exchange resin unit, pole chamber unit and several OFR electro-catalysis unit；Pole chamber unit is put into sodium sulfate as room, pole circulation fluid；Ion exchange resin unit is equipped with ion exchange resin filler, and anion exchange membrane is placed in cathode chamber, and cation exchange membrane is placed in anode region；OFR electro-catalysis unit is equipped with OFR filler special；Formation and collecting region that OFR electro-catalysis unit is dense water in the middle part of device；
Specifically, this device is made up of the most tactic anode region (1), cation exchange area (2), organic matter treating area one (3), dense pool (4), organic matter treating area two (5), anion exchange district (6) and cathode chamber (7)；Anode region (1), cation exchange area (2), separated by cation exchange membrane (8) between organic matter treating area one (3) and dense pool (4), pass through anion exchange membrane (9) between dense pool (4), organic matter treating area two (5), anion exchange district (6) and cathode chamber (7) and separate；Wherein, between organic matter treating area one (3) and cation exchange area (2), connected by connecting tube (10) respectively between cation exchange area (2) and organic matter treating area two (5), between organic matter treating area two (5) and anion exchange district (6)；It is respectively arranged with waterwater entrance (11) on organic matter treating area one (3) and dense pool (4), anion exchange district (6) are provided with process water outlet (12), dense pool (4) are provided with concentrated water drainage outlet (13).
Three-diemsnional electrode device the most according to claim 1, it is characterised in that described anode region (1), organic matter treating area one (3), dense pool (4), organic matter treating area two (5) and cathode chamber (7) inside are covered with OFR Special electric catalytic filler grain respectively；Cation exchange area (2) is internal is covered with cation exchange resin filler grain；Anion exchange district (6) is internal is covered with anion exchange resin filler grain.
Three-diemsnional electrode device the most according to claim 2, it is characterised in that described cation exchange resin filler grain is D001 large hole strong acid styrene system cation exchange resin；Described anion exchange resin filler grain is the D201 macroporous strong basic dilute series anion exchange resin of benzene second.
Three-diemsnional electrode device the most according to claim 2, it is characterized in that, described anode region (1), cation exchange area (2), organic matter treating area one (3), dense pool (4), organic matter treating area two (5), the top and the bottom of cation exchange area (6) and cathode chamber (7) are respectively equipped with the gateway of water, and in these functional areas, cloth full water is to infiltrate filler.
Three-diemsnional electrode device the most according to claim 1, it is characterised in that putting into room, pole circulation fluid in described anode region (1) and cathode chamber (7) to produce soda acid and maintain acid-base condition, room, described pole circulation fluid is metabisulfite solution.
The most according to claim 1, three-diemsnional electrode device, it is characterised in that the anode material of described anode region (1) is graphite electrode plate, the cathode material of cathode chamber (7) is stainless steel electrode.
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| CN105236527A (en) * | 2015-10-30 | 2016-01-13 | 中山大学 | Three-dimensional electrode device and method for synchronously continuously removing salt and organic pollutants from wastewater |
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| CN105236527B (en) * | 2015-10-30 | 2017-08-04 | 中山大学 | A kind of three-diemsnional electrode device and method of the synchronous continuous desalination removal organic polluter of waste water |
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