CN105655616A - Method for preparing univalent selective cation exchange membrane by electrodeposition - Google Patents
Method for preparing univalent selective cation exchange membrane by electrodeposition Download PDFInfo
- Publication number
- CN105655616A CN105655616A CN201511031385.9A CN201511031385A CN105655616A CN 105655616 A CN105655616 A CN 105655616A CN 201511031385 A CN201511031385 A CN 201511031385A CN 105655616 A CN105655616 A CN 105655616A
- Authority
- CN
- China
- Prior art keywords
- chitosan
- aniline
- compartment
- solution
- cation exchange
- 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
- 239000012528 membrane Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 31
- 238000005341 cation exchange Methods 0.000 title claims abstract description 26
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229920001661 Chitosan Polymers 0.000 claims abstract description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 238000004132 cross linking Methods 0.000 claims abstract description 13
- 238000000151 deposition Methods 0.000 claims abstract description 5
- 239000012265 solid product Substances 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 2
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 8
- 239000002346 layers by function Substances 0.000 abstract description 3
- 238000012216 screening Methods 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 230000005611 electricity Effects 0.000 abstract 1
- 230000003100 immobilizing effect Effects 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 230000003068 static effect Effects 0.000 abstract 1
- 238000000909 electrodialysis Methods 0.000 description 8
- 239000003014 ion exchange membrane Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000003321 amplification Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000003199 nucleic acid amplification method Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a method for preparing a univalent selective cation exchange membrane by electrodeposition. The method comprises the steps of firstly, polymerizing aniline/chitosan under acidic conditions, separating out a polymer solid product by a centrifugal method, dissolving the polymer solid product in hydrochloric acid so as to prepare a polymer solution, depositing a polymer of aniline/chitosan on the surface of an cation exchange membrane by an electro-deposition process, and finally, immobilizing a functional layer on the surface of the membrane by a cross-linking method. The univalent selective cation exchange membrane prepared by the method has pore size screening and static electricity repulsing actions, can be used for effectively separating univalent and multivalent ions and shows excellent performance in conductance.
Description
Technical field
The invention belongs to ion exchange membrane field, particularly to be a kind of have one, the preparation method of multivalent ion Selective Separation function and low-resistance cation exchange membrane.
Background technology
Electrodialysis is a very promising water desalination technology, but due to the existence of the multivalent ion in water body, in electrodialytic process, these ions can cause fouling membrane or even the generation of sintering phenomenon. Along with the development of society, the performance requirement of film is had higher requirement by we. Comprehensive literature, film to the separation of ion often difference by means of the affinity between aperture screening and different ions realize, wherein most widely used general, studying the most deep is Coulomb repulsion effect.
In China, entering fluviatic waste water every year increases with the speed of 1,800,000,000 tons, and wherein most is directly discharged in rivers without any process, causes China's water resource pollution problem serious. Increasing energy will be put into field of Environment Protection by China, and the attention degree of environmental problem also will quickly can be improved and active by the Environmental Protection Market of China along with everybody. Now, the demand to product film of China is fast development attitude, and this will promote China's film industrial expansion to a great extent.
SpringerLink periodical Ionics (2012,18:711 717) has reported and has prepared Monovalent selectivity cation exchange membrane by polymine, cross-links with Ammonium persulfate., and uses Cl-, NO3 -, SO4 2-Etc. system, the selection separating property of film is analyzed, test result indicate that the slip of ion is Cl->NO3 ->SO4 2-, it was shown that single multivalent ion is had good separating power by Modified Membrane. But material modified desorption problem is the restricted main cause of said method.
Ace Wei Er periodical Journalofmembranescience (2008,319,5-9) has been reported and has been carried out surface modification with chitosan electro-deposition. To H+/Zn2+/Al3+Separating experiment selects separating power it is shown that Modified Membrane has significantly single multivalence. But it is loaded down with trivial details to there is preparation technology in the method, should not with realize the shortcomings such as industrial applications.
Ace Wei Er periodical Desalination (2013,325,95-10) and ElectrochimicaActa (2007,52,5046-5052) report with aniline modified, prepared organic and inorganic mixer masking, reached the separation process of single multivalent ion.Test result indicate that, the film after aniline modified has obvious unit price to select separating power. But the unstability of long-time operation and the loaded down with trivial details principal element being to limit its popularization of experimentation.
American Chemical Society periodical JournalofPhysicalChemistryB (2005,109,14085-14092) with Ace Wei Er periodical Journalofmembranescience (2006,280,210-218) report aniline respectively, pyrroles etc. are adsorbed in cationic surface, and then with oxidant, it is surface-crosslinked at film, thus form the modified layer of one layer of positively charged on film surface. Film carrying out single multivalence and selects separating experiment, result shows that film has good single multivalence separating effect. Although at resistance, this kind of method has its unique advantage, but to there is material modified price high for this kind of method, and the disagreeableness problem of environment, therefore it is difficult to promote.
Current Monovalent selectivity ion exchange membrane to prepare ubiquity preparation technology loaded down with trivial details, material modified limited, expensive, environment is unfriendly and service life is short problem.
Summary of the invention
It is an object of the invention to provide a kind of while there is single multivalence selection separation function, with the preparation method of the cation exchange membrane of the electrical efficiency improving film.
The present invention provides a kind of method that Monovalent selectivity cation exchange membrane is prepared in electro-deposition, said method comprising the steps of:
(1) aniline is dissolved in the hydrochloric acid of 0.5-1.5mol/L (preferred 1mol/L) and is made into aniline solution, chitosan is dissolved in the aqueous acetic acid of mass fraction 1%-6% (preferably 2%) and is made into chitosan solution, take aniline solution and chitosan solution be sufficiently mixed after add excessive oxidant Ammonium persulfate. and carry out polyreaction, the ratio of the amount of substance of the aniline in described aniline solution and the chitosan in chitosan solution is 0.65��5:1 (preferably 1��3:1, most preferably 1:1), reaction terminates rear centrifugation, the solid separated recentrifuge after aqueous acetic acid dissolving, dry, prepare polymer solids product,
(2) cation exchange membrane is fixed between compartment one and the compartment two of two compartment electric deposition devices, polymer solids product prepared by step (1) is dissolved in the hydrochloric acid of 0.5-1.5mol/L (preferred 1mol/L), it is made into the polymer solution that polymer concentration is 2��10g/L, add in compartment one, compartment two adds the hydrochloric acid of 0.5-1.5mol/L (preferred 1mol/L), compartment one is connected with anode, and compartment two is connected with negative electrode; Cathode, anode being connected with the negative pole of DC source and positive pole respectively, energising carries out electro-deposition, controls electric current density at 25-75mA/cm2(preferred 50mA/cm2), electrodeposition time controls at 1-5h (preferred 4h), film immersion after electro-deposition carries out cross-linking reaction in mass fraction 5%-25% (preferably 25%) glutaraldehyde water solution, take out the film deionized water rinsing after cross-linking reaction, prepare described Monovalent selectivity cation exchange membrane.
In described step (1), the time of polyreaction is 3-12 hour, it is preferable that 10 hours, and the temperature of polyreaction is 15-45 DEG C, it is preferable that room temperature 20��25 DEG C.
In described step (1), in described aniline solution, the volumetric concentration of aniline is 1-25mL/L, it is preferable that 2��10mL/L.
In described step (1), in described chitosan solution, the mass concentration of chitosan is 0.1%-5%, it is preferable that 0.5��1%.
In the present invention, when calculating the amount of substance of chitosan, it is calculated with the molecular weight 161.2 of the cell cube of chitosan.
In described step (1), Ammonium persulfate. is excessive addition, it is preferable that the ratio of the amount of substance of Ammonium persulfate. and chitosan is 1.1��1.5:1.
In described step (1), when adding excessive oxidant Ammonium persulfate., it is generally required to add when nitrogen protection.
In described step (1), utilizing centrifugal method to isolate the polymerizate of aniline/chitosan, centrifugal speed is generally 8000-12000rpm, and centrifugation time is at 5-15min.
In described step (1), the solid of separation recentrifuge after aqueous acetic acid dissolving, the general aqueous acetic acid with mass fraction 1%-6% (preferably 2%).
In described step (2), identical with the concentration of hydrochloric acid added in compartment two for the concentration of the hydrochloric acid of solvent polymerization thing solid product in compartment one, it is preferable that the concentration of hydrochloric acid is 1mol/L.
In described step (2), the temperature of cross-linking reaction is 10-45 DEG C, it is preferable that 35 DEG C, and the time of cross-linking reaction is 2-24 hour, it is preferable that 20��24 hours.
Compared with prior art, the beneficial effects of the present invention is:
(1) present invention adopts material modified as conventional ion exchange membrane Monovalent selectivity separating property of chitosan, and this material source is very extensive, cheap, and environmental friendliness.
(2) due to the addition of aniline so that material modified there is significantly high charge density simultaneously, the improvement of the electric conductivity of film is served facilitation.
(3) present invention adopts electrodeposition process, and by the polymer deposition of aniline and chitosan on film surface, the crosslinking of glutaraldehyde can effectively extend the life-span of Monovalent selectivity ion exchange membrane.
(4) the Monovalent selectivity cation exchange membrane prepared has aperture screening and electrostatic repulsion concurrently, it is possible to effectively single multivalent ion is easily separated, and shows excellent performance on conductance.
First aniline/chitosan is polymerized by the present invention in acid condition, centrifuging is adopted to be separated by product, product dissolved again and uses electrodeposition process that the polymer of aniline/chitosan is deposited in film surface, finally making functional layer be fixed on film surface with cross-linking method. The performance of film is controlled by the ratio and electrodeposition time controlling aniline/chitosan. Series electrodialysis experiments show that, Monovalent selectivity cation exchange membrane prepared by the present invention is in membrane separating process, combined effect due to the aperture sieving actoion of functional layer and Coulomb repulsion, modified ion exchange membrane has good unit price and selects separation function, simultaneously also ideal in membrane resistance.
Accompanying drawing explanation
Fig. 1 is the chemical equation schematic diagram of the film after electro-deposition and glutaraldehyde cross-linking modifying process.
Fig. 2 is environmental microbes comparison diagram before and after membrane modifying, in Fig. 2,500 times that a figure is commodity homogeneous phase cation exchange film before modified are amplified SEM figure, b figure is 500 times of amplification SEM figure that embodiment 1 prepares Monovalent selectivity cation exchange membrane modified for electro-deposition 4h, 10000 times that c figure is commodity homogeneous phase cation exchange film before modified are amplified 10000 times of amplification SEM figure that SEM figure, d figure are Monovalent selectivity cation exchange membrane modified for electro-deposition 4h.
Fig. 3 is before and after membrane modifying and the infrared spectrogram of the reacted polymer product of chitosan, chitosan and aniline polymerization.
Fig. 4 is the Selective Separation schematic diagram in the electrodialytic process of electrodialysis plant figure and embodiment 3.
Fig. 5 is membrane resistance along with electrodeposition time changes block diagram.
Detailed description of the invention
Further describe the present invention below in conjunction with accompanying drawing and by specific embodiment, but protection scope of the present invention is not limited to this.
Embodiment 1
1g chitosan is dissolved in 200mL mass fraction 2% acetum in obtain chitosan solution, 0.578g aniline is dissolved in the 1MHCl solution of 200mL and obtains aniline solution, after the chitosan solution of the aniline solution of above-mentioned 200mL and 200mL is sufficiently mixed, at room temperature N2Under protective condition, it is slowly added dropwise the ammonium persulfate solution of 100mL20g/L concentration. Dripping off rear stirring at normal temperature to react, the response time is 10h, and after reaction terminates, polymer solution centrifuging separates. Centrifugal speed controls at 10000rpm, and centrifugation time is 10min. The polymer solids separated is dissolved in mass fraction 2% aqueous acetic acid again, and recentrifuge, and so operation removes unreacting substance three times. The polymer solids product of last gained the drying baker of 50 DEG C dry 24 hours standby.
Commodity homogeneous phase cation exchange film (Beijing Ting Run membrane technology company limited, J-II-5) being cut into suitable size, is fixed between two compartments of electric deposition device, two compartment both sides are anode and cathode. The 1MHCl solution of polymer put into by compartment one, and wherein the concentration of polymer is 2g/L; 1MHCl solution put into by compartment two. Compartment one is connected with anode, and compartment two is connected with negative electrode; Cathode, anode being connected with the negative pole of DC source and positive pole respectively, energising carries out electro-deposition, and the electric current density of electro-deposition is 50mA/cm2, sedimentation time respectively 1h, 2h, 3h, 4h and 5h. The film that electro-deposition obtains, finally under 35 DEG C of conditions, soaks 24 hours in the glutaraldehyde solution of 500mL mass fraction 25%, rinses well with deionized water, obtain final Monovalent selectivity ion exchange membrane standby. The configuration of surface figure and Infrared Characterization figure of film are as shown in Figures 2 and 3.
In Fig. 2,500 times that a figure is commodity homogeneous phase cation exchange film before modified are amplified SEM figure, b figure is 500 times of amplification SEM figure that embodiment 1 prepares Monovalent selectivity cation exchange membrane modified for electro-deposition 4h, 10000 times that c figure is commodity homogeneous phase cation exchange film before modified are amplified 10000 times of amplification SEM figure that SEM figure, d figure are Monovalent selectivity cation exchange membrane modified for electro-deposition 4h.
Fig. 2 is it can be seen that film surface becomes more homogeneous, it was shown that film surface has the polymer of chitosan and aniline to exist. The polymer of Fig. 3 Infrared Characterization chitosan/aniline is exist with the form of crosslinking on film surface.
Embodiment 2
Modified Membrane and the unmodified commodity homogeneous phase cation exchange film of 5 kinds of different electrodeposition times embodiment 1 prepared are respectively placed in four compartment electrodialysis plants, and the effective area of film is 5cm �� 5cm. Both sides are pole liquid chamber, add 0.5mol/LNa2SO4, middle two compartment 0.5mol/LNaCl measure membrane resistance as measuring solution. Circuit tester connects the electric potential difference of Ag/AgCl electrode measurement film both sides. Experiment adopts current stabilization method, measures both sides voltage respectively when having film and without film, utilizes voltage difference to try to achieve membrane resistance. The membrane resistance of different electrodeposition times is as shown in Figure 5.
Fig. 5 shows the increase along with electrodeposition time, and the resistance on film surface increases, and this is owing to along with the prolongation of electrodeposition time, the thickness of the chitosan/aniline polymer on film surface increases, so that membrane resistance increases.
Embodiment 3
The Modified Membrane of electrodeposition time 4h embodiment 1 prepared is placed in four compartment electrodialysis plants, and as shown in Figure 4, in Fig. 4, M-CEM represents Modified Membrane, and AEM represents anion exchange membrane, and the effective area of film is 5cm �� 5cm.In device, light room is 200mL0.5MH2SO4, dense room be 200mL containing 15g/LZnSO40.5MH2SO4Solution. Pole liquid is 0.5MK2SO4. The electrodialysis time controls to be 100min, and electric current density is 50mA/cm2��
Shown in experimental result, the Zn of film2+Slip drops to 12.5% from the 21% of former film before modified. Membrane resistance is from 6.7 �� cm before modified2Rise to 9.6 �� cm2��
Embodiment 4
The Modified Membrane of electrodeposition time 4h embodiment 1 prepared is used in electrodialysis concentrated seawater desalination, four compartment electrodialysis plant such as Fig. 4, and institute is the difference is that, light room and is separately added into 200mL concentrated seawater in dense room, with 0.5MK2SO4For electrode solution, it is 50mA/cm in electric current density2Lower energising 100 minutes, experimental result display Ca2+And Mg2+Slip drop to modified 34.3% and 25.3% from 57.8% and the 85.4% of former film before modified.
Claims (8)
1. the method that Monovalent selectivity cation exchange membrane is prepared in an electro-deposition, it is characterised in that said method comprising the steps of:
(1) aniline is dissolved in the hydrochloric acid of 0.5-1.5mol/L and is made into aniline solution, chitosan is dissolved in the aqueous acetic acid of mass fraction 1%-6% and is made into chitosan solution; take aniline solution and chitosan solution be sufficiently mixed after add excessive oxidant Ammonium persulfate. and carry out polyreaction; the ratio of the amount of substance of the aniline in described aniline solution and the chitosan in chitosan solution is 0.65��5:1; reaction terminates rear centrifugation; the solid of separation dissolve with aqueous acetic acid after recentrifuge; dry, prepare polymer solids product;
(2) cation exchange membrane is fixed between compartment one and the compartment two of two compartment electric deposition devices, polymer solids product prepared by step (1) is dissolved in the hydrochloric acid of 0.5-1.5mol/L, it is made into the polymer solution that polymer concentration is 2��10g/L, add in compartment one, compartment two adds the hydrochloric acid of 0.5-1.5mol/L, compartment one is connected with anode, and compartment two is connected with negative electrode; Cathode, anode being connected with the negative pole of DC source and positive pole respectively, energising carries out electro-deposition, controls electric current density at 25-75mA/cm2, electrodeposition time controls the film immersion after 1-5h, electro-deposition and carries out cross-linking reaction in mass fraction 5%-25% glutaraldehyde water solution, takes out the film deionized water rinsing after cross-linking reaction, prepares described Monovalent selectivity cation exchange membrane.
2. the method for claim 1, it is characterised in that in described step (1), in described aniline solution, the volumetric concentration of aniline is 1-25mL/L.
3. the method for claim 1, it is characterised in that in described step (1), in described chitosan solution, the mass concentration of chitosan is 0.1%-5%.
4. the method for claim 1, it is characterised in that in described step (1), the ratio of the amount of substance of Ammonium persulfate. and chitosan is 1.1��1.5:1.
5. the method for claim 1, it is characterised in that in described step (1), the time of polyreaction is 3-12 hour, and the temperature of polyreaction is 15-45 DEG C.
6. the method for claim 1, it is characterised in that in described step (2), the temperature of cross-linking reaction is 10-45 DEG C, the time of cross-linking reaction is 2-24 hour.
7. the method for claim 1, it is characterised in that in described step (2), in compartment one, the concentration of hydrochloric acid for adding in the concentration of the hydrochloric acid of solvent polymerization thing solid product and compartment two is 1mol/L.
8. the method for claim 1, it is characterised in that in described step (1), the ratio of the amount of substance of the aniline in described aniline solution and the chitosan in chitosan solution is 1��3:1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201511031385.9A CN105655616A (en) | 2015-12-31 | 2015-12-31 | Method for preparing univalent selective cation exchange membrane by electrodeposition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201511031385.9A CN105655616A (en) | 2015-12-31 | 2015-12-31 | Method for preparing univalent selective cation exchange membrane by electrodeposition |
Publications (1)
Publication Number | Publication Date |
---|---|
CN105655616A true CN105655616A (en) | 2016-06-08 |
Family
ID=56491337
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201511031385.9A Pending CN105655616A (en) | 2015-12-31 | 2015-12-31 | Method for preparing univalent selective cation exchange membrane by electrodeposition |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105655616A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106268984A (en) * | 2016-08-31 | 2017-01-04 | 浙江工业大学 | A kind of renovation process of the cation exchange membrane of the polyethyleneimine-modified of inefficacy |
CN106565854A (en) * | 2016-10-19 | 2017-04-19 | 重庆大学 | Preparation method of oligochitosan-grafted melamine |
CN107596932A (en) * | 2017-10-16 | 2018-01-19 | 黑龙江青谷酒庄有限公司 | A kind of cation-exchange membrane and its preparation method and application |
CN114307690A (en) * | 2021-12-27 | 2022-04-12 | 河北工业大学 | Monovalent cation exchange membrane and preparation method and application thereof |
CN115052680A (en) * | 2019-12-05 | 2022-09-13 | B.G.内盖夫技术和应用有限公司本-古里安大学 | Cation exchange membranes with improved monovalent selectivity, manufacture and use thereof in electrodialysis |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102935389A (en) * | 2012-10-30 | 2013-02-20 | 中国海洋大学 | Method for preparing cation exchange membrane with monovalent preferential separation function |
JP2015108609A (en) * | 2013-10-24 | 2015-06-11 | 栗田工業株式会社 | METHOD AND APPARATUS FOR ELECTRODEPOSITION OF Co AND Fe |
-
2015
- 2015-12-31 CN CN201511031385.9A patent/CN105655616A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102935389A (en) * | 2012-10-30 | 2013-02-20 | 中国海洋大学 | Method for preparing cation exchange membrane with monovalent preferential separation function |
JP2015108609A (en) * | 2013-10-24 | 2015-06-11 | 栗田工業株式会社 | METHOD AND APPARATUS FOR ELECTRODEPOSITION OF Co AND Fe |
Non-Patent Citations (1)
Title |
---|
JIAN LI,ET AL.: "Enhanced conductivity of monovalent cation exchange membranes with chitosan/PANI composite modification", 《RSC ADVANCES》 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106268984A (en) * | 2016-08-31 | 2017-01-04 | 浙江工业大学 | A kind of renovation process of the cation exchange membrane of the polyethyleneimine-modified of inefficacy |
CN106565854A (en) * | 2016-10-19 | 2017-04-19 | 重庆大学 | Preparation method of oligochitosan-grafted melamine |
CN106565854B (en) * | 2016-10-19 | 2019-01-11 | 重庆大学 | A kind of preparation method of chitosan oligosaccharide grafting melamine |
CN107596932A (en) * | 2017-10-16 | 2018-01-19 | 黑龙江青谷酒庄有限公司 | A kind of cation-exchange membrane and its preparation method and application |
CN107596932B (en) * | 2017-10-16 | 2020-11-17 | 黑龙江青谷酒庄有限公司 | Cation exchange membrane and preparation method and application thereof |
CN115052680A (en) * | 2019-12-05 | 2022-09-13 | B.G.内盖夫技术和应用有限公司本-古里安大学 | Cation exchange membranes with improved monovalent selectivity, manufacture and use thereof in electrodialysis |
CN114307690A (en) * | 2021-12-27 | 2022-04-12 | 河北工业大学 | Monovalent cation exchange membrane and preparation method and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Yan et al. | A novel imidazolium-based amphoteric membrane for high-performance vanadium redox flow battery | |
Khan et al. | Development of BPPO-based anion exchange membranes for electrodialysis desalination applications | |
CN105655616A (en) | Method for preparing univalent selective cation exchange membrane by electrodeposition | |
CN105098233B (en) | The preparation method of semi-interpenetrating network polymer gel electrolyte membrane | |
Song et al. | Stable li–organic batteries with nafion‐based sandwich‐type separators | |
Li et al. | Novel polymeric ionic liquid membranes as solid polymer electrolytes with high ionic conductivity at moderate temperature | |
CN101164122B (en) | Conductive material and conductive film and process for producing them | |
Choi et al. | Characteristics of the all-vanadium redox flow battery using anion exchange membrane | |
CN104998560B (en) | A kind of preparation method of the composite membrane containing graphene oxide | |
CN101475699B (en) | Preparation of proton conduction membrane | |
CN107771351A (en) | Solid polymer electrolyte and the electrochemical appliance for including it | |
Zhang et al. | The preparation of a novel anion-exchange membrane and its application in all-vanadium redox batteries | |
CN104868079B (en) | Method for preparing high invasive lithium ion battery diaphragm | |
Kim et al. | Facile surface modification of anion-exchange membranes for improvement of diffusion dialysis performance | |
CN103304833A (en) | Preparation method of molecular imprinted polymer membrane by means of grafting rejection | |
CN102568848A (en) | Preparation method of polyaniline/graphene oxide composite electrode material | |
Fang et al. | Preparation and characterization of quaternized poly (2, 2, 2‐trifluoroethyl methacrylate‐co‐N‐vinylimidazole) membrane for vanadium redox flow battery | |
CN108933258A (en) | The preparation method of the all-solid lithium-ion battery of three-dimensional composition metal cathode of lithium | |
CN107895812A (en) | A kind of solid electrolyte film preparation method based on the macromolecule modified gelatin polymer of natural polysaccharide | |
CN102324481A (en) | Composite diaphragm for lithium ion battery and preparation method thereof | |
Wu et al. | Acid Pretreatment to Enhance Proton Transport of a Polysulfone‐Polyvinylpyrrolidone Membrane for Application in Vanadium Redox Flow Batteries | |
Wu et al. | PVA-based cation exchange hybrid membranes with multifunctional groups prepared from ternary multisilicon copolymer | |
Liu et al. | Correlation between the ion permeation and free volume property in ethyl cellulose film during the acid treatment | |
CN108470879A (en) | A kind of large-scale method for producing of lithium copper composite metal negative plate | |
US11402349B2 (en) | High capacity redox electrodes and their use in cell lysis |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160608 |
|
RJ01 | Rejection of invention patent application after publication |