CN111041513A - Perfluoro ion membrane for chlor-alkali industry and preparation method thereof - Google Patents

Perfluoro ion membrane for chlor-alkali industry and preparation method thereof Download PDF

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CN111041513A
CN111041513A CN201911417863.8A CN201911417863A CN111041513A CN 111041513 A CN111041513 A CN 111041513A CN 201911417863 A CN201911417863 A CN 201911417863A CN 111041513 A CN111041513 A CN 111041513A
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perfluorinated
membrane
chlor
alkali industry
ion exchange
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张永明
张恒
刘烽
陈静
王丽
雷建龙
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Shandong Dongyue Polymer Material Co Ltd
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Shandong Dongyue Future Hydrogen Energy Materials Co Ltd
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    • 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
    • C08J2400/00—Characterised by the use of unspecified polymers
    • C08J2400/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08J2400/102—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms

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Abstract

The invention relates to a perfluorinated ion membrane for chlor-alkali industry and a preparation method thereof, belonging to the technical field of ion exchange membranes. The perfluorinated ion membrane for the chlor-alkali industry comprises a base membrane, wherein both sides of the base membrane are provided with functional surface coatings, the base membrane consists of a perfluorinated sulfonic acid polymer layer and a perfluorinated carboxylic acid polymer layer, and the functional surface coatings are porous rough structures formed by a mixture of perfluorinated ion polymers and metal oxides. The perfluorinated ion membrane for the chlor-alkali industry not only reduces the adhesion of the membrane surface to bubbles, but also improves the effective electrolysis area of the membrane surface, reduces the local polarization phenomenon, 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 and reduce the energy consumption; the invention also provides a simple and feasible preparation method.

Description

Perfluoro ion membrane for chlor-alkali industry and preparation method thereof
Technical Field
The invention relates to a perfluorinated ion membrane for chlor-alkali industry and a preparation method thereof, belonging to the technical field of ion exchange membranes.
Background
The chlor-alkali industry is the basic industry of national economy, and the product is widely applied to various fields of national economy such as agriculture, petrochemical industry, light industry, textile, chemical building materials, electric national defense military industry and the like, and has a great significance in the economic development of China. However, the chlor-alkali industry is a high energy consumption industry in the petroleum and chemical industry in China, and is mainly reflected in the aspect of power consumption in caustic soda production. In 2013, the national caustic soda burn consumption alternating current is about 665 hundred million Kw.h, and accounts for about 1.27% of the total national power generation. Therefore, the energy consumption is one of the important technical indexes in the chlor-alkali industry. Therefore, the reduction of the electrolysis energy consumption has important significance for realizing the sustainable development of national economy.
The groove pressure can be effectively reduced by shortening the distance between the electrodes, and the energy consumption is reduced. However, the perfluorosulfonic acid layer on the anode surface of the chlor-alkali membrane or the perfluorocarboxylic acid layer on the cathode surface of the chlor-alkali membrane has strong adhesion to bubbles under the liquid surface. When the zero polar distance electrolytic bath process is adopted, the electrode is tightly attached to the membrane, so that bubbles generated by the electrode are easily adsorbed on the surface of the membrane, the effective electrolytic area is reduced, and the bath pressure is increased. The hydrophilic coating is prepared by mixing inorganic oxide particles or fluorine-containing particles with fluorine-containing resin on the surface of the membrane, so that the membrane has good bubbling resistance under the liquid surface. Patents CA2446448, CA2444585 and CN104018182 all have detailed descriptions. However, several coating preparation techniques are introduced above, all of which are stacked from dense inorganic oxide particles or fluorine-containing particles to ensure sufficient roughness. The dense inorganic oxide without ion conductivity and the fluorine-containing particles increase the membrane resistance, thereby increasing the cell voltage.
Therefore, a novel chlor-alkali ionic membrane is developed, so that the chlor-alkali ionic membrane has the advantages of low membrane resistance, strong acid and alkali resistance, hydrogen and chlorine corrosion resistance, long-time stable operation, excellent function of driving bubbles to be attached on the surface, great reduction of cell voltage and great significance for chlor-alkali industrial energy consumption.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects in the prior art, and provide the perfluorinated ion membrane for the chlor-alkali industry, which not only reduces the adhesion of the membrane surface to bubbles, but also improves the effective electrolysis area of the membrane surface, reduces the local polarization phenomenon, is suitable for running in a zero polar distance electrolytic cell under the novel high current density condition, can obviously reduce the cell voltage, and reduces the energy consumption; the invention also provides a simple and feasible preparation method.
The perfluorinated ion membrane for the chlor-alkali industry comprises a base membrane, wherein both sides of the base membrane are provided with functional surface coatings, the base membrane consists of a perfluorinated sulfonic acid polymer layer and a perfluorinated carboxylic acid polymer layer, and the functional surface coatings are porous rough structures formed by a mixture of perfluorinated ion polymers and metal oxides.
The thickness of the perfluorosulfonic acid polymer layer is 10-250 μm, preferably 70-150 μm; the exchange capacity of the perfluorosulfonic acid polymer is 0.6 to 1.5 mmol/g, preferably 0.8 to 1.2 mmol/g.
The thickness of the perfluorocarboxylic acid polymer layer is 1-20 μm, preferably 7-15 μm; the exchange capacity of the perfluorocarboxylic acid polymer is from 0.5 to 1.5 mmol/g, preferably from 0.8 to 1.2 mmol/g.
The interior and the surface of the functional surface coating are in porous rough structures, and the thickness of the coating is 0.01-30 μm, preferably 1-10 μm.
The functional surface coating has a roughness Ra value within a range of 10 micrometers to 10 micrometers, and preferably within a range of 50 nanometers to 2 micrometers; the roughness Ra value in the range of 240 microns to 300 microns is between 300 nanometers and 10 microns, preferably between 1 micron and 5 microns.
The pores can be distributed on the surface of the coating or in the coating or can be concentrated in a designated area, the pores can be in a regular or irregular structure such as regular or irregular circles, ellipses, squares, rectangles and the like which are orderly or disorderly arranged, and the volume of the pores in the coating accounts for 5-95% of the volume of the coating, preferably 50-80%.
The perfluorinated ionic polymer is one or two of perfluorinated sulfonic acid polymer or perfluorinated phosphoric acid polymer, and is preferably perfluorinated sulfonic acid polymer.
The exchange capacity of the perfluorinated ion polymer is 0.5-1.5 mmol/g, preferably 0.8-1.1 mmol/g.
The metal oxide is contained in an amount of > 0g, < 12 g, preferably 0.5 to 8g, per square meter.
The metal oxide is an oxide of zirconium, hafnium or cerium in IVB group, and the particle size of the metal oxide is 5 nanometers to 10 micrometers, preferably 50 nanometers to 3 micrometers.
The functional surface coating has extremely low bubble adhesion in 0-300 g/L saline, and in a 0-300 g/L saline environment, the adhesion between bubbles with a volume of 3 microliters and the coating is 0-400 microliters, preferably 0-120 microliters.
The contact angle of 5 microliter bubbles of the functional surface coating is more than or equal to 130 degrees in 250g/L saline water environment at 25 ℃.
The preparation method of the perfluorinated ion membrane for the chlor-alkali industry comprises the following steps:
(1) compounding perfluorinated sulfonic acid resin and perfluorinated carboxylic acid resin into a perfluorinated ion exchange resin base membrane in a coextrusion casting mode to obtain a perfluorinated ion exchange membrane precursor;
(2) carrying out overpressure treatment on the perfluorinated ion exchange membrane precursor prepared in the step (1), and then immersing the perfluorinated ion exchange membrane precursor into a solvent and alkali liquor for transformation to convert the perfluorinated ion exchange membrane precursor into a perfluorinated ion exchange membrane with an ion exchange function;
(3) adding the perfluorinated ionic polymer into a solvent for homogenization treatment to form a perfluorinated ionic polymer solution;
(4) adding a mixture of metal oxide and a pore-forming agent into the perfluorinated ion polymer solution 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 a perfluorinated ion exchange membrane in a coating mode, and etching the surface to form a porous rough structure to obtain the perfluorinated ion membrane for the chlor-alkali industry.
In the step (2), the overpressure treatment conditions are as follows: overpressure treatment is carried out at a temperature of 180 ℃ and 220 ℃ and a pressure of 80-120 tons and at a speed of 45 m/min by using an overpressure machine.
In the step (3), the solvent is prepared from ethanol and isopropanol according to the ratio of 1:1 by weight ratio.
In the step (4), the pore-forming agent is one or more of silicon oxide, aluminum oxide, zinc oxide, potassium carbonate, titanium oxide, silicon carbide, sodium carbonate, polytrimethylene terephthalate fiber, polyurethane fiber, polyvinylidene fluoride (PVDF) or polyethylene terephthalate fiber (PET).
In the step (5), the coating mode is one of spraying, brushing, rolling, transfer printing, dipping or spin coating.
In the step (5), the etching is one or a combination of several processes of alkaline hydrolysis, acid hydrolysis or hydrolysis.
Compared with the prior art, the invention has the following beneficial effects:
(1) the perfluorinated sulfonic acid polymer layer and the perfluorinated carboxylic acid polymer layer are compounded, so that an ion conduction channel is changed, and faster ion conduction is facilitated;
(2) the functional surface coating is a porous rough structure formed by a mixture of a perfluorinated ion polymer and a metal oxide, so that the roughness of the surface of the exchange membrane is improved, the adhesion of the surface of the membrane to bubbles is reduced, the effective electrolysis area of the surface of the membrane is increased, and the local polarization phenomenon is reduced;
(3) the perfluorinated ion membrane for the chlor-alkali industry prepared by the invention has the functions of strong acid resistance and strong alkali resistance, 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 and reduce the energy consumption;
(4) the preparation method of the perfluorinated ion membrane for the chlor-alkali industry, disclosed by the invention, has the advantages of scientific and reasonable design, simplicity and easiness in implementation, and is beneficial to industrial production.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
Example 1
(1) And compounding the perfluorinated ion exchange resin base membrane by adopting perfluorinated sulfonic acid resin with IEC (International electrotechnical Commission) of 1.08mmol/g and perfluorinated carboxylic acid resin with IEC (International electrotechnical Commission) of 0.98mmol/g in a coextrusion casting mode, wherein the thickness of the perfluorinated sulfonic acid resin layer is 90 micrometers, and the thickness of the perfluorinated carboxylic acid resin layer is 7 micrometers to obtain the perfluorinated ion exchange membrane precursor.
(2) And (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 18 wt% of dimethyl sulfoxide and 20 wt% of NaOH at the temperature of 85 ℃ for transformation for 80 minutes to obtain the perfluorinated ion exchange membrane with the 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 200 ℃ in a closed reaction kettle to obtain a uniform perfluorinated sulfonic acid solution with the mass fraction of 5%.
(4) Mixing zinc oxide particles with the average particle size of 400 nanometers and zirconium oxide particles with the average particle size of 200 nanometers according to the mass ratio of 1: and 1, adding the mixture into the perfluorosulfonic acid solution obtained in the step 1, and carrying out ball milling for 36 hours to obtain a dispersion solution with the mass fraction of 28%.
(5) And (3) attaching the dispersion liquid obtained in the step (4) to the two side surfaces of the base membrane of the perfluorinated ion exchange membrane for the chlor-alkali membrane with the thickness of 100 micrometers by adopting a spraying method, and drying at 150 ℃ for 2 hours to obtain the coating with the zirconium oxide content of 2 g per square meter.
(6) And (3) aging the membrane containing the coating obtained in the step (5) in a 20 wt% NaOH solution at 60 ℃ for 3 hours, and drying to obtain the perfluorinated ion membrane for the chlor-alkali industry.
Performance testing
In the functional surface coating, the volume of the pores accounts for 25 percent of the volume fraction of the coating.
The film surface was tested to have a roughness Ra value of 167 nm in the range of 10 microns by 10 microns and a roughness Ra value of 4.3 microns in the range of 240 microns by 300 microns.
The adhesion was measured in 250g/L NaCl solution with 3. mu.l air bubbles to be 76. mu.l.
Carrying out an electrolysis test of a sodium chloride aqueous solution on the prepared ion exchange membrane in an electrolytic cell, supplying 306g/L of the sodium 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 205g/L and the concentration of sodium hydroxide discharged from the cathode chamber is 36%; the test temperature was 89 ℃ and the current density was 6kA/m2After 35 days of electrolysis experiments, the average cell pressure is 2.72V, and the average current efficiency is 99.6%.
The sheet resistance of the resulting film was measured to be 0.52. 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 then a dispersion was prepared in the same manner, except that ZnO particles having an average particle size of 400nm were replaced with ZrO particles having an average particle size of 300nm2The particles were homogenized in a ball mill to form a dispersion having a content of 10 wt%. The resulting zirconia content per square meter of coating was 6 grams.
An ion-exchange membrane was obtained in the same manner as in example 1.
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 3.08V, the average current efficiency was 99.58%, and the sheet resistance was 0.72. omega. cm-2。
Example 2
(1) Adopting perfluorinated sulfonic acid resin with IEC being 0.93mmol/g and perfluorinated carboxylic acid resin with IEC being 0.95mmol/g to compound a perfluorinated ion exchange resin base membrane in a coextrusion casting mode, wherein the thickness of the perfluorinated sulfonic acid resin layer is 100 micrometers, and the thickness of the perfluorinated carboxylic acid resin layer is 8 micrometers, and obtaining the precursor for forming the perfluorinated ion exchange membrane.
(2) And (2) performing overpressure treatment on the perfluorinated ion exchange membrane precursor prepared in the step (1) at the temperature of 200 ℃ and under the pressure of 100 tons by using an overpressure machine at the speed of 45 m/min, and after the overpressure treatment, immersing the perfluorinated ion exchange membrane precursor into a mixed aqueous solution containing 15 wt% of dimethyl sulfoxide and 20 wt% of NaOH at the temperature of 80 ℃ for transformation for 80 minutes to obtain the perfluorinated ion exchange membrane with the ion exchange function.
(3) Mixing ethanol and isopropanol according to the weight ratio of 1:1 to prepare a mixed solution, adding perfluorinated sulfonic acid resin with the exchange capacity of 0.9mmol/g, and treating for 3 hours at 220 ℃ in a closed reaction kettle to obtain a uniform perfluorinated sulfonic acid solution with the mass fraction of 5%.
(4) Mixing zinc oxide particles with the average particle size of 400 nanometers and zirconium oxide particles with the average particle size of 200 nanometers according to the mass ratio of 1: and 1, adding the mixture into the perfluorosulfonic acid solution obtained in the step 1, and performing ball milling for 36 hours to obtain a dispersion solution with the mass fraction of 10%.
(5) And (3) attaching the dispersion liquid obtained in the step (4) to the two side surfaces of the base membrane of the perfluorinated ion exchange membrane for the chlor-alkali membrane with the thickness of 100 microns by adopting a spraying method, and drying at 150 ℃ for 2 hours to obtain the coating with the zirconium oxide content of 3 g per square meter.
(6) And (3) aging the membrane containing the coating obtained in the step (5) in a 10 wt% NaOH solution at 60 ℃ for 3 hours, and drying to obtain the perfluorinated ion membrane for the chlor-alkali industry.
Performance testing
In the functional surface coating, the volume of the pores accounts for 40% of the volume fraction of the coating.
The film surface was tested to have a roughness Ra value of 185 nm in the range of 10 microns by 10 microns and a roughness Ra value of 4.7 microns in the range of 240 microns by 300 microns.
The adhesion was measured in 250g/L NaCl solution with 3. mu.l air bubbles to be 66. mu.l.
Carrying out an electrolysis test of a sodium chloride aqueous solution on the prepared ion exchange membrane in an electrolytic cell, supplying 300g/L of the sodium 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 205g/L and the concentration of sodium hydroxide discharged from the cathode chamber is 34%; the test temperature was 82 ℃ and the current density was 6kA/m2Meridian/channelAfter 35 days of electrolysis experiment, the average cell pressure is 2.84V, and the average current efficiency is 99.3%.
The sheet resistance of the resulting film was measured to be 0.54. omega. cm by the standard SJ/T10171.5 method-2。
Example 3
(1) And compounding the perfluorinated ion exchange resin base membrane by adopting perfluorinated sulfonic acid resin with IEC (International electrotechnical Commission) of 1.3mmol/g and perfluorinated carboxylic acid resin with IEC (International electrotechnical Commission) of 1.22mmol/g in a coextrusion casting mode, wherein the thickness of the perfluorinated sulfonic acid resin layer is 92 micrometers, and the thickness of the perfluorinated carboxylic acid resin layer is 8 micrometers to obtain the perfluorinated ion exchange membrane precursor.
(2) And (2) performing overpressure treatment on the perfluorinated ion exchange membrane precursor prepared in the step (1) at the temperature of 190 ℃ and under the pressure of 100 tons by using an overpressure machine at the speed of 45 m/min, and after the overpressure treatment, immersing the perfluorinated ion exchange membrane precursor into a mixed aqueous solution containing 15 wt% of dimethyl sulfoxide and 15 wt% of NaOH at 80 ℃ for transformation for 80 minutes to obtain the perfluorinated ion exchange membrane with the 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 200 ℃ in a closed reaction kettle to obtain a uniform perfluorinated sulfonic acid solution with the mass fraction of 5%.
(4) Adding polyurethane fiber powder particles with the average length of 200 micrometers and the average particle size of 5 micrometers and cerium oxide particles with the average particle size of 100 nanometers into the perfluorosulfonic acid solution obtained in the step (1) according to the mass ratio of 1:1, and performing ball milling for 42 hours to obtain a dispersion solution with the mass fraction of 25%.
(5) And (3) attaching the dispersion liquid obtained in the step (4) to the two side surfaces of the base membrane of the perfluorinated ion exchange membrane for the chlor-alkali membrane with the thickness of 100 micrometers by adopting a spraying method, and drying at 150 ℃ for 2 hours to obtain the coating with the zirconium oxide content of 4.2 grams per square meter.
(6) And (3) aging the membrane containing the coating obtained in the step (5) in a 20 wt% NaOH solution at 80 ℃ for 2 hours, and drying to obtain the perfluorinated ion membrane for the chlor-alkali industry.
Performance testing
In the functional surface coating, the volume of the pores accounts for 21 percent of the volume of the coating.
The film surface was tested to have a roughness Ra value of 169 nm in the range of 10 microns by 10 microns and a roughness Ra value of 4.1 microns in the range of 240 microns by 300 microns.
The adhesion was measured with 3. mu.l air bubbles in 250g/L NaCl solution to be 81. mu.l.
Carrying out an electrolysis test on the prepared ion exchange membrane in an electrolytic cell by using a sodium chloride aqueous solution, supplying 300g/L of the sodium 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 sodium hydroxide discharged from the cathode chamber is 36%; the test temperature was 89 ℃ and the current density was 6kA/m2After 23 days of electrolysis experiments, the average cell pressure is 2.71V, and the average current efficiency is 99.6%.
The sheet resistance of the resulting film was measured to be 0.50. omega. cm by the standard SJ/T10171.5 method-2。
Example 4
(1) And compounding the perfluorinated ion exchange resin base membrane by adopting perfluorinated sulfonic acid resin with IEC (International electrotechnical Commission) of 1.1mmol/g and perfluorinated carboxylic acid resin with IEC (International electrotechnical Commission) of 1.05mmol/g in a coextrusion casting mode, wherein the thickness of the perfluorinated sulfonic acid resin layer is 105 micrometers, and the thickness of the perfluorinated carboxylic acid resin layer is 6 micrometers to obtain the perfluorinated ion exchange membrane precursor.
(2) And (2) performing overpressure treatment on the perfluorinated ion exchange membrane precursor prepared in the step (1) at the temperature of 190 ℃ and under the pressure of 80 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 15 wt% of dimethyl sulfoxide and 20 wt% of NaOH at 80 ℃ for transformation for 80 minutes to obtain the perfluorinated ion exchange membrane with the 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 200 ℃ in a closed reaction kettle to obtain a uniform perfluorinated sulfonic acid solution with the mass fraction of 5%.
(4) Mixing calcium carbonate particles with the average particle size of 400 nanometers and PVDF powder with the average particle size of 500 nanometers, wherein the mass ratio of the hafnium oxide particles with the average particle size of 200 nanometers is 1: 1: and 1, adding the mixture into the perfluorosulfonic acid solution obtained in the step 1, and carrying out ball milling for 36 hours to obtain a dispersion solution with the mass fraction of 28%.
(5) And (3) attaching the dispersion liquid obtained in the step (4) to the two side surfaces of the base membrane of the perfluorinated ion exchange membrane for the chlor-alkali membrane with the thickness of 100 microns by adopting a spraying method, and drying at 150 ℃ for 2 hours to obtain the coating with the zirconium oxide content of 4.5 grams per square meter.
(6) And (3) aging the membrane containing the coating obtained in the step (5) in a 20 wt% NaOH solution at 60 ℃ for 3 hours, and drying to obtain the perfluorinated ion membrane for the chlor-alkali industry.
Performance testing
In the functional surface coating, the volume of the pores accounts for 23 percent of the volume fraction of the coating.
The film surface was tested to have a roughness Ra value of 188 nm in the range of 10 microns by 10 microns and a roughness Ra value of 4.5 microns in the range of 240 microns by 300 microns.
The adhesion was measured in 250g/L NaCl solution with 3. mu.l air bubbles to be 71. mu.l.
Carrying out an electrolysis test on the prepared ion exchange membrane in an electrolytic cell by using a sodium chloride aqueous solution, supplying 310g/L of the sodium 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 204g/L and the concentration of sodium hydroxide discharged from the cathode chamber is 36%; the test temperature was 89 ℃ and the current density was 6kA/m2After 23 days of electrolysis experiments, the average cell pressure is 2.85V, and the average current efficiency is 99.3%.
The sheet resistance of the resulting film was measured to be 0.51. omega. cm by the standard SJ/T10171.5 method-2。
Example 5
(1) And compounding the perfluorinated ion exchange resin base membrane by adopting perfluorinated sulfonic acid resin with IEC (International electrotechnical Commission) of 1.1mmol/g and perfluorinated carboxylic acid resin with IEC (International electrotechnical Commission) of 1.05mmol/g in a coextrusion casting mode, wherein the thickness of the perfluorinated sulfonic acid resin layer is 120 micrometers, and the thickness of the perfluorinated carboxylic acid resin layer is 12 micrometers to obtain the perfluorinated ion exchange membrane precursor.
(2) And (2) performing overpressure treatment on the perfluorinated ion exchange membrane precursor prepared in the step (1) at 185 ℃ and 80 tons of pressure by using an overpressure machine at the speed of 45 m/min, and after the overpressure treatment, immersing the perfluorinated ion exchange membrane precursor into a mixed aqueous solution containing 15 wt% of dimethyl sulfoxide and 20 wt% of NaOH at 80 ℃ for transformation for 80 minutes to obtain the perfluorinated ion exchange membrane with the 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 1.3mmol/g, and treating for 3 hours at 230 ℃ in a closed reaction kettle to obtain a uniform perfluorinated sulfonic acid solution with the mass fraction of 15%.
(4) Sodium carbonate particles with the average particle size of 1 micron, silicon carbide particles with the average particle size of 500 nanometers and zirconium oxide particles with the average particle size of 200 nanometers are mixed according to the weight ratio of 7: 3: 2, adding the mixture into the perfluorosulfonic acid solution obtained in the step (1), and carrying out ball milling for 36 hours to obtain a dispersion solution with the mass fraction of 25%.
(5) And (3) attaching the dispersion liquid obtained in the step (4) to the two side surfaces of the base membrane of the perfluorinated ion exchange membrane for the chlor-alkali membrane with the thickness of 100 microns by adopting a spraying method, and drying at 150 ℃ for 2 hours to obtain the coating with the zirconium oxide content of 3.3 g per square meter.
(6) And (3) aging the membrane containing the coating obtained in the step (5) in a 20 wt% NaOH solution at 60 ℃ for 3 hours, and drying to obtain the perfluorinated ion membrane for the chlor-alkali industry.
Performance testing
In the functional surface coating, the volume of the pores accounts for 23 percent of the volume fraction of the coating.
The film surface was tested to have a roughness Ra value of 195 nm in the range of 10 microns by 10 microns and a roughness Ra value of 4.5 microns in the range of 240 microns by 300 microns.
The adhesion was measured in 250g/L NaCl solution with 3. mu.l air bubbles to be 58. mu.l.
Carrying out an electrolysis test of a sodium chloride aqueous solution on the prepared ion exchange membrane in an electrolytic cell, supplying 305g/L of the sodium 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 208g/L and the concentration of sodium hydroxide discharged from the cathode chamber is 36%; the test temperature was 89 deg.C, andthe flow density is 6kA/m2After 23 days of electrolysis experiments, the average cell pressure is 2.89V, and the average current efficiency is 99.2%.
The sheet resistance of the resulting film was measured to be 0.72. omega. cm by the Standard SJ/T10171.5 method-2。

Claims (10)

1. A perfluor ionic membrane for chlor-alkali industry comprises a base membrane, wherein two sides of the base membrane are provided with functional surface coatings, the base membrane consists of a perfluor sulfonic acid polymer layer and a perfluor carboxylic acid polymer layer, and the perfluor ionic membrane is characterized in that: the functional surface coating is a porous rough structure formed by a mixture of perfluorinated ionic polymer and metal oxide.
2. The perfluorinated ionic membrane for the chlor-alkali industry of claim 1, characterized in that: the functional surface coating has a roughness Ra value within 10 micrometers to 10 micrometers in a range of 10 nanometers to 5 micrometers, and a roughness Ra value within 240 micrometers to 300 micrometers in a range of 300 nanometers to 10 micrometers.
3. The perfluorinated ionic membrane for the chlor-alkali industry of claim 1, characterized in that: the inner part and the surface of the functional surface coating are in porous rough structures, and the thickness of the coating is 0.01-30 mu m.
4. The perfluorinated ionic membrane for the chlor-alkali industry of claim 1, characterized in that: 0g < 12 g metal oxide per square meter.
5. The perfluorinated ionic membrane for the chlor-alkali industry of claim 1, characterized in that: the metal oxide is the oxide of zirconium, hafnium or cerium in IVB group, and the grain diameter of the metal oxide is 5 nanometers to 10 micrometers.
6. The perfluorinated ionic membrane for the chlor-alkali industry of claim 1, characterized in that: the thickness of the perfluorosulfonic acid polymer layer is 10-250 μm; the exchange capacity of the perfluorosulfonic acid polymer is 0.6 to 1.5 mmol/g.
7. The perfluorinated ionic membrane for the chlor-alkali industry of claim 1, characterized in that: the thickness of the perfluorocarboxylic acid polymer layer is 1-20 μm; the exchange capacity of the perfluorocarboxylic acid polymer is from 0.5 to 1.5 mmol/g.
8. The perfluorinated ionic membrane for the chlor-alkali industry of claim 1, characterized in that: the perfluorinated ionic polymer is one or two of perfluorinated sulfonic acid polymer or perfluorinated phosphoric acid polymer; the exchange capacity of the perfluorinated ion polymer is 0.5-1.5 mmol/g.
9. A method for preparing the perfluorinated ion membrane for chlor-alkali industry according to any of the claims from 1 to 8, characterized by comprising the following steps:
(1) compounding perfluorinated sulfonic acid resin and perfluorinated carboxylic acid resin into a perfluorinated ion exchange resin base membrane in a coextrusion casting mode to obtain a perfluorinated ion exchange membrane precursor;
(2) converting the perfluorinated ion exchange membrane precursor prepared in the step (1) into a perfluorinated ion exchange membrane with an ion exchange function;
(3) adding the perfluorinated ionic polymer into a solvent for homogenization treatment to form a perfluorinated ionic polymer solution;
(4) adding a mixture of metal oxide and a pore-forming agent into the perfluorinated ion polymer solution 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 a perfluorinated ion exchange membrane in a coating mode, and etching the surface to form a porous rough structure to obtain the perfluorinated ion membrane for the chlor-alkali industry.
10. The method for preparing a perfluorinated ionic membrane for chlor-alkali industry according to claim 9, characterized in that: the pore-forming agent in the step (4) is one or more of silicon oxide, aluminum oxide, zinc oxide, titanium oxide, potassium carbonate, silicon carbide, sodium carbonate, polytrimethylene terephthalate fiber, polyurethane fiber, polyvinylidene fluoride or 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 the combination of several technologies of alkaline hydrolysis, acid hydrolysis or hydrolysis.
CN201911417863.8A 2019-12-31 2019-12-31 Perfluoro ion membrane for chlor-alkali industry and preparation method thereof Withdrawn CN111041513A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112126355A (en) * 2020-09-23 2020-12-25 山东东岳高分子材料有限公司 Preparation method of coating solution for ion exchange membrane

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112126355A (en) * 2020-09-23 2020-12-25 山东东岳高分子材料有限公司 Preparation method of coating solution for ion exchange membrane

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