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
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- 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
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- 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
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- 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
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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.
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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 |
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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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)
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| 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 |
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