CN106673144B - A kind of electric nanofiltration device with low salt rejection rate and high rejection to organics rate - Google Patents
A kind of electric nanofiltration device with low salt rejection rate and high rejection to organics rate Download PDFInfo
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- CN106673144B CN106673144B CN201710055219.5A CN201710055219A CN106673144B CN 106673144 B CN106673144 B CN 106673144B CN 201710055219 A CN201710055219 A CN 201710055219A CN 106673144 B CN106673144 B CN 106673144B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
Abstract
The electric nanofiltration device with low salt rejection rate and high rejection to organics rate that the present invention relates to a kind of, the electricity nanofiltration device includes anode plate, cathode plate, anion-exchange membrane, cation-exchange membrane, nanofiltration membrane and DC power supply, anode plate is connected with the anode of DC power supply, cathode plate is connected with the cathode of DC power supply, anode plate is positioned opposite with cathode plate, and amberplex, nanofiltration membrane and amberplex are set gradually between anode plate to cathode plate.Electric nanofiltration proposed by the present invention with low salt rejection rate and high rejection to organics rate, electrodialysis is organically combined with nanofiltration, amberplex is replaced with nanofiltration membrane, by electric field force, pressure, concentration difference as motive force, compared with electrodialysis, although the separating effect of organic matter and inorganic salts decreases, but its investment cost and operating cost is significantly reduced, and resistance to organic contamination performance is also significantly improved, this has better application prospect in industrial wastewater or municipal wastewater process field.
Description
Technical field
The electric nanofiltration device with low salt rejection rate and high rejection to organics rate that the present invention relates to a kind of, is widely used in
The separation of organic matter and inorganic salts is carried out in biochemistry, pharmacy, environmental protection and modern chemical industry production, or between different inorganic salts
Separation and concentration.
Background technique
The major function of common nanofiltration membrane is selective desalination, and desalination mechanism mainly has aperture sieve effect and charge effect
It answers, the collective effect of two kinds of mechanism makes it have unique advantage in terms of separation monovalent ion and high valence ion and organic matter,
In the organic matter and coloration of removal surface water, the hardness of underground water is removed, part removes dissolubility salt, inspissated juice and separation
The fields such as the utility in drug have a wide range of applications.But it also has certain limitation in application aspect, due to receiving
Filter membrane all has higher cutoff performance to high valence ion and organic matter, therefore the more difficult Selective Separation both accomplished, this
Some special feed separation fields be it is undesirable, if dyestuff concentration purify, dyestuff concentration while to inorganic salts
Ion is without concentrated effect.
Lower section is all had to all inorganic ions currently, temporarily can be realized without a kind of industrialized nanofiltration membrane
Stay rate, at the same to molecular weight 200-1000 or so organic matter cutoff performance with higher.The present invention devises a kind of new
The susceptance filtering technology of type is organically combined extra electric field with nanofiltration membrane, and under the action of extra electric field, inorganic ion is penetrated
The rate of nanofiltration membrane obviously increases, and uncharged organic matter is not influenced then through the migration rate of film by electric field, thus real
Nanofiltration membrane is showed with low desalination, the function of high rejection to organics has in some special feed separation fields and widely answers
With value.
Nanofiltration is a kind of pressure-driven membrane separating process between reverse osmosis between ultrafiltration, the aperture model of nanofiltration membrane
Several rans are trapped among, molecular cut off is between 200-1000.The separating mechanism of nanofiltration membrane mainly has aperture screening mechanism
With charge effect mechanism, the collective effect of two kinds of mechanism makes nanofiltration membrane small to ionic radius, the few monovalence of electrically charged amount from
Son has lower rejection, larger to ionic radius, the more divalent of electrically charged amount or with higher section of high valence ion
Rate performance is stayed, at the same time, nanofiltration membrane is to organic matter of the molecular weight between 200-1000 also rejection with higher, if thinking
It realizes that divalent ion and high valence ion are efficiently separated with organic matter, cannot achieve by common nanofiltration membrane.
The method that inorganic salts and organic matter can be completely separated under normal conditions has electroosmose process, and electrodialysis is handed over using ion
The selective penetrated property for changing film realizes the separation of organic matter and inorganic salts, under the action of extra electric field, cation permeable cation
Exchange membrane, anion-permeable anion-exchange membrane, and uncharged organic matter is not influenced then by electric field force, will not through from
Proton exchange, to realize the separation of organic matter and inorganic salts, electrodialysis at present realizes that the separation of organic matter and inorganic salts is main
Using the product in the industrial production, having added value.Separation field of the electroosmose process for inorganic salts and organic matter has
Certain application market, but amberplex is expensive, resistance to organic pollution performance poor (Bazinet L, Araya-
Farias M.Electrodialysis of calcium and carbonate high concentration
solutions and impact on composition in cations of membrane fouling.Journal of
Colloid&Interface Science, 2005,286 (2): 639-646.), investment is higher with operating cost at producing, in object
Material separation aspect, main application in the processing of the centre water of industrial processes, the process field of waste water should have compared with
It is few.
Lower section is all had to all inorganic ions currently, temporarily can be realized without a kind of industrialized nanofiltration membrane
Stay rate, at the same to molecular weight 200-1000 or so organic matter cutoff performance with higher.Currently, commercially available nanofiltration membrane one
As be nanofiltration membrane with negative electric charge, there is lower rejection to cation and univalent anion, but it is to divalent or high price
Anion cutoff performance with higher, therefore its separation for being unsuitable for realization divalent or high-valence anion and organic matter.
Summary of the invention
The present invention provides a kind of electric nanofiltration device, extra electric field is organically combined with nanofiltration membrane, in the work of extra electric field
Under, inorganic ion is obviously increased through the rate of nanofiltration membrane, and uncharged organic matter through film migration rate then not
It is influenced by electric field, to realize nanofiltration membrane with low desalination, the function of high rejection to organics, in some special materials point
It is with a wide range of applications from field.
Specific structure of the invention is as follows:
The electric nanofiltration device with low salt rejection rate and high rejection to organics rate that the present invention provides a kind of, the electricity nanofiltration device
Including anode plate, cathode plate, anion-exchange membrane, cation-exchange membrane, nanofiltration membrane and DC power supply, anode plate and DC power supply
Anode be connected, cathode plate is connected with the cathode of DC power supply, and anode plate is positioned opposite with cathode plate, from anode plate to cathode plate
Between set gradually an amberplex, multiple nanofiltration membranes and an amberplex.
Wherein the nanofiltration membrane is arranged in pairs, and guarantees that the chamber close to amberplex is all to produce water chamber.
Wherein the anode plate is titanium ruthenium material, and cathode plate is stainless steel plate.
With filter interval to generate water stream channel between any of them two panels film.
The a piece of nanofiltration membrane two sides of any of them are respectively intake chamber and production water chamber.
Wherein, when the amberplex close to anode plate is cation-exchange membrane, the amberplex close to cathode plate is
Anion-exchange membrane, then anode pole water and cathode pole water circulate respectively.
Wherein, when the amberplex close to anode plate is anion-exchange membrane, the amberplex close to cathode plate is
Cation-exchange membrane, then anode pole water and cathode pole water circulate respectively.
Wherein, when the amberplex close to anode plate and the amberplex close to cathode plate are cation-exchange membrane
Or be anion-exchange membrane, then the pole water in anode pole water chamber and cathode pole water chamber is integrated, series circulation flowing.
It wherein further include into water reservoir and producing water reservoir, the water inlet in reservoir of intaking enters by pump, flowmeter
Intake chamber returns to water inlet reservoir by valve later, and the production water for producing water reservoir enters production water chamber by pump, flowmeter, it
It is returned afterwards by valve and produces water reservoir.
It wherein further include anode pole water reservoir and cathode pole water reservoir, the pole water in the water reservoir of anode pole passes through
Pump, flowmeter enter anode pole water chamber, return to anode pole water reservoir, the pole water warp of cathode pole water reservoir by valve later
Cross pump, flowmeter enters cathode pole water chamber, later by valve return cathode pole water reservoir.
Detailed description of the invention
In order to be easier to understand technical solution of the present invention and beneficial technical effect, by referring to what is be shown in the accompanying drawings
A specific embodiment of the invention is described in detail the present invention.These attached drawings depict only typical implementation of the invention
Mode does not constitute the limitation to protection scope of the present invention, in which:
Fig. 1 is an embodiment party of the electric nanofiltration device according to the present invention with low salt rejection rate and high rejection to organics rate
The structural schematic diagram of formula.
Fig. 2 is the susceptance filtering technology of the electric nanofiltration device according to the present invention with low salt rejection rate and high rejection to organics rate
Separate the schematic illustration of organic matter and inorganic salts.
In the appended drawing reference indicated in Fig. 1-2:
1: anode plate；2: cathode plate；3: cation-exchange membrane；4: anion-exchange membrane；5: nanofiltration membrane；6: intake chamber；7:
Produce water chamber；8: anode pole water chamber；9: cathode pole water chamber；10: DC power supply；11: pump；12: flowmeter；13: water inlet reservoir；
14: producing water reservoir；15: anode pole water reservoir；16: cathode pole water reservoir；17: valve.
Specific embodiment
Fig. 1 is an embodiment party of the electric nanofiltration device according to the present invention with low salt rejection rate and high rejection to organics rate
The structural schematic diagram of formula, the electricity nanofiltration device include anode plate 1, cathode plate 2, cation-exchange membrane 3, anion-exchange membrane 4, receive
Filter membrane 5 and DC power supply 10.Anode plate 1 is connected with the anode of DC power supply 10, the cathode phase of cathode plate 2 and DC power supply 10
Even, positioned opposite from anode plate 1 and cathode plate 2, from anode plate 1 to setting gradually cation-exchange membrane 3 cathode plate 2, receive
Filter membrane 5 and anion-exchange membrane 4.Anode plate 1 is titanium ruthenium material, and cathode plate 2 is stainless steel plate.Anion and cation exchange membrane is one
Piece, effect are to prevent from producing (such as calcium and magnesium) cationic in water chamber into cathode chamber generation fouling, prevent anion from entering anode chamber
The enrichment of acid is caused, the centre of anion and cation exchange membrane is nanofiltration membrane 5, these nanofiltration membranes occur in pairs to guarantee to hand over close to ion
The chamber for changing film is production water chamber, and its logarithm is arbitrary number, between any two panels film (amberplex and nanofiltration membrane it
Between, between nanofiltration membrane and nanofiltration membrane) with filter interval.Between cation-exchange membrane 3 and anode plate 1 be anode pole water chamber 8, yin from
It is cathode pole water chamber 9 between proton exchange 4 and cathode plate 2.
This technique separates the form of organic matter and inorganic salts as batch-type processing, and the water inlet in reservoir 13 of intaking is by pump
11, flowmeter 12 enters intake chamber 6, returns to water inlet reservoir 13 later, produces the production water of water reservoir 14 by pump 11, flowmeter
12 enter production water chamber 7, return produce water reservoir 14 later.Equally, the pole water in anode pole water reservoir 15 is by pump 11, flow
Meter 12 enters anode pole water chamber 8, returns to anode pole water reservoir 15 later, the pole water of cathode pole water reservoir 16 by pump 11,
Flowmeter 12 enters cathode pole water chamber 9, returns to cathode pole water reservoir 16 later.Enter containing the water body of inorganic salts and organic matter
Intake chamber 6 makes intake chamber 6 by control valve 17 and produces water chamber 7 with certain pressure difference, under pressure, intake chamber 6
In liquid can constantly enter produce water chamber 7, by adjust the runing time control system rate of recovery, when reaching certain rate of recovery,
The water inlet more renewed produces water then most of outlet, only retains small part as the circulation fluid for producing water chamber.
It is to contain MgSO with water inlet4For the solution of glucose, illustrate the present invention is how to realize low salt rejection rate and height
The performance of rejection to organics rate.
Assuming that MgSO in water inlet4Concentration is 1.0mol/L, produces MgSO in water4Concentration is 0.1mol/L, is applied when in film two sides
After one DC electric field, directional migration can occur under electric field action for ion, and anion can penetrate nanofiltration membrane 5 to 1 side of anode plate
Mobile, cation can be mobile to 2 side of cathode plate through nanofiltration membrane 5, and electric field strength is bigger, and the rate of Ion transfer is faster.Such as
Shown in Fig. 2, it is assumed that enter the SO produced in water chamber 7 by a piece of nanofiltration membrane 5 by intake chamber 6 whithin a period of time4 2-Quantity is 100
It is a, due to the SO in intake chamber 64 2-Concentration, which is apparently higher than, produces SO in water chamber 74 2-Concentration, then passing through a piece of nanofiltration by production water chamber 7
Film 5 enters the SO in intake chamber 64 2-Quantity then can be solely 20, and same reason is entered by intake chamber 6 and produced in water chamber 7
Mg2+Quantity also can be significantly hotter than the Mg entered in intake chamber 6 by production water chamber 72+Quantity, but the transmitting on every film yin from
The quantity of electric charge of son and cationic institute's band be it is identical, to guarantee that the size of current on every film is identical.In general, extra electric field
It promotes inorganic ions and production water chamber 7 is entered by intake chamber 6 through nanofiltration membrane 5, reduce the salt rejection rate of nanofiltration membrane.At the same time,
Glucose does not dissociate, and extra electric field will not influence the migration rate of organic matter, therefore, retention of the nanofiltration membrane 5 to organic matter
Rate influences little.The final technique can be realized to inorganic salts with lower cutoff performance and to higher section of organic matter
Stay performance.
The key point of this technique is that intake chamber and production water chamber must have certain concentration difference, as long as experiment is prepared when starting
Have a concentration difference into producing between water, experiment runs laggard aqueous volume and constantly reduces, and concentration is constantly concentrated, dense between water into producing
Degree difference will be continuously increased, it is ensured that moving to the ion populations produced in water chamber from intake chamber and being much larger than from production water makes to move into water
Ion populations in room.Furthermore oxygen evolution reaction occurs for anode chamber, generates H+, cathode chamber generation evolving hydrogen reaction, production OH-, H+With
OH-It can constantly enter and produce water chamber to transmit electric current, but be into the H produced in water chamber+And OH-It can neutralize rapidly, not influence to produce water
Acid-base property.
Embodiment 1:
Water inlet is concentrated water of the municipal wastewater by MBR+ after reverse osmosis, conductance 3025us/cm, it is contained therein it is main from
Son is SO4 2-、Mg2+, COD (COD) is 200mg/L, and the separation of inorganic salts and organic matter is realized with the technique.
Water inlet is above-mentioned reverse osmosis concentrated water, and the sodium chloride for preparing the 250ppm of certain volume in advance, which is used as, produces water, pole water
For 1% metabisulfite solution, water inlet, production water, anode pole water and cathode pole water circulate respectively, prepare production water in advance and are simultaneously producing
The purpose of water chamber circulation is to reduce the boundary layer thickness for producing water chamber film surface, improves limiting current density.Water inlet chamber pressure be
0.35MPa, produces water chamber, the pressure of pole water chamber is respectively less than 0.005MPa, and the rate of recovery 80% is tested in 10A/m2Current density
Salt rejection rate and rejection to organics rate are tested in lower operation.Experimental data such as table 1:
The electric nanofiltration separating inorganic salts of table 1 and organic matter
Analysis: as it can be seen from table 1 electric nanofiltration is compared with blank assay, total salt rejection rate reduces 58.6%, SO4 2-
Rejection reduces 57.6%, and rejection to organics rate reduced by only 1.7%, illustrate electric nanofiltration can be realized low salt rejection rate,
The function of high rejection to organics rate.Simultaneously, electric nanofiltration can also significantly improve the flux of nanofiltration membrane, with blank assay phase
Than the flux of susceptance filter improves 17.4Lm-2·h-1, about improve 38.5%.
Embodiment 2:
Water inlet is that water is used among certain food processing, and conductance 2604us/cm, leading ion contained therein is PO4 3-, COD
(COD) is 1040mg/L, separates PO while realizing organic matter concentration with the technique4 3-。
Water inlet is that water is used among above-mentioned food processing, and the above-mentioned raw water after dilution produces water, the sulphur that pole water is 1% as initial
Acid sodium solution, water inlet, anode pole water and cathode pole water circulate respectively, and water inlet chamber pressure is 0.35MPa, produce water chamber, pole water
The pressure of room is respectively less than 0.005MPa, and the rate of recovery 50% is tested respectively in 10A/m2And 30A/m2Current density under run,
Test total salt rejection rate, PO4 3-Rejection and rejection to organics rate.Experimental data such as table 2:
PO in the electric nanofiltration removal food water of table 24 3-Experimental study
Analysis: it is obtained by table 2, in 50A/m2Current density under, compared with blank assay, electric nanofiltration adds food
The salt rejection rate of water can reduce by 58.1%, PO among work4 3-Rejection can reduce by 41.9%, and increase electric current in a certain range
Density advantageously reduces nanofiltration membrane to PO4 3-Rejection.
Electric nanofiltration proposed by the present invention with low salt rejection rate and high rejection to organics rate, electrodialysis and nanofiltration are had
The combination of machine replaces amberplex with nanofiltration membrane, by electric field force, pressure, concentration difference as motive force, with electric osmose phase separation
Than, although the separating effect of organic matter and inorganic salts decreases, but its investment cost and operating cost is significantly reduced,
And resistance to organic contamination performance is also significantly improved, this has preferably application in industrial wastewater or municipal wastewater process field
Prospect.
The present invention can embody in the form of other are specific, such as in the combination of amberplex, close
The amberplex of anode plate can be changed to anion-exchange membrane, and the amberplex close to cathode plate is then cationic exchange
Film, and anode pole water and cathode pole water circulate respectively；In the combination of amberplex, close to cathode plate and anode
The amberplex of plate can be cation-exchange membrane, and the pole water in anode pole water chamber and cathode pole water chamber is integrated at this time,
Series circulation flowing；In the combination of amberplex, the amberplex close to cathode plate and anode plate can be
Anion-exchange membrane, the pole water in anode pole water chamber and cathode pole water chamber is integrated at this time, series circulation flowing.But this can't
It is detached from protection scope of the present invention, protection scope of the present invention is defined only by the following claims.
Claims (8)
1. a kind of electric nanofiltration device with low salt rejection rate and high rejection to organics rate, which includes anode plate, yin
Pole plate, anion-exchange membrane, cation-exchange membrane, nanofiltration membrane and DC power supply, anode plate are connected with the anode of DC power supply, yin
Pole plate is connected with the cathode of DC power supply, and anode plate is positioned opposite with cathode plate, sets gradually between anode plate to cathode plate
One amberplex, multiple nanofiltration membranes and an amberplex, and multiple described nanofiltration membranes are arranged in pairs, any of them
One nanofiltration membrane two sides is respectively intake chamber and production water chamber.
2. electricity nanofiltration device according to claim 1, wherein the anode plate is titanium ruthenium material, cathode plate is stainless steel
Plate.
3. electricity nanofiltration device according to claim 1, logical to generate water flow with filter interval between any of them two panels film
Road.
4. electricity nanofiltration device according to claim 1, wherein when the amberplex close to anode plate is cation exchange
Film, the amberplex close to cathode plate is anion-exchange membrane, then anode pole water and cathode pole water circulate respectively.
5. electricity nanofiltration device according to claim 1, wherein when the amberplex close to anode plate is anion exchange
Film, the amberplex close to cathode plate is cation-exchange membrane, then anode pole water and cathode pole water circulate respectively.
6. electricity nanofiltration device according to claim 1, wherein when the amberplex close to anode plate and close to cathode plate
Amberplex be cation-exchange membrane or be anion-exchange membrane, then in anode pole water chamber and cathode pole water chamber
Pole water is integrated, series circulation flowing.
7. electricity nanofiltration device according to claim 1 to 6 further includes into water reservoir and producing water reservoir, into
Water inlet in water reservoir enters intake chamber by pump, flowmeter, returns to water inlet reservoir by valve later, produces water reservoir
Production water by pump, flowmeter enter production water chamber, later by valve return produce water reservoir.
8. electricity nanofiltration device according to any one of claims 1-5, further includes anode pole water reservoir and cathode pole water
Reservoir, the pole water in the water reservoir of anode pole enter anode pole water chamber by pump, flowmeter, return to anode by valve later
The pole water of pole water reservoir, cathode pole water reservoir enters cathode pole water chamber by pump, flowmeter, returns to yin by valve later
Pole pole water reservoir.
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| CN107522268B (en) * | 2017-08-15 | 2020-11-03 | 中国科学院青岛生物能源与过程研究所 | Device for water treatment and material separation and separation method thereof |
| CN110975628A (en) * | 2019-12-24 | 2020-04-10 | 福州大学 | Loose electric nanofiltration device and process for efficiently separating dye and inorganic salt |
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| JP2002143854A (en) * | 2000-11-08 | 2002-05-21 | Matsushita Electric Ind Co Ltd | Electrochemical water treating device |
| CN103572051A (en) * | 2013-11-15 | 2014-02-12 | 吴鋆 | Dechlorination method of zinc sulfate solution |
| CN105771665A (en) * | 2016-03-23 | 2016-07-20 | 内蒙古天环境技术有限公司 | Disc tube type membrane component using columnar dielectrophoresis electrodes |
| CN104524976B (en) * | 2015-01-21 | 2016-08-24 | 中国科学技术大学 | A kind of electric nanofiltration device for one/multivalent ion Selective Separation |
-
2017
- 2017-01-24 CN CN201710055219.5A patent/CN106673144B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002143854A (en) * | 2000-11-08 | 2002-05-21 | Matsushita Electric Ind Co Ltd | Electrochemical water treating device |
| CN103572051A (en) * | 2013-11-15 | 2014-02-12 | 吴鋆 | Dechlorination method of zinc sulfate solution |
| CN104524976B (en) * | 2015-01-21 | 2016-08-24 | 中国科学技术大学 | A kind of electric nanofiltration device for one/multivalent ion Selective Separation |
| CN105771665A (en) * | 2016-03-23 | 2016-07-20 | 内蒙古天环境技术有限公司 | Disc tube type membrane component using columnar dielectrophoresis electrodes |
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Address after: 301800 No.10, Fuli Road, plastic products industrial zone, Baodi District, Tianjin Patentee after: Oseco membrane technology (Tianjin) Co.,Ltd. Address before: 301800 No.10, Fuli Road, plastic products industrial zone, Baodi District, Tianjin Patentee before: TIANJIN BISHUIYUAN MEMBRANE MATERIAL Co.,Ltd. |