CN116603396A - High-flux cation exchange membrane and application thereof in electrodialysis concentration of salt lake brine - Google Patents
High-flux cation exchange membrane and application thereof in electrodialysis concentration of salt lake brine Download PDFInfo
- Publication number
- CN116603396A CN116603396A CN202310837223.2A CN202310837223A CN116603396A CN 116603396 A CN116603396 A CN 116603396A CN 202310837223 A CN202310837223 A CN 202310837223A CN 116603396 A CN116603396 A CN 116603396A
- Authority
- CN
- China
- Prior art keywords
- cation exchange
- exchange membrane
- membrane
- flux
- high flux
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 117
- 238000005341 cation exchange Methods 0.000 title claims abstract description 56
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 55
- 239000012267 brine Substances 0.000 title claims abstract description 54
- 238000000909 electrodialysis Methods 0.000 title claims abstract description 43
- 230000004907 flux Effects 0.000 claims abstract description 63
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 239000002135 nanosheet Substances 0.000 claims abstract description 21
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims abstract description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 8
- 229920006380 polyphenylene oxide Polymers 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 238000005266 casting Methods 0.000 claims abstract description 3
- 239000011521 glass Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000007790 scraping Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 21
- 238000002360 preparation method Methods 0.000 abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 2
- 239000011777 magnesium Substances 0.000 abstract description 2
- 229910052749 magnesium Inorganic materials 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 14
- 229910001416 lithium ion Inorganic materials 0.000 description 14
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 13
- 229910001425 magnesium ion Inorganic materials 0.000 description 13
- 229920001955 polyphenylene ether Polymers 0.000 description 12
- 238000010586 diagram Methods 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 235000011152 sodium sulphate Nutrition 0.000 description 7
- 238000011033 desalting Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 239000003014 ion exchange membrane Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002064 nanoplatelet Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000003011 anion exchange membrane Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 2
- 230000005501 phase interface Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 206010042496 Sunburn Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 230000007646 directional migration Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/422—Electrodialysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/301—Polyvinylchloride
-
- 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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Urology & Nephrology (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a high flux cation exchange membrane and application thereof in electrodialysis concentration salt lake brine, wherein Ti is added into solution of sulfonated polyphenylene oxide 3 C 2 T x Preparing sulfonated polyphenyl ether membrane liquid from the nano-sheets, coating the membrane liquid on a substrate, casting into a membrane, and performing heat treatment to obtain the nano-sheet. The cation exchange membrane has high magnesium and lithium plasma flux, simple preparation process, easy operation,The required raw materials are few, and the method is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of ion exchange membrane preparation and salt lake brine concentration, and particularly relates to a high-flux cation exchange membrane and application thereof in electrodialysis concentration of salt lake brine.
Background
China is one of countries with abundant salt lake resources in the world, however, the concentration of more salt lake brine is low and is far lower than the saturation degree of the contained salt, for example: journal "chemical minerals and processing" (2006, 6:11-14) reports that the average kci content in the brine in the north of the salt lake of balun mart is only 0.6%; the Xinhua newspaper industry net reports that the lithium ion concentration in the Xinjiang salt lake brine is at least 120ppm and the ion concentration of the eastern part brine of the Nalge salt lake is only 50ppm in 2023, 5 months and 29 days (http:// www.xhby.net/sy/cb/202305/t20230529_7955541. Shtml). In order to fully utilize the salt resources in the low-concentration salt lake brine, a method for concentrating and enriching the low-concentration salt lake brine is needed, and the method provides possibility for developing the salt resources in the low-concentration salt lake brine.
Chinese patent No. CN103496720 reports a method for concentrating unsaturated salt lake brine at low temperature, which includes three-stage freezing concentration, and the method has the advantages of simple process, low cost, energy saving and environmental protection, however, the method needs to be realized by natural climate environment (the temperature must be lower than-10 ℃ to-5 ℃ of the freezing point of unsaturated brine), and a concentration tank is required to store brine, and continuous concentration cannot be realized. The Chinese patent No. 111039311A reports a method for sun-drying and concentrating salt lake brine with high magnesium-lithium ratio, which comprises three steps of sun-drying and evaporating a sodium salt pond, sun-drying and concentrating a sulfur mixed ore pond and sun-drying and concentrating a potassium mixed salt pond, and has the advantages of simple process, easy operation and obvious economic benefit, however, the method has high requirements on sites, and continuous concentration can not be realized.
Electrodialysis is an electric field driven ion exchange membrane process, the action of the electric field causing the ions to developThe directional migration is generated, and the selective permeation effect of the ion exchange membrane is combined, so that the effect of concentrating or desalting the salt solution is generated. Because of the advantages of simple operation, environment-friendly process, high working efficiency, continuous operation and the like, electrodialysis is widely applied to the fields of dye wastewater treatment, biological macromolecule purification, food processing, sea water desalination and the like. The academic paper published in journal (2020, 6:19-24.) is used for concentrating and enriching lithium-containing brine of a salt lake of a Qaidam basin after primary nanofiltration magnesium-lithium separation by adopting an electrodialysis method, and the result shows the potential application value of electrodialysis in a salt lake brine system. However, most of the existing electrodialysis methods used for concentrating and enriching salt lake brine are commercial ion exchange membranes, which are all universal. The salt lake brine system is complex and contains Li + 、Na + 、K + 、Cl - 、Br - Isomonovalent cations and anions, further comprising Mg 2+ 、Ca 2+ 、SO 4 2- The divalent cations and anions, each of which is susceptible to "competing migration" during transmembrane migration, result in a low ion transmembrane flux. Furthermore, until now, there has been no report on ion exchange membranes specially developed for electrodialysis in salt lake brine systems.
Therefore, based on the current research situation and aiming at the defects of the prior art, the invention provides a high-flux cation exchange membrane, a preparation method thereof and application thereof in electrodialysis concentration salt lake brine.
Disclosure of Invention
In order to overcome the defects of the prior art, the primary aim of the invention is to provide a preparation method of a high-flux cation exchange membrane, which is simple and easy to operate; another object is to provide a high flux cation exchange membrane prepared by the above method; it is a further object of the present invention to provide the use of the above-described high flux cation exchange membrane in electrodialysis concentration of salt lake brine. The invention solves the problems of low ion flux and the like of the conventional electrodialysis concentration salt lake brine cation exchange membrane.
The aim of the invention is achieved by the following technical scheme:
a method for preparing a high flux cation exchange membrane, comprising the steps of:
step 1, dissolving sulfonated polyphenyl ether in an organic solvent, uniformly stirring, and then adding Ti 3 C 2 T x Preparing nano-sheets into sulfonated polyphenyl ether membrane liquid;
step 2, coating film liquid on a substrate, casting and forming a film, and drying to obtain a film;
and 3, performing heat treatment on the membrane.
Preferably, ti in step (1) 3 C 2 T x The nanoplatelets are single-or few-layered nanoplatelets prepared by reference to document "Electromagnetic interference shielding with 2D transition metal carbides (MXenes)" (Science, 2016,6304 (353): 1137-1140) and document "Two-dimensional MXene incorporated graphene oxide composite membrane with enhanced water purification performance" (Journal ofMembrane Science,2020,593: 117431).
Preferably, in the step 1, the sulfonation degree of the sulfonated polyphenylene ether is 10 to 90%.
Preferably, in the step 1, the mass fraction of the sulfonated polyphenylene oxide in the sulfonated polyphenylene oxide membrane liquid is 10-20%.
Preferably, in step 1, the organic solvent may be N-methylpyrrolidone or N, N-dimethylformamide.
Preferably, in step 1, the Ti is 3 C 2 T x The mass fraction of the nano-sheet in the sulfonated polyphenylene oxide membrane liquid is 0.1-1.0%.
Preferably, in step 2, the substrate may be a glass plate, a polytetrafluoroethylene plate or a polyvinyl chloride plate.
Preferably, in step 2, the film liquid coating process is performed using a doctor blade having a thickness of 500 to 1000 μm.
Preferably, in the step 3, the heating rate of the heat treatment is 10-20 ℃/h, the heat treatment temperature is 80-120 ℃, and the heat treatment time is 1-3 hours.
The high-flux cation exchange membrane is prepared by the method.
The application of the high-flux cation exchange membrane in electrodialysis concentration of salt lake brine can adopt a method comprising the following steps:
(1) The high-flux cation exchange membrane and the commercial anion exchange membrane are arranged in an electrodialysis membrane stack, so that anode chambers and cathode chambers are formed at two sides of the membrane stack, and repeated units with alternately arranged desalting chambers and concentrating chambers are formed between the anode chambers and the cathode chambers. And then the electrodialysis concentration salt lake brine equipment is formed by matching a pump, a direct current power supply, a solution tank (an electrode liquid tank, a desalting chamber tank, a concentrating chamber tank), a piping and the like.
(2) Respectively filling electrode liquid, desalted liquid and concentrated liquid into an electrode liquid tank, a desalting chamber tank and a concentrating chamber tank of the equipment in the step (1), starting pumps, and pumping each solution into a compartment corresponding to the electrodialysis membrane stack for circulation; and (3) starting a direct current power supply, setting constant current or voltage, and concentrating salt lake brine.
(3) And reading the current or voltage value of the direct current power supply every time, and simultaneously sampling and analyzing the ion concentration in the desalting chamber tank and the concentrating chamber tank.
The invention provides a high-flux cation exchange membrane, a preparation method thereof and application thereof in salt lake brine concentration. Compared with the prior art, the method has the following beneficial effects:
(1)Ti 3 C 2 T x the nano-sheet has excellent hydrophilicity and negative charge, and is beneficial to cation migration from the desalting chamber to the concentrating chamber through the cation exchange membrane; in addition, ti 3 C 2 T x The nano-sheet is inorganic and can generate a phase interface with an organic polymer matrix, and the phase interface is beneficial to the transmission of ions through the membrane; therefore, compared with the case where Ti is not added 3 C 2 T x The cation exchange membrane of the nano-sheet has the advantages that the magnesium ion flux of the high-flux cation exchange membrane is increased by at least 90.5 percent, and the lithium ion flux is increased by at least 288.9 percent.
(2) After the high-flux cation exchange membrane is subjected to heat treatment, the ion channels in the membrane become regular, so that the ion flux of the membrane is improved, for example, the heat treatment at 120 ℃ can increase the flux of magnesium ions and lithium ions by 2.5% and 45.3% respectively compared with the heat treatment at 80 ℃.
(3) The high-flux cation exchange membrane has the advantages of simple preparation process, easy operation, less required raw materials, suitability for industrial production, and large ion flux, 55.1 percent of magnesium ion flux and 138.6 percent of lithium ion flux compared with the existing domestic cation membranes and imported cation membranes.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of an apparatus for concentrating salt lake brine using high flux cation exchange membrane electrodialysis in accordance with an embodiment of the invention;
FIG. 2 is a graph of voltage versus time for a high flux cation exchange membrane of an embodiment of the present invention in an electrodialysis concentration salt lake brine application process;
FIG. 3 is a cross-sectional SEM image of a high flux cation exchange membrane obtained in example 1 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The sulfonated polyphenylene ether used in the examples described below had a sulfonation degree of 25%.
Example 1
A method for preparing a high flux cation exchange membrane, comprising the steps of:
(1) Preparation of Ti 3 C 2 T x Nanosheets: 3g of Ti 3 AlC 2 Adding the powder into 60mL of mixed solution (lithium fluoride: 3mol/L, hydrochloric acid: 9 mol/L), heating in 35 ℃ water bath, stirring, and reacting for 48 hours to obtain Ti 3 C 2 T x A suspension; centrifugally washing the suspension for 3 times (the rotating speed is 3500 rpm) by using 1mol/L hydrochloric acid solution, and washing the suspension by using deionized water at the same rotating speed until the pH is more than or equal to 5; shaking to peel the suspension layer, and centrifuging at 4500rpm to obtain single-layer and few-layer Ti 3 C 2 T x Is a suspension of (a); finally, adding trimethylamine solution with the mass fraction of 1% into the suspension to lead Ti to be 3 C 2 T x Coagulation, centrifuging again (at a speed of 6000 rpm), decanting supernatant, and freeze-drying to obtain Ti 3 C 2 T x A nano-sheet.
(2) 1g of sulfonated polyphenylene ether and 0.033g of Ti 3 C 2 T x Adding the nano-sheet into 5.66g of N-methylpyrrolidone to obtain the sulfonated polyphenyl ether with the mass fraction of 15 percent and Ti 3 C 2 T x And the mass fraction of the membrane liquid is 0.5 percent.
(3) And (3) taking 3mL of the film liquid obtained in the step (2), coating the film liquid on a glass plate by using a 750 mu m film scraping knife, and drying the film liquid on a film dryer at 60 ℃ to obtain the film sheet.
(4) The membrane is taken off from the glass plate and placed in an oven, the temperature rising rate of the oven is set to be 15 ℃/h, the temperature is raised to 80 ℃, the membrane is taken out after the temperature is kept for two hours, and then the membrane is soaked in 0.3mol/L sodium sulfate solution for standby.
The application of the high-flux cation exchange membrane obtained in the embodiment in electrodialysis concentration of salt lake brine: the device shown in fig. 1 is adopted, and comprises two anion exchange membranes (one on each of the left side and the right side) and one cation exchange membrane (middle position); the anion exchange membrane was derived from AMVn of Asahi Karakui, the cation exchange membrane was a high flux cation exchange membrane prepared in this example, and the effective area of the individual membrane was S (7.07 cm 2 ) The method comprises the steps of carrying out a first treatment on the surface of the 200mL of 0.3mol/L sodium sulfate solution is introduced into the anode chamber, and the cathode chamber200mL of 0.3mol/L sodium chloride solution is introduced, and simulated brine (200 mL,0.1mol/L lithium chloride solution and 0.1mol/L magnesium chloride solution) is introduced into each of the compartments on both sides of the cation exchange membrane; the direct current power supply is regulated to be in a constant current mode, and the value is 0.1A; and continuously and stably operating for 3 hours, reading the voltage value of the direct current power supply at intervals, and taking the solution in the compartments at the two sides of the cation exchange membrane to analyze the concentration of lithium ions and magnesium ions. Ion flux of membranesThe calculation formula is as follows:
wherein, the liquid crystal display device comprises a liquid crystal display device,and->M in the right-hand compartment (concentrating compartment) of the cation exchange membrane at times t and 0, respectively n+ Concentration, V is the concentrating compartment volume, t is the operating time.
The ion flux of the high flux cation exchange membrane prepared in this example during the application of electrodialysis concentrated brine is shown in table 1, and the voltage-time diagram during the electrodialysis concentrated brine is shown in fig. 2. The flux of magnesium ions and lithium ions of this example (7.88E-08 mol/(m) 2 ·s)、3.53E-08mol/(m 2 S)) are higher than comparative example 1 (3.72E-08 mol/(m) 2 ·s)、9.25E-09mol/(m 2 S) to describe Ti 3 C 2 T x The addition of the nanoplatelets contributes to an increase in ion flux; in addition, the flux of both magnesium ions and lithium ions in this example was higher than that of commercial membrane CMVn (5.83E-08 mol/(m) 2 ·s)、2.54E-08mol/(m 2 S)) and SYMC (5.21E-08 mol/(m) 2 ·s)、2.15E-08mol/(m 2 ·s))。
Example 2
A method for preparing a high flux cation exchange membrane, comprising the steps of:
(1) Preparation of Ti 3 C 2 T x Nanosheets: the same procedure as in example 1 was used.
(2) 1g of sulfonated polyphenylene ether and 0.017g of Ti 3 C 2 T x Adding the nano-sheet into 5.66g of N-methylpyrrolidone to obtain a membrane solution with the mass fraction of sulfonated polyphenylene oxide of 15% and the mass fraction of Ti3C2Tx of 0.25%;
(3) And (3) taking 3mL of the film liquid obtained in the step (2), coating the film liquid on a glass plate by using a 750 mu m film scraping knife, and drying the film liquid on a film dryer at 60 ℃ to obtain the film sheet.
(4) The membrane is taken off from the glass plate and placed in an oven, the temperature rising rate of the oven is set to be 15 ℃/h, the temperature is raised to 80 ℃, the membrane is taken out after the temperature is kept for two hours, and then the membrane is soaked in 0.3mol/L sodium sulfate solution for standby.
In this example, the performance of the resulting high flux cation exchange membrane in electrodialysis concentration salt lake brine was tested in the same manner as in example 1.
The ion flux of the high flux cation exchange membrane prepared in this example during the application of electrodialysis concentrated brine is shown in table 1, and the voltage-time diagram during the electrodialysis concentrated brine is shown in fig. 2. The flux of magnesium ions and lithium ions of this example (7.09E-08 mol/(m) 2 ·s)、3.50E-08mol/(m 2 S) are lower than in example 1 (7.88E-08 mol/(m) 2 ·s)、3.53E-09mol/(m 2 S) to describe Ti 3 C 2 T x The addition amount of the nano-sheets has an influence on the performance of the membrane, and the larger the addition amount is, the larger the ion flux is; the magnesium ion and lithium ion fluxes of this example are higher than those of comparative example 2 (5.65E-08 mol/(m) 2 ·s)、1.92E-08mol/(m 2 S)) indicating that heat treatment at 80 ℃ favors an increase in the ion flux of the membrane; in addition, the magnesium ion and lithium ion fluxes of this example were also higher than those of commercial membrane CMVn (5.83E-08 mol/(m) 2 ·s)、2.54E-08mol/(m 2 S)) and SYMC (5.21E-08 mol/(m) 2 ·s)、2.15E-08mol/(m 2 ·s))。
Example 3
A method for preparing a high flux cation exchange membrane, comprising the steps of:
(1) Preparation of Ti 3 C 2 T x Nanosheets: the same procedure as in example 1 was used.
(2) 1g of sulfonated polyphenylene ether and 0.033g of Ti 3 C 2 T x Adding the nano-sheet into 5.66g of N-methylpyrrolidone to obtain the sulfonated polyphenyl ether with the mass fraction of 15 percent and Ti 3 C 2 T x And the mass fraction of the membrane liquid is 0.5 percent.
(3) And (3) taking 3mL of the film liquid obtained in the step (2), coating the film liquid on a glass plate by using a 750 mu m film scraping knife, and drying the film liquid on a film dryer at 60 ℃ to obtain the film sheet.
(4) And (3) removing the membrane from the glass plate, placing the membrane in an oven, setting the heating rate of the oven to 15 ℃/h, heating to 100 ℃, keeping the temperature for two hours, taking out the membrane, and soaking the membrane in 0.3mol/L sodium sulfate solution for standby.
In this example, the performance of the resulting high flux cation exchange membrane in electrodialysis concentration salt lake brine was tested in the same manner as in example 1.
The ion flux of the high flux cation exchange membrane prepared in this example during the application of electrodialysis concentrated brine is shown in table 1, and the voltage-time diagram during the electrodialysis concentrated brine is shown in fig. 2. The flux of magnesium ions and lithium ions of this example (7.27E-08 mol/(m) 2 ·s)、3.44E-08mol/(m 2 S) are lower than in example 1 (7.88E-08 mol/(m) 2 ·s)、3.53E-09mol/(m 2 S)) that the heat treatment at 100℃causes unstable decomposition of a part of the sulfonic acid groups of the sulfonated polyphenylene ether, thereby causing a decrease in the ion flux of the membrane; in addition, the magnesium ion and lithium ion fluxes of this example were also higher than those of commercial membrane CMVn (5.83E-08 mol/(m) 2 ·s)、2.54E-08mol/(m 2 S)) and SYMC (5.21E-08 mol/(m) 2 ·s)、2.15E-08mol/(m 2 ·s))。
Example 4
A method for preparing a high flux cation exchange membrane, comprising the steps of:
(1) Preparation of Ti 3 C 2 T x Nanosheets: the same procedure as in example 1 was used.
(2) 1g of sulfonated polyphenylene ether and 0.033g of Ti 3 C 2 T x Adding the nano-sheet into 5.66g of N-methylpyrrolidone to obtain the sulfonated polyphenyl ether with the mass fraction of 15 percent and Ti 3 C 2 T x And the mass fraction of the membrane liquid is 0.5 percent.
(3) And (3) taking 3mL of the film liquid obtained in the step (2), coating the film liquid on a glass plate by using a 750 mu m film scraping knife, and drying the film liquid on a film dryer at 60 ℃ to obtain the film sheet.
(4) And (3) removing the membrane from the glass plate, placing the membrane in an oven, setting the heating rate of the oven to 15 ℃/h, heating to 120 ℃, keeping the temperature for two hours, taking out the membrane, and soaking the membrane in 0.3mol/L sodium sulfate solution for standby.
In this example, the performance of the resulting high flux cation exchange membrane in electrodialysis concentration salt lake brine was tested in the same manner as in example 1.
The ion flux of the high flux cation exchange membrane prepared in this example during the application of electrodialysis concentrated brine is shown in table 1, and the voltage-time diagram during the electrodialysis concentrated brine is shown in fig. 2. The magnesium ion and lithium ion fluxes of the present example (8.08E-08 mol/(m) 2 ·s)、5.13E-09mol/(m 2 S) is higher than example 1 (7.88E-08 mol/(m) 2 ·s)、3.53E-09mol/(m 2 S)) that the heat treatment at 120℃leads to unstable decomposition of a part of the sulfonic acid groups of the sulfonated polyphenylene ether, but leads to a structural regularity in the interior of the membrane, thereby increasing the ion flux; in addition, the magnesium ion and lithium ion fluxes of this example were also higher than those of commercial membrane CMVn (5.83E-08 mol/(m) 2 ·s)、2.54E-08mol/(m 2 S)) and SYMC (5.21E-08 mol/(m) 2 ·s)、2.15E-08mol/(m 2 ·s))。
Comparative example 1 (pure SPPO film)
The cation exchange membrane of comparative example 1 is a pure sulfonated polyphenylene ether membrane without Ti3C2Tx nanoplatelets added, and the preparation method comprises the following steps:
(1) 1g of sulfonated polyphenylene ether was added to 5.66. 5.66g N-methylpyrrolidone to obtain a membrane solution with a mass fraction of the sulfonated polyphenylene ether of 15%.
(2) And (3) taking 3mL of the film liquid obtained in the step (1), coating the film liquid on a glass plate by using a 750 mu m film scraping knife, and drying the film liquid on a film dryer at 60 ℃ to obtain the film sheet.
(3) The membrane is taken off from the glass plate and placed in an oven, the temperature rising rate of the oven is set to be 15 ℃/h, the temperature is raised to 80 ℃, the membrane is taken out after the temperature is kept for two hours, and then the membrane is soaked in 0.3mol/L sodium sulfate solution for standby.
This comparative example the performance of the obtained cation exchange membrane in electrodialysis concentration salt lake brine was tested in the same manner as in example 1.
The ion flux during the application of the electrodialysis concentrated brine is shown in table 1, and the voltage-time diagram during the electrodialysis concentrated brine is shown in fig. 2.
Comparative example 2 (without heat treatment)
The cation exchange membrane of comparative example 2 was a cation exchange membrane that had not been heat treated, and the preparation method included the following steps:
(1) Preparation of Ti 3 C 2 T x Nanosheets: the same procedure as in example 1 was used.
(2) 1g of sulfonated polyphenylene ether and 0.017g of Ti 3 C 2 T x Adding the nano-sheet into 5.66g of N-methylpyrrolidone to obtain the sulfonated polyphenyl ether with the mass fraction of 15 percent and Ti 3 C 2 T x And the mass fraction of the membrane liquid is 0.25%.
(3) And (3) taking 3mL of the membrane liquid obtained in the step (2), coating the membrane liquid on a glass plate by using a 750 mu m membrane scraping knife, drying the membrane liquid on a film dryer at 60 ℃ to obtain a membrane, and soaking the membrane in 0.3mol/L sodium sulfate solution for later use.
This comparative example the performance of the obtained cation exchange membrane in electrodialysis concentration salt lake brine was tested in the same manner as in example 1.
The ion flux during the application of the electrodialysis concentrated brine is shown in table 1, and the voltage-time diagram during the electrodialysis concentrated brine is shown in fig. 2.
Comparative example 3 (commercial film CMVn)
Comparative example 3 is a CMVn film produced by the japanese sunburn company.
The ion flux during the application of the electrodialysis concentrated brine was determined in the same manner as in examples 1 to 4 and comparative examples 1 to 2, the results are shown in table 1, and the voltage-time diagram of the electrodialysis concentrated brine in comparative example 3 is shown in fig. 2.
Comparative example 4 (commercial film SYMC)
Comparative example 4 is SYMC film manufactured by the applied America family of cationic membrane technologies Co.
The ion flux during the application of the electrodialysis concentrated brine was determined in the same manner as in examples 1 to 4 and comparative examples 1 to 3, the results are shown in table 1, and the voltage-time diagram of the electrodialysis concentrated brine in comparative example 4 is shown in fig. 2.
Table 1 shows ion flux of the high flux cation exchange membrane of the present invention in the electrodialysis concentrated brine test process
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (9)
1. A method for preparing a high flux cation exchange membrane, comprising the steps of:
step 1, dissolving sulfonated polyphenyl ether in an organic solvent, uniformly stirring, and then adding Ti 3 C 2 T x Preparing nano-sheets into sulfonated polyphenyl ether membrane liquid;
step 2, coating film liquid on a substrate, casting and forming a film, and drying to obtain a film;
and 3, performing heat treatment on the membrane.
2. The method for preparing a high flux cation exchange membrane according to claim 1, wherein: in the step 1, the mass fraction of the sulfonated polyphenylene oxide in the sulfonated polyphenylene oxide membrane liquid is 10-20%.
3. The method for preparing a high flux cation exchange membrane according to claim 1, wherein: in the step 1, the organic solvent is N-methyl pyrrolidone or N, N-dimethylformamide.
4. The method for preparing a high flux cation exchange membrane according to claim 1, wherein: in step 1, the Ti is 3 C 2 T x The mass fraction of the nano-sheet in the sulfonated polyphenylene oxide membrane liquid is 0.1-1.0%.
5. The method for preparing a high flux cation exchange membrane according to claim 1, wherein: in the step 2, the substrate is a glass plate, a polytetrafluoroethylene plate or a polyvinyl chloride plate.
6. The method for preparing a high flux cation exchange membrane according to claim 1, wherein: in the step 2, the film liquid coating process is realized by using a film scraping knife with the thickness of 500-1000 mu m.
7. The method for preparing a high flux cation exchange membrane according to claim 1, wherein: in the step 3, the heating rate of the heat treatment is 10-20 ℃/h, the heat treatment temperature is 80-120 ℃, and the heat treatment time is 1-3 hours.
8. A high flux cation exchange membrane made by the method of any one of claims 1 to 7.
9. Use of the high flux cation exchange membrane of claim 8 in electrodialysis concentration of salt lake brine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310837223.2A CN116603396A (en) | 2023-07-10 | 2023-07-10 | High-flux cation exchange membrane and application thereof in electrodialysis concentration of salt lake brine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310837223.2A CN116603396A (en) | 2023-07-10 | 2023-07-10 | High-flux cation exchange membrane and application thereof in electrodialysis concentration of salt lake brine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116603396A true CN116603396A (en) | 2023-08-18 |
Family
ID=87674948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310837223.2A Pending CN116603396A (en) | 2023-07-10 | 2023-07-10 | High-flux cation exchange membrane and application thereof in electrodialysis concentration of salt lake brine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116603396A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116808832A (en) * | 2023-08-29 | 2023-09-29 | 杭州匠容道环境科技有限公司 | Method and device for producing lithium hydroxide by displacement electrodialysis process |
-
2023
- 2023-07-10 CN CN202310837223.2A patent/CN116603396A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116808832A (en) * | 2023-08-29 | 2023-09-29 | 杭州匠容道环境科技有限公司 | Method and device for producing lithium hydroxide by displacement electrodialysis process |
| CN116808832B (en) * | 2023-08-29 | 2023-12-22 | 杭州匠容道环境科技有限公司 | Method and device for producing lithium hydroxide by displacement electrodialysis process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Guo et al. | Prefractionation of LiCl from concentrated seawater/salt lake brines by electrodialysis with monovalent selective ion exchange membranes | |
| CN104524976B (en) | A kind of electric nanofiltration device for one/multivalent ion Selective Separation | |
| KR102070243B1 (en) | Sea water desalination system | |
| AU2019200391A1 (en) | Electrochemical desalination system | |
| CN110217931B (en) | Recycling treatment process for waste acid | |
| CN107720786A (en) | A kind of LITHIUM BATTERY lithium hydroxide preparation method based on UF membrane coupled method | |
| CN107720785A (en) | A kind of LITHIUM BATTERY lithium hydroxide preparation method based on UF membrane coupled method | |
| CN116603396A (en) | High-flux cation exchange membrane and application thereof in electrodialysis concentration of salt lake brine | |
| Ying et al. | Layer-by-layer assembly of cation exchange membrane for highly efficient monovalent ion selectivity | |
| KR102186074B1 (en) | Concentration method of lithium by electrodialysis | |
| CN113262648B (en) | Lithium ion selective permeation membrane and application thereof | |
| CN109701397B (en) | Application of two-dimensional MXene membrane prepared by electrophoretic deposition method in ion interception | |
| Lee et al. | Comparison of the property of homogeneous and heterogeneous ion exchange membranes during electrodialysis process | |
| NZ556310A (en) | Increased conductivity and enhanced electrolytic and electrochemical processes | |
| CN110902898B (en) | Device and method for removing nitrogen and phosphorus in sewage by magnesium anode electrodialysis method | |
| CN106823815A (en) | Electrodialysis plant | |
| CN108218101A (en) | A kind of high saliferous gas water low-cost processes and method of resource | |
| CN113694733B (en) | Lithium separation method based on bipolar membrane electrodialysis device | |
| CN102992522B (en) | Desalination system and method | |
| CN110773240A (en) | Preparation method of cation exchange membrane with high temperature resistance and organic solvent resistance | |
| CN107930420B (en) | Hydrophobic acid-resistant high-conductivity anion exchange membrane and preparation method thereof | |
| CN112588327A (en) | Preparation method and application of organic solvent-resistant cation exchange membrane | |
| Ahmed et al. | Effect of pretreatment of Carbon based electrodes in their adsorption performance in capacitive deionization | |
| CN114405286A (en) | Ion-crosslinked amphoteric ion exchange membrane, preparation method and application thereof in selective electrodialysis | |
| CN105502596A (en) | Method for processing waste water in carrageenan production technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |