CN106925357A - A kind of preparation method of Monovalent selectivity anion-exchange membrane - Google Patents
A kind of preparation method of Monovalent selectivity anion-exchange membrane Download PDFInfo
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- CN106925357A CN106925357A CN201710119805.1A CN201710119805A CN106925357A CN 106925357 A CN106925357 A CN 106925357A CN 201710119805 A CN201710119805 A CN 201710119805A CN 106925357 A CN106925357 A CN 106925357A
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- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 239000011780 sodium chloride Substances 0.000 claims abstract description 20
- 230000008021 deposition Effects 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 239000012528 membrane Substances 0.000 claims description 44
- 238000005341 cation exchange Methods 0.000 claims description 10
- 229920001661 Chitosan Polymers 0.000 claims description 3
- 238000005349 anion exchange Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- AJXBTRZGLDTSST-UHFFFAOYSA-N amino 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON AJXBTRZGLDTSST-UHFFFAOYSA-N 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract description 13
- 238000004062 sedimentation Methods 0.000 abstract description 3
- 238000004520 electroporation Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 16
- 150000001450 anions Chemical class 0.000 description 8
- 125000000129 anionic group Chemical group 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000007832 Na2SO4 Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004590 computer program Methods 0.000 description 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- RUUHDEGJEGHQKL-UHFFFAOYSA-M 2-hydroxypropyl(trimethyl)azanium;chloride Chemical class [Cl-].CC(O)C[N+](C)(C)C RUUHDEGJEGHQKL-UHFFFAOYSA-M 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
- B01D61/48—Apparatus therefor having one or more compartments filled with ion-exchange material, e.g. electrodeionisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
- B01D61/48—Apparatus therefor having one or more compartments filled with ion-exchange material, e.g. electrodeionisation
- B01D61/485—Specific features relating to the ion-exchange material
-
- 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
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Urology & Nephrology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
A kind of preparation method of Monovalent selectivity anion-exchange membrane, including：(1) first NaCl solution is added in dense room, and make Na toward the mixed solution of addition NSBC and NaCl in feed liquid room2SO4Solution is full of electrode chamber A and electrode chamber B, then sets electric pulse parameter, and energization carries out electro-pulse deposition makes NSBC deposit on anion-exchange membrane；(2) after deposition certain hour, solution in feed liquid room is replaced with into the mixed solution of HACC and NaCl, and exchange the both sides sense of current, keeps that electric pulse parameter is constant to proceed electro-pulse deposition, HACC is deposited on anion-exchange membrane；(3) operation of repeat step (1) and step (2), so that NSBC sugar and HACC alternating deposits obtain being attached with the anion-exchange membrane of multilayer NSBC/HACC on anion-exchange membrane.In the present invention, modified film surface mass depositing homogeneous and monovalention are selectively improved；Electroporation can improve the utilization ratio and Multilayer stable of electric current, reduce sedimentation time and cost of investment.
Description
Technical field
The present invention relates to a kind of preparation method of Monovalent selectivity anion-exchange membrane, particularly relate to one kind and use electric pulse
The preparation method of technology modified anion exchange membrane.
Background technology
Electrodialytic technique is to process sewage, a kind of important method of production fresh water in the world, is widely used in bitter
Desalination and salting liquid concentration.Its core is the amberplex for using.The most important characteristic of amberplex is right
The selectivity of ion is through effect.People are finding side of the raising to the selective penetrated property control of amberplex for a long time
Method.Anion-exchange membrane improves to it and selection of anion is passed through in recent years as a part important in amberplex
Property aspect mainly by anion-exchange membrane it is surface-crosslinked it is modified formation one strata anionic species, so as to improve anion
The Monovalent selectivity of exchange membrane.By LBL self-assembly method, respectively inhaled by electrostatic on commercial anionic exchange membrane surface
Attached effect forms the novel ion exchange membrane of multiple modified layers by wide coverage.However, time mistake used by above-mentioned sedimentation
Long, film resistance is excessive, and the stability of ion-selective permeability and modified layer is not high.Also article reports using alternately electro-deposition side
Method, though this can modified anion exchange membrane, its modified performance that can only be tested under a kind of current-mode, in electrodeposition process
In, there is certain extreme difference potential between the electropolymer and film surface in feed liquid room, so as to cause the utilization ratio of electric current
Reduce.
The content of the invention
It is an object of the invention to provide a kind of preparation method of Monovalent selectivity anion-exchange membrane.
For achieving the above object, the present invention is adopted the following technical scheme that：
A kind of preparation method of Monovalent selectivity anion-exchange membrane, the preparation method is filled in " film of four Room three " membrane modifying
Carried out in putting, " film of four Room three " the membrane modifying device is by battery lead plate A, cation-exchange membrane A, anion exchange to be modified
Film, cation-exchange membrane B, battery lead plate B are spaced composition electrode chamber A, feed liquid room, dense room and electrode chamber B, wherein to be modified
Anion-exchange membrane it is to be modified facing to feed liquid room；
Described preparation method includes：
(1) first toward the mixed solution of addition N- neighbours' benzene sulfonic acid sodium salt benzyl shitosan (NSBC) and NaCl in feed liquid room, its
The concentration of middle N- neighbours' benzene sulfonic acid sodium salt benzyl shitosan (NSBC) and NaCl is respectively 0.5~2g/L and 0.1~1M, adds in dense room
Enter 0.1~1M NaCl solutions, and 0.1~1M Na are made by electrode solution circulating pump2SO4Solution is full of electrode chamber A and electrode chamber B,
Then electric pulse parameter is set, and energization carries out electro-pulse deposition makes N- neighbour's benzene sulfonic acid sodium salt benzyl chitosan precipitations be handed over to anion
Change on film；
(2) after deposition certain hour, solution in feed liquid room is replaced with into 2- HACCs
(HACC) and NaCl mixed solution, the concentration of wherein 2- HACCs (HACC) and NaCl is respectively
0.5~2g/L and 0.1~1M, and exchange the both sides sense of current, keeps that electric pulse parameter is constant to proceed electro-pulse deposition, makes
2- HACCs are deposited on anion-exchange membrane；
(3) operation of repeat step (1) and step (2), so that N- neighbour's benzene sulfonic acid sodium salt benzyl shitosans and 2- hydroxypropyls
Base trimethyl ammonium chloride shitosan alternating deposit obtains being attached with the anion of multilayer NSBC/HACC on anion-exchange membrane
Exchange membrane.
In the present invention, deposition modifying process deposits HACC after need to keeping first pulsed deposition NSBC, on anion-exchange membrane
Obtain the bilayer modified layers of multiple NSBC/HACC.The number of plies of the preferably bilayer modified layers of NSBC/HACC of the invention is 5-10, more excellent
Elect 8-10 as.
In the present invention, the battery lead plate of described " film of four Room three " membrane modifying device connects with the electrode in electrochemical workstation
Connect, described electrochemical workstation is by computer system control.In described " film of four Room three " membrane modifying device, battery lead plate A, B
Can be ruthenium according to battery lead plate；Cation-exchange membrane A, B can be any commercialized films；Anion-exchange membrane to be modified is optional
Select homogeneous Japanese FUJIFILM commercial anionics exchange membrane.Anion-exchange membrane needs to be pre-processed before electro-pulse deposition,
First can be rinsed with ultra-pure water, then film after cleaning be soaked in 0.1~1M NaCl solutions 8-48 hours it is stand-by.
In the present invention, electric pulse parameter is DC pulse, totally 1~1000 cycle, preferably 450 cycles；Each cycle 1
~10s, preferably 4s；The pulse current maximum of face is 0~18mA/cm2, preferred maximum is 7.5mA/cm2；The arteries and veins of face
Current minimum is rushed for 0mA/cm2。
N- neighbours' benzene sulfonic acid sodium salt benzyl shitosan (NSBC) and 2- hydroxypropyl-trimethyl ammonium chlorides shell that the present invention is used are poly-
The structural formula of sugared (HACC) is respectively as shown in formula (I) and (II)：
The beneficial effects of the present invention are：The preparation method of the Monovalent selectivity anion-exchange membrane, modified film
Surface mass depositing homogeneous and monovalention selectively raising；Electroporation can reduce the electropolymer in electrodeposition process
The extreme difference potential existed between film surface, improves the utilization ratio and Multilayer stable of electric current, reduces sedimentation time and investment
Cost.
Brief description of the drawings
The present invention is further described with reference to the accompanying drawings and examples.
Fig. 1 is the system flow schematic diagram of electro-pulse deposition of the present invention；Wherein 1- computer control systems, 2- electrochemistry works
Stand, 3- reference electrodes, 4- working electrodes, 5- " film of four Room three " membrane modifying device, 6- ruthenium iridium electrode plates, 7- cation exchanges
Film, 8- anion-exchange membranes；
Fig. 2 is the differential permeability instrumentation plan of inventive film, wherein 9- modified layers, 10- anodes, 11- negative electrodes, 12-
Mechanical agitation rod；
Fig. 3 is Monovalent selectivity Anion separation design sketch of the invention, wherein (a) is the former film of business；B () is embodiment
Modified Membrane described in 1；C () is the Modified Membrane described in embodiment 2；D () is the Modified Membrane described in embodiment 3；
Fig. 4 is the Monovalent selectivity Anion separation design sketch by after reverse current 12h of the invention, wherein (a) is
The former film of business；B () is the Modified Membrane described in embodiment 4；C () is the Modified Membrane described in embodiment 5；D () is in embodiment 6
Described Modified Membrane.
Specific embodiment
Technical scheme is described further with specific embodiment below, but protection scope of the present invention is not limited
In this：
The NSBC that the embodiment of the present invention is used from laboratory synthesis (building-up process bibliography Y.Zhao, H.M.Liu,
K.N.Tang,Y.L.Jin,J.F.Pan,B.V.Bruggen,J.N.Shen*,C.J.Gao.Mimicking the cell
membrane:bio-inspired simultaneous functions with monovalent anion
selectivity and antifouling properties of anion exchange membrane.Scientific
Reports,2016srep37285)；HACC is purchased from Shandong region Tian Hua biological assistants Co., Ltd (classification HACC-103, substitution
Spend for 98%).Anion-exchange membrane to be modified uses homogeneous Japanese FUJIFILM commercial anionics exchange membrane (AEM-Type
1).Cation-exchange membrane A and B are from Japan's FUJIFILM commercial cationics exchange membrane (CEM-Type 1).Battery lead plate A and B are adopted
With ruthenium according to battery lead plate.
Embodiment 1：The preparation method of Monovalent selectivity anion-exchange membrane
The preparation method of Monovalent selectivity anion-exchange membrane of the present invention, comprises the following steps：
Electric pulse parameter is set, and electric pulse parameter is to use galvanostatic technique, totally 450 cycles, each cycle 4s, cycle
It is divided into upper and lower two parts, each section duration is 2s, and the intermittent time is 0.1s, part on pulsing parameters set
Face electric current is 7.5mA/cm2, the face electric current of lower part is 0mA/cm2.Former anion-exchange membrane first is rinsed with ultra-pure water, then
Film after cleaning be soaked in 0.5M NaCl solutions 24 hours it is stand-by.The system flow of electro-pulse deposition is as shown in figure 1, dress
Good " film of four Room three " membrane modifying device, wherein anion-exchange membrane (8) to be modified is vertically fixed in the middle of equipment, face to be modified
Towards feed liquid room, cation-exchange membrane (7) is respectively and vertically fixed between electrode chamber and feed liquid room and electrode chamber and dense room.It is dense
Indoor addition 0.5M NaCl solutions, feed liquid room adds the mixed solution of 1g/L NSBC and 0.5M NaCl, is circulated by electrode solution
Pump makes 0.2M Na2SO4Solution is full of two electrode chambers, and is electrified stream.Start computer program, after 30min, feed liquid is changed to
The mixed solution of 1.25g/L HACC and 0.5M NaCl, exchanging electric current direction starts computer program.Above step is repeated, repeatedly
Replace feed liquid room solution and exchange the both sides sense of current, each electric pulse parameter keeps constant.Until 8.5 bilayers are obtained,
It is designated as (NSBC/HACC)8.5Layer.
Then resulting film is carried out into selective measurement, differential permeability instrumentation plan such as Fig. 2 of film.Middle two Room
The solution of addition is the mixed solution of sodium chloride solution and metabisulfite solution, and both are 0.05mol/L；Electrode chamber is added
The metabisulfite solution of 0.2mol/L is used as electrolyte.In 7.65mA/cm2Run under current density, light room is pipetted every 30min
The feed liquid of (i.e. feed liquid room), common 90min determines its Cl by anion chromatographic-And SO4 2-Concentration simultaneously calculates its corresponding list
Valency selectivity, usesAnion Monovalent selectivity size is represented, computing formula is as follows：
Wherein tiIt is by the transference number of ions of film, JiFor ionic flux, (unit is mol/m2S), c is light indoor ion
Concentration (unit is mol/L).Work as P>When 1, represent that the film has good Monovalent selectivity, and bigger Monovalent selectivity is more
It is good, on the contrary do not have Monovalent selectivity then.
JiComputing formula is as follows：
Wherein, V is the volume of the electrolyte solution in light room, takes 1L；A takes 19.625cm effectively to contact membrane area2。
(b) is represented in result such as Fig. 3；Unmodified commercial anionic exchange membrane is chosen simultaneously surveys the cloudy selectivity of its unit price,
(a) is represented in result such as Fig. 3.
Embodiment 2
Electric pulse parameter is set, and electric pulse parameter is to use galvanostatic technique, totally 450 cycles, each cycle 4s, cycle
It is divided into upper and lower two parts, each section duration is 2s, and the intermittent time is 0.1s, the face of part in pulse parameter
Electric current is 7.5mA/cm2, the face electric current of lower part is also 7.5mA/cm2.Business membrane modifying is carried out according to embodiment 1, and is determined
Its Monovalent selectivity and the selective effect of calculating, as a result as Fig. 3 (c) is represented.
Embodiment 3
Electric pulse parameter is set, and electric pulse parameter is to use galvanostatic technique, totally 450 cycles, each cycle 4s, cycle
It is divided into upper and lower two parts, each section duration is 2s, and the intermittent time is 0.1s, the face of part in pulse parameter
Electric current is 0mA/cm2, the face electric current of lower part is also 0mA/cm2.Business membrane modifying is carried out according to embodiment 1, and determines its list
Valency selectivity and the selective effect of calculating, as a result (d) is represented such as in Fig. 3.
Embodiment 4
The stability that Modified Membrane obtained by embodiment 1 is modified layer is investigated, the Modified Membrane is selected, is put into
" film of two Room one " membrane modifying device (removes the cation-exchange membrane in " film of four Room three ", by battery lead plate A, modified anion
Exchange membrane, battery lead plate B constitute two electrode chambers), wherein modified anion-exchange membrane is vertically fixed in the middle of equipment, by electricity
Pole liquid circulating pump makes 0.2M Na2SO4Solution is full of two electrode chambers, and modified layer is led into upper DC current, direct current towards anode
Surface current size is 65mA/cm2, conduction time is 12h, is then taken out modified anion-exchange membrane, according still further to embodiment 1
Method determine its Monovalent selectivity, as a result as shown in (b) in Fig. 4, while choose unmodified commercial anionic exchange membrane surveying
The cloudy selectivity of its unit price, as a result such as (a) expression in Fig. 4.
Embodiment 5
The stability that Modified Membrane obtained by embodiment 2 is modified layer is investigated, the Modified Membrane is selected, is put into
" film of two Room one " membrane modifying device, wherein modified anion-exchange membrane is vertically fixed in the middle of equipment, is circulated by electrode solution
Pump makes 0.2M Na2SO4Solution is full of two electrode chambers, and by modified layer towards the logical upper DC current of anode, direct current surface current is big
Small is 65mA/cm2, conduction time is 12h, then takes out modified anion-exchange membrane, and the method according still further to embodiment 1 is surveyed
Fixed its Monovalent selectivity, in such as Fig. 4 shown in (c).
Embodiment 6
The stability that Modified Membrane obtained by embodiment 3 is modified layer is investigated, the Modified Membrane is selected, is put into
" film of two Room one " membrane modifying device, wherein modified anion-exchange membrane is vertically fixed in the middle of equipment, is circulated by electrode solution
Pump makes 0.2M Na2SO4Solution is full of two electrode chambers, and by modified layer towards the logical upper DC current of anode, direct current surface current is big
Small is 65mA/cm2, conduction time is 12h, then takes out modified anion-exchange membrane, and the method according still further to embodiment 1 is surveyed
Fixed its Monovalent selectivity, in such as Fig. 4 shown in (d).
Claims (8)
1. a kind of preparation method of Monovalent selectivity anion-exchange membrane, it is characterised in that：The preparation method is in " four Room three
Carried out in film " membrane modifying device, " film of four Room three " the membrane modifying device is by battery lead plate A, cation-exchange membrane A, to be modified
Anion-exchange membrane, cation-exchange membrane B, battery lead plate B be spaced composition electrode chamber A, feed liquid room, dense room and electrode chamber B,
Anion-exchange membrane wherein to be modified it is to be modified facing to feed liquid room；
Described preparation method includes：
(1) first toward the mixed solution of addition N- neighbours' benzene sulfonic acid sodium salt benzyl shitosan (NSBC) and NaCl in feed liquid room, wherein N-
The concentration of adjacent benzene sulfonic acid sodium salt benzyl shitosan (NSBC) and NaCl is respectively 0.5~2g/L and 0.1~1M, is added in dense room
0.1~1M NaCl solutions, and 0.1~1M Na are made by electrode solution circulating pump2SO4Solution is full of electrode chamber A and electrode chamber B, so
After electric pulse parameter is set, energization carries out electro-pulse deposition makes N- neighbour's benzene sulfonic acid sodium salt benzyl chitosan precipitations to anion exchange
On film；
(2) deposition certain hour after, by solution in feed liquid room replace with 2- HACCs (HACC) and
The mixed solution of NaCl, the concentration of wherein 2- HACCs (HACC) and NaCl is respectively 0.5~2g/
L and 0.1~1M, and exchange the both sides sense of current, keeps that electric pulse parameter is constant to proceed electro-pulse deposition, makes 2- hydroxypropyls
Trimethyl ammonium chloride chitosan precipitation is on anion-exchange membrane；
(3) operation of repeat step (1) and step (2), so that N- neighbour's benzene sulfonic acid sodium salt benzyl shitosans and 2- hydroxypropyls three
Ammonio methacrylate shitosan alternating deposit obtains being attached with the anion exchange of multilayer NSBC/HACC on anion-exchange membrane
Film.
2. the preparation method of Monovalent selectivity anion-exchange membrane as claimed in claim 1, it is characterised in that：NSBC/HACC
The number of plies of bilayer modified layer is 5-10.
3. the preparation method of Monovalent selectivity anion-exchange membrane as claimed in claim 1, it is characterised in that：NSBC/HACC
The number of plies of bilayer modified layer is 8-10.
4. the preparation method of the Monovalent selectivity anion-exchange membrane as described in one of claims 1 to 3, it is characterised in that：Electricity
Pulse parameter is：DC pulse, totally 1~1000 cycle, 1~10s of each cycle, the pulse current maximum of face for 0~
18mA/cm2, the pulse current minimum value of face is 0mA/cm2。
5. the preparation method of Monovalent selectivity anion-exchange membrane as claimed in claim 4, it is characterised in that：Electric pulse parameter
For：Totally 450 cycles；Each cycle 4s；The pulse current maximum of face is 7.5mA/cm2；The pulse current of face is minimum
It is 0mA/cm to be worth2。
6. the preparation method of Monovalent selectivity anion-exchange membrane as claimed in claim 1, it is characterised in that：Described " four
The battery lead plate of the film of room three " membrane modifying device is connected with the electrode in electrochemical workstation, and described electrochemical workstation is by calculating
Machine system is controlled.
7. the preparation method of Monovalent selectivity anion-exchange membrane as claimed in claim 1, it is characterised in that：Described " four
In the film of room three " membrane modifying device, battery lead plate A, B are rutheniums according to battery lead plate.
8. the preparation method of Monovalent selectivity anion-exchange membrane as claimed in claim 1, it is characterised in that：Cation exchange
Film is needed to be pre-processed before electro-pulse deposition, is first rinsed with ultra-pure water, then the film after cleaning is soaked in into 0.1~1M NaCl
In solution 24 hours it is stand-by.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110813387A (en) * | 2019-09-11 | 2020-02-21 | 浙江工业大学 | Preparation method of monovalent anion exchange membrane |
| CN112957924A (en) * | 2021-02-04 | 2021-06-15 | 河北工程大学 | Preparation method of monovalent selective anion exchange membrane |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1747902A (en) * | 2002-12-27 | 2006-03-15 | 株式会社荏原制作所 | Electric demineralizer |
| WO2012051608A1 (en) * | 2010-10-15 | 2012-04-19 | Siemens Industry, Inc. | Anion exchange membranes and process for making |
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| CN110813387A (en) * | 2019-09-11 | 2020-02-21 | 浙江工业大学 | Preparation method of monovalent anion exchange membrane |
| CN110813387B (en) * | 2019-09-11 | 2022-05-24 | 浙江工业大学 | Preparation method of monovalent anion exchange membrane |
| CN112957924A (en) * | 2021-02-04 | 2021-06-15 | 河北工程大学 | Preparation method of monovalent selective anion exchange membrane |
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| CN106925357B (en) | 2019-05-31 |
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