CN102941026B - Ion exchange composite film with selectivity on single cation - Google Patents
Ion exchange composite film with selectivity on single cation Download PDFInfo
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- CN102941026B CN102941026B CN201210506889.1A CN201210506889A CN102941026B CN 102941026 B CN102941026 B CN 102941026B CN 201210506889 A CN201210506889 A CN 201210506889A CN 102941026 B CN102941026 B CN 102941026B
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Abstract
The invention provides an ion exchange composite film with selectivity on a single cation as well as a preparation method and an application thereof. The composite film comprises a cation ion exchange base film and a polyethyleneimine modified layer, wherein the depositing amount of polyethyleneimine on the cation ion exchange base film is 2.0-200.0 g/m<2>; and the thickness of the ion exchange composite film is 50-500 microns. The single cation is Cu<2+>, Zn<2+>, Ni<2+>, Hg<2+>, Ag<2+>, Pt<2+>, Co<2+> and Cr<3+> and the ion exchange composite film can replace the common ion exchange composite films to be mounted in an electrodialyzer. The ion exchange composite film disclosed by the invention has the advantages of simple operation of a preparation method, green and non-toxic preparation process and adaptation to large-scale industrial production.
Description
Technical field
The present invention relates to membrane separation technique field, specifically a kind of have optionally ion-exchange composite membranes its preparation method and application to single cation.
Background technology
Membrane separation technique is because it is convenient to continued operation, is easy to amplify, low, the capacity usage ratio advantages of higher of energy consumption, be counted as the typical case of one " Green Chemistry ", in the separating of the industries such as medicine, food, chemical industry and agricultural, analysis and preparation process, all related to or wished using membrane separating technology.The resource of single cation selective diffusion barrier rare metal ion in seawater of function admirable is extracted and is had broad application prospects aspect the resource recycling of heavy metal or precious metal ion waste water.The film that can realize at present ion selectivity separation in commercial membrane mainly contains amberplex and NF membrane.Amberplex is realized separating between anion and cation by Donnan repelling effect; NF membrane mainly according to surface with the repulsive interaction difference of electric charge to different valence state ion, can realize the Selective Separation between monovalention and highly charged ions.CN 101472672A discloses a kind of preparation method containing the ionophoric compound lithium ion selective membrane of lithium ion selectivity, for measuring the concentration of fluid lithium ion; CN1302223A has disclosed a kind of preparation method that need not extrude solvent and make ion selective membrane and this film; CN1265334A has reported a kind of a kind of method that is made ion selective membrane by cationic polymer and anionic polymer on setting braid substrate, and this film can be used for electrolyte osmosis.But ion selective membrane prepared by these methods is limited to concentration analysis mostly, can not meet the application of diffusion barrier in selective extraction and the serialization recovery of large-scale single ionic.
Molecular recognition is being played the part of indispensable role at nature, and it is most of bioprocess, the basis of being carried out as ligand-receptor combination, substrate-enzyme interacting etc.Molecular imprinting is just by the existing this Molecular Recognization of simulating nature circle, in polymeric material, introduce molecular recognition site, preparation on space and binding site with the polymer of target molecule perfect matching, be molecularly imprinted polymer, to realize, the specificity of target molecule selected.Molecular engram film has the feature of selective and membrane technology continued operation and the low energy consumption of molecular imprinting concurrently, becomes the effective means that separates specific target molecules from structure similar mixtures.As an important branch of molecular engram film, possess equally above advantage to separate specific single ionic as the ion blotting diffusion barrier of target, thereby become the effective way of preparing single ionic selective membrane.
At present, the many employings of ion blotting film do not possess the polymer of ionic conduction characteristic, and its application only limits to diffusion dialysis, and this ion isolation method flux promoting by film both sides concentration difference is low, production efficiency is poor.Literature search shows, before the present invention completes, does not find take amberplex as basement membrane, by the preparation of ion blotting technology, single cation is had the method for specific optionally amberplex.This film is assembled in electrodialysis plant, can utilize electric field to significantly improve permeation flux and the separating power of film.
Summary of the invention
Technical problem to be solved by this invention is: a kind of single cationic ion-exchange composite membranes of Selective Separation and preparation method thereof and application thereof from mixed solution is provided, and this ion-exchange composite membranes reclaims single cation for optionally extracting from the mixed aqueous solution that contains different kinds of ions; A kind of functional polymer polymine (PEI) of introducing on cation exchange basement membrane by sedimentation, and utilize the preparation of ion blotting technology to there is the optionally method of ion-exchange composite membranes to single cation, this film is assembled in electrodialysis plant, can provide a kind of technique simply, selective good, the separation method that moves and be applicable to continuously the mixed ion solutions of large-scale production.Feature of the present invention has been to design a kind ofly has optionally ion-exchange composite membranes and its preparation method and application based on polymine to single cation, why select polyethyleneimine polymers, because it has good ion chelating characteristic, after crosslinked, can form the action site matching with template ion, thereby template ion is had to good seeing through selectively.
The present invention solves this technical problem adopted technical scheme:
A kind of have optionally ion-exchange composite membranes to single cation, and this composite membrane comprises cation exchange basement membrane and polyethyleneimine-modified layer, and wherein polymine is 2.0-200.0g/m at the epilamellar deposition of cation exchange
2;
Described cation exchange basement membrane, its polymer backbone is hydrocarbon main chain, partially fluorinated hydrocarbon main chain or fluoridized hydrocarbon main chain, has sulfonic group, phosphate, carboxylic acid group or phenolic hydroxyl group on the polymer backbone of this basement membrane; The thickness of this ion-exchange composite membranes is 50-500 μ m.
Described single cation is specially Cu
2+, Zn
2+, Ni
2+, Hg
2+, Ag
+, Pt
2+, Co
2+or Cr
3+, described metal ion can form stable chelate with polymine.
The preparation method of described ion-exchange composite membranes comprises following concrete steps:
The first step is introduced polymer P EI on cation exchange basement membrane, for following two kinds of methods arbitrary:
Method 1: static sedimentation method: cation exchange basement membrane is immersed in the PEI aqueous solution that concentration is 0.5-30g/L, soaks 0.5-160h under room temperature;
Or, method 2, electrodeposition process: adopt four chamber devices, four Room are respectively dense chamber, light chamber and 2 utmost point chambers; The dense indoor sodium chloride solution that adds; Light chamber adds the sodium chloride solution containing PEI, and extremely indoor is electrolyte solution; The current strength of electro-deposition is 1-100mA/cm
2, energising obtains the cation-exchange membrane of PEI modification after 20-120min;
Described employing four chamber devices, for four chamber devices that formed by three cation-exchange membranes and wall, wherein cation exchange basement membrane to be deposited is fixed on middle, be separated to form He Dan chamber, dense chamber with the cation-exchange membrane of the left and right sides, the cation-exchange membrane of both sides and wall are separated to form respectively again two utmost point chambers; Treat that deposited film is light chamber near anode one side, opposite side is dense chamber.
Electrolyte solution in described utmost point chamber is one or more in sodium chloride solution, metabisulfite solution and sulfuric acid, and in solution, cation concn is 0.1-2mol/L.
Second step, the absorption of template ion and PEI's is crosslinked
The aqueous solution that the cation-exchange membrane of the PEI modification that the first step is obtained is placed in template ion soaks 10-24h and carries out ionic adsorption, after taking out, water washes down surface solution, be placed in the cross-linking reaction that cross-linking agent solution carries out PEI, obtain template ion absorption and the crosslinked amberplex of PEI;
The aqueous solution of described template ion is for only containing a kind of cationic aqueous solution of templated metal ion, and concentration is 0.005-0.5mol/L, and pH value is 4-9; The concentration of cross-linking agent solution is 1-50g/L, and crosslinking temperature is 20-60 ℃, and crosslinking time is 20-120min;
The 3rd step, the wash-out of template ion
The sodium ethylene diamine tetracetate solution that is placed in 0.01-0.1mol/L through the absorption of second step template ion and the crosslinked amberplex of PEI is carried out to the wash-out of template ion, what obtain containing the action site that mates with template ion has optionally cation-exchange membrane to certain cationic.
Cation exchange basement membrane in the described first step is sulfonated polyether sulfone (SPES) film, sulfonated polyether-ether-ketone (SPEEK) film, perfluorocarboxylic acid cation-exchange membrane or phosphatic type cation-exchange membrane.
Described first step middle-jiao yang, function of the spleen and stomach ion-exchange basement membrane is specially the Selemion CMV film of LE-HoCM-0_SH film, Beijing global Li Da environmental protection equipment JCM-of Co., Ltd I film of Zhejiang Qianqiu Environmental Water Treatment Co., Ltd., Japanese Asahi Glass company, the Neosepta CM-1 film of Japanese Tokuyama company or the Nafion film of Dopont company of the U.S..
The concentration of sodium chloride solution when above-mentioned preparation method's first step electro-deposition in dense chamber, light chamber used is 0.1-3mol/L.
When described first step electro-deposition, in the concentration of sodium chloride solution of light chamber PEI used, PEI content is 0.1-30g/L,
In described second step, only containing the cationic aqueous solution of a kind of templated metal is copper nitrate solution, zinc nitrate solution, nickel nitrate solution, liquor argenti nitratis ophthalmicus, platinum nitrate solution, cobalt chloride solution or chromium chloride solution.
In the cross-linking agent solution of described second step, solute is epoxychloropropane, glycerin triglycidyl ether or glutaraldehyde, and solvent is ethanol or water;
Described has the optionally application of ion-exchange composite membranes to single cation, can substitute conventional cation-exchange membrane and be assembled in electric dialyzator.When assembling, guarantee that a side that has deposited PEI layer on composite membrane is towards material liquid, this is because be effective separating layer of the ion-exchange composite membranes that makes through the PEI layer of ion blotting on film surface.
The invention has the beneficial effects as follows:
(1) the present invention is take cation-exchange membrane as basement membrane, realize the polyethyleneimine-modified of cation-exchange membrane by electrodeposition process, sulfonic acid group, phosphate group, hydroxy-acid group or the phenolic hydroxyl group group of polymine on film is combined by electrostatic interaction, through template ion absorption and polymine forms after crosslinked and template ion matches action site, thereby make composite membrane there is good selection separating property to template ion;
(2) ion-exchange composite membranes of the present invention can be advantageously used in the assembling of electric dialyzator, under electric field action, high flux ground separates the ion identical with template ion in film-forming process in mixed solution, and can be used for strong acid, strong alkali environment, separating property is stable, and suitable environment is wide;
(3) preparation method of ion-exchange composite membranes of the present invention is simple to operate, and preparation process is green non-poisonous, is applicable to large-scale industrial production.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the present invention is further described.
Fig. 1 is polymine electric deposition device schematic diagram of the present invention.
Fig. 2 is embodiment 1-6, and sulfonic group amberplex is that basement membrane, epoxychloropropane are the reaction mechanism schematic diagram that crosslinking agent is prepared copper ion selective membrane preparation process in 9,10.
The specific embodiment
Mechanism of the present invention is:
Below by example, the invention will be further described:
Embodiment 1
Take the LE-HoCM-0_SH sulfonic acid type cation exchange membrane of Zhejiang Qianqiu Environmental Water Treatment Co., Ltd. as basement membrane, utilize four chamber devices shown in Fig. 1 to carry out electro-deposition.To treat that deposited film is fixed on middle, two auxiliary film are cation-exchange membrane.When energising, treat that the both sides of deposited film form respectively He Dan chamber, dense chamber.Wherein, near the Wei Dan chamber, chamber of anode, opposite side is dense chamber.It is the aqueous solution that 0.1mol/L, polymine concentration are 3g/L that light chamber adds sodium chloride concentration, and the dense indoor sodium chloride solution that adds 0.1mol/L, take the sodium chloride solution of 1mol/L as utmost point water, at electric current 4mA/cm
2lower deposition 120min completes the polymine deposition on film; The film that has deposited polymine is taken out, and it is that 0.08mol/L, pH value are adjusted to 5.5 Cu (NO that concentration is immersed on washed with de-ionized water film surface afterwards
3)
2in the aqueous solution, absorption is taken out after 24h, is placed on 30 ℃ of crosslinked 1h in the ethanolic solution of the epoxychloropropane that pH is 9, concentration is 10g/L with washed with de-ionized water film surface; By the film after crosslinked with putting into triangular flask behind deionized water rinsing surface, add the wash-out that carries out template ion in the sodium ethylene diamine tetracetate solution of 0.1mol/L, after half an hour, outwell and pour new edta solution continuation wash-out into, rear pattern plate ion wash-out is complete in triplicate, obtains the selective cation-exchange membrane of copper ion.The process of copper absorption, wash-out and the polymine of above film is all carried out under room temperature in shaking table.
The mechanism of this film-forming process as shown in Figure 2.Electronegative sulfonic acid group generation electrostatic interaction and be deposited on film surface on the PEI molecule of positively charged and cation exchange basement membrane in solution; PEI molecule and Cu on film
2+occur after chelating suction-operated, because the crosslinked of epoxychloropropane fixed the structure of PEI; Template ion Cu
2+after wash-out, make Cu
2+there is optionally ion-exchange composite membranes.
This film is tested in electrodialysis plant, and He Dan chamber, dense chamber passes into respectively the salpeter solution of 0.1mol/L and the copper that pH is 1, the copper zinc mixed solution that zinc ion concentration is 0.03mol/L, at 12mA/cm
2current strength under move the transit dose of measuring copper, zinc ion after 60min, calculate it and see through selective.Why selecting zinc ion is competing ions, is because zinc ion has identical valence state and similar ionic radius with copper ion.Record the permeation flux of film and selectively list in table 1.
Embodiment 2
The present embodiment 2 is with reference to the method for embodiment 1.Difference is: when electro-deposition, dense chamber, cation-exchange membrane to be deposited both sides and light indoor concentration of sodium chloride solution are 0.2mol/L, and deposition current is 20mA/cm
2, electrodeposition time is 60min.The Product Films obtaining under the same terms of describing at above-described embodiment 1 is as shown in table 1 to the separating effect of copper zinc mixed solution.
Embodiment 3
The present embodiment 3 is with reference to the method for embodiment 1.Difference is: the concentration that adds the polyethyleneimine: amine aqueous solution of light chamber when electro-deposition is 10g/L, and electrodeposition time is 60min.The Product Films obtaining under the same terms of describing at above-described embodiment 1 is as shown in table 1 to the separating effect of copper zinc mixed solution.
Embodiment 4
The present embodiment 4 is with reference to the method for embodiment 1.Difference is: when electro-deposition, the concentration of polyethyleneimine: amine aqueous solution used is 1g/L, and cation-exchange membrane to be deposited both sides sodium chloride concentration is respectively 0.5mol/L, and deposition current is 40mA/cm
2, sedimentation time is 20min.The Product Films obtaining under the same terms of describing at above-described embodiment 1 is as shown in table 1 to the separating effect of copper zinc mixed solution.
Embodiment 5
The present embodiment 5 is with reference to the method for embodiment 1.Difference is: polyethyleneimine-modified film Cu (NO used during to copper absorption
3)
2solution concentration is 0.01mol/L.The Product Films obtaining under the same terms of describing at above-described embodiment 1 is as shown in table 1 to the separating effect of copper zinc mixed solution.
Embodiment 6
The present embodiment 6 is with reference to the method for embodiment 1.Difference is: polyethyleneimine-modified film Cu (NO used during to copper absorption
3)
2solution concentration is 0.10mol/L, and pH value is adjusted to 5.The Product Films obtaining under the same terms of describing at above-described embodiment 1 is as shown in table 1 to the separating effect of copper zinc mixed solution.
Embodiment 7
The present embodiment 7 is with reference to the method for embodiment 1.Difference is: the crosslinked condition of polyethyleneimine-modified film is: 20 ℃ of crosslinked 120min of glutaraldehyde water solution that pH is 3, concentration is 10g/L.The Product Films obtaining under the same terms of describing at above-described embodiment 1 is as shown in table 1 to the separating effect of copper zinc mixed solution.
Embodiment 8
The present embodiment 8 is with reference to the method for embodiment 1.Difference is: the crosslinked condition of polyethyleneimine-modified film is: 60 ℃ of crosslinked 40min of the glycerin triglycidyl ether aqueous solution that pH is 9, concentration is 20g/L.The Product Films obtaining under the same terms of describing at above-described embodiment 1 is as shown in table 1 to the separating effect of copper zinc mixed solution.
Embodiment 9
The present embodiment 9 is with reference to the method for embodiment 1.Difference is: selected basement membrane is the homemade sulfonated polyether-ether-ketone in laboratory (SPEEK) film, and the LE-HoCM-0_SH film that substitutes Zhejiang Qianqiu Environmental Water Treatment Co., Ltd. is made basement membrane.The Product Films obtaining under the same terms of describing at above-described embodiment 1 is as shown in table 1 to the separating effect of copper zinc mixed solution.
Embodiment 10
The present embodiment 10 is with reference to the method for embodiment 1.Difference is: selected basement membrane is the JCM-I film of Beijing global Li Da environmental protection equipment Co., Ltd, and the LE-HoCM-0_SH film that substitutes Zhejiang Qianqiu Environmental Water Treatment Co., Ltd. is made basement membrane.The Product Films obtaining under the same terms of describing at above-described embodiment 1 is as shown in table 1 to the separating effect of copper zinc mixed solution.
Embodiment 11
The present embodiment 11 is with reference to the method for embodiment 1.Difference is: selected basement membrane is the polyacrylonitrile hydrolyzed carboxylic acid type cation-exchange membrane obtaining, and the LE-HoCM-0_SH film that substitutes Zhejiang Qianqiu Environmental Water Treatment Co., Ltd. is made basement membrane.The Product Films obtaining under the same terms of describing at above-described embodiment 1 is as shown in table 1 to the separating effect of copper zinc mixed solution.
Table 1
Embodiment 12
The present embodiment 12 is with reference to the method for embodiment 1.Difference is: the trace ion of the cation-exchange membrane absorption after polyethyleneimine-modified is Zn
2+, trace adsorbent solution used is that 0.08mol/L, pH value are adjusted to 5.5 Zn (NO
3)
2the aqueous solution, adsorption time is 10h.The Product Films obtaining under the same terms of describing at above-described embodiment 1 is as shown in table 2 to the separating effect of copper zinc mixed solution.
Table 2
Embodiment 13
The present embodiment 13 is with reference to the method for embodiment 1.Difference is: the trace ion of the cation-exchange membrane absorption after polyethyleneimine-modified is Ni
2+, solution used is that 0.08mol/L, pH value are adjusted to 6 Ni (NO
3)
2the aqueous solution, adsorption time is 20h.The solution that light chamber passes in the time of film selectivity test is the copper nickel mixed solution that copper, nickel ion concentration are 0.03mol/L.The Product Films obtaining under the same terms of describing at above-described embodiment 1 is as shown in table 3 to the separating effect of copper nickel mixed solution.
Table 3
Embodiment 14
The present embodiment 14 is with reference to the method for embodiment 1.Difference is: the trace ion of the cation-exchange membrane absorption after polyethyleneimine-modified is Co
2+, solution used is that 0.08mol/L, pH value are adjusted to 6 CoCl
2the aqueous solution, adsorption time is 20h.The solution that light chamber passes in the time of film selectivity test is the copper nickel mixed solution that copper, concentration of cobalt ions are 0.03mol/L.The Product Films obtaining under the same terms of describing at above-described embodiment 1 is as shown in table 4 to the separating effect of copper cobalt mixed solution.
Table 4
Embodiment 15
The present embodiment 15 is with reference to the method for embodiment 1.Difference is: the trace ion of the cation-exchange membrane absorption after polyethyleneimine-modified is Ag
+, solution used is that 0.08mol/L, pH value are adjusted to 6 AgNO
3the aqueous solution, adsorption time is 24h.The solution that light chamber passes in the time of film selectivity test is the copper nickel mixed solution that copper, concentration of silver ions are 0.03mol/L.The Product Films obtaining under the same terms of describing at above-described embodiment 1 is as shown in table 5 to the separating effect of copper, silver-colored mixed solution.
Table 5
Embodiment 16
The present embodiment 16 is with reference to the method for embodiment 1.Difference is: selected basement membrane is the Nafion film of Dopont company of the U.S., and this film is a kind of perfluorinated sulfonic acid type amberplex, and PEI is basement membrane to be soaked in the PEI aqueous solution of 0.5g/L at epilamellar deposition process, after 160h, takes out.The Product Films obtaining under the same terms of describing at above-described embodiment 1 is as shown in table 6 to the separating effect of copper zinc mixed solution.
Embodiment 17
The present embodiment 17 is with reference to the method for embodiment 1.Difference is: selected basement membrane is sulfonated polyether-ether-ketone film prepared by laboratory, and PEI is basement membrane to be soaked in the PEI aqueous solution of 30g/L at epilamellar deposition process, after 0.5h, takes out.The Product Films obtaining under the same terms of describing at above-described embodiment 1 is as shown in table 6 to the separating effect of copper zinc mixed solution.
Table 6
Claims (7)
1. one kind has the optionally preparation method of ion-exchange composite membranes to single cation, it is characterized by this composite membrane and comprise cation exchange basement membrane and polyethyleneimine-modified layer, wherein polymine is 2.0-200.0g/m at the epilamellar deposition of cation exchange
2;
Described cation exchange basement membrane, its polymer backbone is hydrocarbon main chain, partially fluorinated hydrocarbon main chain or fluoridized hydrocarbon main chain, has sulfonic group, phosphate, carboxylic acid group or phenolic hydroxyl group on the polymer backbone of this basement membrane; The thickness of this ion-exchange composite membranes is 50-500 μ m;
Described single cation is specially Cu
2+, Zn
2+, Ni
2+, Hg
2+, Ag
+, Pt
2+, Co
2+or Cr
3+;
Described preparation method comprises the steps:
The first step is introduced polymer P EI on cation exchange basement membrane, for following two kinds of methods arbitrary:
Method 1: static sedimentation method: cation exchange basement membrane is immersed in the PEI aqueous solution that concentration is 0.5-30g/L, soaks 0.5-160h under room temperature;
Or, method 2, electrodeposition process: adopt four chamber devices, four Room are respectively dense chamber, light chamber and 2 utmost point chambers; The dense indoor sodium chloride solution that adds; Light chamber adds the sodium chloride solution containing PEI, and extremely indoor is electrolyte solution; The current strength of electro-deposition is 1-100mA/cm
2, energising obtains the cation-exchange membrane of PEI modification after 20-120min;
Described employing four chamber devices, for four chamber devices that formed by three cation-exchange membranes and wall, wherein cation exchange basement membrane to be deposited is fixed on middle, be separated to form He Dan chamber, dense chamber with the cation-exchange membrane of the left and right sides, the cation-exchange membrane of both sides and wall are separated to form respectively again two utmost point chambers; Treat that deposited film is light chamber near anode one side, opposite side is dense chamber;
Electrolyte solution in described utmost point chamber is one or more in sodium chloride solution, metabisulfite solution and sulfuric acid, and in solution, cation concn is 0.1-2mol/L.
Second step, the absorption of template ion and PEI's is crosslinked
The aqueous solution that the cation-exchange membrane of the PEI modification that the first step is obtained is placed in template ion soaks 10-24h and carries out ionic adsorption, after taking out, water washes down surface solution, be placed in the cross-linking reaction that cross-linking agent solution carries out PEI, obtain template ion absorption and the crosslinked amberplex of PEI;
The aqueous solution of described template ion is for only containing a kind of cationic aqueous solution of templated metal ion, and concentration is 0.005-0.5mol/L, and pH value is 4-9; The concentration of cross-linking agent solution is 1-50g/L, and crosslinking temperature is 20-60 ℃, and crosslinking time is 20-120min;
The 3rd step, the wash-out of template ion
The sodium ethylene diamine tetracetate solution that is placed in 0.01-0.1mol/L through the absorption of second step template ion and the crosslinked amberplex of PEI is carried out to the wash-out of template ion, what obtain containing the action site that mates with template ion has optionally cation-exchange membrane to certain cationic.
2. as claimed in claim 1 have the optionally preparation method of ion-exchange composite membranes to single cation, and the cation exchange basement membrane it is characterized by the described first step is sulfonated polyether sulfone (SPES) film, sulfonated polyether-ether-ketone (SPEEK) film, perfluorocarboxylic acid cation-exchange membrane or phosphatic type cation-exchange membrane.
3. as claimed in claim 1 have the optionally preparation method of ion-exchange composite membranes to single cation, it is characterized by the Selemion CMV film of LE-HoCM-0_SH film, Beijing global Li Da environmental protection equipment JCM-of Co., Ltd I film that described first step middle-jiao yang, function of the spleen and stomach ion-exchange basement membrane is specially Zhejiang Qianqiu Environmental Water Treatment Co., Ltd., Japanese Asahi Glass company, the Neosepta CM-1 film of Japanese Tokuyama company or the Nafion film of Dopont company of the U.S..
4. as claimed in claim 1 have the optionally preparation method of ion-exchange composite membranes to single cation, and the concentration of the sodium chloride solution while it is characterized by above-mentioned preparation method's first step electro-deposition in dense chamber, light chamber used is 0.1-3mol/L.
5. as claimed in claim 1 have the optionally preparation method of ion-exchange composite membranes to single cation, and while it is characterized by described first step electro-deposition, in the concentration of sodium chloride solution of light chamber PEI used, PEI content is 0.1-30g/L.
6. as claimed in claim 1 have the optionally preparation method of ion-exchange composite membranes to single cation, and in the second step described in it is characterized by, only containing the cationic aqueous solution of a kind of templated metal is copper nitrate solution, zinc nitrate solution, nickel nitrate solution, liquor argenti nitratis ophthalmicus, platinum nitrate solution, cobalt chloride solution, chromium chloride solution, solution of ferrous chloride or ferric chloride solution.
7. as claimed in claim 1 have the optionally preparation method of ion-exchange composite membranes to single cation, in the cross-linking agent solution of the second step described in it is characterized by, solute is epoxychloropropane, glycerin triglycidyl ether or glutaraldehyde etc., and solvent is ethanol or water.
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| CN104275168A (en) * | 2013-07-05 | 2015-01-14 | 中国科学院大连化学物理研究所 | Cation exchange chromatography stationary phase and preparation method thereof |
| CN105597557B (en) * | 2015-09-28 | 2017-11-17 | 河北工业大学 | A kind of preparation method being used for from the composite membrane of extracting lithium from salt lake brine |
| CN106099147A (en) * | 2016-06-30 | 2016-11-09 | 中国科学院青岛生物能源与过程研究所 | One has selective ion exchange membrane of monovalention and its production and use |
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| CN112516808A (en) * | 2020-12-31 | 2021-03-19 | 山东天维膜技术有限公司 | Preparation method of cross-linked bipolar membrane |
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| CN115364679B (en) * | 2022-07-27 | 2023-06-27 | 中国地质大学（武汉） | Potassium ion selective film and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5989426A (en) * | 1995-07-05 | 1999-11-23 | Nitto Denko Corp. | Osmosis membrane |
| CN1281497C (en) * | 2003-12-20 | 2006-10-25 | 中国科学院青海盐湖研究所 | Method for separating magnesium and concentrating lithium from brine in salt lake |
| CN1298414C (en) * | 2005-04-06 | 2007-02-07 | 南京工业大学 | Organic-inorganic substances compound membrane and its preparation method |
| CN101530748B (en) * | 2009-03-17 | 2012-07-11 | 郑州大学 | Method for preparing composite charged mosaic membrane via interfacial polymerization |
| CN102451621A (en) * | 2010-10-27 | 2012-05-16 | 中国科学院大连化学物理研究所 | Polyether-b-polyamide multilayer composite film and preparation method thereof |
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