CN114917777B - Preparation method of firm and organic solvent-resistant cation exchange membrane - Google Patents
Preparation method of firm and organic solvent-resistant cation exchange membrane Download PDFInfo
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- CN114917777B CN114917777B CN202210532470.7A CN202210532470A CN114917777B CN 114917777 B CN114917777 B CN 114917777B CN 202210532470 A CN202210532470 A CN 202210532470A CN 114917777 B CN114917777 B CN 114917777B
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- 239000012528 membrane Substances 0.000 title claims abstract description 62
- 238000005341 cation exchange Methods 0.000 title claims abstract description 31
- 239000003960 organic solvent Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229920000271 Kevlar® Polymers 0.000 claims abstract description 21
- 239000004761 kevlar Substances 0.000 claims abstract description 21
- 239000002121 nanofiber Substances 0.000 claims abstract description 17
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 16
- 108010025899 gelatin film Proteins 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000010612 desalination reaction Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 72
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 48
- 239000011259 mixed solution Substances 0.000 claims description 18
- 238000007790 scraping Methods 0.000 claims description 14
- 239000012634 fragment Substances 0.000 claims description 12
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000011976 maleic acid Substances 0.000 claims description 8
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 7
- 159000000000 sodium salts Chemical class 0.000 claims description 7
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000000909 electrodialysis Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000003014 ion exchange membrane Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 238000011033 desalting Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000007605 air drying Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
Images
Classifications
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- 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
- B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
-
- 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
- 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
-
- 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
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a method for preparing a firm and organic solvent-resistant cation exchange membrane, which comprises the following steps: film preparation; immersing the scraped film into pure water immediately for phase conversion for 15-45 minutes to obtain a gel film; the gel film is washed by pure water until the pH of the washing liquid reaches 5 to 8. The beneficial effects of the invention are as follows: the material shows excellent stability and organic solvent resistance due to the existence of hydrogen bonds, intermolecular pi-pi bonds and the like among the Kevlar nanofibers, so that the Kevlar nanofibers are applied to the field of ion exchange membrane materials; the preparation process is simple and convenient, the operation is easy, and the preparation method is nontoxic and environment-friendly; the prepared cation exchange membrane has an interpenetrating network structure, has the performance of resisting organic solvents and has high desalination performance; the Polyethyleneimine (PEI) is added in the preparation process, so that the mechanical strength of the cation exchange membrane is improved, the stability of the membrane is enhanced, and the service life of the membrane is prolonged.
Description
Technical Field
The invention belongs to the field of ion exchange membranes, and particularly relates to a preparation method of a firm and organic solvent-resistant cation exchange membrane.
Background
With the rapid progress of technology, the development of advanced composite membranes for ion energy extraction or ion removal of high-purity organic solvents for high-technology industrial production has received great attention. In particular, the ion exchange membrane, which is a core element of electrodialysis technology, has unique advantages in terms of ion desalination or high-concentration brine concentration, etc., as compared with other pressure-driven membranes. Ion exchange membranes are mainly divided into anion exchange membranes and cation exchange membranes, and are currently used in the processes of desalination, salt concentration, salt extraction and the like.
However, due to the limitation of complex components of the water environment, the traditional ion exchange membrane material cannot meet the increasingly updated actual industrial requirements. The current cation exchange membrane may be chemically degraded in the environment of strong organic solvent aqueous solution, so that the ion exchange capacity is reduced, and the ion desalting performance is affected. This phenomenon greatly causes failure of the membrane function, limiting the application of the membrane; meanwhile, the service life of the membrane is also reduced, and the cost for replacing the membrane is increased. For example, the inclusion of small amounts of salts in organic solvent solutions can result in reduced device performance during the fabrication of high-end, high-precision, technology material devices using organic solvent etching.
Thus, finding and designing suitable membrane materials for preparing strong and organic solvent resistant cation exchange membranes has become an ongoing need for development.
The Kevlar nanofiber is an ultra-tough material and has wide application in the fields of aerospace, body armor manufacturing, high-temperature-resistant and organic corrosion-resistant protective clothing and the like.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of a cation exchange membrane which is firm and resistant to organic solvents.
The preparation method of the cation exchange membrane which is firm and resistant to organic solvents comprises the following steps:
step 1, film making;
step 1.1, mixing poly (4-styrenesulfonic acid-co-maleic acid) sodium salt and polyethyleneimine with deionized water according to the mass ratio of (0.3:1) - (5:1) for a set period of time at room temperature to obtain PSSMA aqueous solution with the mass concentration of 50% -100%; the sodium salt of poly (4-styrenesulfonic acid-co-maleic acid), also known as poly (4-styrenesulfonic acid-co-maleic acid), abbreviated PSSMA; polyethylenimine abbreviated PEI;
step 1.2, sequentially adding potassium hydroxide and dimethyl sulfoxide with set mass fractions into PSSMA aqueous solution, and stirring in an oil bath at 50-100 ℃ for 15-60 minutes to obtain mixed solution; the mass fraction of the potassium hydroxide is 1-20% and the mass fraction of the dimethyl sulfoxide is 80-99% based on 100% of the total mass of the potassium hydroxide and the dimethyl sulfoxide;
step 1.3, adding Kevlar nanofiber fragments into the mixed solution obtained in the step 1.2, and continuously stirring and rectifying for 10-30 hours at 50-100 ℃ to obtain a casting solution; scraping the film casting solution on a horizontally placed dry glass plate to prepare a film; the mass consumption of the Kevlar nanofiber fragments is 0.5-6% of the total mass consumption of potassium hydroxide and dimethyl sulfoxide;
step 2, immediately immersing the film obtained by scraping in the step 1.3 into pure water for phase conversion for 15-45 minutes to obtain a gel film; washing the gel film with pure water until the pH of the washing liquid reaches 5-8; then immersing the gel membrane into a mixed solution of 4-amino-2, 6-tetramethylpiperidine-1-oxyl free radical (ATTO), 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC.HCl) and N-hydroxysuccinimide (NHS) with set concentration and sealing, taking out the gel membrane after immersing the gel membrane for 24-96 hours, and drying to obtain the cation exchange membrane.
Preferably, in the step 1.1, poly (4-styrenesulfonic acid-co-maleic acid) sodium salt and polyethyleneimine are mixed with deionized water for 5 to 45 minutes according to the mass ratio of (0.5:1) to (4:1), so as to obtain PSSMA aqueous solution with the mass concentration of 67 to 90 percent; sequentially adding potassium hydroxide and dimethyl sulfoxide with set mass fractions into PSSMA aqueous solution in step 1.2, and stirring in an oil bath at 60-80 ℃ for 30-60 minutes; in the step 1.2, the mass fraction of the potassium hydroxide is 2-8% and the mass fraction of the dimethyl sulfoxide is 92-98% based on 100% of the total mass of the potassium hydroxide and the dimethyl sulfoxide.
Preferably, the poly (4-styrenesulfonic acid-co-maleic acid) sodium salt and polyethyleneimine are mixed with deionized water for 15 minutes; potassium hydroxide and dimethyl sulfoxide with set mass fractions are added into PSSMA water solution in sequence, and then stirred in an oil bath at 70 ℃.
Preferably, the amount of the Kevlar nanofiber fragments added in the step 1.3 is 1% -5% of the total mass amount of potassium hydroxide and dimethyl sulfoxide, and the Kevlar nanofiber fragments are continuously stirred and rectified for 15-25 hours at 60-80 ℃ after being added.
Preferably, the amount of the added Kevlar nanofiber chips is 4.2% of the total mass amount of potassium hydroxide and dimethyl sulfoxide, and the Kevlar nanofiber chips are continuously stirred and rectified at 70 ℃ for 20 hours after being added.
Preferably, the step 2 is: immersing the film obtained by scraping in the step 1.3 into pure water immediately for phase conversion for 20-40 minutes to obtain a gel film; washing the gel film with pure water until the pH of the washing liquid reaches 6-7; then immersing the gel membrane into a mixed solution of 1-5 g/L of 4-amino-2, 6-tetramethyl piperidine-1-oxygen free radical, 0.1-5 g/L of 1-ethyl-3- (3-dimethyl amino propyl) carbodiimide hydrochloride and 0.1-5 g/L of N-hydroxysuccinimide and sealing, taking out the gel membrane and drying after immersing the gel membrane for 30-90 hours, thus obtaining the cation exchange membrane.
Preferably, the gel film is immersed in a mixed solution of 3.5g/L of 4-amino-2, 6-tetramethylpiperidine-1-oxyl, 1.5g/L of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 0.8g/L of N-hydroxysuccinimide and sealed.
The application method of the cation exchange membrane is applied to electrodialysis desalination, and the salt to be removed is NaCl and Na 2 SO 4 At least one of them.
The beneficial effects of the invention are as follows:
the material shows excellent stability and organic solvent resistance due to the existence of hydrogen bonds, intermolecular pi-pi bonds and the like among the Kevlar nanofibers, so that the Kevlar nanofibers are applied to the field of ion exchange membrane materials; the preparation process is simple and convenient, the operation is easy, and the preparation method is nontoxic and environment-friendly; the prepared cation exchange membrane has an interpenetrating network structure, and has the performance of resisting organic solvents and high desalination performance.
The Polyethyleneimine (PEI) is added in the preparation process, so that the mechanical strength of the cation exchange membrane is improved, the stability of the membrane is enhanced, and the service life of the membrane is prolonged.
Drawings
FIG. 1 is a bar graph of the mechanical strength of a cation exchange membrane prepared according to the present invention;
FIG. 2 is a bar graph of ion exchange capacity and water cut of ion exchange membranes prepared in accordance with the present invention;
FIG. 3 is a graph showing the desalting efficiency of the ion exchange membrane prepared according to the present invention after soaking in an organic solution (acetone) for 72 hours.
Detailed Description
The invention is further described below with reference to examples. The following examples are presented only to aid in the understanding of the invention. It should be noted that it will be apparent to those skilled in the art that modifications can be made to the present invention without departing from the principles of the invention, and such modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
Example 1
1.0g PSSMA and 1.0g PEI were weighed out and dissolved in 1.0. 1.0g H 2 O was added to a 250mL round bottom flask and a clean magnetic stirrer was added and stirred on a magnetic stirrer for 15 minutes; after 15 minutes, 3.0g of potassium hydroxide and 45g of dimethyl sulfoxide are added into a round-bottom flask, the round-bottom flask is placed into an oil bath, the temperature of the oil bath is controlled to be 70 ℃, and magnetic stirring is started; after 30 minutes, adding 2.0g of Kevlar fiber fragments into the mixed solution of the round-bottom flask, and keeping the temperature of 70 ℃ for continuous stirring and rectification; after 20 hours, the clean and dry glass plate is put into a horizontal constant temperature and constant humidity operation box, the temperature of the operation box is regulated and controlled to 25 ℃, the humidity is 10 percent, the thickness of a film scraping knife is 250 mu m, and the glass plate is fedAnd scraping the film. Immersing the scraped film immediately in 5L of pure water; after the phase inversion was completed for 30 minutes, the film was washed with pure water until the pH reached 7, and then immersed in a mixed solution of 3.5g/L ATTO,1.5 g/LEDC. HCl and 0.8g/L NHS and sealed; after 48 hours, the membrane was leveled in a forced air drying oven at 45℃and after 12 hours, the membrane was taken out to obtain a cation exchange membrane having an interpenetrating network structure and having high desalting performance and designated M-1.0.
Example 2
Weigh 3.0g PSSMA and 1.0g PEI in 1.0g H 2 O was added to a 250mL round bottom flask and a clean magnetic stirrer was added and stirred on a magnetic stirrer for 15 minutes; after 15 minutes, 3.0g of potassium hydroxide and 45g of dimethyl sulfoxide are added into a round-bottom flask, the round-bottom flask is placed into an oil bath, the temperature of the oil bath is controlled to be 70 ℃, and magnetic stirring is started; after 30 minutes, adding 2.0g of Kevlar fiber fragments into the mixed solution of the round-bottom flask, and keeping the temperature of 70 ℃ for continuous stirring and rectification; after 20 hours, the clean and dry glass plate is placed in a horizontal constant temperature and constant humidity operation box, the temperature of the operation box is regulated and controlled to 25 ℃, the humidity is 10%, the thickness of a film scraping knife is 250 mu m, and film scraping is carried out on the glass plate. Immersing the scraped film immediately in 5L of pure water; after the phase inversion was completed for 30 minutes, the film was washed with pure water until the pH reached 7, and then immersed in a mixed solution of 3.5g/L ATTO,1.5 g/LEDC. HCl and 0.8g/L NHS and sealed; after 48 hours, the membrane was leveled in a forced air drying oven at 45℃and after 12 hours, the membrane was taken out to obtain a cation exchange membrane having an interpenetrating network structure and having high desalting performance and designated M-3.0.
Example 3
Weigh 4.5g PSSMA with 1.0g PEI in 1.0. 1.0g H 2 O was added to a 250mL round bottom flask and a clean magnetic stirrer was added and stirred on a magnetic stirrer for 15 minutes; after 15 minutes, 3.0g of potassium hydroxide and 45g of dimethyl sulfoxide are added into a round-bottom flask, the round-bottom flask is placed into an oil bath, the temperature of the oil bath is controlled to be 70 ℃, and magnetic stirring is started; after 30 minutes, adding 2.0g of Kevlar fiber fragments into the mixed solution of the round-bottom flask, and keeping the temperature of 70 ℃ for continuous stirring and rectification;after 20 hours, the clean and dry glass plate is placed in a horizontal constant temperature and constant humidity operation box, the temperature of the operation box is regulated and controlled to 25 ℃, the humidity is 10%, the thickness of a film scraping knife is 250 mu m, and film scraping is carried out on the glass plate. Immersing the scraped film immediately in 5L of pure water; after the phase inversion was completed for 30 minutes, the film was washed with pure water until the pH reached 7, and then immersed in a mixed solution of 3.5g/L ATTO,1.5 g/LEDC. HCl and 0.8g/L NHS and sealed; after 48 hours, the membranes were flattened in a forced air drying oven at 45℃and after 12 hours the membranes were removed, thus obtaining cation exchange membranes with interpenetrating network structure and high desalination performance and designated M-4.5.
Example 4
Weigh 6.0g PSSMA and 1.0g PEI in 1.0g H 2 O was added to a 250mL round bottom flask and a clean magnetic stirrer was added and stirred on a magnetic stirrer for 15 minutes; after 15 minutes, 3.0g of potassium hydroxide and 45g of dimethyl sulfoxide are added into a round-bottom flask, the round-bottom flask is placed into an oil bath, the temperature of the oil bath is controlled to be 70 ℃, and magnetic stirring is started; after 30 minutes, adding 2.0g of Kevlar fiber fragments into the mixed solution of the round-bottom flask, and keeping the temperature of 70 ℃ for continuous stirring and rectification; after 20 hours, the clean and dry glass plate is placed in a horizontal constant temperature and constant humidity operation box, the temperature of the operation box is regulated and controlled to 25 ℃, the humidity is 10%, the thickness of a film scraping knife is 250 mu m, and film scraping is carried out on the glass plate. Immersing the scraped film immediately in 5L of pure water; after the phase inversion was completed for 30 minutes, the film was washed with pure water until the pH reached 7, and then immersed in a mixed solution of 3.5g/L ATTO,1.5 g/LEDC. HCl and 0.8g/L NHS and sealed; after 48 hours, the membrane was placed flat in a forced air drying oven at 45℃and after 12 hours, the membrane was taken out to give a cation exchange membrane having an interpenetrating network structure and having high desalting performance and designated M-6.0.
The mechanical strength bar charts of the ion exchange membranes prepared in examples 1 to 4 are shown in fig. 1, and the ion exchange capacity and water content bar charts of the ion exchange membranes prepared in examples 1 to 4 are shown in fig. 2.
Example 5
The ion exchange membranes prepared in examples 1-4 were immersed in an organic solution acetone for 72 hours, and the desalting efficiency was as shown in FIG. 3.
Claims (8)
1. A process for the preparation of a strong and organic solvent resistant cation exchange membrane comprising the steps of:
step 1, film making;
step 1.1, mixing poly (4-styrenesulfonic acid-co-maleic acid) sodium salt and polyethyleneimine with deionized water according to the mass ratio of (0.3:1) - (5:1) for a set period of time at room temperature to obtain PSSMA aqueous solution with the mass concentration of 50% -100%;
step 1.2, sequentially adding potassium hydroxide and dimethyl sulfoxide with set mass fractions into PSSMA aqueous solution, and stirring in an oil bath at 50-100 ℃ for 15-60 minutes to obtain mixed solution; the mass fraction of the potassium hydroxide is 1-20% and the mass fraction of the dimethyl sulfoxide is 80-99% based on 100% of the total mass of the potassium hydroxide and the dimethyl sulfoxide;
step 1.3, adding Kevlar nanofiber fragments into the mixed solution obtained in the step 1.2, and continuously stirring and rectifying for 10-30 hours at 50-100 ℃ to obtain a casting solution; scraping the film casting solution on a horizontally placed dry glass plate to prepare a film; the mass consumption of the Kevlar nanofiber fragments is 0.5-6% of the total mass consumption of potassium hydroxide and dimethyl sulfoxide;
step 2, immediately immersing the film obtained by scraping in the step 1.3 into pure water for phase conversion for 15-45 minutes to obtain a gel film; washing the gel film with pure water until the pH of the washing liquid reaches 5-8; then immersing the gel membrane into a mixed solution of 4-amino-2, 6-tetramethyl piperidine-1-oxygen free radical, 1-ethyl-3- (3-dimethyl amino propyl) carbodiimide hydrochloride and N-hydroxyl succinimide with set concentration, sealing, immersing the gel membrane for 24-96 hours, taking out the gel membrane and drying to obtain the cation exchange membrane.
2. The method for preparing a firm and organic solvent resistant cation exchange membrane according to claim 1, wherein in the step 1.1, poly (4-styrenesulfonic acid-co-maleic acid) sodium salt and polyethyleneimine are mixed with deionized water for 5 to 45 minutes according to the mass ratio of (0.5:1) to (4:1) to obtain PSSMA aqueous solution with the mass concentration of 67 to 90 percent; sequentially adding potassium hydroxide and dimethyl sulfoxide with set mass fractions into PSSMA aqueous solution in step 1.2, and stirring in an oil bath at 60-80 ℃ for 30-60 minutes; in the step 1.2, the mass fraction of the potassium hydroxide is 2-8% and the mass fraction of the dimethyl sulfoxide is 92-98% based on 100% of the total mass of the potassium hydroxide and the dimethyl sulfoxide.
3. The method for preparing a strong and organic solvent resistant cation exchange membrane according to claim 2, wherein the mixing time of poly (4-styrenesulfonic acid-co-maleic acid) sodium salt and polyethyleneimine with deionized water is 15 minutes; potassium hydroxide and dimethyl sulfoxide with set mass fractions are added into PSSMA water solution in sequence, and then stirred in an oil bath at 70 ℃.
4. The method for preparing a strong and organic solvent resistant cation exchange membrane according to claim 1, wherein the amount of the Kevlar nanofiber fragments added in the step 1.3 is 1% -5% of the total mass amount of potassium hydroxide and dimethyl sulfoxide, and the Kevlar nanofiber fragments are continuously stirred and rectified for 15-25 hours at 60-80 ℃.
5. The method of preparing a strong and organic solvent resistant cation exchange membrane according to claim 4, wherein the amount of the added Kevlar nanofiber chips is 4.2% of the total mass of potassium hydroxide and dimethyl sulfoxide, and the Kevlar nanofiber chips are continuously stirred and rectified at 70 ℃ for 20 hours.
6. The method of preparing a strong and organic solvent resistant cation exchange membrane according to claim 1, wherein step 2 is: immersing the film obtained by scraping in the step 1.3 into pure water immediately for phase conversion for 20-40 minutes to obtain a gel film; washing the gel film with pure water until the pH of the washing liquid reaches 6-7; then immersing the gel membrane into a mixed solution of 1-5 g/L of 4-amino-2, 6-tetramethyl piperidine-1-oxygen free radical, 0.1-5 g/L of 1-ethyl-3- (3-dimethyl amino propyl) carbodiimide hydrochloride and 0.1-5 g/L of N-hydroxysuccinimide and sealing, taking out the gel membrane and drying after immersing the gel membrane for 30-90 hours, thus obtaining the cation exchange membrane.
7. The method for preparing a strong and organic solvent resistant cation exchange membrane according to claim 1, wherein: the gel film was immersed in a mixed solution of 3.5g/L of 4-amino-2, 6-tetramethylpiperidine-1-oxyl, 1.5g/L of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 0.8g/L of N-hydroxysuccinimide and sealed.
8. A method of using the cation exchange membrane prepared by the method of any one of claims 1 to 7, wherein: applied to electrodialysis desalination, the salt to be removed is NaCl and Na 2 SO 4 At least one of them.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210532470.7A CN114917777B (en) | 2022-05-12 | 2022-05-12 | Preparation method of firm and organic solvent-resistant cation exchange membrane |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210532470.7A CN114917777B (en) | 2022-05-12 | 2022-05-12 | Preparation method of firm and organic solvent-resistant cation exchange membrane |
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| CN114917777A CN114917777A (en) | 2022-08-19 |
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| GB1493164A (en) * | 1975-02-03 | 1977-11-23 | Tokuyama Sola Kk | Electrolytic diaphragms and method of electrolysis using the same |
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| GB905101A (en) * | 1961-01-27 | 1962-09-05 | Wolfen Filmfab Veb | Process for separating a mixture of gases into fractions by selective permeation through membranes |
| US7550216B2 (en) * | 1999-03-03 | 2009-06-23 | Foster-Miller, Inc. | Composite solid polymer electrolyte membranes |
| CN101905125B (en) * | 2010-07-21 | 2012-06-27 | 杭州水处理技术研究开发中心有限公司 | Preparation method of polystyrolsulfon acid salt/polyethyleneimine crosslinking nanofiltration membrane |
| CN108219170A (en) * | 2017-12-31 | 2018-06-29 | 浙江工业大学 | A kind of preparation and application using the crosslinked PECH/nylon composite anion exchange membranes of PEI |
| CN109758917B (en) * | 2018-09-18 | 2021-07-02 | 张伟 | Preparation method of divalent cation selective ion exchange membrane |
| CN110449048B (en) * | 2019-07-30 | 2022-04-22 | 南京工业大学 | Nanofiltration membrane, preparation method and dye separation method |
| CN112588327A (en) * | 2020-10-23 | 2021-04-02 | 浙江工业大学 | Preparation method and application of organic solvent-resistant cation exchange membrane |
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| GB1493164A (en) * | 1975-02-03 | 1977-11-23 | Tokuyama Sola Kk | Electrolytic diaphragms and method of electrolysis using the same |
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