CN106925143A - A kind of preparation method of the anion-exchange membrane with single multivalence selection separation function - Google Patents
A kind of preparation method of the anion-exchange membrane with single multivalence selection separation function Download PDFInfo
- Publication number
- CN106925143A CN106925143A CN201710207460.5A CN201710207460A CN106925143A CN 106925143 A CN106925143 A CN 106925143A CN 201710207460 A CN201710207460 A CN 201710207460A CN 106925143 A CN106925143 A CN 106925143A
- Authority
- CN
- China
- Prior art keywords
- das
- solution
- anion
- pss
- exchange membrane
- 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.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/26—Electrical properties
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A kind of preparation method of the anion-exchange membrane with single multivalence selection separation function, including：(1) PSS/NaCl mixed solutions and HACC/NaCl mixed solutions are prepared；(2) anion-exchange membrane is fixed in electric deposition device, PSS is first deposited on anion-exchange membrane surface, HACC is deposited on PSS layer surface again after pure water immersion, by constantly alternating deposit, polyelectrolyte multilayer modified layer is obtained on anion-exchange membrane surface；(3) DAS solution is prepared；(4) polyelectrolyte multilayer Modified Membrane one side is immersed in DAS solution, DAS is penetrated into inside polyelectrolyte multilayer；(5) Modified Membrane is carried out into ultraviolet light again, makes to be crosslinked between DAS and polyelectrolyte multilayer and film surface, form the cross-linking modified layer of stabilization；(6) film after crosslinking is immersed in NaCl solution, to remove DAS molecules, obtains the anion-exchange membrane that there is single multivalence to select separation function.Obtained anion-exchange membrane of the invention has good unit price selection separation function and stability.
Description
Technical field
The invention belongs to separate technical field of membrane, and in particular to it is a kind of with single multivalence selection separation function it is cloudy from
The preparation method of proton exchange.
Background technology
With the continuous aggravation of the increasingly depleted and water pollution of global water resources, the problem of shortage of water resources has become mesh
One of maximum challenge that the preceding whole world faces.Desalinization, bitter desalination and waste water treating and reutilizing are to solve water resources problems
Important channel.At present in water treatment field, form including micro-filtration, ultrafiltration, nanofiltration, counter-infiltration and method etc. electrodialysis
Unique water treatment system.Wherein, electrodialysis is the selective penetrated property energy to ion using amberplex, in applying direct current electric field
Under the promotion of power so that ion directional migration, so as to reach a special kind of skill of the separation, purification and concentration of electrolyte solution.And
Electrodialytic technique because its Water Sproading rate is high, service life of equipment is long and operating cost is low, simultaneously for non-same sex ion, even same
Property ion between separation have not replaceable huge advantage and receive much concern.
But the progress of the increasing, Chemical Manufacture with drinking water treatment difficulty and the raising of aquatic products class requirement,
People are consequently increased to electrodialytic expectation.Accordingly, for the demand of the amberplex with special separating power
Grow to even greater heights, for example：During electrodialysis Utilization of Seawater by Solar, it would be desirable to can with Selective Separation sulfate ion so as to
Avoid the generation of fouling.Process underground drinking water in, it is also desirable to can preferably remove harmful monovalent ion such as nitrate anion,
Fluorine ion etc. is so as to guarantee drinking water safety of increasing water quality.Therefore research has the anion of Selective Separation one, multivalent ion
Exchange membrane has great application prospect.
Research shows, anion-exchange membrane the selectivity of different ions is relied primarily on ion hydration energy and film it is hydrophilic
Property, and film institute band the quantity of electric charge.Anion-exchange membrane surface will be formed at the material modified of negative electrical charge, by aperture sieve
Divide effect and electrostatic repulsion, be capable of achieving Selective Separation of the anion-exchange membrane to one, multivalent anions.
Journal of Membrane Science (2016,520,262-271) proposes a kind of electro-deposition layer by layer and is modified
Commercial anionic exchange membrane obtains the method with monovalent anion selective ion exchange membrane.By the use of chitosan quaternary ammonium salt as
Polycation electrolyte, polyvinylbenzenesulfonic acid sodium as polyanion electrolyte, by the means of electro-deposition, in commercial anionic
The surface layer electro-deposition polyelectrolyte of exchange membrane.In SO4 2-/Cl-Preferable list, multivalence are obtained in the electrodialysis experiment of system
Cl during ion selectivity separating property, wherein 9 bilayers of electro-deposition-With respect to SO4 2-Selectivity reach 2.9, obtain with single
The anion-exchange membrane of valency selectivity.But between modified layer and film surface electrostatic interaction is relied solely on to be attached together, it is impossible to
Overcome the problem of less stable, be unfavorable for using for a long time.
It is a kind of effective preparation one, two to deposit polyanion and polycation electrolyte in amberplex surface layer
The method of valency ion selective membrane, but electrostatic interaction is only relied between polymer and is linked together, in use
Modified layer is easy to fall off.Chemical crosslinking makes to form stable chemical bond between polyelectrolyte, is that a kind of effective stability that improves changes
Property layer method.
The content of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of long service life, selection
Property separating property significantly have single multivalence selection separation function anion-exchange membrane preparation method.
For achieving the above object, the present invention is adopted the following technical scheme that：
A kind of preparation method of the anion-exchange membrane with single multivalence selection separation function, comprises the following steps：
(1) polyelectrolyte solution is prepared：Respectively by a certain amount of PSS (kayexalate) and HACC (shitosan seasons
Ammonium salt) it is dissolved in pure water with NaCl, obtain certain density PSS/NaCl mixed solutions and HACC/NaCl mixed solutions；
(2) anion-exchange membrane (AEM) is fixed in electric deposition device, PSS is deposited on anion-exchange membrane first
Surface, pure water immersion, then HACC is deposited on PSS layer surface, by constantly alternating deposit, obtained on anion-exchange membrane surface
To polyelectrolyte multilayer modified layer；
(3) DAS (4,4 '-two -2,2 '-sodium disulfonate of nitrine talan) solution is prepared：Weigh a certain amount of DAS powder
And NaCl, it is dissolved in pure water, and DAS solution is obtained to 2.0-8.0 with the pH value of hydrochloric acid conditioning solution；
(4) polyelectrolyte multilayer Modified Membrane one side is immersed in DAS solution, DAS is penetrated into polyelectrolyte multilayer
It is internal；
(5) Modified Membrane processed by step (4) is carried out into ultraviolet light, makes DAS and polyelectrolyte multilayer and film table
Crosslinked between face, form the cross-linking modified layer of stabilization；
(6) film after being crosslinked through step (5) is immersed in the NaCl solution of 0.1~1.0M, to remove DAS associated with friendship
Molecule, obtains the anion-exchange membrane that there is single multivalence to select separation function, during film finally preserved into sub- pure water；
The structural formula difference of described PSS, HACC and DAS is as follows：
In the step (1), the PSS molecular weight Mw=80,000, HACC molecular weight Mw=20,000.
In the step (1), the concentration of PSS or HACC is 1.0-5.0g/L, preferably 1.0g/L in polyelectrolyte solution；
NaCl concentration is 0.5-2.0M, preferably 0.5M.
In the step (2), described anion-exchange membrane can be using AEM-Type I of Japanese fuji film company etc..Institute
Electric deposition device is stated for four compartments, anion-exchange membrane is fixed in the middle of compartment two and compartment three, compartment one and compartment two, compartment
A cation-exchange membrane is fixed between three and compartment four respectively, described cation-exchange membrane can use Japanese fuji film company
CEM-Type II etc..Wherein, compartment one and compartment four are electrode chamber, and 0.05~1.0M (preferably 0.2M) is filled with electrode chamber
NaSO4Solution；And compartment two is feed liquid room, built-in polyelectrolyte solution；The built-in 0.5-2.0M of compartment three (preferably 0.5M)
NaCl solution.Compartment one and compartment four are respectively arranged with negative electrode and anode, the negative electrode and anode of electric deposition device respectively with direct current
The negative pole of power supply is connected with positive pole.In electrodeposition process, after the complete a certain polyelectrolyte (such as PSS) of electro-deposition, in need to pouring out
Between two Room solution, import pure water immersion, fully immersion after pour out pure water again electro-deposition another kind polyelectrolyte (such as HACC), such as
This is alternately reciprocal.During each electro-deposition PSS layer or HACC layer, preferably electrodeposition time is 30-120min, more preferably
30min；It is preferred that current density is 1.0-20.0mA/cm2, more preferably 5.0mA/cm2；Temperature is room temperature, and electrodeposition process will be held
It is continuous to stir to avoid concentration polarization.Pure water soak time is preferably 5-20min.
In the step (2), the number of plies of the alternating deposit is 2.5-8.5 bilayer, and resulting Modified Membrane can be marked
It is designated as, for example (PSS/HACC)2PSS、(PSS/HACC)5PSS、(PSS/HACC)8PSS.It is preferred that the number of plies of alternating deposit is 5.5
Individual bilayer.
In the step (3), DAS solubility is 0.5-5.0mg/ml, preferably 1mg/mL in the DAS solution；NaCl is dense
It is 0.5-2.0M to spend, preferably 0.5M.The pH of present invention regulation DAS solution can make DAS be easier to penetrate between 2-8
In polyelectrolyte multilayer.
In the step (4), the DAS solution soak time is 10-60min, preferably 30min.
In the step (5), the ultraviolet lighting time is 10-60min, preferably 30min.
In the step (6), soak time is 8~30 hours, preferably 24 hours.
The present invention specifically recommends the preparation method to carry out in accordance with the following steps：
(1) polyelectrolyte solution is prepared：A certain amount of PSS and HACC and NaCl are dissolved in pure water respectively, obtain certain
The PSS/NaCl mixed solutions and HACC/NaCl mixed solutions of concentration, the concentration of wherein PSS or HACC is 1.0-5.0g/L,
NaCl concentration is 0.5-2.0M；
(2) anion-exchange membrane is fixed in electric deposition device, PSS is deposited on anion-exchange membrane surface first,
HACC is deposited on PSS layer surface again after pure water immersion, by constantly alternating deposit, is gathered on anion-exchange membrane surface
Electrolytic multi-layer modified layer, the number of plies of alternating deposit is 2.5-8.5 bilayer；
(3) DAS solution is prepared：A certain amount of DAS powder and NaCl are weighed, is dissolved in pure water, and use hydrochloric acid conditioning solution
PH value to 2.0-8.0, obtain DAS solution, wherein DAS solubility is 0.5-5.0mg/ml, and NaCl concentration is 0.5-2.0M；
(4) the polyelectrolyte multilayer Modified Membrane one side for obtaining step (2) is immersed in DAS solution, and soak time is 10-
60min, makes DAS penetrate into inside polyelectrolyte multilayer；
(5) Modified Membrane processed by step (4) is carried out into ultraviolet light, makes DAS and polyelectrolyte multilayer and film table
Crosslinked between face, the cross-linking modified layer of stabilization is formed after 10-60min；
(6) film after being crosslinked through step (5) is immersed in 8-30 hours in the NaCl solution of 0.1~1.0M, to remove friendship
Associated with DAS molecules, during film finally preserved into sub- pure water, obtain the anion-exchange membrane that there is single multivalence to select separation function.
By using above-mentioned technology, compared with prior art, beneficial effects of the present invention are as follows：
The present invention forms LbL structures using electro-deposition techniques layer by layer on the surface of anion-exchange membrane, is permeated after recycling
By small molecule photocrosslinking agent --- DAS is introduced into polymer modification layer, azido group produces reaction high to live to method under ultraviolet lighting
The nitrene type free base of property, chemically reacts with polymer, makes shape between polymer multi-layer and multilayer and film surface
Into cross-linked network, the stability of modified layer is improved；Meanwhile, DAS molecules carry two sulfonic acid groups, can increase the negative electricity of modified layer
Property, improve dianion selection performance.Serial electrodialysis experiment shows that Monovalent selectivity anion prepared by the present invention is handed over
Film is changed in membrane separating process, aperture sieving actoion and the collective effect of Coulomb repulsion due to functional layer, modified ion
Exchange membrane has good unit price selection separation function, while membrane stability is also greatly improved.
Brief description of the drawings
Fig. 1 is the preparation process schematic diagram of monovalent anion selective diffusion barrier of the present invention；
Fig. 2 is electro-deposition PSS process schematics of the present invention；
Fig. 3 is electro-deposition HACC process schematics of the present invention；
Fig. 4 is the infrared spectrogram of former film and each Modified Membrane
Fig. 5 is film scanning electron microscope (SEM) photograph
Fig. 6 is Monovalent selectivity electrodialysis experimentation schematic diagram；
Fig. 7 is the ion selectivity of former film and Modified Membrane
Fig. 8 is former film and Modified Membrane in diluting compartment intermediate ion concentration changes with time figure
Fig. 9 is light room ion concentration in 5.5 bilayer modified film longtime runnings
Specific embodiment
The preferred embodiments of the present invention are described in detail below, so that present disclosure feature is easy to by this area
In researcher understand, but protection scope of the present invention not limited to this.
Embodiment 1
1.0g PSS and 29.22g NaCl are dissolved in PSS solution are obtained in 1000mL pure water, by 1.0g HACC and
29.22gNaCl obtains HACC solution in being dissolved in 1000mL pure water, by commodity homogeneous-phase anion exchange film (AEM-Type I,
Fujifilm Corp.Japan) suitable size is cut into, it is immersed in pure water, to remove the hydroaropic substance on surface, it is stored in pure
It is standby in water.
Electro-deposition experimental provision is made up of four compartments, and feed liquid room is the PSS solution of 100mL, and another room is the NaCl of 0.5M
Solution, two electrode chambers are the NaSO of 0.2M4Solution.The cathode of electric deposition device, anode is negative with dc source respectively
Pole connects with positive pole, and energization carries out electro-deposition, and current density is 5.0mA/cm2, effective membrane area is 19.625cm2, during electro-deposition
Between be 30min, electrodeposition process will continue stirring to avoid concentration polarization, process is as shown in Figure 2.After the complete PSS of electro-deposition, pour out
The solution of middle two Room, imports pure water immersion 5min, then electro-deposition HACC layers, and feed liquid room is the PSS solution of 100mL, another room
It is the NaCl solution of 0.5M, two electrode chambers are the NaSO of 0.2M4Solution.By the cathode of electric deposition device, anode respectively with
The negative pole of dc source is connected with positive pole, and energization carries out electro-deposition, and current density is 5.0mA/cm2, effective membrane area is
19.625cm2, electrodeposition time is 30min, and electrodeposition process will continue stirring to avoid concentration polarization, and process is as shown in Figure 3.
Alternately electro-deposition is so constantly carried out, the modified number of plies is respectively 2.5 bilayers, and obtained Modified Membrane is labeled as (PSS/HACC)2PSS。
After obtaining electrodeposited film layer by layer, film one side is immersed in (pH in the NaCl mixed solutions of the DAS of 1mg/mL and 0.5M
=3.8) 30min, is then taken the film out, and 30min is crosslinked under ultraviolet light, and the film after crosslinking is immersed in the NaCl solution of 0.5M
In 24h with remove be crosslinking DAS molecules, during film finally preserved into sub- pure water, labeled as CL- (PSS/HACC)2PSS。
Embodiment 2
It is 5.5 bilayers that the electro-deposition number of plies in above-described embodiment 1 is increased, and other steps and condition are constant, obtain
Film is respectively labeled as (PSS/HACC)5PSS, CL- (PSS/HACC)5PSS。
Embodiment 3
It is 8.5 bilayers that the electro-deposition number of plies in above-described embodiment 1 is increased, and other steps and condition are constant, obtain
Film is respectively labeled as (PSS/HACC)8PSS, CL- (PSS/HACC)8PSS。
The IR Characterization figure and configuration of surface figure of film are as shown in Figure 4 and Figure 5.
By the infrared spectrogram that Fig. 4 is former film and each Modified Membrane, it can be seen that with the increase of the modified number of plies, film surface
Sulfonic acid group be continuously increased；And the characteristic absorption peak of sulfonic acid group also strengthens after the film crosslinking of identical modified layer, because small point
Sub- crosslinking agent DAS carries two sulfonic acid groups, also causes that the sulfonic acid group amount on film surface increases after crosslinking.2120cm-1It is folded to locate
The characteristic absorption peak of nitrogen groups, the film after crosslinking is in 2120cm-1Almost there is not absworption peak in place, illustrates DAS in ultraviolet lighting
It is lower to be crosslinked with polyelectrolyte multilayer film.
Fig. 5 is the SEM figures of former film and Modified Membrane, it can be seen that alternately electro-deposition caudacoria surface is more coarse layer by layer, and hands over
Connection caudacoria is again relatively smooth, shows that crosslinking makes polyelectrolyte multilayer be combined on film surface even closer.
Embodiment 4
Monovalent selectivity test uses the electrodialysis plant of four compartments, other two compartments of auxiliary to be used for preventing ion from oozing
Ion is leaked and supplies, as shown in Figure 5.Middle two Room add 100mL concentration to be the NaCl and Na of 0.02M2SO4Mixed solution,
Electrode chamber adds 100mL 0.2M Na2SO4Solution, current density is 5mA/cm2, effective membrane area is 19.625cm2.Every
20min takes the solution of the light rooms of 0.5mL, and Cl is determined with anion-exchange chromatography-With SO4 2-The change of concentration, and calculate Cl-Relatively
SO4 2-Selectivity is through value.
As shown in fig. 7, as can be seen from Figure, modified caudacoria all has certain dianion selectivity to experimental result,
Compare with uncrosslinked film, its relative selectivity P is improved with the increase of the electro-deposition number of plies, this is the increase due to depositing the number of plies
So that the enlarged in thickness on film surface, to bivalent ions repulsion barrier increase, makes SO4 2-It is more difficult to by polyelectrolyte multilayer film table
Face.Compare the cross linking membrane and uncrosslinked film of the identical modified number of plies, the relative choosing after the 2.5 double-deck Modified Membrane crosslinkings with 5.5 bilayers
Selecting property is all significantly improved, especially 5.5 bilayer modified film, and its average relative selectivity reaches 8.71 after crosslinking；Because crosslinking
Agent DAS carries two sulfonic acid groups, can increase the elecrtonegativity on film surface, improves to SO4 2-Repulsive force, while crosslinking cause it is heavy
Polyelectrolyte multilayer network of the product on film surface is finer and close, improves the effect of aperture screening.
Embodiment 5
Membrane stability by cross linking membrane and uncrosslinked film in long-time electrodialysis running to a dianion
Selectivity changes to compare.Select uncrosslinked (PSS/HACC)5PSS and crosslinking (PSS/HACC)5PSS films, electrodialysis condition and choosing
Selecting property test condition is identical, and middle two Room adds 100mL concentration to be the NaCl and Na of 0.02M2SO4Mixed solution, electrode chamber
Add 100mL 0.2M Na2SO4Solution, current density is 5mA/cm2, effective membrane area is 19.625cm2.Take one within every 2 hours
Secondary light room water sample, the solution renewed again after pure water cleaning is powered, with this continuous circulation.
Experimental result is as shown in figure 9, uncrosslinked film is uncrosslinked (PSS/HACC)5PSS selectively starts drop after 6h is run
It is low, lose a divalent selectivity completely after 30h is run, and cross linking membrane (PSS/HACC)5PSS one after continuous operation 76h
Divalent selectivity is almost unchanged；Show that the stability for being crosslinked post-modification layer is greatly improved.
Claims (10)
1. a kind of preparation method of the anion-exchange membrane with single multivalence selection separation function, comprises the following steps：
(1) polyelectrolyte solution is prepared：A certain amount of PSS and HACC and NaCl are dissolved in pure water respectively, obtain finite concentration
PSS/NaCl mixed solutions and HACC/NaCl mixed solutions；
(2) anion-exchange membrane is fixed in electric deposition device, PSS is deposited on anion-exchange membrane surface, pure water first
HACC is deposited on PSS layer surface again after immersion, by constantly alternating deposit, poly- electrolysis is obtained on anion-exchange membrane surface
Matter multilayer modified layer；
(3) DAS solution is prepared：A certain amount of DAS powder and NaCl are weighed, is dissolved in pure water, and with the pH of hydrochloric acid conditioning solution
Value obtains DAS solution to 2.0-8.0；
(4) the polyelectrolyte multilayer Modified Membrane one side for obtaining step (2) is immersed in DAS solution, DAS is penetrated into poly- electricity
Solution matter more internal；
(5) Modified Membrane processed by step (4) is carried out into ultraviolet light, make DAS and polyelectrolyte multilayer and film surface it
Between crosslink, formed stabilization cross-linking modified layer；
(6) film after being crosslinked through step (5) is immersed in the NaCl solution of 0.1~1.0M, to remove DAS points associated with friendship
Son, obtains the anion-exchange membrane that there is single multivalence to select separation function；
The structural formula difference of described PSS, HACC and DAS is as follows：
2. preparation method as claimed in claim 1, it is characterised in that：In the step (1), in polyelectrolyte solution PSS or
The concentration of HACC is 1.0-5.0g/L, and NaCl concentration is 0.5-2.0M.
3. preparation method as claimed in claim 1 or 2, it is characterised in that：In the step (2), the electric deposition device is
Four compartments, anion-exchange membrane is fixed in the middle of compartment two and compartment three, between compartment one and compartment two, compartment three and compartment four
A cation-exchange membrane is fixed respectively；Wherein, compartment one and compartment four are electrode chamber, are filled with 0.05~1.0M's in electrode chamber
NaSO4Solution；And compartment two is feed liquid room, built-in polyelectrolyte solution；The built-in 0.5-2.0M NaCl solutions of compartment three；Compartment
One and compartment four be respectively arranged with negative electrode and anode, the negative electrode and anode of electric deposition device respectively with the negative pole of dc source and just
Pole connects；In electrodeposition process, after a kind of complete polyelectrolyte of electro-deposition, the solution in middle two compartment need to be poured out, imported pure
Water is soaked, and pure water electro-deposition another kind polyelectrolyte again is fully poured out after immersion, so alternately reciprocal；Each electro-deposition PSS layer
Or during HACC layers, electrodeposition time is 30-120min, current density is 1.0-20.0mA/cm2, temperature is room temperature, and electricity is heavy
Product process lasts stir to avoid concentration polarization.
4. the preparation method as described in one of claims 1 to 3, it is characterised in that：In the step (2), the layer of alternating deposit
Number is double-deck for 2.5-8.5.
5. preparation method as claimed in claim 4, it is characterised in that：In the step (2), the number of plies of alternating deposit is 5.5
Individual bilayer.
6. preparation method as claimed in claim 1 or 2, it is characterised in that：In the step (3), DAS in the DAS solution
Solubility is 0.5-5.0mg/ml, and NaCl concentration is 0.5-2.0M.
7. preparation method as claimed in claim 1, it is characterised in that：In the step (4), the DAS solution soak time
It is 10-60min.
8. preparation method as claimed in claim 1, it is characterised in that：In the step (5), the ultraviolet lighting time is
10-60min。
9. preparation method as claimed in claim 1, it is characterised in that：In the step (6), soak time is 8~30 hours.
10. preparation method as claimed in claim 3, it is characterised in that the preparation method is carried out in accordance with the following steps：
(1) polyelectrolyte solution is prepared：A certain amount of PSS and HACC and NaCl are dissolved in pure water respectively, obtain finite concentration
PSS/NaCl mixed solutions and HACC/NaCl mixed solutions, the concentration of wherein PSS or HACC is 1.0-5.0g/L, and NaCl is dense
It is 0.5-2.0M to spend；
(2) anion-exchange membrane is fixed in electric deposition device, PSS is deposited on anion-exchange membrane surface, pure water first
HACC is deposited on PSS layer surface again after immersion, by constantly alternating deposit, poly- electrolysis is obtained on anion-exchange membrane surface
Matter multilayer modified layer, the number of plies of alternating deposit is 2.5-8.5 bilayer；
(3) DAS solution is prepared：A certain amount of DAS powder and NaCl are weighed, is dissolved in pure water, and with the pH of hydrochloric acid conditioning solution
Value obtains DAS solution to 2.0-8.0, and wherein DAS solubility is 0.5-5.0mg/ml, and NaCl concentration is 0.5-2.0M；
(4) the polyelectrolyte multilayer Modified Membrane one side for obtaining step (2) is immersed in DAS solution, and soak time is 10-
60min, makes DAS penetrate into inside polyelectrolyte multilayer；
(5) Modified Membrane processed by step (4) is carried out into ultraviolet light, make DAS and polyelectrolyte multilayer and film surface it
Between crosslink, formed after 10-60min stabilization cross-linking modified layer；
(6) film after being crosslinked through step (5) is immersed in 8-30 hours in the NaCl solution of 0.1~1.0M, is used with removing crosslinking
DAS molecules, during film finally preserved into sub- pure water, obtain the anion-exchange membrane that there is single multivalence to select separation function.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710207460.5A CN106925143A (en) | 2017-03-31 | 2017-03-31 | A kind of preparation method of the anion-exchange membrane with single multivalence selection separation function |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710207460.5A CN106925143A (en) | 2017-03-31 | 2017-03-31 | A kind of preparation method of the anion-exchange membrane with single multivalence selection separation function |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106925143A true CN106925143A (en) | 2017-07-07 |
Family
ID=59425569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710207460.5A Pending CN106925143A (en) | 2017-03-31 | 2017-03-31 | A kind of preparation method of the anion-exchange membrane with single multivalence selection separation function |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106925143A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107998900A (en) * | 2017-07-21 | 2018-05-08 | 义乌赛蓝膜科技有限公司 | A kind of preparation method for the anion-exchange membrane that there is single multivalence to select separation function |
| CN108479405A (en) * | 2018-03-15 | 2018-09-04 | 浙江工业大学 | A kind of preparation for the modified anion exchange membrane having both Monovalent selectivity and resistance tocrocking |
| CN110665373A (en) * | 2019-06-30 | 2020-01-10 | 浙江工业大学 | Preparation method of PDA- (HACC-CN & Ag) -PDA nanofiltration membrane with anti-pollution and antibacterial properties |
| CN110813387A (en) * | 2019-09-11 | 2020-02-21 | 浙江工业大学 | Preparation method of monovalent anion exchange membrane |
| CN112457518A (en) * | 2020-11-03 | 2021-03-09 | 浙江理工大学 | Laser foaming polyelectrolyte film and area pore-forming process thereof |
| CN112795039A (en) * | 2021-01-15 | 2021-05-14 | 浙江理工大学 | Preparation method of foaming polyelectrolyte film |
| CN112957924A (en) * | 2021-02-04 | 2021-06-15 | 河北工程大学 | Preparation method of monovalent selective anion exchange membrane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104815568A (en) * | 2015-04-20 | 2015-08-05 | 中国海洋大学 | Preparation method of anion exchange membrane with monovalent selective separation function |
| CN105110323A (en) * | 2015-07-31 | 2015-12-02 | 中国地质大学（北京） | Preparation method for graphene oxide freestanding ultrathin film |
-
2017
- 2017-03-31 CN CN201710207460.5A patent/CN106925143A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104815568A (en) * | 2015-04-20 | 2015-08-05 | 中国海洋大学 | Preparation method of anion exchange membrane with monovalent selective separation function |
| CN105110323A (en) * | 2015-07-31 | 2015-12-02 | 中国地质大学（北京） | Preparation method for graphene oxide freestanding ultrathin film |
Non-Patent Citations (4)
| Title |
|---|
| （德）劳滕巴赫（R RAUTENBACH）: "《膜工艺：组件和装置设计基础》", 31 May 1998, 化学工业出版社 * |
| JI FANQIN等: "Fabrication of Covalently Linked PAH/PVS Layer-by-layer Assembled Multilayers via a Post-photochemical Cross-linking Strategy", 《CHEMICAL RESEARCH IN CHINESE UNIVERSITIES》 * |
| YAN ZHAO 等: "An anion exchange membrane modified by alternate electro-deposition layers with enhanced monovalent selectivity", 《JOURNAL OF MEMBRANE SCIENCE》 * |
| 金银河: "《包装印刷》", 31 July 1997, 印刷工业出版社 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107998900A (en) * | 2017-07-21 | 2018-05-08 | 义乌赛蓝膜科技有限公司 | A kind of preparation method for the anion-exchange membrane that there is single multivalence to select separation function |
| CN107998900B (en) * | 2017-07-21 | 2020-12-08 | 浙江赛特膜技术有限公司 | Preparation method of anion exchange membrane with single-multivalent selective separation function |
| CN108479405A (en) * | 2018-03-15 | 2018-09-04 | 浙江工业大学 | A kind of preparation for the modified anion exchange membrane having both Monovalent selectivity and resistance tocrocking |
| CN108479405B (en) * | 2018-03-15 | 2021-04-06 | 浙江工业大学 | Preparation of modified anion exchange membrane with monovalent selectivity and pollution resistance |
| CN110665373A (en) * | 2019-06-30 | 2020-01-10 | 浙江工业大学 | Preparation method of PDA- (HACC-CN & Ag) -PDA nanofiltration membrane with anti-pollution and antibacterial properties |
| 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 |
| CN112457518A (en) * | 2020-11-03 | 2021-03-09 | 浙江理工大学 | Laser foaming polyelectrolyte film and area pore-forming process thereof |
| CN112795039A (en) * | 2021-01-15 | 2021-05-14 | 浙江理工大学 | Preparation method of foaming polyelectrolyte film |
| CN112957924A (en) * | 2021-02-04 | 2021-06-15 | 河北工程大学 | Preparation method of monovalent selective anion exchange membrane |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106925143A (en) | A kind of preparation method of the anion-exchange membrane with single multivalence selection separation function | |
| Ge et al. | Electrodialysis with nanofiltration membrane (EDNF) for high-efficiency cations fractionation | |
| Zhao et al. | Metal organic framework enhanced SPEEK/SPSF heterogeneous membrane for ion transport and energy conversion | |
| EP2857441B1 (en) | Ion exchange membrane used in reverse electrodialysis device and reverse electrodialysis device including this membrane | |
| Paltrinieri et al. | Functionalized anion-exchange membranes facilitate electrodialysis of citrate and phosphate from model dairy wastewater | |
| Afsar et al. | SPPO-based cation exchange membranes with a positively charged layer for cation fractionation | |
| CN104437675B (en) | Flowing electrode capacitance deionizer amberplex and the flowing electrode capacitance deionizer comprising it | |
| CN104028110B (en) | A kind of thin layer composite forward osmosis membrane and preparation method thereof | |
| CN104495991B (en) | A kind of high performance membrane capacitive deionization array based on flow-type electrode | |
| CN104524976A (en) | Electric nanofiltration device for selective separation of monovalent/multivalent ions | |
| EP2470290A1 (en) | Ion exchange membranes | |
| Xiao et al. | Anion permselective membranes with chemically-bound carboxylic polymer layer for fast anion separation | |
| CN109758917B (en) | Preparation method of divalent cation selective ion exchange membrane | |
| CN109075369A (en) | Composite membrane for flow battery | |
| CN111111478A (en) | Preparation method of PVDF-based cation exchange membrane | |
| Lee et al. | Comparison of the property of homogeneous and heterogeneous ion exchange membranes during electrodialysis process | |
| CN107930417A (en) | A kind of method that LBL self-assembly prepares polyvinylidene fluoride hollow fiber forward osmosis membrane | |
| CN114100374A (en) | Monovalent ion selective cation exchange membrane and preparation method and application thereof | |
| CN113262648A (en) | Lithium ion selective permeation membrane and application thereof | |
| Sun et al. | Covalent organic framework-based membrane improved the performance of reverse electrodialysis under Na+/Mg2+ mixed solution | |
| CN113169366A (en) | Diaphragm for redox flow battery and method for manufacturing same | |
| CN107998900B (en) | Preparation method of anion exchange membrane with single-multivalent selective separation function | |
| CN108479405A (en) | A kind of preparation for the modified anion exchange membrane having both Monovalent selectivity and resistance tocrocking | |
| Chen et al. | Highly symmetric spongy porous poly (ether sulfone) membranes with selective open-cells for vanadium flow battery application | |
| CN109513355B (en) | Preparation and application of anion exchange membrane for internal crosslinking by using BMP |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170707 |