CN111188065A - Enhanced perfluorinated sulfonic acid ion exchange membrane for chloride electrolysis and preparation method thereof - Google Patents
Enhanced perfluorinated sulfonic acid ion exchange membrane for chloride electrolysis and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of ion exchange membranes, and particularly relates to a reinforced perfluorinated sulfonic acid ion exchange membrane for chloride electrolysis and a preparation method thereof. The perfluorosulfonic acid ion exchange membrane comprises a perfluorosulfonic acid polymer layer, wherein a functional surface coating is coated on the surface of the perfluorosulfonic acid polymer layer, the functional surface coating is composed of perfluoropolymer and has a porous rough structure, a reinforcing material layer is embedded in the perfluorosulfonic acid polymer layer, and the reinforcing material layer is provided with a hollowed-out tunnel structure. The perfluorinated ion polymer with the ion conduction function is adopted to replace a perfluorinated sulfonic acid coating containing metal oxides in the existing product, and meanwhile, the porous channel formed can improve the surface roughness of the membrane, so that the anti-foaming performance of the membrane is improved.
Description
Technical Field
The invention belongs to the technical field of ion exchange membranes, and particularly relates to a reinforced perfluorinated sulfonic acid ion exchange membrane for chloride electrolysis and a preparation method thereof.
Background
Ion exchange membranes have excellent permselectivity and have been widely used in electrolytic oxidation and reduction operations. 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. As a high energy consumption industry, the development of lower power consumption electrolysis technology has been the direction of effort. With the development of technology, the cell voltage can be effectively reduced by reducing the cell gap between the anode and the 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.
Patent CN104018182 describes the preparation of a rough hydrophilic coating using particles of a fluorine-containing resin as filler. 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.
At present, perfluorosulfonic acid ion exchange membranes all have the problems of high exchange capacity, low mechanical strength, high mechanical strength and low exchange capacity. In addition, in practical application, the requirements on the mechanical strength and the service life of the diaphragm are quite high, and the existing perfluorinated sulfonic acid ion exchange membrane cannot meet the requirements.
In CN102024928A, polytetrafluoroethylene mesh cloth is used as a reinforcing material to increase the mechanical strength of the base film, but the reinforcing material inevitably increases the resistance of the base film, which affects the ion exchange capacity of the base film.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the reinforced perfluorinated sulfonic acid ion exchange membrane for chloride electrolysis has good mechanical properties, low membrane resistance and capability of meeting higher requirements; meanwhile, the invention also provides a preparation method of the compound, which is scientific, reasonable, simple and easy to operate and is suitable for industrial production.
The reinforced perfluorosulfonic acid ion exchange membrane for chloride electrolysis comprises a perfluorosulfonic acid polymer layer, wherein a functional surface coating is coated on the surface of the perfluorosulfonic acid polymer layer, the functional surface coating is composed of perfluoropolymer and has a porous rough structure, a reinforcing material layer is embedded in the perfluorosulfonic acid polymer layer, and the reinforcing material layer is provided with a hollow tunnel structure.
The thickness of the perfluorinated sulfonic acid polymer layer is 50-250 μm, preferably 70-200 μm, and the Ion Exchange Capacity (IEC) 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 perfluorinated sulfonic acid polymer layer contains criss-cross hollow tunnels; the distance between two adjacent main fibers in the reinforcing material net is 0.5-1.5mm, and the two adjacent main fibers contain 32-500 hollow tunnels; the diameter of the single tunnel is 1 to 50 μm, preferably 5 to 20 μm. The tunnel is in the shape of regular or irregular circle, ellipse, square, triangle and the like. The hollow tunnels can be arranged in a single way or can be formed by twisting a plurality of hollow tunnels to form a large channel.
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 reinforced perfluorinated sulfonic acid ion exchange membrane for chloride electrolysis comprises the following steps:
(1) obtaining a perfluorinated ion exchange resin base membrane from perfluorinated sulfonic acid resin by adopting an extrusion casting mode, and compounding a reinforcing material net 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.
The reinforcing material net in the step (1) is formed by weaving perfluorocarbon reinforcing threads and hydrocarbon polymer soluble threads, has a porosity of 20-99%, preferably 60-80%, and a thickness of 40-200 μm, preferably 50-100 μm.
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 forms an ion exchange membrane with an ion cluster channel, and meanwhile, a dissolving and discarding line in the reinforcing material net is dissolved and discarded in the step to form a hollow tunnel structure.
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 perfluorinated polymer reinforcing net is added in the perfluorinated sulfonic acid membrane, and the hollow tunnel is prepared in the membrane, so that the perfluorinated sulfonic acid membrane has better mechanical property and lower membrane resistance.
2. The invention adopts the perfluorinated ionic polymer with the ion conduction function to replace the perfluorinated sulfonic acid coating containing metal oxide in the existing product, and the porous channel formed at the same time can improve the surface roughness of the membrane, thereby improving the anti-foaming performance of the membrane.
3. The 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 is scientific and reasonable, simple and easy to operate, and 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 reinforced perfluorinated sulfonic acid ion exchange membrane for chloride electrolysis comprises the following steps:
(1) obtaining a perfluorinated ion exchange resin base membrane by adopting a perfluorinated sulfonic acid resin extrusion casting mode with IEC (1.08 mmol/g), wherein the thickness of the perfluorinated sulfonic acid resin layer is 100 mu m, soaking a reinforcing material net compounded and woven by polytetrafluoroethylene and silk into a trifluoro trichloroethane solvent subjected to ultrasonic treatment for 1.5 hours, wherein the thickness of a porous reinforcing material is 50 mu m, the volume ratio of the polytetrafluoroethylene to the silk is 1:1, the porosity of the reinforcing material net is 30%, taking out, drying, and then compounding with the perfluorinated ion exchange resin base membrane in a rolling mode to form a perfluorinated sulfonic acid ion exchange membrane precursor;
(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 at the speed of 45 m/min by using an overpressure machine, immersing the perfluorinated ion exchange membrane precursor into a mixed aqueous solution containing 18 wt% of dimethyl sulfoxide and 20 wt% of NaOH at the temperature of 85 ℃ for transformation for 80 minutes after the overpressure treatment, converting the perfluorinated ion exchange membrane precursor into a perfluorinated ion exchange membrane with an ion exchange function, and simultaneously dissolving and discarding silk in a reinforcing material net to form a hollowed-out tunnel structure; in the obtained ion exchange membrane, the distance between two adjacent main fibers in the reinforcing material net is 1.0 +/-0.2 mm, and the two adjacent main fibers contain 468 hollow tunnels; the diameter of the single tunnel is 3 +/-0.5 mu m;
(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 3;
(4) adding ZnO particles with the average particle size of 50nm into the perfluorosulfonic acid solution in the step (3), and performing ball milling for 36 hours to obtain a 10 wt% 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 4.5 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 10 wt% NaOH solution for 3 hours at normal temperature.
Performance testing
The surface roughness Ra of the prepared perfluorinated sulfonic acid ion exchange membrane is 260nm 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 mu m at 240 mu m multiplied by 300 mu m. The adhesion was measured to be 75. mu.N in 250g/L NaCl solution using 3. mu.L of air bubbles.
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 70 ℃ and the current density was 6.5kA/m2After 60 days of electrolysis experiments, the average cell pressure is 3.01V, and the average current efficiency is 98.5%.
According to the standardThe sheet resistance of the film obtained by the SJ/T10171.5 method test was 0.55. omega. cm-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 then a dispersion was prepared in the same manner, except that ZnO particles having an average particle size of 50nm were replaced with ZrO particles having an average particle size of 50nm2The 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 prepared perfluorosulfonic acid ion-exchange membrane had a surface roughness Ra of 10. mu. m.times.10 μm of 50nm and a surface roughness Ra of 240. mu. m.times.300 μm of 3 μm, and had an adhesion of 180. mu.N as measured by 3. mu.L of air bubbles in 250g/L of 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 3.2V, the average current efficiency was 99.5%, and the sheet resistance was 0.62. omega. cm-2。
Example 2
The preparation method of the reinforced perfluorinated sulfonic acid ion exchange membrane for chloride electrolysis comprises the following steps:
(1) obtaining a perfluorinated ion exchange resin base membrane by adopting a perfluorinated sulfonic acid resin extrusion casting mode with IEC (0.75 mmol/g), wherein the thickness of the perfluorinated sulfonic acid resin layer is 250 mu m, soaking a reinforced material net compounded and woven by polytetrafluoroethylene and silk into a trifluoro trichloroethane solvent subjected to ultrasonic treatment for 1.5 hours, wherein the thickness of a porous reinforced material is 100 mu m, the volume ratio of the polytetrafluoroethylene to the silk is 1:2, the porosity of the reinforced material net is 20%, taking out, drying and then compounding the reinforced material net with the perfluorinated ion exchange resin base membrane in a rolling mode, thereby forming a perfluorinated sulfonic acid ion exchange membrane precursor;
(2) performing overpressure treatment on the perfluorinated ion exchange membrane precursor prepared in the step (1) at the temperature of 210 ℃ and under the pressure of 100 tons at the speed of 45 m/min by using an overpressure machine, immersing the perfluorinated ion exchange membrane precursor into a mixed aqueous solution containing 15 wt% of dimethyl sulfoxide and 15 wt% of NaOH at the temperature of 80 ℃ for transformation for 80 minutes after the overpressure treatment, converting the perfluorinated ion exchange membrane precursor into a perfluorinated ion exchange membrane with an ion exchange function, and simultaneously dissolving and discarding silk in a reinforcing material net to form a hollowed-out tunnel structure; in the obtained ion exchange membrane, the distance between two adjacent main fibers in the reinforcing material net is 1.2 +/-0.2 mm, and the two adjacent main fibers contain 315 hollow tunnels; the diameter of the single tunnel is 5 +/-1 mu m.
(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 1.5mmol/g, and treating for 4 hours at 240 ℃ in a closed reaction kettle to obtain a uniform perfluorinated sulfonic acid solution with the weight percent of 10;
(4) adding polytrimethylene terephthalate resin particles with the average particle size of 1 mu m and ZnO nanoparticles with the particle size of 200nm into the perfluorosulfonic acid solution obtained in the step (3) according to the mass ratio of 1:1, and performing ball milling for 42 hours to obtain a 30 wt% 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 6 mu m, and drying at 150 ℃ for 2 hours;
(6) the film containing the coating obtained in step (5) was treated in a 10 wt% NaOH solution at 60 ℃ for 1 hour.
Performance testing
The surface roughness Ra of the prepared perfluorinated sulfonic acid ion exchange membrane is 210nm at 10 mu m multiplied by 10 mu m, and the surface roughness Ra of the prepared perfluorinated sulfonic acid ion exchange membrane is 4 mu m at 240 mu m multiplied by 300 mu m. The adhesion was measured to be 92. mu.N in 250g/L NaCl solution using 3. mu.L of air bubbles.
Carrying out an electrolysis test of a potassium chloride aqueous solution on the prepared perfluorinated sulfonic acid ion exchange membrane in an electrolytic cell, supplying 250g/L of the potassium chloride aqueous solution to an anode chamber, supplying water to a cathode chamber, and ensuring that the concentration of sodium chloride discharged from the anode chamber is 200g/L and the concentration of potassium hydroxide discharged from the cathode chamber is 29%; the test temperature was 65 ℃ and the current density was 5.0kA/m2After 60 days of electrolysis experiments, the average cell pressure is 3.26V, and the average current efficiency is 99.1%.
According to the standard SJ/T10171.5 methodThe surface resistance of the obtained film was 1.3. omega. cm by the method-2。
Comparative example 2
An ion membrane-based film and a perfluorosulfonic acid solution were prepared in the same manner as in example 2, and then a dispersion was prepared in the same manner, except that 1 μm zirconia powder and 200nm zirconia powder were used in the dispersion instead of 1 μm polytrimethylene terephthalate resin particles and 200nm ZnO nanoparticles in a mass ratio of 1:1, and homogenization treatment was performed 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 prepared perfluorosulfonic acid ion-exchange membrane had a surface roughness Ra of 10. mu. m.times.10 μm of 112nm and a surface roughness Ra of 240. mu. m.times.300 μm of 8 μm, and had an adhesion of 210. mu.N measured by 3. mu.L of air bubbles in 250g/L of NaCl solution.
An electrolytic test of a potassium chloride solution was carried out under the same conditions as in example 2, and after an electrolytic experiment for 60 days, the average cell pressure was 3.50V, the average current efficiency was 98.1%, and the sheet resistance was 1.7. 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 (10)
1. A reinforced perfluorinated sulfonic acid ion exchange membrane for chloride electrolysis is characterized in that: the coating comprises a perfluorosulfonic acid polymer layer, wherein a functional surface coating is coated on the surface of the perfluorosulfonic acid polymer layer, the functional surface coating is composed of perfluoropolymer and has a porous rough structure, a reinforcing material layer is embedded in the perfluorosulfonic acid polymer layer, and the reinforcing material layer is provided with a hollow tunnel structure.
2. The enhanced perfluorosulfonic acid ion exchange membrane for chloride electrolysis according to claim 1, wherein: the thickness of the perfluorinated sulfonic acid polymer layer is 50-250 mu m, and the ion exchange capacity is 0.6-1.5 mmol/g.
3. The enhanced perfluorosulfonic acid ion exchange membrane for chloride electrolysis according to claim 1, wherein: the functional surface coating is composed of perfluoropolymer with ion exchange function, the perfluoropolymer is one or more of perfluorosulfonic acid polymer, perfluorocarboxylic acid polymer or perfluorophosphoric acid polymer, and the ion exchange capacity of the perfluoropolymer is 0.5-1.5 mmol/g.
4. The enhanced perfluorosulfonic acid ion exchange membrane for chloride electrolysis according to claim 1, wherein: the interior and the surface of the functional surface coating are both porous rough structures, the volume of the pores accounts for 5-95% of the volume of the functional surface coating, the thickness of the coating is 10nm-30 μm, the surface roughness Ra value of the functional surface coating is 10nm-5 μm, and the surface roughness Ra value of the functional surface coating is 240 μm-300 μm and is 300nm-10 μm.
5. The enhanced perfluorosulfonic acid ion exchange membrane for chloride electrolysis according to claim 1, wherein: the perfluorinated sulfonic acid polymer layer contains criss-cross hollow tunnels; the distance between two adjacent main fibers in the reinforcing material net is 0.5-1.5mm, and the two adjacent main fibers contain 32-500 hollow tunnels; the diameter of the single tunnel is 1-50 μm.
6. The enhanced perfluorosulfonic acid ion exchange membrane for chloride electrolysis according to claim 1, wherein: the functional surface coating has the adhesion force of 3 mu L of bubbles and the functional surface coating in 0-300g/L saline water environment of 0-400 mu N.
7. A process for the preparation of the enhanced perfluorosulfonic acid ion exchange membrane for chloride electrolysis according to any one of claims 1 to 6, characterized in that: the method comprises the following steps:
(1) obtaining a perfluorinated ion exchange resin base membrane from perfluorinated sulfonic acid resin by adopting an extrusion casting mode, and compounding a reinforcing material net 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.
8. The method of preparing a reinforced perfluorosulfonic acid ion exchange membrane for chloride electrolysis according to claim 7, wherein: the reinforcing material net in the step (1) is formed by weaving perfluorocarbon compound reinforcing wires and hydrocarbon polymer soluble wires, the void ratio is 20-99%, and the thickness is 40-200 mu m.
9. The method of preparing a reinforced perfluorosulfonic acid ion exchange membrane for chloride electrolysis according to claim 7, wherein: 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.
10. The method of preparing a reinforced perfluorosulfonic acid ion exchange membrane for chloride electrolysis according to claim 7, wherein: 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.
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Cited By (4)
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| CN112481658A (en) * | 2020-11-26 | 2021-03-12 | 山东东岳高分子材料有限公司 | Enhanced chlor-alkali ion conduction membrane containing hollowed-out tunnel and preparation method thereof |
| CN114226193A (en) * | 2021-11-29 | 2022-03-25 | 山东东岳高分子材料有限公司 | Post-treatment process of surface coating of fluorine-containing ion exchange membrane |
| CN114288855A (en) * | 2021-11-25 | 2022-04-08 | 国家电投集团氢能科技发展有限公司 | Water electrolysis membrane and preparation method thereof |
| CN114959794A (en) * | 2022-04-12 | 2022-08-30 | 山东东岳高分子材料有限公司 | Diaphragm for producing chemicals through electrolysis |
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| CN114959794A (en) * | 2022-04-12 | 2022-08-30 | 山东东岳高分子材料有限公司 | Diaphragm for producing chemicals through electrolysis |
| CN114959794B (en) * | 2022-04-12 | 2023-11-14 | 山东东岳高分子材料有限公司 | Diaphragm for electrolytically producing chemicals |
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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. |
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Effective date of registration: 20201110 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. |
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Application publication date: 20200522 |