CN111188050B - Ultrathin perfluorinated sulfonic acid ion exchange membrane for alkali chloride electrolysis and preparation method thereof - Google Patents
Ultrathin perfluorinated sulfonic acid ion exchange membrane for alkali chloride electrolysis and preparation method thereof Download PDFInfo
- Publication number
- CN111188050B CN111188050B CN201911418374.4A CN201911418374A CN111188050B CN 111188050 B CN111188050 B CN 111188050B CN 201911418374 A CN201911418374 A CN 201911418374A CN 111188050 B CN111188050 B CN 111188050B
- Authority
- CN
- China
- Prior art keywords
- ion exchange
- sulfonic acid
- membrane
- perfluorinated sulfonic
- perfluorinated
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
- C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2287—After-treatment
- C08J5/2293—After-treatment of fluorine-containing membranes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/02—Diaphragms; Spacing elements characterised by shape or form
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08J2300/102—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention belongs to the technical field of ion exchange membranes, and particularly relates to an ultrathin perfluorinated sulfonic acid ion exchange membrane for alkali chloride electrolysis and a preparation method thereof. The ultrathin perfluorinated sulfonic acid ion exchange membrane for alkali metal chloride electrolysis comprises a perfluorinated sulfonic acid polymer layer, wherein a functional surface coating is coated on the surface of the perfluorinated sulfonic acid polymer layer, the functional surface coating is composed of a perfluorinated polymer and has a porous rough structure, and the porous non-woven polymer layer is embedded in the perfluorinated sulfonic acid polymer layer. The invention adopts the ultrathin porous non-woven polymer as a reinforcing material, so that the membrane has better mechanical property and lower membrane resistance. The perfluorinated sulfonic acid polymer with the ion conduction function can improve the surface roughness of the membrane, further improve the anti-foaming performance of the membrane, is suitable for running in a zero polar distance electrolytic cell under the novel high current density condition, and can obviously reduce the cell voltage. The preparation method provided by the invention has simple and reasonable process and is easy for industrial production.
Description
Technical Field
The invention belongs to the technical field of ion exchange membranes, and particularly relates to an ultrathin perfluorinated sulfonic acid ion exchange membrane for alkali chloride electrolysis and a preparation method thereof.
Background
Ion exchange membranes have been widely used in electrolytic oxidation and reduction operations due to their excellent permselectivity. The use of perfluorinated ion exchange membranes in the salt electrolysis industry has led to a revolutionary change in the chlor-alkali industry. In addition, the method has wide application in the fields of potassium carbonate preparation by potassium chloride electrolysis, sodium carbonate preparation by sodium chloride electrolysis, sodium sulfite preparation by sodium chloride electrolysis, caustic soda preparation by sodium sulfate electrolysis, sulfuric acid preparation and the like. Ion exchange membranes are known as "chips" for electrolysis, and therefore the development of ion exchange membranes with lower power consumption and more durability has been the direction of effort. The mechanical strength of the membrane can be effectively improved by adding the reinforcing net into the membrane, and the durability of the membrane is improved; the cell voltage can be effectively reduced by reducing the cell spacing between the anode and cathode. However, when the distance between the electrodes is reduced to a certain distance, bubbles generated during the electrolysis are easily adhered to the surface of the membrane and are difficult to release because the membrane is tightly attached to the electrodes. A large number of bubbles are gathered on the surface of the membrane to block a current channel, so that the effective electrolysis area of the membrane is reduced, the local polarization effect is obviously increased, and the cell pressure is increased.
To overcome the disadvantages associated with bubble adhesion, and to allow rapid release of adhered bubbles from the membrane surface, hydrophilic coating methods have been developed. In the chlor-alkali industry, a layer of inorganic micro-nano particles and resin with an ion conduction function are prepared on the surface of a double-layer membrane, so that the surface of the membrane is roughened, and the adhesion of bubbles can be effectively reduced. Patents CA2446448 and CA2444585 describe the preparation of rough hydrophilic coatings using inorganic materials as fillers, and patent CN104018182 describes the preparation of rough hydrophilic coatings using fluorine-containing resin particles as fillers. In order to achieve sufficient roughness, 40 to 90% of inorganic oxide particles or fluorine-containing resin particles are contained as a filler in the volume of the coating layer, but the inorganic oxide particles or fluorine-containing resin particles themselves have no function of conducting ions. A large amount of inorganic oxide particles and fluorine-containing resin particles without ion conductivity obstruct an ion transmission path and increase membrane resistance.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the defects of the prior art are overcome, the ultrathin perfluorinated sulfonic acid ion exchange membrane for the electrolysis of the alkali metal chloride is provided, the ultrathin perfluorinated sulfonic acid ion exchange membrane has better mechanical property and lower membrane resistance, is suitable for a zero-polar-distance electrolytic cell under a novel high-current density condition, can effectively reduce the cell voltage, reduce the electrolysis energy consumption, reduce the production cost, reduce the thickness of a base membrane and enlarge the application field of the ultrathin perfluorinated sulfonic acid ion exchange membrane. Meanwhile, the preparation method is scientific and reasonable and is suitable for industrial production.
The ultrathin perfluorinated sulfonic acid ion exchange membrane for alkali metal chloride electrolysis comprises a perfluorinated sulfonic acid polymer layer, wherein a functional surface coating is coated on the surface of the perfluorinated sulfonic acid polymer layer, the functional surface coating is composed of a perfluorinated polymer and has a porous rough structure, and the porous non-woven polymer layer is embedded in the perfluorinated sulfonic acid polymer layer.
The thickness of the perfluorinated sulfonic acid polymer layer is 10-80 μm, preferably 20-60 μm, and the ion exchange capacity is 0.6-1.5mmol/g, preferably 0.8-1.2 mmol/g.
The surface and the inside of the functional surface coating do not contain metal oxide and consist of perfluoropolymer with ion exchange function, the perfluoropolymer is one or more of perfluorosulfonic acid polymer, perfluorocarboxylic acid polymer or perfluorophosphoric acid polymer, preferably perfluorosulfonic acid polymer, and the Ion Exchange Capacity (IEC) of the perfluoropolymer is 0.5-1.5mmol/g, preferably 0.8-1.1 mmol/g.
The functional surface coating has a porous rough structure inside and on the surface, pores can be distributed on the surface of the coating or inside the coating or in a designated area, the pores can be in a regular or irregular structure such as regular or irregular round, oval, square, rectangle and the like which are orderly or disorderly arranged, the volume of the pores accounts for 5-95%, preferably 50-80% of the volume of the functional surface coating, the coating thickness is 10nm-30 μm, preferably 500nm-10 μm, the raised or recessed porous rough surface formed by perfluoropolymer, the surface roughness Ra value of the functional surface coating is 10nm-5 μm, preferably 50nm-2 μm, and the surface roughness Ra value of the functional surface coating is 300nm-10 μm, preferably 1-5 μm.
The porous non-woven polymer layer is made of one or more of polytetrafluoroethylene, polyvinylidene fluoride, polyimide and polyether ether ketone, the thickness is 3-50 mu m, preferably 10-40 mu m, and the porosity is 20-99%, preferably 60-80%.
The functional surface coating has extremely low bubble adhesion in 0-300g/L saline water environment, and the adhesion of 3 mu L of bubbles and the functional surface coating is 0-400 mu N, preferably 0-120 mu N.
The functional surface coating has a 5 mu L bubble contact angle of more than or equal to 130 degrees in 250g/L saline environment at 25 ℃.
The preparation method of the ultrathin perfluorinated sulfonic acid ion exchange membrane for alkali chloride electrolysis comprises the following steps:
(1) obtaining a perfluorinated ion exchange resin base membrane from perfluorinated sulfonic acid resin in an extrusion casting mode, and compounding the porous non-woven polymer membrane with the perfluorinated ion exchange resin base membrane after soaking treatment by using a solvent so as to form a perfluorinated sulfonic acid ion exchange membrane precursor;
(2) carrying out overpressure treatment on the perfluorinated sulfonic acid ion exchange resin base membrane obtained in the step (1), and then carrying out hydrolysis treatment in an alkali metal hydroxide solution to convert the perfluorinated sulfonic acid ion exchange resin base membrane into a perfluorinated ion exchange membrane with an ion exchange function;
(3) adding the perfluoropolymer into a solvent for homogenization treatment to form a perfluoropolymer solution;
(4) adding a pore-forming agent into the perfluoropolymer solution obtained in the step (3), and performing ball milling to obtain a dispersion liquid;
(5) and (3) attaching the dispersion liquid obtained in the step (4) to the surface of the perfluorinated ion exchange membrane with the ion exchange function obtained in the step (2) in a coating mode, and etching the surface to form a porous rough structure after drying and curing.
In the step (2), when the hydrolysis treatment is carried out in the alkali metal hydroxide solution, an organic solvent can be added to swell the membrane so as to accelerate the hydrolysis reaction rate, wherein the organic solvent is one or a mixture of more than one of dimethyl sulfoxide, dimethyl formamide, propanol, ethanol or ethylene glycol. In which the functional groups in the membrane are converted to-SO3Na, forming an ion exchange membrane with ion cluster channels.
The solvent used in step (3) is a polar solvent, and is usually one or more selected from water, low-boiling monohydric alcohol, dihydric alcohol, and nitrogen-containing organic solvent.
The pore-forming agent in the step (4) is one or a composition of more than one of silicon oxide, aluminum oxide, zinc oxide, titanium oxide, potassium carbonate, silicon carbide, sodium carbonate, polytrimethylene terephthalate fiber, polyurethane fiber, polyvinylidene fluoride and polyethylene terephthalate fiber.
The film coating mode in the step (5) is one of spraying, brushing, roller coating, transfer printing, dipping or spin coating; the etching is one or more of alkaline hydrolysis, acid hydrolysis and hydrolysis.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts the ultrathin porous non-woven polymer as a reinforcing material to prepare the ultrathin perfluorinated sulfonic acid ion exchange membrane suitable for electrolysis, so that the perfluorinated sulfonic acid ion exchange membrane has better mechanical property and lower membrane resistance.
2. The invention adopts the perfluorosulfonic acid polymer with the ion conduction function to improve the surface roughness of the membrane and further improve the anti-foaming performance of the membrane.
3. The ultrathin perfluorinated sulfonic acid ion exchange membrane prepared by the invention is suitable for running in a novel zero-polar-distance electrolytic cell under a high-current density condition, and can obviously reduce the cell voltage.
4. The preparation method provided by the invention has simple and reasonable process and is easy for industrial production.
Detailed Description
The present invention will be further described with reference to the following examples.
The starting materials used in the examples are commercially available unless otherwise specified.
Example 1
The preparation method of the ultrathin perfluorinated sulfonic acid ion exchange membrane for alkali chloride electrolysis comprises the following steps:
(1) adding 1.08mmol/g of perfluorosulfonic acid resin IEC into a mixed solution prepared from ethanol and isopropanol according to a weight ratio of 1:1 to prepare 10wt% perfluorosulfonic acid resin solution, soaking a polytetrafluoroethylene porous non-woven membrane with the thickness of 5 microns into a trifluorotrichloroethane solvent subjected to ultrasonic treatment for 1.5 hours, taking out the porous non-woven membrane and drying the porous non-woven membrane, fixing the porous non-woven membrane on a prepared simple frame, coating the perfluorosulfonic acid resin solution on two sides of the porous non-woven membrane by spraying, and drying and forming to form a perfluorosulfonic acid ion exchange membrane precursor with the perfluorosulfonic acid resin layer thickness of 10 microns;
(2) performing overpressure treatment on the perfluorinated ion exchange membrane precursor prepared in the step (1) at the temperature of 180 ℃ and under the pressure of 120 tons and at the speed of 45 m/min by using an overpressure machine, and after the overpressure treatment, immersing the perfluorinated ion exchange membrane precursor into a mixed aqueous solution containing 18wt% of dimethyl sulfoxide and 20wt% of NaOH at the temperature of 85 ℃ for transformation for 80 minutes to convert the perfluorinated ion exchange membrane precursor into a perfluorinated ion exchange membrane with an ion exchange function;
(3) preparing ethanol and isopropanol into a mixed solution according to the weight ratio of 1:1, adding perfluorinated sulfonic acid resin with the exchange capacity of 1.2mmol/g, and treating for 3 hours at 230 ℃ in a closed reaction kettle to obtain a uniform perfluorinated sulfonic acid solution with the weight percent of 5;
(4) adding ZnO particles with the average particle size of 50nm and NaCl particles with the average particle size of 700nm into the perfluorosulfonic acid solution obtained in the step (3) according to the mass ratio of 2:1, and performing ball milling for 36 hours to obtain a 10wt% dispersion solution;
(5) adopting a spraying method, attaching the dispersion liquid obtained in the step (4) to the surfaces of the two sides of the perfluorinated ion exchange membrane base membrane with the ion exchange function obtained in the step (2), wherein the average thickness of the coating is 4.0 mu m, and drying the coating at 150 ℃ for 2 hours;
(6) and (3) treating the film containing the coating obtained in the step (5) in a 10wt% NaOH solution for 3 hours at normal temperature.
Performance testing
The surface roughness Ra of the prepared perfluorinated sulfonic acid ion exchange membrane is 350nm at 10 mu m multiplied by 10 mu m, and the surface roughness Ra of the prepared perfluorinated sulfonic acid ion exchange membrane is 3.6 mu m at 240 mu m multiplied by 300 mu m. The adhesion was 80. mu.N in 250g/L NaCl solution, measured with 3. mu.L air bubbles.
The prepared perfluorosulfonic acid ion exchange membrane is subjected to an electrolysis test of a sodium chloride aqueous solution in an electrolytic cell, 290g/L of the sodium chloride aqueous solution is supplied to an anode chamber, water is supplied to a cathode chamber, and the discharge of the sodium chloride aqueous solution from the anode chamber is ensuredThe concentration of sodium chloride is 200g/L, and the concentration of sodium hydroxide discharged from the cathode chamber is 30 percent; the test temperature was 80 ℃ and the current density was 6.5kA/m2After 60 days of electrolysis experiments, the average cell pressure is 3.31V, and the average current efficiency is 99.5%.
The sheet resistance of the resulting film was measured to be 0.2. omega. cm by the standard SJ/T10171.5 method-2。
Comparative example 1
An ion membrane-based film and a perfluorosulfonic acid solution were prepared in the same manner as in example 1, and thereafter a dispersion was prepared in the same manner, except that ZnO particles having an average particle size of 500nm and NaCl particles having an average particle size of 700nm were replaced with ZrO particles having an average particle size of 500nm and 700nm2The particles were homogenized in a ball mill to form a dispersion having a content of 10 wt%. A perfluorosulfonic acid ion-exchange membrane was obtained in the same manner as in example 1.
Performance testing
The surface roughness Ra of the prepared perfluorinated sulfonic acid ion exchange membrane is 110nm at 10 mu m multiplied by 10 mu m, 2.5 mu m at 240 mu m multiplied by 300 mu m, and the adhesion is 190 mu N measured by 3 mu L of air bubbles in 250g/L NaCl solution.
An electrolytic test of a sodium chloride solution was carried out under the same conditions as in example 1, and after an electrolytic experiment for 35 days, the average cell pressure was 3.5V, the average current efficiency was 99.5%, and the sheet resistance was 0.26. omega. cm-2。
Example 2
The preparation method of the ultrathin perfluorinated sulfonic acid ion exchange membrane for alkali chloride electrolysis comprises the following steps:
(1) adding 0.7mmol/g of perfluorosulfonic acid resin IEC into a mixed solution prepared from ethanol and isopropanol according to a weight ratio of 1:1 to prepare a 10wt% perfluorosulfonic acid resin solution, soaking a polytetrafluoroethylene porous non-woven membrane with the thickness of 5 microns into a trifluorotrichloroethane solvent subjected to ultrasonic treatment for 1.5 hours, taking out the porous non-woven membrane, drying, fixing the porous non-woven membrane on a prepared simple frame, coating the perfluorosulfonic acid resin solution on two sides of the porous non-woven membrane by spraying, and drying and forming to form a perfluorosulfonic acid ion exchange membrane precursor with the perfluorosulfonic acid resin layer thickness of 80 microns;
(2) performing overpressure treatment on the perfluorinated ion exchange membrane precursor prepared in the step (1) at the temperature of 180 ℃ and under the pressure of 120 tons and at the speed of 45 m/min by using an overpressure machine, and after the overpressure treatment, immersing the perfluorinated ion exchange membrane precursor into a mixed aqueous solution containing 18wt% of dimethyl sulfoxide and 20wt% of NaOH at the temperature of 85 ℃ for transformation for 80 minutes to convert the perfluorinated ion exchange membrane precursor into a perfluorinated ion exchange membrane with an ion exchange function;
(3) preparing ethanol and isopropanol into a mixed solution according to the weight ratio of 1:1, adding perfluorinated sulfonic acid resin with the exchange capacity of 1.2mmol/g, and treating for 3 hours at 230 ℃ in a closed reaction kettle to obtain a uniform perfluorinated sulfonic acid solution with the weight percent of 5;
(4) adding NaCl particles with the average particle size of 1.5 mu m into the perfluorosulfonic acid solution in the step (3), and performing ball milling for 36 hours to obtain a 10wt% dispersion solution;
(5) adopting a spraying method, attaching the dispersion liquid obtained in the step (4) to the surfaces of the two sides of the perfluorinated ion exchange membrane base membrane with the ion exchange function obtained in the step (2), wherein the average thickness of the coating is 7.0 mu m, and drying the coating at 150 ℃ for 2 hours;
(6) and (3) treating the film containing the coating obtained in the step (5) in an aqueous solution at normal temperature for 3 hours.
Performance testing
The surface roughness Ra of the prepared perfluorinated sulfonic acid ion exchange membrane is 1200nm at 10 mu m multiplied by 10 mu m, and the surface roughness Ra of the prepared perfluorinated sulfonic acid ion exchange membrane is 5.2 mu m at 240 mu m multiplied by 300 mu m. The adhesion was measured in 250g/L NaCl solution with 3. mu.L air bubbles and was 50. mu.N.
Carrying out an electrolysis test on the prepared perfluorosulfonic acid ion exchange membrane in an electrolytic cell by using a sodium chloride aqueous solution, wherein 290g/L of the sodium chloride aqueous solution is supplied to an anode chamber, water is supplied to a cathode chamber, and the concentration of sodium chloride discharged from the anode chamber is ensured to be 200g/L and the concentration of sodium hydroxide discharged from the cathode chamber is ensured to be 30%; the test temperature was 80 ℃ and the current density was 3.5kA/m2After 60 days of electrolysis experiments, the average cell pressure is 2.61V, and the average current efficiency is 99.1%.
The sheet resistance of the resulting film was 0.42. omega. as measured by Standard SJ/T10171.5 method·cm-2。
Comparative example 2
An ion membrane-based membrane and a perfluorosulfonic acid solution were prepared in the same manner as in example 2, and thereafter a dispersion was prepared in the same manner, except that NaCl particles having an average particle size of 1.5 μm were replaced with ZrO particles having an average particle size of 1.5 μm2The particles were homogenized in a ball mill to form a dispersion having a content of 10 wt%. A perfluorosulfonic acid ion-exchange membrane was obtained in the same manner as in example 2.
Performance testing
The surface roughness Ra of the prepared perfluorosulfonic acid ion exchange membrane is 950nm at 10 mu m multiplied by 10 mu m, the surface roughness Ra of the prepared perfluorosulfonic acid ion exchange membrane is 4.2 mu m at 240 mu m multiplied by 300 mu m, and the adhesion is 185 mu N measured by 3 mu L of air bubbles in 250g/L NaCl solution.
An electrolytic test of a sodium chloride solution was carried out under the same conditions as in example 1, and after an electrolytic experiment for 35 days, the average cell pressure was 2.90V, the average current efficiency was 99.5%, and the sheet resistance was 0.49. omega. cm-2。
The performance data for the perfluorosulfonic acid ion exchange membranes prepared in examples 1-2 and comparative examples 1-2 are shown in Table 1.
TABLE 1 Performance data for perfluorosulfonic acid ion exchange membranes prepared in examples 1-2 and comparative examples 1-2
Of course, the foregoing is only a preferred embodiment of the invention and should not be taken as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit and scope of the present invention should be construed as being included in the scope of the present invention.
Claims (1)
1. A preparation method of an ultrathin perfluorinated sulfonic acid ion exchange membrane for alkali chloride electrolysis is characterized by comprising the following steps: the method comprises the following steps:
(1) adding perfluorinated sulfonic acid resin with IEC =1.08mmol/g into a mixed solution prepared from ethanol and isopropanol according to a weight ratio of 1:1 to prepare a 10wt% perfluorinated sulfonic acid resin solution, soaking a polytetrafluoroethylene porous non-woven membrane with the thickness of 5 microns into a trifluorotrichloroethane solvent subjected to ultrasonic treatment for 1.5 hours, taking out and drying the polytetrafluoroethylene porous non-woven membrane, fixing the porous non-woven membrane on a prepared simple frame, coating the perfluorinated sulfonic acid resin solution on two sides of the porous non-woven membrane by spraying, and drying and forming to form a perfluorinated sulfonic acid ion exchange membrane precursor with the thickness of the perfluorinated sulfonic acid resin layer of 10 microns;
(2) performing overpressure treatment on the perfluorinated ion exchange membrane precursor prepared in the step (1) at the temperature of 180 ℃ and under the pressure of 120 tons and at the speed of 45 m/min by using an overpressure machine, and after the overpressure treatment, immersing the perfluorinated ion exchange membrane precursor into a mixed aqueous solution containing 18wt% of dimethyl sulfoxide and 20wt% of NaOH at the temperature of 85 ℃ for transformation for 80 minutes to convert the perfluorinated ion exchange membrane precursor into a perfluorinated ion exchange membrane with an ion exchange function;
(3) preparing ethanol and isopropanol into a mixed solution according to the weight ratio of 1:1, adding perfluorinated sulfonic acid resin with the exchange capacity of 1.2mmol/g, and treating for 3 hours at 230 ℃ in a closed reaction kettle to obtain a uniform perfluorinated sulfonic acid solution with the weight percent of 5;
(4) adding ZnO particles with the average particle size of 50nm and NaCl particles with the average particle size of 700nm into the perfluorosulfonic acid solution obtained in the step (3) according to the mass ratio of 2:1, and performing ball milling for 36 hours to obtain a 10wt% dispersion solution;
(5) adopting a spraying method, attaching the dispersion liquid obtained in the step (4) to the surfaces of the two sides of the perfluorinated ion exchange membrane base membrane with the ion exchange function obtained in the step (2), wherein the average thickness of the coating is 4.0 mu m, and drying the coating at 150 ℃ for 2 hours;
(6) and (3) treating the film containing the coating obtained in the step (5) in a 10wt% NaOH solution for 3 hours at normal temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911418374.4A CN111188050B (en) | 2019-12-31 | 2019-12-31 | Ultrathin perfluorinated sulfonic acid ion exchange membrane for alkali chloride electrolysis and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911418374.4A CN111188050B (en) | 2019-12-31 | 2019-12-31 | Ultrathin perfluorinated sulfonic acid ion exchange membrane for alkali chloride electrolysis and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111188050A CN111188050A (en) | 2020-05-22 |
| CN111188050B true CN111188050B (en) | 2021-07-09 |
Family
ID=70705997
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911418374.4A Active CN111188050B (en) | 2019-12-31 | 2019-12-31 | Ultrathin perfluorinated sulfonic acid ion exchange membrane for alkali chloride electrolysis and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111188050B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117543039A (en) * | 2022-08-02 | 2024-02-09 | 北京清驰科技有限公司 | Coating liquid for proton exchange membrane and preparation method and application thereof |
| CN115364905A (en) * | 2022-08-20 | 2022-11-22 | 西藏旭升矿业开发有限公司 | Recyclable electrode liquid ion exchange membrane and preparation method thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE808542A (en) * | 1972-12-12 | 1974-06-12 | Asahi Chemical Ind | DIAPHRAGM MEMBRANE OF NEW STRUCTURE |
| US4003818A (en) * | 1974-02-08 | 1977-01-18 | Rhone-Poulenc Industries | Method of obtaining a micro-porous membrane and novel product thus obtained |
| CN85109358A (en) * | 1984-11-30 | 1986-08-27 | 旭硝子株式会社 | Multi-layered diaphragm for electrolysis |
| JPS62146926A (en) * | 1985-12-20 | 1987-06-30 | Asahi Glass Co Ltd | Fluorine-containing cation exchange membrane for electrolysis |
| JPS62199629A (en) * | 1986-02-28 | 1987-09-03 | Asahi Glass Co Ltd | Novel multi-layer permeable membrane for electrolysis |
| JPS62247093A (en) * | 1986-04-18 | 1987-10-28 | Asahi Glass Co Ltd | Novel multilayered diaphragm |
| JPS62277433A (en) * | 1986-05-27 | 1987-12-02 | Asahi Glass Co Ltd | Reinforced ion-exchange membrane |
| JP2000256486A (en) * | 1999-03-09 | 2000-09-19 | Asahi Chem Ind Co Ltd | Reinforced cation exchange membrane |
| JP2000297164A (en) * | 1999-04-13 | 2000-10-24 | Asahi Chem Ind Co Ltd | Ion-exchange film and its preparation |
| CN102596411A (en) * | 2009-10-26 | 2012-07-18 | 旭化成化学株式会社 | Cation-exchange membrane, electrolytic cell utilizing same and method for producing cation-exchange membrane |
| CN104018180A (en) * | 2014-06-06 | 2014-09-03 | 山东东岳高分子材料有限公司 | Zero-polar-distance ion exchange membrane and preparation method thereof |
| CN105322119A (en) * | 2014-07-28 | 2016-02-10 | 中国科学院大连化学物理研究所 | Application of porous diaphragm in lithium sulfur secondary battery |
| CN107916436A (en) * | 2016-10-06 | 2018-04-17 | 旭化成株式会社 | Amberplex |
-
2019
- 2019-12-31 CN CN201911418374.4A patent/CN111188050B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE808542A (en) * | 1972-12-12 | 1974-06-12 | Asahi Chemical Ind | DIAPHRAGM MEMBRANE OF NEW STRUCTURE |
| US4003818A (en) * | 1974-02-08 | 1977-01-18 | Rhone-Poulenc Industries | Method of obtaining a micro-porous membrane and novel product thus obtained |
| CN85109358A (en) * | 1984-11-30 | 1986-08-27 | 旭硝子株式会社 | Multi-layered diaphragm for electrolysis |
| JPS62146926A (en) * | 1985-12-20 | 1987-06-30 | Asahi Glass Co Ltd | Fluorine-containing cation exchange membrane for electrolysis |
| JPS62199629A (en) * | 1986-02-28 | 1987-09-03 | Asahi Glass Co Ltd | Novel multi-layer permeable membrane for electrolysis |
| JPS62247093A (en) * | 1986-04-18 | 1987-10-28 | Asahi Glass Co Ltd | Novel multilayered diaphragm |
| JPS62277433A (en) * | 1986-05-27 | 1987-12-02 | Asahi Glass Co Ltd | Reinforced ion-exchange membrane |
| JP2000256486A (en) * | 1999-03-09 | 2000-09-19 | Asahi Chem Ind Co Ltd | Reinforced cation exchange membrane |
| JP2000297164A (en) * | 1999-04-13 | 2000-10-24 | Asahi Chem Ind Co Ltd | Ion-exchange film and its preparation |
| CN102596411A (en) * | 2009-10-26 | 2012-07-18 | 旭化成化学株式会社 | Cation-exchange membrane, electrolytic cell utilizing same and method for producing cation-exchange membrane |
| CN104018180A (en) * | 2014-06-06 | 2014-09-03 | 山东东岳高分子材料有限公司 | Zero-polar-distance ion exchange membrane and preparation method thereof |
| CN105322119A (en) * | 2014-07-28 | 2016-02-10 | 中国科学院大连化学物理研究所 | Application of porous diaphragm in lithium sulfur secondary battery |
| CN107916436A (en) * | 2016-10-06 | 2018-04-17 | 旭化成株式会社 | Amberplex |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111188050A (en) | 2020-05-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111188065A (en) | Enhanced perfluorinated sulfonic acid ion exchange membrane for chloride electrolysis and preparation method thereof | |
| CN111188050B (en) | Ultrathin perfluorinated sulfonic acid ion exchange membrane for alkali chloride electrolysis and preparation method thereof | |
| CN104018181B (en) | Ionic conduction membrane for chlor-alkali industry and preparation method thereof | |
| CN111074295B (en) | Novel low-resistance ion conduction membrane for chlor-alkali industry and preparation method thereof | |
| WO2015184571A1 (en) | Ion-conducting membrane and preparation method therefor | |
| CN111188060B (en) | Diaphragm of reinforced low-resistance chlor-alkali electrolytic cell and preparation method thereof | |
| CN111041514A (en) | Enhanced low-resistance chlor-alkali perfluorinated ion exchange membrane and preparation method thereof | |
| CN111074297A (en) | Electrolytic cell diaphragm for chlor-alkali industry and preparation method thereof | |
| CN111188064B (en) | Enhanced perfluorinated sulfonic acid ion exchange membrane for alkali chloride electrolysis and preparation method thereof | |
| CN111101152B (en) | Perfluorocarboxylic acid ion exchange membrane with rough coating and preparation method thereof | |
| CN111188061A (en) | Perfluorosulfonic acid ion exchange membrane and preparation method thereof | |
| CN111020630B (en) | Ultrathin perfluorocarboxylic acid ion exchange membrane with bubble-dispelling function and preparation method thereof | |
| CN111188063B (en) | Novel low-resistance ion conduction membrane for chlor-alkali industry and preparation method thereof | |
| CN111074299B (en) | Ultrathin perfluorinated sulfonic acid ion exchange membrane for alkali metal chloride electrolysis and preparation method thereof | |
| CN111074296B (en) | Air bubble dispersing coating with ion conduction function and preparation method thereof | |
| CN111118541B (en) | Ultrathin low-resistance chlor-alkali perfluorinated ion exchange membrane and preparation method thereof | |
| CN111188059B (en) | Novel ultrathin low-resistance ion conduction membrane for chlor-alkali industry and preparation method thereof | |
| CN111118542B (en) | Ultrathin perfluorocarboxylic acid ion exchange membrane with rough coating and preparation method thereof | |
| CN111118543A (en) | Enhanced perfluorocarboxylic acid ion exchange membrane with bubble-dispelling function and preparation method thereof | |
| CN104592540A (en) | A preparing method of a perfluorosulfonic acid-carboxylic acid composite membrane by multilayer solution tape casting | |
| CN111041524A (en) | Ultrathin low-resistance chlor-alkali electrolytic cell diaphragm and preparation method thereof | |
| CN111074298B (en) | Perfluorosulfonic acid ion exchange membrane for chloride electrolysis and preparation method thereof | |
| CN112126355B (en) | Preparation method of coating solution for ion exchange membrane | |
| CN111041513A (en) | Perfluoro ion membrane for chlor-alkali industry and preparation method thereof | |
| CN111020629A (en) | Perfluorocarboxylic acid ion exchange membrane with bubble-dispelling function and preparation method thereof |
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 | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 256401 Zibo Huantai County, Shandong Province, Tangshan town Dongyue Fluorosilicic Industrial Park Applicant after: Shandong Dongyue future hydrogen energy materials Co.,Ltd. Address before: 256401 Zibo Huantai County, Shandong Province, Tangshan town Dongyue Fluorosilicic Industrial Park Applicant before: Shandong Dongyue future hydrogen energy materials Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20201113 Address after: 256401 Tangshan Town, Huantai County, Zibo, Shandong Applicant after: SHANDONG DONGYUE POLYMER MATERIAL Co.,Ltd. Address before: 256401 Zibo Huantai County, Shandong Province, Tangshan town Dongyue Fluorosilicic Industrial Park Applicant before: Shandong Dongyue future hydrogen energy materials Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |