CN103708586B - Electrodeionization device based on ion exchange fabric filling and application thereof - Google Patents
Electrodeionization device based on ion exchange fabric filling and application thereof Download PDFInfo
- Publication number
- CN103708586B CN103708586B CN201310722653.6A CN201310722653A CN103708586B CN 103708586 B CN103708586 B CN 103708586B CN 201310722653 A CN201310722653 A CN 201310722653A CN 103708586 B CN103708586 B CN 103708586B
- Authority
- CN
- China
- Prior art keywords
- ion
- fabric
- ion exchange
- exchange
- filling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004744 fabric Substances 0.000 title claims abstract description 94
- 238000005342 ion exchange Methods 0.000 title claims abstract description 79
- 238000011049 filling Methods 0.000 title claims abstract description 51
- 238000009296 electrodeionization Methods 0.000 title abstract description 41
- 239000013505 freshwater Substances 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 31
- 239000012528 membrane Substances 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- -1 polypropylene Polymers 0.000 claims abstract description 8
- 239000004743 Polypropylene Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
- 229920001155 polypropylene Polymers 0.000 claims abstract description 7
- 239000002351 wastewater Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims description 31
- 229920005989 resin Polymers 0.000 claims description 27
- 239000011347 resin Substances 0.000 claims description 25
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 18
- 239000003456 ion exchange resin Substances 0.000 claims description 17
- 239000000835 fiber Substances 0.000 claims description 16
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 16
- 239000003011 anion exchange membrane Substances 0.000 claims description 11
- 238000005341 cation exchange Methods 0.000 claims description 11
- 125000002091 cationic group Chemical group 0.000 claims description 11
- 229910021645 metal ion Inorganic materials 0.000 claims description 11
- 150000001450 anions Chemical class 0.000 claims description 7
- 238000005349 anion exchange Methods 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 4
- 239000003957 anion exchange resin Substances 0.000 claims description 3
- 239000003729 cation exchange resin Substances 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 238000010612 desalination reaction Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 9
- 238000001556 precipitation Methods 0.000 abstract description 9
- 239000012498 ultrapure water Substances 0.000 abstract description 8
- 229910000000 metal hydroxide Inorganic materials 0.000 abstract description 5
- 150000004692 metal hydroxides Chemical class 0.000 abstract description 5
- 230000005012 migration Effects 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 238000010559 graft polymerization reaction Methods 0.000 abstract 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 19
- 230000000694 effects Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 229910001385 heavy metal Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 230000037427 ion transport Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004382 potting Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000003010 ionic group Chemical group 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007646 directional migration Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses an electrodeionization device based on ion exchange fabric filling and application thereof, wherein the device comprises: the ion exchange fabric is filled in at least one fresh water chamber or the concentrated water chamber, is vertical or parallel to the surface of the ion exchange membrane, is prepared by modifying the surface of a polypropylene non-woven material based on graft polymerization, and has the surface density of 20-400 g/square meter and the fabric grafting ratio of 30-300%. Effectively reduces the resistance of the membrane stack, improves the ion migration rate and the electrodeionization efficiency, accelerates the hydrolysis, relieves the precipitation of metal hydroxide on the surface of the ion exchange membrane, can be widely applied to the preparation of high-purity water and the treatment of chemical wastewater, and has wide application prospect.
Description
Technical field
The present invention relates to a kind of electric deionizer based on ion exchange fabric, electronics, electric power, medicine and other fields preparation of high-purity water and chemical wastewater treatment can be applied to; Belong to water treatment field.
Background technology
Electrodeionization technology (EDI) is a kind of pure water manufacturing technology ionic energy transfer membrane technique, ion-exchange and electromigration techniques combined.That is, under the effect of DC electric field, the freshwater room intermediate ion generation displacement of electrodialyzer, based on ion-exchange membrane to the selection of ion through effect, anions and canons in freshwater room is made constantly to move in dense hydroecium, thus make former water reach purification, purification, and conductive impurities obtains concentrated water technology.Electrodeionization water purification technology has continuous effluent, without the need to acid-alkali regeneration, the advantage such as easy and simple to handle, is applied widely gradually in the preparation of high-purity water of the industries such as electronics, electric power, medicine.
In recent years, some experts and scholars attempt process EDI being used for effluent containing heavy metal ions both at home and abroad, EDI device is used for recycling heavy metal wastewater thereby by Dillon etc., experimental result shows: this device can obtain high purity water and certain density dense water (SemmensMJ, DillonCD, RileyC.Anevaluationofcontinuouselectrodeionizationasanin-lineprocessforplatingrinsewaterrecovery, EnvironmentalProgress, 2001,20 (4): 251-60).Guan Shan etc. design EDI device and for Cu
2+wastewater treatment, experiment draws: freshwater room goes out resistivity of water can reach 2.2-5.6M Ω cm, and Cu
2+concentration lower than the Monitoring lower-cut of instrument, Cu in dense water
2+mass concentration can reach 800-1200mg/L, but also finds that dense hydroecium female die surface forms Cu (OH)
2precipitation (Guan Shan, electrodeionization (EDI) process and for Cu in water
2+removing and concentrated research [D] of ion, Tianjin: University Of Tianjin, 2004), that is, in current EDI technical finesse high volence metal ion waste water process, can precipitation of hydroxide be produced, thus reduce the operation stability of device.
In existing EDI device, freshwater room fills spherical ion exchange resin usually, and spherical resin diameter reaches hundreds of micron, and this causes it to be difficult to evenly in narrower freshwater room, filling densely; Under flow action, the resin of non-dense packing effect there will be " drift ", forms partial water flow short-circuit.According to the Porous-Plug model that Wyllie proposes, because electrical conductivity of water is lower than the specific conductivity of resin, so the ion-conductance that the filling of this eakiness and current short circuit reduce EDI device goes efficiency.Meanwhile, large diameter spherical resin causes that ion diffuse and migration distance are large, ion transport rate reduction.But ion-exchange fiber filament diameter only has some tens of pm, and ion diffusion layer is thin, this will shorten ion diffuse and migration distance, and ion transport speed is increased; And ionic group is gathered in fiber surface, this accelerates again ion-exchange speed and shortens the recovery time.In theory, ion-exchange fiber is more suitable for the stopping composition serving as EDI.Wei Junfu etc. attempt with ion-exchange fiber substitutional ion exchange resin, but its experimental result shows: fill ion-exchange fiber and make resistance raise on the contrary, this be due to the orientation consistency of fiber filled and compactness all poor, and the ionic group content (Liu Huiran on the low side of ion transport in unit volume, can be supplied, Wei Junfu, Guan Shan, Zhang Huan, Zhao Kongyin, ion-exchange fiber EDI technology prepares the research of ultrapure water, Tianjin University of Technology's journal, 30(2): 19-22,2011).In utility model patent 96244874.5, Wang Fang attempts to overcome the shortcoming of filling ion-exchange fiber, use ion-exchange fiber cloth instead and replace ion exchange resin, claim this cloth to fill evenly, and electricity goes device to have without the advantage such as leaking and water purification speed is fast.But because yarn diameter slightly reaches 500 microns, cause that fabric pore size is bigger than normal, porosity is on the low side, easily occur current short circuit and make ion-conductance go efficiency to reduce.Simultaneously due to ion fiber surface ion group wetting ability, cause weaving process difficulty.
Summary of the invention
For solving the deficiencies in the prior art, the object of the present invention is to provide a kind of electric deionizer based on ion-exchange polypropylene nonwoven fabric by low temperature RF, on the one hand, effectively reducing resistance, improving ion mobility and electrodeionization efficiency; On the other hand, accelerate hydrolytic action, suppress the precipitation of heavy metal ion oxyhydroxide on film surface.
In order to realize above-mentioned target, the present invention adopts following technical scheme:
Based on the electric deionizer that ion exchange fabric is filled, comprise: the cathode compartment and the anolyte compartment that are positioned at device two ends, also comprise the spaced multiple dense hydroecium and freshwater room separated with ion-exchange membrane, have at least in a freshwater room or dense hydroecium and be filled with ion exchange fabric, described ion exchange fabric is made up based on after modification of graft of polypropylene fibre nonwoven material surface, and area density is 20-400g/m
2, fabric percentage of grafting is 30-300%.Wherein, polypropylene fibre nonwoven material refers to viscose non-woven material and spunbond and melt-blown composite nonwoven material, area density refers to the weight of the ion exchange fabric of unit surface, and fabric percentage of grafting refers to the mass percentage of the ion-exchange polymer that the polypropylene fabric surface of unit mass is accessed.
The ion exchange fabric that the present invention adopts also is that the present inventor is obtained by the research of a series of novelty, and be carried out in detail openly in CN102965929A at publication number, so, refer to above-mentioned patent about the acquiring way of this ion exchange fabric and preparation method, do not repeat in the present invention.
Foregoing ion exchanges fabric and comprises cation-exchange fabric and anion-exchange fabric, adopt anion/cation to exchange fabric during filling fill separately or mix filling, the middle anionic group of cation-exchange fabric comprises one or more in sulfonate radical, carboxylate radical and phosphonate radical, and the cationic groups in one of anion-exchange fabric is quaternary ammonium salt.During filling, ion exchange fabric is vertical or parallel to ion-exchange membrane surface and fills.
Also be filled with anionite-exchange resin and/or Zeo-karb in aforementioned freshwater room or dense hydroecium, during filling, adopt anion/cation exchange resin fill separately or mix filling.
As further improvement, between the ion exchange fabric of filling and between ion exchange fabric and ion-exchange membrane, be also filled with of the same race and/or xenogenesis ion exchange resin.
As a kind of concrete structure, electric deionizer of filling based on ion exchange fabric of the present invention, comprise: cathode compartment, anolyte compartment, near the first freshwater room that cathode compartment is arranged, the 3rd freshwater room arranged near anolyte compartment, centre is provided with the second freshwater room, be arranged at the first dense hydroecium between the first freshwater room and the second freshwater room, the second dense hydroecium between second freshwater room and the 3rd freshwater room, cathode compartment, anolyte compartment and each freshwater room, ion-exchange membrane is adopted to separate between dense hydroecium, wherein, parallel or vertically fill ion exchange fabric in first dense hydroecium, parallel or vertically fill ion exchange fabric in second dense hydroecium.Set gradually from negative electrode anode direction: the first anion-exchange membrane, the second anion-exchange membrane, the first cationic exchange membrane, trianion exchange membrane, the second cationic exchange membrane, three cation exchange membrane.Preferably, be also filled with one deck ion exchange resin between the ion exchange fabric of filling in described second dense hydroecium and trianion exchange membrane, can hydrolysis rate be turned down at side filling ion-exchange resin, take into account electrodeionization efficiency and electrodeionization speed; Also can fill pellicular resins in both sides simultaneously, fabric hydrolysis rate can be made lower, electrodeionization speed and efficiency on the low side.When desalination, the water (flow) direction of fresh water is followed successively by: the 3rd freshwater room → the second freshwater room → the first freshwater room, and flow path is S shape; The water (flow) direction of collecting the dense hydroecium of foreign ion is the dense hydroecium of the second dense hydroecium → the first, and flow path is U-shaped.The electrodeionization works very well of this device, can be applicable to the preparation of pure water.
As another kind of concrete structure, electric deionizer of filling based on ion exchange fabric of the present invention, comprise: the second dense hydroecium that anolyte compartment, cathode compartment, the first dense hydroecium arranged near anolyte compartment, close cathode compartment are arranged, between two dense hydroeciums, freshwater room is set, parallel or vertically fill ion exchange fabric in freshwater room.Set gradually from negative electrode anode direction: the first anion-exchange membrane, the first cationic exchange membrane, the second anion-exchange membrane, the second cationic exchange membrane.When electricity removes metal ion, treat freshet obtained reuse water, the first dense hydroecium and second dense hydroecium difference water outlet or the mixing water outlet through freshwater room except metal ion.This device can be applicable to remove the concentrated of metal ion in wastewater from chemical industry or metal ion.Freshwater room water outlet, dense hydroecium water outlet can be recycled respectively, this device can remove metal ion, particularly harmful separated removal such as heavy metal ion, rare earth ion, but salts contg is high, specific conductivity is still large, and dense hydroecium water outlet and freshwater room water outlet redistribution on demand can be back to production process respectively.
Illustrate the electric deionizer of two kinds of structures herein, just in order to understand the present invention better, but we know, some combinations and change can also be done in the basis of these two kinds of structures, such as: increase freshwater room, dense hydroecium quantity; Dense hydroecium, freshwater room can fill single resin, fabric, hybrid resin and fabric simultaneously, but have at least a Room to be filled with ion exchange fabric, the effect of the metal ion that desalts to improve, removes; Water (flow) direction can be two S shape, dual U-shaped, W shape, M shape and combination thereof, and these technical schemes are all easy to expect and realize on basis of the present invention, also fall into protection scope of the present invention.
In the freshwater room that ion-exchange polypropylene nonwoven fabric by low temperature RF is filled into electric deionizer by the present invention and dense hydroecium, electrolysis regeneration and fabric hydrolysis regeneration two kinds of modes are combined, on the one hand, directed filling fabric significantly reduces resistance, improves ion mobility and electrodeionization efficiency, on the other hand, directed filling fabric fast hydrolyzing acts on the precipitation that inhibit heavy metal ion oxyhydroxide on ion-exchange membrane surface to a certain extent.
Electric deionizer of the present invention can improve current efficiency, contriver by analysis, think that reason fills based on fabric to have directivity, when ion exchange fabric is vertical with ion-exchange membrane fill time, anions and canons quick along fabric face, directedly will conduct (only having Plug mode to conduct), is conducive to improving electrodeionization efficiency and ion conduction rate.And when filling spherical resin, ionic conduction mode is that Plug is equivalent to resin surface in resin surface-water medium-resin surface, i.e. Plug-pore-Plug mode, because ion-exchange group is distributed in inside and the surface of spherical resin, this makes ionic conduction lengthening distance; Pore is equivalent to water, and water intermediate ion conduction resistance is large, and therefore, ion conduction rate is low, electrodeionization efficiency is low.
When ion exchange fabric filling, in the freshwater room that ion exchange fabric can be filled into electric deionizer respectively and dense hydroecium.Filling mode comprises two kinds: filling parallel with ion-exchange membrane and vertically with ion-exchange membrane to fill.During parallel filling, can mix with of the same race, xenogenesis ion exchange resin and fill.Advantage shows: when ion exchange fabric is parallel with ion-exchange membrane fill time, itself and different charge ion exchange membrane form similar Bipolar Membrane structure, this increase hydrolysis rate, effectively slow down the precipitation of metal hydroxides on ion-exchange membrane surface; There is the thickness of similar increase ion-exchange membrane with like charges film, accelerate the travelling speed of ion.When ion exchange fabric is vertical with ion-exchange membrane, effectively reduces resistance, improve ion mobility and electrodeionization efficiency.
Compared with spherical ions exchange resin, because resin diameter reaches hundreds of micron, equably more difficult and be filled in comparatively narrow freshwater room densely, there will be resin " drift ", " floating " and occur rare short in application process, electrodeionization efficiency reduces.Compared with ion-exchange fiber, fill because " cotton-shaped " ion-exchange fiber is difficult to even compact, and flow action and ion-exchange easily make fiber that " flocculation " occurs, and destroy packing layer homogeneity, can there is current short circuit phenomenon in local, electrodeionization efficiency reduces.Similarly, compared with filling cloth, because yarn is thicker, " aperture " larger gap is formed between yarn in weaving process, and more easily formed obviously " gap " between layers when filling, can be there is current short circuit phenomenon in local, and can cause when ion-exchange yam surface introduces more ion-exchange group and weave difficulty, and the ion exchange fabric loading capacity therefore formed by ion-exchange yarn is low.
To sum up, usefulness of the present invention is: electric deionizer of filling based on ion exchange fabric of the present invention, significantly reduce resistance, improve ion mobility, namely electrodeionization efficiency (can be removed the efficiency of foreign ion) and improve 20%-300%, also accelerate hydrolytic action simultaneously, alleviate the precipitation of metal hydroxides on ion-exchange membrane surface, the preparation of high purity water and the process of wastewater from chemical industry can be widely used in, have broad application prospects.
Accompanying drawing explanation
Fig. 1 is the structural representation of the EDI device of reference examples 1 of the present invention;
Fig. 2 is the current-voltage figure of reference examples 1 of the present invention;
Fig. 3 is the dense hydroecium specific conductivity-time diagram of reference examples 1 of the present invention;
Fig. 4 is the structural representation of the EDI device of reference examples 2 of the present invention;
Fig. 5 is two rooms specific conductivity-time diagram of reference examples 2 of the present invention;
Fig. 6 is the structural representation of the EDI device of embodiments of the invention 1;
Fig. 7 is the current-vs-time figure of embodiments of the invention 1;
Fig. 8 is the dense hydroecium specific conductivity-time diagram of embodiments of the invention 1;
Fig. 9 be in embodiments of the invention 1 cupric ion along the distribution plan (after gray proces) of water (flow) direction;
Figure 10 be in embodiments of the invention 1 cupric ion along direction of an electric field distribution plan (after gray proces);
Figure 11 is the structural representation of the EDI device of embodiments of the invention 2;
Figure 12 is two rooms specific conductivity-time diagram of embodiments of the invention 2.
Embodiment
Below in conjunction with the drawings and specific embodiments, concrete introduction being done to the present invention, in order to better the present invention is described, first having done two groups of reference examples, to compare.
Reference examples 1
Fig. 1 is the EDI device schematic diagram of the single filling freshwater room of ion exchange resin, wherein, filled circles is Zeo-karb, real thick line is cationic exchange membrane, empty thick line is anion-exchange membrane, arrow represents water (flow) direction, lower same, and the EDI device detecting the single filling freshwater room of this ion exchange resin removes the effect of cupric ion.
The thickness of the highly acidic cation exchange membrane that this reference examples uses and strong alkali anion exchange membrane is 0.48mm, the ion exchange capacity of cationic exchange membrane is 2mmol/g, the ion exchange capacity of anion-exchange membrane is 1.8mmol/g, and selectivity transmitance is 90%.The ion exchange capacity 4.2mmol/g of storng-acid cation exchange resin, the ion exchange capacity 3.0mmol/g of strongly basic anion exchange resin, granularity is (0.3-1.2mm) >=95%.EDI membrane stack is that sheet-pile shape construction module is assembled, and material is transparent organic glass.Freshwater room thickness is 10mm, and dense hydroecium thickness is 5mm; Anode is titanium plating ruthenium pole plate, and negative electrode is stainless steel polar plate; Water pipe adopts outer cloth, and peristaltic pump supplies water so that online stability monitoring effluent quality at different levels.Former water is the copper-bath of copper ion concentration 50mg/L, and pole water is 0.01M metabisulfite solution, and the flow velocity of former water, pole water and dense water is 1L/h.
About detection: copper ion concentration ThermoElectron company iCAP6300 type inductively coupled plasma atomic emission spectrometer measures; PH value thunder magnetic pHS-3c type pH meter on-line determination; Specific conductivity thunder magnetic DDB-303A type electric conductivity instrument on-line determination.
From Fig. 2 and Fig. 3, the critical hydrolysis voltage of positive resin infill system is about 20V, and cupric ion clearance is greater than 99%.
Reference examples 2
Fig. 4 is the EDI device of two rooms filling ion-exchange resin, and wherein, open circles is anionite-exchange resin, detects the effect that this device removes cupric ion.
Ion-exchange membrane and resin, electrode, Yuan Shui, pole water, flow rate of water flow are with reference examples 1, by the freshwater room filling male ion-exchange resin of anolyte compartment, freshwater room by cathode compartment fills anionite-exchange resin, middle freshwater room fills hybrid resin (volume ratio 1:1), volts DS is 20V, pole water is 0.01M metabisulfite solution, and initial dense water is deionized water, and the copper ion concentration of former water is the copper-bath of 50mg/L.As shown in Figure 5, when working time reaches about 80h, freshwater room specific conductivity is lower than 60 μ s/cm, and the specific conductivity of dense hydroecium is up to 5000 μ s/cm, and the clearance of cupric ion is up to 99%.
Embodiment 1
Fig. 6 is the EDI device of the single vertical filling freshwater room of ion exchange fabric, and wherein, real sea line is that Subacidity cation exchanges fabric, detects the effect that this device removes cupric ion.
Ion-exchange membrane, electrode, Yuan Shui, pole water, flow rate of water flow and device are with reference examples 1, and the Subacidity cation that freshwater room is filled exchanges fabric, and percentage of grafting is 50%, and ion exchange capacity is about 4.5mmol/g, and volts DS is 50V.Comparison diagram 2 and Fig. 7 are not difficult to find, during filling ion exchange fabric, current maxima reaches about 53mA, and the electric current of steady running is about 47mA.And during potting resin, the electric current of same electrical pressure is about 23mA.Comparison diagram 3 and 8 is visible similarly, and the specific conductivity of dense hydroecium also rises to 1000 μ s/cm of filling fabric from 600 μ s/cm of potting resin.As can be seen here, filling fabric reduces resistance, is conducive to the directional migration of ion, and cupric ion clearance is greater than 99%, particularly suitable removal of heavy metal ions or heavy metal ion concentrated.
In addition, cupric ion when we apply the present embodiment is analyzed along the distribution of water (flow) direction and direction of an electric field, analytical results shows: cupric ion is in saturated adsorption state or failure state in inhalant region, and is be in guard mode in outlet area, and cupric ion adsorption is little; Very little near anode side copper absorption, and a lot of near cathode side copper absorption.This illustrates that cation-exchange fabric is in excellent working order, and cupric ion shows good orientation transporting action, is conducive to improving ion mobility and electrodeionization efficiency.Fig. 9 and Figure 10 proves this result, illustrates, Fig. 9 and Figure 10 is the effect after experiment photo carries out gray proces, and cupric ion (cupric ion should be blue) has been adsorbed in grey representative, and color is darker then represents that adsorptive capacity is larger.
Embodiment 2
Figure 11 is freshwater room potting resin, dense hydroecium is filled in the EDI device of ion exchange fabric and resin, and real vertical curve is cation-exchange fabric, and empty vertical curve is anion-exchange fabric, detects the effect that this device removes cupric ion.Result proves, the removal effect of this device is good, can be applied to the preparation of high purity water.
Ion-exchange membrane and resin, electrode, Yuan Shui, pole water, flow rate of water flow are with reference examples 2, cation-exchange fabric filled by dense hydroecium by anolyte compartment, fill freshwater room side near mixing and also fill thin layer Zeo-karb, anion-exchange fabric filled by the dense hydroecium by cathode compartment.As shown in figure 12, when working time reaches about 80h, freshwater room specific conductivity is up to 300 μ s/cm, and the specific conductivity of dense hydroecium is up to 6000-7000 μ s/cm, and the clearance of cupric ion is still greater than 99%.Specific conductivity raise be due to when ion exchange fabric is parallel with ion-exchange membrane fill time, itself and different charge ion exchange membrane form similar Bipolar Membrane structure, Bipolar Membrane hydrolytic action causes freshwater room specific conductivity slightly to increase, and with like charges ion-exchange membrane touching position, ion exchange fabric touching position, then be equivalent to the thickness adding ion-exchange membrane, accelerate ion migration speed and electrodeionization efficiency, dense hydroecium specific conductivity also obviously increases simultaneously, illustrates that resistance greatly reduces.
The present embodiment is compared to comparative example 2, the specific conductivity of dense hydroecium and freshwater room all raises, explanation hydrolysis accelerates, ultimate principle be anions and canons fabric or membrane interface contact time, all there will be acceleration hydrolysis phenomena at the operation later stage that freshwater room is filled, the initial operating stage of filling at dense hydroecium.
In addition, after operation for some time, the ion-exchange membrane of comparative example 2 and embodiment 2, ion exchange resin are taken out and compares, naked eyes can find intuitively, and the electric deionizer that ion exchange fabric is filled effectively slow down the precipitation of metal hydroxides on ion-exchange membrane and ion exchange resin surface.
In order to embody beneficial effect of the present invention better, table 1 lists the detection data of relevant parameter of comparative example 1, comparative example 2 and embodiment 1, embodiment 2.
The detection data of table 1 comparative example 1, comparative example 2, embodiment 1, embodiment 2
In sum, electric deionizer of filling based on ion exchange fabric of the present invention, significantly reduce resistance, improve ion mobility, namely electrodeionization efficiency (can be removed the efficiency of foreign ion) and improve 20%-300%, also accelerate hydrolysis simultaneously, alleviate the precipitation of metal hydroxides on ion-exchange membrane surface, the preparation of high purity water and the process of wastewater from chemical industry can be widely used in, have broad application prospects.
More than show and describe ultimate principle of the present invention, principal character and advantage.The technician of the industry should understand, and above-described embodiment does not limit the present invention in any form, the technical scheme that the mode that all employings are equal to replacement or equivalent transformation obtains, and all drops on protection scope of the present invention.
Claims (10)
1. based on the electric deionizer that ion exchange fabric is filled, it is characterized in that, comprise: the cathode compartment and the anolyte compartment that are positioned at device two ends, also comprise the spaced multiple dense hydroecium and freshwater room separated with ion-exchange membrane, have at least in a freshwater room or dense hydroecium and be filled with ion exchange fabric, ion exchange fabric is vertical or parallel to ion-exchange membrane surface and fills, described ion exchange fabric is made up based on after modification of graft of polypropylene fibre nonwoven material surface, area density is 20-400g/ ㎡, and fabric percentage of grafting is 30-300%.
2. electric deionizer of filling based on ion exchange fabric according to claim 1, it is characterized in that, described ion exchange fabric comprises cation-exchange fabric and anion-exchange fabric, adopt anion/cation to exchange fabric during filling fill separately or mix filling, anionic group in cation-exchange fabric comprises one or more in sulfonate radical, carboxylate radical and phosphonate radical, and the cation group in anion-exchange fabric is quaternary ammonium salt; Also be filled with anionite-exchange resin and/or Zeo-karb in described freshwater room or dense hydroecium, during filling, adopt anion/cation exchange resin fill separately or mix filling.
3. electric deionizer of filling based on ion exchange fabric according to claim 1 and 2, it is characterized in that, between the ion exchange fabric of filling and between ion exchange fabric and ion-exchange membrane, be also filled with of the same race and/or xenogenesis ion exchange resin.
4. electric deionizer of filling based on ion exchange fabric according to claim 1, it is characterized in that, comprise: cathode compartment, anolyte compartment, near the first freshwater room that cathode compartment is arranged, the 3rd freshwater room arranged near anolyte compartment, centre is provided with the second freshwater room, be arranged at the first dense hydroecium between the first freshwater room and the second freshwater room, the second dense hydroecium between second freshwater room and the 3rd freshwater room, cathode compartment, anolyte compartment and each freshwater room, ion-exchange membrane is adopted to separate between dense hydroecium, wherein, parallel or vertically fill ion exchange fabric in first dense hydroecium, parallel or vertically fill ion exchange fabric in second dense hydroecium.
5. electric deionizer of filling based on ion exchange fabric according to claim 4, it is characterized in that, set gradually from negative electrode anode direction: the first anion-exchange membrane, the second anion-exchange membrane, the first cationic exchange membrane, trianion exchange membrane, the second cationic exchange membrane, three cation exchange membrane; One deck ion exchange resin is also filled with between the ion exchange fabric of filling in described second dense hydroecium and trianion exchange membrane.
6. electric deionizer of filling based on ion exchange fabric according to claim 5, it is characterized in that, during desalination, the water (flow) direction of fresh water is followed successively by: the 3rd freshwater room → the second freshwater room → the first freshwater room, and flow path is S shape; The water (flow) direction of collecting the dense hydroecium of foreign ion is the dense hydroecium of the second dense hydroecium → the first, and flow path is U-shaped.
7. the electric deionizer based on ion exchange fabric filling described in any one of application rights requirement 4-6 is in the preparation of pure water.
8. electric deionizer of filling based on ion exchange fabric according to claim 1, it is characterized in that, comprise: the second dense hydroecium that anolyte compartment, cathode compartment, the first dense hydroecium arranged near anolyte compartment, close cathode compartment are arranged, between two dense hydroeciums, freshwater room is set, parallel or vertically fill ion exchange fabric in freshwater room.
9. electric deionizer of filling based on ion exchange fabric according to claim 8, it is characterized in that, set gradually from negative electrode anode direction: the first anion-exchange membrane, the first cationic exchange membrane, the second anion-exchange membrane, the second cationic exchange membrane; When electricity removes metal ion, treat freshet except metal ion through freshwater room obtained reuse water, the first dense hydroecium and the second dense hydroecium be water outlet or mixing water outlet respectively.
10. application rights requires the electric deionizer based on ion exchange fabric filling described in 8 or 9 in the metal ion removed in wastewater from chemical industry or metal ion is concentrated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310722653.6A CN103708586B (en) | 2013-12-24 | 2013-12-24 | Electrodeionization device based on ion exchange fabric filling and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310722653.6A CN103708586B (en) | 2013-12-24 | 2013-12-24 | Electrodeionization device based on ion exchange fabric filling and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103708586A CN103708586A (en) | 2014-04-09 |
| CN103708586B true CN103708586B (en) | 2015-11-11 |
Family
ID=50401989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310722653.6A Active CN103708586B (en) | 2013-12-24 | 2013-12-24 | Electrodeionization device based on ion exchange fabric filling and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103708586B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107162127A (en) * | 2017-07-24 | 2017-09-15 | 赵寰宇 | A kind of electric deionizer |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016183767A1 (en) * | 2015-05-18 | 2016-11-24 | 佛山市顺德区美的洗涤电器制造有限公司 | Dish washing machine |
| CN111302450B (en) * | 2020-03-03 | 2021-01-29 | 中国科学院生态环境研究中心 | Method for regulating and controlling retention rate of soluble salt in aqueous solution and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2280095Y (en) * | 1996-11-29 | 1998-04-29 | 清华大学 | Electric de-ionized water purification apparatus |
| CN102965929A (en) * | 2012-10-12 | 2013-03-13 | 苏州大学 | Preparation method and application of modified polypropylene non-woven fabric |
-
2013
- 2013-12-24 CN CN201310722653.6A patent/CN103708586B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2280095Y (en) * | 1996-11-29 | 1998-04-29 | 清华大学 | Electric de-ionized water purification apparatus |
| CN102965929A (en) * | 2012-10-12 | 2013-03-13 | 苏州大学 | Preparation method and application of modified polypropylene non-woven fabric |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107162127A (en) * | 2017-07-24 | 2017-09-15 | 赵寰宇 | A kind of electric deionizer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103708586A (en) | 2014-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103058425B (en) | desalination system and method | |
| CN100345615C (en) | Electric deionisation method and apparatus for producing superpure water using bipolar membrane | |
| KR101004707B1 (en) | Electrode and electronic cell using it for eliminating ions in water | |
| CN103723799A (en) | Electrodialyzer and near-zero-release industrial wastewater recycling technique | |
| CN103708586B (en) | Electrodeionization device based on ion exchange fabric filling and application thereof | |
| KR20140069581A (en) | Capacitive deionization apparatus and methods of treating fluid using the same | |
| CN102976454B (en) | Method for separating cations of NH4<+> and Mg<2+> with same electric properties in fermentation wasterwater by using packed bed electrodialyzer | |
| KR102186074B1 (en) | Concentration method of lithium by electrodialysis | |
| CN103708585A (en) | Technology and device for removing heavy metal ions in electroplating wastewater | |
| CN104495991A (en) | Efficient membrane capacitive deionizing array based on flowing electrodes | |
| CN201553635U (en) | Electro deionization device for filling ion exchange fibers in electrolyte water compartment and concentrated water compartment | |
| CN112159902A (en) | Electricity-water lithium extraction co-production system based on capacitance method | |
| Kumar et al. | In-sight studies on concentration polarization and water splitting during electro-deionization for rapid production of ultrapure water (@ 18.2 MΩ cm) with improved efficiency | |
| CN203668077U (en) | Electric deionizing device based on ion exchange fabric filling | |
| CN1184005A (en) | Electrical ion exchange resin regenerating method and equipment | |
| CN105236527B (en) | A kind of three-diemsnional electrode device and method of the synchronous continuous desalination removal organic polluter of waste water | |
| CN105253991B (en) | A kind of electromagnetic field couples desalter and method for having the dirty function of drop concurrently | |
| CN102992522A (en) | Desalination system and method | |
| CN111410274B (en) | Titanium-based material, preparation method thereof and application thereof in flow electrode | |
| CN108002604A (en) | A kind of method of concentrated seawater recycling | |
| CN107118105A (en) | The method that coupling bipolar membrane electrodialysis and membrane distillation prepare methyl triethylammonium hydroxide | |
| CN208856965U (en) | A kind of EDI membrane stack of long-life | |
| CN102745783A (en) | Water-based solution ion separation device and method | |
| CN102953082B (en) | A kind of method reducing precipitation qualifying liquid pH value | |
| KR102019318B1 (en) | Hybrid generating device and method for electricity and concentrated water and desalting |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191114 Address after: 710018 unit 1, building 1, Wangjing international building, Fengcheng 6th Road, Xi'an Economic and Technological Development Zone, Shaanxi Province Patentee after: Shaanxi one intellectual property operation Co., Ltd. Address before: 215000 Suzhou Industrial Park, Jiangsu Road, No. 199 Patentee before: Soochow University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200619 Address after: 215500 No.13, Caotang Road, Changshu, Suzhou, Jiangsu Province Patentee after: Changshu intellectual property operation center Co.,Ltd. Address before: 710018 unit 1, building 1, Wangjing international building, Fengcheng 6th Road, Xi'an Economic and Technological Development Zone, Shaanxi Province Patentee before: SHAANXI ZHUANYI INTELLECTUAL PROPERTY OPERATION Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200805 Address after: Building 5, No.2, Kaicheng Road, Zhitang Town, Changshu City, Suzhou City, Jiangsu Province Patentee after: Suzhou Jieyou Sanitary Material Technology Co., Ltd Address before: 215500 No.13, Caotang Road, Changshu, Suzhou, Jiangsu Province Patentee before: Changshu intellectual property operation center Co.,Ltd. |
|
| TR01 | Transfer of patent right |