CN114053879A - Preparation method of potassium ion exchange membrane - Google Patents
Preparation method of potassium ion exchange membrane Download PDFInfo
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- CN114053879A CN114053879A CN202111536562.4A CN202111536562A CN114053879A CN 114053879 A CN114053879 A CN 114053879A CN 202111536562 A CN202111536562 A CN 202111536562A CN 114053879 A CN114053879 A CN 114053879A
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- graphene
- ion exchange
- exchange membrane
- dispersion liquid
- graft polymer
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- 229910001414 potassium ion Inorganic materials 0.000 title claims abstract description 64
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical group [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000003014 ion exchange membrane Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 113
- 239000007788 liquid Substances 0.000 claims abstract description 94
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 86
- 239000006185 dispersion Substances 0.000 claims abstract description 85
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 81
- FCFNRCROJUBPLU-DNDCDFAISA-N valinomycin Chemical compound CC(C)[C@@H]1NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC(=O)[C@H](C(C)C)NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC(=O)[C@H](C(C)C)NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC1=O FCFNRCROJUBPLU-DNDCDFAISA-N 0.000 claims abstract description 44
- 108010067973 Valinomycin Proteins 0.000 claims abstract description 43
- FCFNRCROJUBPLU-UHFFFAOYSA-N compound M126 Natural products CC(C)C1NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC(=O)C(C(C)C)NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC(=O)C(C(C)C)NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC1=O FCFNRCROJUBPLU-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000012528 membrane Substances 0.000 claims abstract description 41
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 238000005266 casting Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 150000001408 amides Chemical group 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 62
- 239000002244 precipitate Substances 0.000 claims description 52
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 31
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 17
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 14
- 229920003213 poly(N-isopropyl acrylamide) Polymers 0.000 claims description 14
- 229920005601 base polymer Polymers 0.000 claims description 12
- NRHMKIHPTBHXPF-TUJRSCDTSA-M sodium cholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 NRHMKIHPTBHXPF-TUJRSCDTSA-M 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- HYISVWRHTUCNCS-UHFFFAOYSA-N pyrene-1-carboxylic acid Chemical compound C1=C2C(C(=O)O)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 HYISVWRHTUCNCS-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims 3
- 239000011261 inert gas Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 19
- 239000002090 nanochannel Substances 0.000 abstract description 6
- 230000037427 ion transport Effects 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 34
- 229960001701 chloroform Drugs 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 239000011521 glass Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 239000004952 Polyamide Substances 0.000 description 12
- 229920002647 polyamide Polymers 0.000 description 12
- 230000009471 action Effects 0.000 description 11
- 230000001965 increasing effect Effects 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 230000000379 polymerizing effect Effects 0.000 description 11
- 230000001376 precipitating effect Effects 0.000 description 11
- 238000003828 vacuum filtration Methods 0.000 description 11
- 239000013505 freshwater Substances 0.000 description 10
- 238000009210 therapy by ultrasound Methods 0.000 description 10
- 238000002137 ultrasound extraction Methods 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 229910001415 sodium ion Inorganic materials 0.000 description 7
- 239000012267 brine Substances 0.000 description 6
- 238000000909 electrodialysis Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000004815 dispersion polymer Substances 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 239000002064 nanoplatelet Substances 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229930195482 Validamycin Natural products 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- -1 sodium salt Chemical class 0.000 description 3
- JARYYMUOCXVXNK-IMTORBKUSA-N validamycin Chemical compound N([C@H]1C[C@@H]([C@H]([C@H](O)[C@H]1O)O[C@H]1[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O1)O)CO)[C@H]1C=C(CO)[C@H](O)[C@H](O)[C@H]1O JARYYMUOCXVXNK-IMTORBKUSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- ZWYAVGUHWPLBGT-UHFFFAOYSA-N bis(6-methylheptyl) decanedioate Chemical group CC(C)CCCCCOC(=O)CCCCCCCCC(=O)OCCCCCC(C)C ZWYAVGUHWPLBGT-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium nitrate Inorganic materials [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 235000015598 salt intake Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/78—Graft polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/17—Organic material containing also inorganic materials, e.g. inert material coated with an ion-exchange resin
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/26—Electrical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/42—Ion-exchange membranes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
Abstract
The invention provides a preparation method of a potassium ion exchange membrane, which comprises the following steps: adding graphene and a dispersing agent into a solvent to obtain a graphene dispersion liquid; mixing a liquid basic polymer with a side chain containing an amide structure with valinomycin, and reacting at 25-50 ℃ to obtain a graft polymer; adding the prepared graft polymer into graphene dispersion liquid to prepare graphene-graft polymer mixed dispersion liquid; and (3) casting the mixed dispersion liquid into a film to prepare the potassium ion exchange membrane. In the ion exchange membrane prepared by the invention, the valinomycin reacts with the basic polymer to form the graft polymer, so that the valinomycin in the obtained ion exchange membrane is not easy to fall off, the stability of the ion exchange membrane in the use process is ensured, and the service life of the ion exchange membrane can be prolonged; the graphene is compounded in the middle of the ion exchange membrane, and the 2D nano-channel of the graphene is utilized for carrying out ion transport, so that the dielectric property and the stability of the membrane are improved.
Description
Technical Field
The invention relates to the technical field of ion exchange membranes, in particular to a preparation method of a potassium ion exchange membrane.
Background
With the increasing shortage of fresh water resources, obtaining fresh water from seawater has become an important means for solving the problem of shortage of fresh water resources. After the seawater is desalted, two parts of desalted fresh water and concentrated brine are formed, the concentrated brine contains a large amount of metal salt components such as sodium, potassium, calcium, magnesium and the like, and the salt components are usually required in other industrial production, so that the salt components extracted from the concentrated brine can obtain higher economic benefit.
The resources can be extracted from the concentrated brine, and the method has higher economic benefit and environmental advantage compared with seawater, for example, potassium salt in the seawater can be used for producing potassium fertilizer. For the production of potash fertilizers, obtaining high purity and high concentration of potassium salt from concentrated brine is an essential process, however, in concentrated brine, potassium salt usually exists together with a large amount of ionic salts such as sodium salt, and separation has various difficulties, for example: the product yield of the recrystallization process is relatively low, the energy consumption of the electrostatic adsorption process is too high, and the salt consumption of the ion exchange process is very high. Compared with the traditional separation technology, the membrane technology has the advantages of modularization, strong expandability, low energy consumption and the like, is a method for separating potassium salt with industrial prospect, however, the method depends on the performance of an exchange membrane, and in order to realize the separation efficiency of potassium ions, the exchange membrane with high selectivity and high permeability of the potassium ions needs to be obtained.
Patent document No. cn201110422887.x discloses an induction membrane for a potassium ion selective electrode, a production method and an application thereof, wherein the induction membrane is prepared from a casting solution, and the casting solution comprises the following components: 20-40% of polymer, 50-80% of plasticizer, 2-10% of ion selective carrier and 0.1-2% of lipid-soluble salt, wherein the total content of solute is 150-400 mg/mL in terms of weight percentage of the total weight of solute; the polymer is one or more of carboxyl polyvinyl chloride, high molecular weight polyvinyl chloride or polyurethane; the plasticizer is diisooctyl sebacate; the ion selective carrier is valinomycin; the fat-soluble salt is potassium tetra (4-chlorphenyl) boric acid; the solvent is tetrahydrofuran or a mixture of tetrahydrofuran and acetone. The patent utilizes polymer to load valinomycin with high potassium ion selectivity to prepare the sensing membrane with high potassium ion selectivity, and improves the selectivity of potassium ions, but the selectivity still needs to be further improved.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a potassium ion exchange membrane, so as to obtain the exchange membrane which has high potassium ion selectivity, long service life and low pollution possibility.
To achieve the above object. The invention adopts the following technical scheme:
a preparation method of a potassium ion exchange membrane comprises the following steps:
s1, adding graphene and a dispersing agent into a solvent to obtain a graphene dispersion liquid;
s2, mixing the liquid basic polymer with the side chain containing the amide structure with valinomycin, and reacting at 25-50 ℃ to obtain a graft polymer;
s3, adding the grafted polymer prepared in the step S2 into the graphene dispersion liquid prepared in the step S1 to prepare a graphene-grafted polymer mixed dispersion liquid;
and S4, casting the mixed dispersion liquid into a film to obtain the potassium ion exchange membrane.
The invention firstly utilizes the liquid basic polymer with side chain containing amide structure to be mixed with the valinomycin to prepare the graft polymer formed by the basic polymer-the valinomycin. Specifically, the amide structure of the base polymer in the present invention is formed by condensation of carboxyl groups directly or indirectly linked to the polymer backbone with an amine group-containing compound, which is removed during the reaction of the base polymer with valinomycin and replaced by valinomycin. The term "liquid" as used herein refers to a base polymer which is in a liquid state at normal temperature, and most commonly: poly (N-isopropylacrylamide), poly (N-t-butylacrylamide), and the like. In the invention, the main structure of the membrane is formed by the basic polymer, and the valinomycin and the side chain of the basic polymer are reacted, so that the valinomycin and the basic polymer form an integrated structure, and the valinomycin in the prepared potassium ion exchange membrane is not easy to fall off. The method also adopts graphene to modify the potassium ion exchange membrane, specifically, in the formation process of the membrane, a layer of intermediate base material is formed by the basic polymer-valinomycin graft polymer, and the graphene is deposited and compounded on the intermediate base material to obtain a three-layer structure similar to graphene-intermediate base material-graphene. Graphene is a regular network structure, the graphene has uniformly distributed 2D nano-channels, ions in a 2D nano-channel solution contact with an intermediate substrate, and due to the fact that validamycin in the intermediate substrate has an ion channel with high potassium ion selectivity, potassium ions in the ions passing through the 2D nano-channels can be preferentially selected, so that high potassium ion selectivity is obtained, meanwhile, the graphene layer-shaped structure can also play a surface protection role in the intermediate substrate, and the phenomena that the validamycin falls off and the validamycin is polluted by impurities in the solution to lose the selection role of the potassium ions are avoided.
Further, step S2 includes the step of removing unreacted base polymer in the graft polymer, which includes the following steps: dissolving the graft polymer obtained by the reaction in excess anhydrous ether, and then adding tetrahydrofuran to precipitate the graft polymer out and separating; extracting the precipitate obtained by separation with tetrahydrofuran; and drying the precipitate to obtain the graft polymer without the basic polymer. The unreacted base polymer can be dissolved in tetrahydrofuran, and the base polymer-valinomycin graft polymer can form precipitate, so that the separation of the base polymer and the graft polymer can be realized by the above mode, and the purity of the graft polymer is improved. In order to further enhance the purification effect, the obtained precipitate can be circularly dissolved, precipitated and extracted for a plurality of times before being dried.
Further, step S4 includes the following steps: filtering the mixed dispersion liquid obtained in the step S3 through a microporous filter membrane to obtain graphene-polymer solid, re-dispersing the graphene-polymer solid in a third solvent to obtain a newly prepared mixed dispersion liquid, and finally casting the newly prepared mixed dispersion liquid into a film. After removing the unreacted base polymer, there is a possibility that valinomycin remains in the mixed dispersion, so that the mixed dispersion obtained in step S3 may be subjected to a filtration process using a microfiltration membrane (e.g., a polyamide microfiltration membrane) having a pore size larger than that of valinomycin and smaller than that of the graft polymer, so that the graft polymer is intercepted to form a precipitate, and the valinomycin is removed with the solvent. The resulting graft polymer precipitate is redissolved in an organic solvent to obtain a further purified freshly mixed dispersion.
Further, the dispersing agent is selected from one or more of Sodium Dodecyl Benzene Sulfonate (SDBS), Sodium Cholate (SC), polyvinyl chloride (PVC), polyvinylpyrrolidone (PVP) and 1-pyrenecarboxylic acid (PCA).
Further, the first solvent is selected from one or more of chloroform, dichloromethane, tetrahydrofuran, N-methyl-2-pyrrolidone (NMP) and N, N-Dimethylformamide (DMF).
Further, the mass ratio of the graphene to the dispersing agent is (0.5-2): 1.
Further, in the mixed dispersion liquid, the mass ratio of the graft polymer to the graphene is (0.05-0.3): 1; preferably, in the mixed dispersion liquid, the mass ratio of the graft polymer to the graphene is (0.15-0.2): 1.
Further, in step S2, the mass ratio of valinomycin to the base polymer is (0.002-0.01): 1.
further, the reaction in S2 was performed under a nitrogen atmosphere.
Further, the base polymer is poly (N-isopropylacrylamide).
In summary, the following beneficial effects can be achieved by applying the technical scheme of the invention:
(1) the potassium ion exchange membrane prepared by the invention contains valinomycin, the valinomycin is a high potassium ion selective material, the diffusion rate of potassium ions can be greatly improved, the diffusion rate of sodium ions is basically not changed, and potassium salt is purified from sodium salt which is difficult to separate.
(2) In the prepared potassium ion exchange membrane, the valinomycin reacts with the basic polymer to form the graft polymer, so that the valinomycin in the obtained ion exchange membrane is not easy to fall off, the stability of the ion exchange membrane in the using process is ensured, and the service life of the ion exchange membrane can be prolonged.
(3) The invention also compounds graphene in the potassium ion exchange membrane, and utilizes the 2D nano-channel of the graphene to carry out ion transport. The addition of the graphene material can effectively improve the dielectric property and stability of the film.
(4) The invention has mild preparation conditions and relatively simple process.
Drawings
FIG. 1 is an SEM photograph of a potassium ion exchange membrane prepared in example 2;
FIG. 2 is an SEM photograph of the potassium ion exchange membrane prepared in example 5.
Detailed Description
The present invention will be described in detail with reference to specific examples. The operation methods related to the invention are all conventional methods in the field if no special description is provided; reagents and materials used in this experiment were commercially available unless otherwise specified.
Example 1
Weighing 20mg of graphene and 20mg of sodium dodecyl benzene sulfonate, adding the graphene and the sodium dodecyl benzene sulfonate into 200mL of chloroform, and performing ultrasonic-assisted extraction at 25 ℃ to obtain a graphene dispersion liquid, wherein the ultrasonic time is 48 hours;
stirring 5g of poly (N-isopropylacrylamide) and 50 mg of valinomycin in a constant-temperature bath at 40 ℃, vibrating and polymerizing for 18h under the action of nitrogen pressure to obtain a graft polymer, dissolving the graft polymer by using anhydrous ether, adding tetrahydrofuran into the anhydrous ether to obtain a precipitate of the graft polymer, separating the precipitate of the graft polymer, repeating the dissolving and precipitating processes twice, extracting the precipitate by using tetrahydrofuran, and drying the precipitate for 18h under vacuum to obtain a purified graft polymer for later use;
mixing 1mg of the graft polymer obtained in the step II with the graphene dispersion liquid prepared in the step I, and performing ultrasonic treatment for 1 hour to obtain a mixed dispersion liquid;
fourthly, performing vacuum filtration on the mixed dispersion liquid obtained in the third step by using a polyamide microporous filter membrane, and then putting the solid obtained by filtration into trichloromethane again to obtain a new mixed dispersion liquid;
and fifthly, casting the newly prepared mixed dispersion liquid on a glass substrate to form a film, drying the film at normal temperature and normal pressure, and stripping the film to obtain the potassium ion exchange membrane.
Example 2
Weighing 20mg of graphene and 20mg of sodium dodecyl benzene sulfonate, adding the graphene and the sodium dodecyl benzene sulfonate into 200mL of chloroform, and performing ultrasonic-assisted extraction at 25 ℃ to obtain a graphene dispersion liquid, wherein the ultrasonic time is 48 hours;
stirring 5g of poly (N-isopropylacrylamide) and 50 mg of valinomycin in a constant-temperature bath at 40 ℃, vibrating and polymerizing for 18h under the action of nitrogen pressure to obtain a graft polymer, dissolving the graft polymer by using anhydrous ether, adding tetrahydrofuran into the anhydrous ether to obtain a precipitate of the graft polymer, separating the precipitate of the graft polymer, repeating the dissolving and precipitating processes twice, extracting the precipitate by using tetrahydrofuran, and drying the precipitate for 18h under vacuum to obtain a purified graft polymer for later use;
mixing the graft polymer obtained in the second step 2mg with the graphene dispersion liquid prepared in the first step, and performing ultrasonic treatment for 1 hour to obtain a mixed dispersion liquid;
fourthly, performing vacuum filtration on the mixed dispersion liquid obtained in the third step by using a polyamide microporous filter membrane, and then putting the solid obtained by filtration into trichloromethane again to obtain a new mixed dispersion liquid;
and fifthly, casting the newly prepared mixed dispersion liquid on a glass substrate to form a film, drying the film at normal temperature and normal pressure, and stripping the film to obtain the potassium ion exchange membrane.
Example 3
Weighing 20mg of graphene and 20mg of sodium dodecyl benzene sulfonate, adding the graphene and the sodium dodecyl benzene sulfonate into 200mL of chloroform, and performing ultrasonic-assisted extraction at 25 ℃ to obtain a graphene dispersion liquid, wherein the ultrasonic time is 48 hours;
stirring 5g of poly (N-isopropylacrylamide) and 50 mg of valinomycin in a constant-temperature bath at 40 ℃, vibrating and polymerizing for 18h under the action of nitrogen pressure to obtain a graft polymer, dissolving the graft polymer by using anhydrous ether, adding tetrahydrofuran into the anhydrous ether to obtain a precipitate of the graft polymer, separating the precipitate of the graft polymer, repeating the dissolving and precipitating processes twice, extracting the precipitate by using tetrahydrofuran, and drying the precipitate for 18h under vacuum to obtain a purified graft polymer for later use;
mixing 3mg of the graft polymer obtained in the step II with the graphene dispersion liquid prepared in the step I, and performing ultrasonic treatment for 1 hour to obtain a mixed dispersion liquid;
fourthly, performing vacuum filtration on the mixed dispersion liquid obtained in the third step by using a polyamide microporous filter membrane, and then putting the solid obtained by filtration into trichloromethane again to obtain a new mixed dispersion liquid;
and fifthly, casting the newly prepared mixed dispersion liquid on a glass substrate to form a film, drying the film at normal temperature and normal pressure, and stripping the film to obtain the potassium ion exchange membrane.
Example 4
Weighing 20mg of graphene and 20mg of sodium cholate, adding the graphene and the sodium cholate into 200mL of chloroform, and performing ultrasonic-assisted extraction at 25 ℃ to obtain a graphene dispersion liquid, wherein the ultrasonic time is 48 hours;
stirring 5g of poly (N-isopropylacrylamide) and 50 mg of valinomycin in a constant-temperature bath at 40 ℃, vibrating and polymerizing for 18h under the action of nitrogen pressure to obtain a graft polymer, dissolving the graft polymer by using anhydrous ether, adding tetrahydrofuran into the anhydrous ether to obtain a precipitate of the graft polymer, separating the precipitate of the graft polymer, repeating the dissolving and precipitating processes twice, extracting the precipitate by using tetrahydrofuran, and drying the precipitate for 18h under vacuum to obtain a purified graft polymer for later use;
mixing 4mg of the graft polymer obtained in the step II with the graphene dispersion liquid prepared in the step I, and performing ultrasonic treatment for 1 hour to obtain a mixed dispersion liquid;
fourthly, performing vacuum filtration on the mixed dispersion liquid obtained in the third step by using a polyamide microporous filter membrane, and then putting the solid obtained by filtration into trichloromethane again to obtain a new mixed dispersion liquid;
and fifthly, casting the newly prepared mixed dispersion liquid on a glass substrate to form a film, drying the film at normal temperature and normal pressure, and stripping the film to obtain the potassium ion exchange membrane.
Example 5
Weighing 20mg of graphene and 20mg of sodium cholate, adding the graphene and the sodium cholate into 200mL of chloroform, and performing ultrasonic-assisted extraction at 25 ℃ to obtain a graphene dispersion liquid, wherein the ultrasonic time is 48 hours;
stirring 5g of poly (N-isopropylacrylamide) and 50 mg of valinomycin in a constant-temperature bath at 40 ℃, vibrating and polymerizing for 18h under the action of nitrogen pressure to obtain a graft polymer, dissolving the graft polymer by using anhydrous ether, adding tetrahydrofuran into the anhydrous ether to obtain a precipitate of the graft polymer, separating the precipitate of the graft polymer, repeating the dissolving and precipitating processes twice, extracting the precipitate by using tetrahydrofuran, and drying the precipitate for 18h under vacuum to obtain a purified graft polymer for later use;
mixing the graft polymer obtained in the step (6) with the graphene dispersion liquid prepared in the step (i), and performing ultrasonic treatment for 1 hour to obtain a mixed dispersion liquid;
fourthly, performing vacuum filtration on the mixed dispersion liquid obtained in the third step by using a polyamide microporous filter membrane, and then putting the solid obtained by filtration into trichloromethane again to obtain a new mixed dispersion liquid;
and fifthly, casting the newly prepared mixed dispersion liquid on a glass substrate to form a film, drying the film at normal temperature and normal pressure, and stripping the film to obtain the potassium ion exchange membrane.
Example 6
Weighing 20mg of graphene and 20mg of sodium cholate, adding the graphene and the sodium cholate into 200mL of chloroform, and performing ultrasonic-assisted extraction at 25 ℃ to obtain a graphene dispersion liquid, wherein the ultrasonic time is 48 hours;
stirring 5g of poly (N-isopropylacrylamide) and 50 mg of valinomycin in a constant-temperature bath at 40 ℃, vibrating and polymerizing for 18h under the action of nitrogen pressure to obtain a graft polymer, dissolving the graft polymer by using anhydrous ether, adding tetrahydrofuran into the anhydrous ether to obtain a precipitate of the graft polymer, separating the precipitate of the graft polymer, repeating the dissolving and precipitating processes twice, extracting the precipitate by using tetrahydrofuran, and drying the precipitate for 18h under vacuum to obtain a purified graft polymer for later use;
mixing 7mg of the graft polymer obtained in the step II with the graphene dispersion liquid prepared in the step I, and performing ultrasonic treatment for 1 hour to obtain a mixed dispersion liquid;
fourthly, performing vacuum filtration on the mixed dispersion liquid obtained in the third step by using a polyamide microporous filter membrane, and then putting the solid obtained by filtration into trichloromethane again to obtain a new mixed dispersion liquid;
and fifthly, casting the newly prepared mixed dispersion liquid on a glass substrate to form a film, drying the film at normal temperature and normal pressure, and stripping the film to obtain the potassium ion exchange membrane.
Example 7
Weighing 20mg of graphene and 20mg of sodium dodecyl benzene sulfonate, adding the graphene and the sodium dodecyl benzene sulfonate into 200mL of chloroform, and performing ultrasonic-assisted extraction at 25 ℃ to obtain a graphene dispersion liquid, wherein the ultrasonic time is 48 hours;
stirring 5g of poly (N-isopropylacrylamide) and 40 mg of valinomycin in a constant-temperature bath at 40 ℃, vibrating and polymerizing for 18h under the action of nitrogen pressure to obtain a graft polymer, dissolving the graft polymer by using anhydrous ether, adding tetrahydrofuran into the anhydrous ether to obtain a precipitate of the graft polymer, separating the precipitate of the graft polymer, repeating the dissolving and precipitating processes twice, extracting the precipitate by using tetrahydrofuran, and drying the precipitate for 18h under vacuum to obtain a purified graft polymer for later use;
mixing 4mg of the graft polymer obtained in the step II with the graphene dispersion liquid prepared in the step I, and performing ultrasonic treatment for 1 hour to obtain a mixed dispersion liquid;
fourthly, performing vacuum filtration on the mixed dispersion liquid obtained in the third step by using a polyamide microporous filter membrane, and then putting the solid obtained by filtration into trichloromethane again to obtain a new mixed dispersion liquid;
and fifthly, casting the newly prepared mixed dispersion liquid on a glass substrate to form a film, drying the film at normal temperature and normal pressure, and stripping the film to obtain the potassium ion exchange membrane.
Example 8
Weighing 20mg of graphene and 20mg of sodium dodecyl benzene sulfonate, adding the graphene and the sodium dodecyl benzene sulfonate into 200mL of chloroform, and performing ultrasonic-assisted extraction at 25 ℃ to obtain a graphene dispersion liquid, wherein the ultrasonic time is 48 hours;
stirring 5g of poly (N-isopropylacrylamide) and 20mg of valinomycin in a constant-temperature bath at 40 ℃, vibrating and polymerizing for 18h under the action of nitrogen pressure to obtain a graft polymer, dissolving the graft polymer by using anhydrous ether, adding tetrahydrofuran into the anhydrous ether to obtain a precipitate of the graft polymer, separating the precipitate of the graft polymer, repeating the dissolving and precipitating processes twice, extracting the precipitate by using tetrahydrofuran, and drying the precipitate for 18h under vacuum to obtain a purified graft polymer for later use;
mixing 4mg of the graft polymer obtained in the step II with the graphene dispersion liquid prepared in the step I, and performing ultrasonic treatment for 1 hour to obtain a mixed dispersion liquid;
fourthly, performing vacuum filtration on the mixed dispersion liquid obtained in the third step by using a polyamide microporous filter membrane, and then putting the solid obtained by filtration into trichloromethane again to obtain a new mixed dispersion liquid;
and fifthly, casting the newly prepared mixed dispersion liquid on a glass substrate to form a film, drying the film at normal temperature and normal pressure, and stripping the film to obtain the potassium ion exchange membrane.
Example 9
Weighing 20mg of graphene and 20mg of sodium dodecyl benzene sulfonate, adding the graphene and the sodium dodecyl benzene sulfonate into 200mL of chloroform, and performing ultrasonic-assisted extraction at 25 ℃ to obtain a graphene dispersion liquid, wherein the ultrasonic time is 48 hours;
stirring 5g of poly (N-isopropylacrylamide) and 10mg of valinomycin in a constant temperature bath at 40 ℃, vibrating and polymerizing for 18h under the action of nitrogen pressure to obtain a graft polymer, dissolving the graft polymer by using anhydrous ether, adding tetrahydrofuran into the anhydrous ether to obtain a precipitate of the graft polymer, separating the precipitate of the graft polymer, repeating the dissolving and precipitating processes twice, extracting the precipitate by using tetrahydrofuran, and drying the precipitate for 18h under vacuum to obtain a purified graft polymer for later use;
mixing 4mg of the graft polymer obtained in the step II with the graphene dispersion liquid prepared in the step I, and performing ultrasonic treatment for 1 hour to obtain a mixed dispersion liquid;
fourthly, performing vacuum filtration on the mixed dispersion liquid obtained in the third step by using a polyamide microporous filter membrane, and then putting the solid obtained by filtration into trichloromethane again to obtain a new mixed dispersion liquid;
and fifthly, casting the newly prepared mixed dispersion liquid on a glass substrate to form a film, drying the film at normal temperature and normal pressure, and stripping the film to obtain the potassium ion exchange membrane.
Example 10
Weighing 20mg of graphene and 20mg of sodium dodecyl benzene sulfonate, adding the graphene and the sodium dodecyl benzene sulfonate into 200mL of chloroform, and performing ultrasonic-assisted extraction at 25 ℃ to obtain a graphene dispersion liquid, wherein the ultrasonic time is 48 hours;
stirring 5g of poly (N-isopropylacrylamide) and 60mg of valinomycin in a constant-temperature bath at 40 ℃, vibrating and polymerizing for 18h under the action of nitrogen pressure to obtain a graft polymer, dissolving the graft polymer by using anhydrous ether, adding tetrahydrofuran into the anhydrous ether to obtain a precipitate of the graft polymer, separating the precipitate of the graft polymer, repeating the dissolving and precipitating processes twice, extracting the precipitate by using tetrahydrofuran, and drying the precipitate for 18h under vacuum to obtain a purified graft polymer for later use;
mixing 4mg of the graft polymer obtained in the step II with the graphene dispersion liquid prepared in the step I, and performing ultrasonic treatment for 1 hour to obtain a mixed dispersion liquid;
fourthly, performing vacuum filtration on the mixed dispersion liquid obtained in the third step by using a polyamide microporous filter membrane, and then putting the solid obtained by filtration into trichloromethane again to obtain a new mixed dispersion liquid;
and fifthly, casting the newly prepared mixed dispersion liquid on a glass substrate to form a film, drying the film at normal temperature and normal pressure, and stripping the film to obtain the potassium ion exchange membrane.
Comparative example 1
An induction membrane for a potassium ion selective electrode, which comprises the following specific steps:
(1) adding a solvent into the mixture of the solutes in a room temperature fume hood, adding clean magnetons, sealing the opening of a bottle by using a sealing film, and stirring the solution on a magnetic stirrer at the stirring speed of 500 plus 800r/min for 12 hours to fully and uniformly stir the solutes and the solvent;
(2) transferring the uniformly stirred solution into a flat and clean stainless steel membrane container by using a glass liquid transfer gun, and covering a glass cover on the outer surface of the container to slowly volatilize the membrane liquid and keep the membrane liquid clean; .
(3) The film prepared after the solvent in the solution is volatilized for 72 hours is the potassium ion induction film.
The solute consists of 30 percent of high molecular weight polyvinyl chloride, 65 percent of diisooctyl sebacate, 4 percent of valinomycin and 1 percent of potassium tetra (4-chlorphenyl) boric acid, and the solvent is tetrahydrofuran.
Comparative example 2
Example 4
Stirring 5g of poly (N-isopropylacrylamide) and 50 mg of valinomycin in a constant-temperature bath at 40 ℃, vibrating and polymerizing for 18h under the action of nitrogen pressure to obtain a graft polymer, dissolving the graft polymer by using anhydrous ether, adding tetrahydrofuran into the anhydrous ether to obtain a precipitate of the graft polymer, separating the precipitate of the graft polymer, repeating the dissolving and precipitating processes twice, extracting the precipitate by using tetrahydrofuran, and drying the precipitate for 18h under vacuum to obtain a purified graft polymer for later use;
dispersing the graft polymer into trichloromethane to form graft polymer dispersion liquid, performing vacuum filtration on the graft polymer dispersion liquid by using a polyamide microporous filter membrane, and then adding the solid obtained by filtration into the trichloromethane again to obtain new graft polymer dispersion liquid;
and fifthly, casting the newly prepared graft polymer dispersion solution on a glass substrate to form a film, drying at normal temperature and normal pressure, and stripping to obtain the potassium ion exchange membrane.
The performance of the films obtained in examples 1 to 10 and comparative example were tested.
The ion exchange experiment was carried out using a self-made electrodialysis apparatus consisting of two polar chambers, a concentrated water chamber and a concentrated water chamber, with a channel diameter of 4 cm. First, the graft polymer-graphene film was cut into a circular shape having a diameter of 4.5cm, and then, the graft polymer-graphene film was mounted inside. The effective area of the membrane in the permeation experiment is 16cm2. The fresh water side is filled with a salt solution (i.e., KNO)3，NaNO3，LiNO3，Pb(NO3)2，Ca(NO3)2，Mg(NO3)2，Cr(NO3)30.1mol/L, 200 mL), while the concentrate side is filled with deionized water to the same level (200 mL). The fresh water side and the concentrated water side are always stirred, and the polar water chamber is circulated. The permeation experiment lasted 24 hours. The concentrations of the different ions were then tested by using inductively coupled plasma emission spectroscopy (ICP). The ion permeation experiment for each salt solution was repeated at least three times with the same membrane to minimize experimental error.
(1) The volume of the solution in each chamber is not changed during the electrodialysis operation, K+/Na+The selectivity (S) is calculated as follows:
in the formula: s is K+For Na+The selective permeability coefficient of (1); delta CK +Is a fresh water chamber K before and after electrodialysis+Concentration difference (mol/L); delta CNa +Is a fresh water chamber Na before and after electrodialysis+Concentration difference (mol/L); cK +Is K in fresh water chamber of electrodialysis device+Initial concentration (mol/L); cNa +Na in fresh water chamber of electrodialysis device+Initial concentration (mol/L). The selectivity data are recorded in table 1.
(2) For the graft polymer-graphene films prepared in examples 1 to 6, after a permeation experiment was performed for 24 hours, the graft polymer-graphene films were taken out, touched and pressed by a glass rod, and whether the films were easily damaged or not was observed. The results are reported in table 2.
TABLE 1
TABLE 2
In summary, it can be seen from Table 1 that the potassium ion exchange membranes prepared by the method of the present invention in examples 1-10 all have separated Na except for example 6+And K+Effect of (A), K+/Na+The selectivity was over 2 and was better than the membrane prepared in the comparative example using the prior art. Obviously, the dosage of valinomycin in the comparative example is obviously higher than that in the example of the invention, but the selectivity of the examples 2-9 of the invention to potassium ions is higher than that in the comparative example, because the 2D channel formed by the graphene can improve the selection effect on the potassium ions, so that the 2D channel and the valinomycin form a synergistic effect. According to the data of examples 1 to 6, it can be seen that K of the potassium ion exchange membrane is increased as the content of the graft polymer in the potassium ion exchange membrane is increased+/Na+The selectivity was also increased gradually, mainly because the graft polymer had a gradually increasing amount of valinomycin, but in combination with table 2, when the graft polymer content in the potassium ion exchange membrane was increased to a certain extent, i.e. the graft polymer: with graphene =0.3:1, the durability and physical strength of the film decreased, and as the ratio of graft polymer to graphene further increased to 0.35:1, the film had been severely damaged after being disturbed by glass rods, and the K of the film obtained in example 6 was lost according to the data of example 6 in table 1+/Na+Selectivity, also due to insufficient membrane strength, during useThe medium structure gradually collapses, so that the function of separating two polar chambers is lost, and the inventor analyzes that the phenomenon is considered that the mass ratio of the graft polymer to the graphene in the invention is preferably (0.15-0.2): 1 because the mass ratio of the graft polymer is increased, the mechanical property of the membrane is deteriorated, the tensile strength is reduced, and the pi-pi attraction between graphene nanosheets is influenced, so that the stability in water is deteriorated, the long-term use is not realized, and the service life is short. In combination with comparative example 2, the membrane prepared in comparative example 2 has serious structural damage after 24h of experiment, and loses selectivity to potassium ions, so that it can be judged that the physical strength of the membrane in the using process can be enhanced after graphene is added. From the data of example 4 and examples 7 to 10, it can be seen that the increase in the amount of valinomycin added in the preparation of a potassium ion exchange membrane can increase K+/Na+However, in examples 4 and 10, since a higher selectivity can be obtained already when the amount of valinomycin is 1%, and the selectivity is less affected by further increasing the amount of valinomycin, the optimum range of the amount of valinomycin should be 0.2% to 1%.
From the attached drawings, fig. 1 is a microstructure diagram of a potassium ion exchange membrane when the ratio of the graft polymer to the graphene is 0.1:1, and fig. 2 is a microstructure diagram of a potassium ion exchange membrane when the ratio of the graft polymer to the graphene is 0.3:1, it can be seen that the surface structure of the membrane in fig. 1 is relatively flat, the graphene is orderly stacked, and the surface structure of the membrane in fig. 2 is in a disordered gully shape. The above change is caused by grafting, due to van der waals interaction between the graphene nanoplatelets and the graft polymer, the graft polymer can be regarded as a 'network' structure uniformly distributed in two-dimensional nanochannels between the graphene nanoplatelets, as the proportion of the graft polymer relative to the graphene is gradually increased, the graft polymer between the graphene nanoplatelets is gradually increased, and the microstructure of the graft polymer is irregular, so that the graphene nanoplatelets are influenced to become irregular arrangement, and under the condition of irregular arrangement, the structural stability of the membrane is greatly reduced.
In conclusion, in the potassium ion exchange membrane prepared by the invention, the graphene can play a role in enhancing the grafted polymer membrane, the physical strength and the service life of the membrane are improved, and the graphene and the valinomycin can form a synergistic effect to further enhance the selectivity of the valinomycin to potassium ions.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; within the idea of the invention, also technical features in the above embodiments or in different embodiments may be combined, steps may be implemented in any order, and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a potassium ion exchange membrane comprises the following steps:
s1, adding graphene and a dispersing agent into a solvent to obtain a graphene dispersion liquid;
s2, mixing the liquid basic polymer with the side chain containing the amide structure with valinomycin, and reacting at 25-50 ℃ to obtain a graft polymer;
s3, adding the grafted polymer prepared in the step S2 into the graphene dispersion liquid prepared in the step S1 to prepare a graphene-grafted polymer mixed dispersion liquid;
and S4, casting the mixed dispersion liquid into a film to obtain the potassium ion exchange membrane.
2. The method for preparing a potassium ion exchange membrane according to claim 1, wherein the method comprises the following steps: step S2 further comprises removing unreacted base polymer from the graft polymer by the following steps: dissolving the copolymer obtained by the reaction in excessive anhydrous ether, and then adding tetrahydrofuran to precipitate the copolymer and separating; extracting the precipitate obtained by separation with tetrahydrofuran; and drying the precipitate to obtain the copolymer without the base material polymer.
3. The method for preparing a potassium ion exchange membrane according to claim 1, wherein the method comprises the following steps: the step S4 further includes the steps of: filtering the mixed dispersion liquid prepared in the step S3 through a microporous filter membrane to obtain graphene-polymer solid, re-dispersing the graphene-polymer solid in a solvent to obtain a newly prepared mixed dispersion liquid, and finally casting the newly prepared mixed dispersion liquid into a film.
4. The method for preparing a potassium ion exchange membrane according to claim 1, wherein the method comprises the following steps: the dispersing agent is selected from one or more of sodium dodecyl benzene sulfonate, sodium cholate, polyvinyl chloride, polyvinylpyrrolidone and 1-pyrenecarboxylic acid.
5. The method for preparing a potassium ion exchange membrane according to claim 1, wherein the method comprises the following steps: in step S1, the mass ratio of the graphene to the dispersant is (0.5-2): 1.
6. The method for preparing a potassium ion exchange membrane according to claim 1, wherein the method comprises the following steps: in step S3, the mass ratio of the graft polymer to the graphene in the mixed dispersion liquid is (0.05-0.3): 1.
7. The method for preparing a potassium ion exchange membrane according to claim 1, wherein the method comprises the following steps: in step S2, the mass ratio of valinomycin to the base polymer is (0.002-0.01): 1.
8. the method for preparing a potassium ion exchange membrane according to claim 1, wherein the method comprises the following steps: in step S2, the reaction is performed under an inert gas atmosphere.
9. The method for preparing a potassium ion exchange membrane according to claim 1, wherein the method comprises the following steps: the base polymer is poly (N-isopropylacrylamide).
10. The method for preparing a potassium ion exchange membrane according to claim 6, wherein: in the mixed dispersion liquid, the mass ratio of the graft polymer to the graphene is (0.15-0.2): 1.
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| CN111533937A (en) * | 2020-06-01 | 2020-08-14 | 广东省生物工程研究所（广州甘蔗糖业研究所） | Modified graphene oxide/Nafion composite proton exchange membrane and preparation method and application thereof |
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| CN102558724A (en) * | 2011-12-16 | 2012-07-11 | 上海惠中医疗科技有限公司 | Sensing film for potassium ion-selective electrode, production method and application thereof |
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