CN111188051A - Novel ultra-thin low-resistance ion conduction membrane for chlor-alkali industry and preparation method thereof - Google Patents

Novel ultra-thin low-resistance ion conduction membrane for chlor-alkali industry and preparation method thereof Download PDF

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CN111188051A
CN111188051A CN201911423931.1A CN201911423931A CN111188051A CN 111188051 A CN111188051 A CN 111188051A CN 201911423931 A CN201911423931 A CN 201911423931A CN 111188051 A CN111188051 A CN 111188051A
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acid polymer
membrane
polymer
perfluorosulfonic acid
perfluorocarboxylic
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张永明
雷建龙
张恒
张江山
陈静
薛帅
戴琼
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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
    • 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
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    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
    • D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0088—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/18—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials
    • D06N3/186—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials one of the layers is on one surface of the fibrous web and the other layer is on the other surface of the fibrous web

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Abstract

The invention belongs to the technical field of ion exchange membranes, and particularly relates to a novel ultrathin low-resistance ion conduction membrane for chlor-alkali industry and a preparation method thereof. The composite material consists of a first perfluorocarboxylic acid-perfluorosulfonic acid polymer composite layer, a second perfluorocarboxylic acid-perfluorosulfonic acid polymer composite layer, a porous non-woven polymer layer and a functional surface coating; wherein the functional surface coating is a porous rough structure composed of perfluorinated ionic polymer. According to the novel ultrathin low-resistance ion-conducting membrane for chlor-alkali industry, a small amount of perfluorocarboxylic acid is added into a perfluorosulfonic acid layer, so that the current efficiency of the membrane is improved, and the membrane resistance is reduced by adding a small amount of perfluorosulfonic acid into the perfluorosulfonic acid layer; the ultrathin porous non-woven polymer layer is used as a reinforcing material, so that the thickness of the membrane is greatly reduced, and the resistance of the membrane is reduced; the usage amount of inorganic oxide or fluorine-containing particles in the traditional coating is reduced, the resistance of the composite film body is reduced, and the rapid transmission of ions is facilitated.

Description

Novel ultra-thin low-resistance ion conduction membrane for chlor-alkali industry and preparation method thereof
Technical Field
The invention belongs to the technical field of ion exchange membranes, and particularly relates to a novel ultrathin low-resistance ion conduction membrane for chlor-alkali industry and a preparation method thereof.
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, the novel ultrathin low-resistance chlor-alkali ion conduction membrane is developed, has the advantages of lower 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 as follows: overcomes the defects of the prior art and provides a novel ultrathin low-resistance ion conduction membrane for chlor-alkali industry. The novel ultra-thin low-resistance ion conduction membrane for chlor-alkali industry operates in a novel zero-polar-distance electrolytic cell under the condition of high current density, so that the cell voltage can be obviously reduced; the invention also provides a preparation method thereof.
The novel ultrathin low-resistance ion-conducting membrane for chlor-alkali industry consists of a first perfluorocarboxylic acid-perfluorosulfonic acid polymer composite layer, a second perfluorocarboxylic acid-perfluorosulfonic acid polymer composite layer, a porous non-woven polymer layer and a functional surface coating; wherein the functional surface coating is a porous rough structure composed of perfluorinated ionic polymer.
Wherein:
the thickness of the first perfluorocarboxylic acid-perfluorosulfonic acid polymer composite layer is 10-80 microns, and the mass ratio of the perfluorocarboxylic acid polymer to the perfluorosulfonic acid polymer is 0-40%, preferably 0.5-10%; the perfluorosulfonic acid polymer has an exchange capacity of 0.6 to 1.5 mmol/g, preferably 0.8 to 1.2 mmol/g; the perfluorocarboxylic acid polymer has an exchange capacity of from 0.5 to 1.5 mmol/g, preferably from 0.8 to 1.2 mmol/g.
The thickness of the second perfluorocarboxylic acid-perfluorosulfonic acid polymer composite layer is 1 to 20 micrometers, preferably 6 to 15 micrometers; the mass ratio of the perfluorinated sulfonic acid polymer to the perfluorinated carboxylic acid polymer is 0-40%, preferably 0.5-10%; the perfluorosulfonic acid polymer has an exchange capacity of 0.6 to 1.5 mmol/g, preferably 0.8 to 1.2 mmol/g; the perfluorocarboxylic acid polymer has an exchange capacity of from 0.5 to 1.5 mmol/g, preferably from 0.8 to 1.2 mmol/g.
And the mass ratio of the perfluorocarboxylic acid polymer in the first perfluorocarboxylic acid-perfluorosulfonic acid polymer composite layer to the perfluorosulfonic acid polymer is not 0 at the same time as the mass ratio of the perfluorosulfonic acid polymer in the second perfluorocarboxylic acid-perfluorosulfonic acid polymer composite layer to the perfluorocarboxylic acid polymer.
The porous non-woven polymer layer is made of one or a combination of more of polytetrafluoroethylene, polyvinylidene fluoride, polyimide or polyether ether ketone, preferably polytetrafluoroethylene, has a porosity of 20-99%, preferably 60-80%, and has a thickness of 3-50 micrometers, preferably 10-40 micrometers.
The inside 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, preferably 1-10 mu m.
The functional surface coating has a roughness Ra value in the range of 10 micrometers to 10 micrometers in the range of 10 nanometers to 5 micrometers, preferably 50 nanometers to 2 micrometers, and a roughness Ra value in the range of 240 micrometers to 300 micrometers in the range of 300 nanometers to 10 micrometers, preferably 1 micrometer to 5 micrometers.
The volume of the pores of the functional surface coating accounts for 5 to 95 percent, preferably 50 to 80 percent of the volume fraction of the coating.
The exchange capacity of the perfluorinated ion polymer in the functional surface coating is 0.5-1.5 mmol/g, preferably 0.8-1.1 mmol/g; the perfluoroionomer is one or both of a perfluorosulfonic acid polymer or a perfluorophosphoric acid polymer, preferably a perfluorosulfonic acid polymer.
The pores of the porous rough structure of the functional surface coating are distributed on the surface of the coating and in the coating and can also be concentrated in a designated area, and the pores are in a regular or irregular structure which is orderly or disorderly arranged, such as regular or irregular circles, ellipses, squares, rectangles and the like.
The functional surface coating has extremely low bubble adhesion in 0-300 g/L saline, and in 0-300 g/L saline environment, the adhesion between bubbles with the volume of 3 microliter and the coating is 0-400 micro-newton, preferably 0-120 micro-newton.
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 invention relates to a preparation method of a novel ultrathin low-resistance ion conduction membrane for chlor-alkali industry, which comprises the following steps:
(1) mixing and extruding a perfluorosulfonic acid polymer and a perfluorocarboxylic acid polymer for granulation, using the mixture as a material A, and dissolving the material A in a polar solution to prepare a perfluorosulfonic acid-perfluorocarboxylic acid resin solution; mixing a perfluorosulfonic acid polymer and a perfluorocarboxylic acid polymer into a material B to prepare a second perfluorosulfonic acid-perfluorocarboxylic acid composite membrane; soaking the porous non-woven polymer layer material into a trifluoro-trichloroethane solvent subjected to ultrasonic treatment for treatment, taking out and drying for later use, spraying a perfluorosulfonic acid-perfluorocarboxylic acid resin solution on the upper surface and the lower surface of the porous non-woven polymer, drying, and compounding with a second perfluorosulfonic acid-perfluorocarboxylic acid composite membrane to form 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 transforming the perfluorinated ion exchange membrane 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 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 the perfluorinated ion exchange membrane prepared in the step (2) in a coating mode, and etching the surface to form a porous rough structure.
Wherein:
in the step (1), the mass ratio of the perfluorocarboxylic acid polymer in the material A to the perfluorosulfonic acid polymer is 0-40%, the mass ratio of the perfluorosulfonic acid polymer in the material B to the perfluorocarboxylic acid polymer is 0-40%, and the mass ratios of the perfluorocarboxylic acid polymer and the perfluorosulfonic acid polymer are not 0 at the same time.
The overpressure treatment in step (2) is carried out on an overpressure machine at 180 ℃, 120 tons of pressure and 45 m/min of speed.
The transformation in the step (2) is carried out in a mixed aqueous solution of dimethyl sulfoxide and NaOH, the concentration of the dimethyl sulfoxide is 18 wt%, the concentration of the NaOH is 15 wt%, the temperature of the mixed solution is 85 ℃, and the transformation time is 80 minutes.
The perfluorinated ionic polymer in the step (3) is one or two of perfluorinated sulfonic acid polymer or perfluorinated phosphoric acid polymer, and is preferably perfluorinated sulfonic acid polymer.
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.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the novel ultrathin low-resistance ion-conducting membrane for chlor-alkali industry, a small amount of perfluorocarboxylic acid is added into a perfluorosulfonic acid layer, so that the current efficiency of the membrane is improved, and the membrane resistance is reduced by adding a small amount of perfluorosulfonic acid into the perfluorosulfonic acid layer; the ultrathin porous non-woven polymer layer is used as a reinforcing material, so that the thickness of the membrane is greatly reduced, and the resistance of the membrane is reduced; the usage amount of inorganic oxide or fluorine-containing particles in the traditional coating is reduced, the resistance of the composite film body is reduced, and the rapid transmission of ions is facilitated.
(2) According to the novel ultrathin low-resistance ion conduction membrane for chlor-alkali industry, disclosed by the invention, a functional surface coating porous structure is prepared on the surface of the membrane, so that the surface roughness of the membrane is improved, the adhesion of the membrane to bubbles is reduced, the effective electrolysis area of the membrane is increased, and the local polarization phenomenon is reduced.
(3) The novel ultrathin low-resistance ion conduction membrane for chlor-alkali industry, disclosed by the invention, is applied to a novel zero polar distance electrolytic cell under a high current density condition for operation, the interior of the novel ultrathin low-resistance ion conduction membrane is reinforced by a porous non-woven polymer, the surface of the novel ultrathin low-resistance chlor-alkali industry membrane has an excellent function of driving bubbles to adhere to the membrane, and the voltage of the electrolytic cell can be effectively reduced.
(4) The novel ultrathin low-resistance ion conduction membrane for chlor-alkali industry has strong acid, strong alkali, hydrogen and chlorine corrosion resistance, can stably run for a long time, has an excellent function of driving bubbles to adhere on the surface, can greatly reduce the voltage of a tank, and has important significance on energy consumption of chlor-alkali industry.
(5) The preparation method of the novel ultrathin low-resistance ion conduction membrane for chlor-alkali industry, disclosed by the invention, has the advantages of simple and reasonable process, simplicity and convenience in use and easiness in industrial production.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
The novel ultrathin low-resistance ion-conducting membrane for chlor-alkali industry described in this example 1 is composed of a first perfluorocarboxylic acid-perfluorosulfonic acid polymer composite layer, a perfluorocarboxylic acid polymer layer, a porous non-woven polymer layer, and a functional surface coating; wherein the functional surface coating is a porous rough structure composed of perfluorinated ionic polymer.
The preparation method of the novel ultrathin low-resistance ion-conducting membrane for chlor-alkali industry described in this example 1 comprises the following steps:
(1) adopting a perfluorinated sulfonic acid resin with IEC being 1.0mmol/g and a perfluorinated carboxylic acid resin with IEC being 0.8mmol/g according to a mass ratio of 10: 3, obtaining a material A by melting and granulating, and dissolving the material A in a polar solvent (a solvent prepared from ethanol and isopropanol according to the weight ratio of 1: 1) to prepare a perfluorosulfonic acid-perfluorocarboxylic acid resin solution; soaking a polytetrafluoroethylene porous non-woven membrane into a trifluoro trichloroethane solvent subjected to ultrasonic treatment for 1.5 hours, wherein the thickness of the porous non-woven polymer layer is 10 micrometers, the porosity is 85%, taking out and drying the porous non-woven polymer layer for later use, spraying a perfluorosulfonic acid-perfluorocarboxylic acid resin solution on the upper surface and the lower surface of the porous non-woven polymer layer, drying the porous non-woven polymer layer, and compounding the porous non-woven polymer layer with a perfluorocarboxylic acid resin film with IEC (0.8 mmol/g) to form a perfluorinated ion exchange membrane precursor; wherein: the thickness of the perfluorosulfonic acid resin layer containing a small amount of perfluorocarboxylic acid resin was 20 μm, and the thickness of the perfluorocarboxylic acid resin layer was 7 μm.
(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 15 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) Mixing ethanol and isopropanol according to a ratio of 1:1, then adding perfluorinated sulfonic acid resin with the exchange capacity of 1.2 mmol/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 3%.
(4) And (3) adding zinc oxide particles with the average particle size of 400 nanometers into the perfluorosulfonic acid solution in the step (3), and performing ball milling for 36 hours to obtain a dispersion solution with the mass fraction of 20%.
(5) And (3) attaching the dispersion liquid obtained in the step (4) to two sides of the perfluorinated ion exchange membrane with the thickness of 42 microns prepared in the step (2) by adopting a spraying method, and drying the perfluorinated ion exchange membrane for 2 hours at 150 ℃ to obtain the perfluorinated ion exchange membrane with the thickness of 5 microns.
(6) And (4) aging the membrane obtained in the step (5) in a sodium hydroxide solution with the mass fraction of 20% for 3 hours at the temperature of 60 ℃, and drying to form a finished product.
Through the test: the film surface had a roughness Ra value of 310 nm in the range of 10 microns by 10 microns, a roughness Ra value of 5.6 microns in the range of 240 microns by 300 microns, and an adhesion of 48 μ n measured in a 250g/l nacl solution with 3 μ l air bubbles.
Carrying out an electrolysis test of a sodium chloride aqueous solution in an electrolytic cell by using the prepared ion exchange membrane, wherein 310g/L of the sodium chloride aqueous solution is supplied to an anode chamber, water is supplied to a cathode chamber, 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 30%; the test temperature was 81 ℃ and the current density was 6kA/m2After 60 days of electrolysis experiments, the average cell pressure is 2.48V, and the average current efficiency is 99.53%.
The sheet resistance of the resulting film was measured to be 0.29. omega. cm by the standard SJ/T10171.5 method-2。
Comparative example 1
A perfluoroion-exchange membrane-based membrane 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 400 nm zinc oxide particles were replaced with 400 nm ZrO2The particles were homogenized in a ball mill to form a dispersion having a content of 25 wt%. By usingAn ion exchange membrane having inorganic oxide coatings attached to both sides thereof was obtained in the same manner as in example 1, and the surface of the obtained coating had a roughness Ra value of 298 nm in the range of 10 μm to 10 μm, a roughness Ra value of 5.3 μm in the range of 240 μm to 300 μm, and an adhesion of 86 μ n was measured in a 250g/l of NaCl solution using 3. mu.l of air bubbles.
Electrolytic testing of sodium chloride solution was carried out under the same conditions as in example 1, with a test temperature of 81 ℃ and a current density of 6kA/m2After 60 days of electrolysis experiment, the average cell voltage was 2.77V, the average current efficiency was 99.93%, and the sheet resistance was 0.47. omega. cm-2。
Example 2
The novel ultrathin low-resistance ion-conducting membrane for chlor-alkali industry described in this embodiment 2 is composed of a perfluorosulfonic acid polymer layer, a second perfluorocarboxylic acid-perfluorosulfonic acid polymer composite layer, a porous non-woven polymer layer, and a functional surface coating; wherein the functional surface coating is a porous rough structure composed of perfluorinated ionic polymer.
The preparation method of the novel ultrathin low-resistance ion-conducting membrane for chlor-alkali industry described in this example 2 comprises the following steps:
(1) dissolving a perfluorinated sulfonic acid resin with IEC (1.0 mmol/g) in a polar solvent (a solvent prepared from ethanol and isopropanol in a weight ratio of 1: 1) to prepare a perfluorinated sulfonic acid resin solution; soaking a polytetrafluoroethylene porous non-woven membrane into an ultrasonically-treated trifluorotrichloroethane solvent for treatment for 1.5 hours, wherein the thickness of a porous non-woven polymer layer is 40 micrometers, the porosity is 85%, taking out and drying for later use, then spraying perfluorinated sulfonic acid resin solution on the upper surface and the lower surface of the porous non-woven polymer, and drying, wherein the perfluorinated sulfonic acid resin with IEC (1.0 mmol/g) and perfluorinated carboxylic acid resin with IEC (0.8 mmol/g) are adopted according to a mass ratio of 1: 10 compounding the perfluorinated sulfonic acid-perfluorinated carboxylic acid composite membrane prepared by mixing to form a perfluorinated ion exchange membrane precursor; wherein: the thickness of the perfluorocarboxylic acid resin layer containing a small amount of perfluorosulfonic acid resin was 7 μm, and the thickness of the perfluorosulfonic acid resin layer was 45 μm.
(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 15 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) Mixing ethanol and isopropanol according to a ratio of 1:1, then adding perfluorinated sulfonic acid resin with the exchange capacity of 1.2 mmol/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 3%.
(4) And (3) adding zinc oxide particles with the average particle size of 700 nanometers into the perfluorosulfonic acid solution in the step (3), and performing ball milling for 36 hours to obtain a dispersion solution with the mass fraction of 20%.
(5) And (3) attaching the dispersion liquid obtained in the step (4) to two sides of the perfluorinated ion exchange membrane with the thickness of 100 micrometers prepared in the step (2) by adopting a spraying method, and drying at 150 ℃ for 2 hours to obtain a coating with the average thickness of about 7 micrometers.
(6) And (4) aging the membrane obtained in the step (5) in a sodium hydroxide solution with the mass fraction of 20% for 3 hours at the temperature of 60 ℃, and drying to form a finished product.
The membrane surface was tested for roughness Ra value 520 nm at 10 microns x 10 microns, roughness Ra value 7.4 microns at 240 microns x 300 microns and adhesion was measured as 70 μ n in 250g/l nacl solution using 3 μ l air bubbles.
Carrying out an electrolysis test of a sodium chloride aqueous solution in an electrolytic cell by using the prepared ion exchange membrane, wherein the sodium chloride aqueous solution of 300g/L is supplied to an anode chamber, water is supplied to a cathode chamber, 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 30%; the test temperature was 85 ℃ and the current density was 7kA/m2After 60 days of electrolysis experiments, the average cell pressure is 2.63V, and the average current efficiency is 99.97%.
The sheet resistance of the resulting film was measured to be 0.49. omega. cm by the standard SJ/T10171.5 method-2。
Comparative example 2
A perfluorocarboxylic acid layer was used in place of a perfluorocarboxylic acid polymer layer containing a small amount of perfluorosulfonic acid, a perfluoroion exchange membrane-based membrane 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 as in example 2, followed by spray coating.
The membrane surface was tested for roughness Ra value 520 nm at 10 microns x 10 microns, roughness Ra value 7.4 microns at 240 microns x 300 microns and adhesion was measured as 70 μ n in 250g/l nacl solution using 3 μ l air bubbles.
Electrolytic testing of sodium chloride solution was carried out under the same conditions as in example 2, at a test temperature of 85 ℃ and a current density of 7kA/m2After 60 days of electrolysis experiment, the average cell voltage is 2.68V, the average current efficiency is 99.98 percent, and the surface resistance is 0.52 omega cm-2。
Example 3
The novel ultrathin low-resistance ion-conducting membrane for chlor-alkali industry described in this embodiment 3 is composed of a first perfluorocarboxylic acid-perfluorosulfonic acid polymer composite layer, a second perfluorocarboxylic acid-perfluorosulfonic acid polymer composite layer, a porous non-woven polymer layer, and a functional surface coating; wherein the functional surface coating is a porous rough structure composed of perfluorinated ionic polymer.
The preparation method of the novel ultrathin low-resistance ion-conducting membrane for chlor-alkali industry described in this example 3 comprises the following steps:
(1) adopting a perfluorinated sulfonic acid resin with IEC being 1.0mmol/g and a perfluorinated carboxylic acid resin with IEC being 0.8mmol/g according to a mass ratio of 10: 1, obtaining a material A by melting and granulating, and dissolving the material A in a polar solvent (a solvent prepared from ethanol and isopropanol according to a weight ratio of 1: 1) to prepare a perfluorosulfonic acid-perfluorocarboxylic acid resin solution; soaking a polytetrafluoroethylene porous non-woven membrane into an ultrasonically-treated trifluorotrichloroethane solvent for treatment for 1.5 hours, wherein the thickness of a porous non-woven polymer layer is 10 micrometers, the porosity is 85%, taking out and drying for later use, then spraying a perfluorosulfonic acid-perfluorocarboxylic acid resin solution on the upper surface and the lower surface of the porous non-woven polymer, and drying the porous non-woven polymer layer by adopting 1.0mmol/g of perfluorosulfonic acid resin and 0.8mmol/g of perfluorocarboxylic acid resin according to a mass ratio of 1: 10 compounding the perfluorinated sulfonic acid-perfluorinated carboxylic acid composite membrane prepared by mixing to form a perfluorinated ion exchange membrane precursor; wherein: the thickness of the perfluorosulfonic acid resin layer containing a small amount of perfluorocarboxylic acid resin was 20 μm, and the thickness of the perfluorocarboxylic acid resin layer containing a small amount of perfluorosulfonic acid resin was 7 μm.
(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 15 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) Mixing ethanol and isopropanol according to a ratio of 1:1, then adding perfluorinated sulfonic acid resin with the exchange capacity of 1.5 mmol/g, and treating for 4 hours at 240 ℃ in a closed reaction kettle to obtain a uniform perfluorinated sulfonic acid solution with the mass fraction of 10%.
(4) And (3) adding the polytrimethylene terephthalate resin particles with the average particle size of 1 micron into the perfluorosulfonic acid solution in the step (3), and performing ball milling for 42 hours to obtain a dispersion solution with the mass fraction of 30%.
(5) And (3) attaching the dispersion liquid obtained in the step (4) to the two side surfaces of the perfluorinated ion exchange membrane base membrane with the thickness of 50 micrometers by adopting a spraying method, wherein the average thickness of the surface layer is 8 micrometers, and drying at 150 ℃ for 2 hours.
(6) And (3) treating the film containing the coating obtained in the step (5) in a 10% NaOH solution for 1 hour at 60 ℃.
Performance testing
The hydrophobic bubble coating with the ion conduction function has the pore volume accounting for 65 percent of the volume fraction of the coating.
The film surface was tested to have a roughness Ra value of 975 nm in the range of 10 microns by 10 microns and a roughness Ra value of 8.1 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.
Subjecting the prepared ion exchange membrane to electrolysis test of potassium chloride aqueous solution in an electrolytic cell, supplying 300g/L potassium chloride aqueous solution to an anode chamber, supplying water to a cathode chamber, and ensuring that the concentration of potassium chloride discharged from the anode chamber is equal to205g/L, the concentration of potassium hydroxide discharged from the cathode chamber is 34 percent; the test temperature was 82 ℃ and the current density was 5.5kA/m2After 35 days of electrolysis experiments, the average cell pressure is 2.49V, and the average current efficiency is 99.66%.
The sheet resistance of the resulting film was measured to be 0.39. omega. cm by the standard SJ/T10171.5 method-2。
Example 4
The novel ultrathin low-resistance ion-conducting membrane for chlor-alkali industry described in this embodiment 4 is composed of a first perfluorocarboxylic acid-perfluorosulfonic acid polymer composite layer, a second perfluorocarboxylic acid-perfluorosulfonic acid polymer composite layer, a porous non-woven polymer layer, and a functional surface coating; wherein the functional surface coating is a porous rough structure composed of perfluorinated ionic polymer.
The preparation method of the novel ultrathin low-resistance ion-conducting membrane for chlor-alkali industry described in this example 4 comprises the following steps:
(1) the mass ratio of IEC (1.0 mmol/g) perfluorinated sulfonic acid resin to IEC (0.8 mmol/g) perfluorinated carboxylic acid resin is 20: 1, obtaining a material A by melting and granulating, and dissolving the material A in a polar solvent (a solvent prepared from ethanol and isopropanol according to a weight ratio of 1: 1) to prepare a perfluorosulfonic acid-perfluorocarboxylic acid resin solution; soaking a polytetrafluoroethylene porous non-woven membrane into an ultrasonically-treated trifluorotrichloroethane solvent for treatment for 1.5 hours, wherein the thickness of a porous non-woven polymer layer is 10 micrometers, the porosity is 85%, taking out and drying for later use, then spraying a perfluorosulfonic acid-perfluorocarboxylic acid resin solution on the upper surface and the lower surface of the porous non-woven polymer, and drying the porous non-woven polymer layer by adopting 1.0mmol/g of perfluorosulfonic acid resin and 0.8mmol/g of perfluorocarboxylic acid resin according to a mass ratio of 1: 20 compounding the perfluorinated sulfonic acid-perfluorinated carboxylic acid composite membrane prepared by mixing to form a perfluorinated ion exchange membrane precursor; wherein: the thickness of the perfluorosulfonic acid resin layer containing a small amount of perfluorocarboxylic acid resin was 50 μm, and the thickness of the perfluorocarboxylic acid resin layer containing a small amount of perfluorosulfonic acid resin was 15 μm.
(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 15 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) Mixing ethanol and isopropanol according to a ratio of 1:1, then adding perfluorinated sulfonic acid resin with the exchange capacity of 1.3 mmol/g, and treating for 3 hours at 250 ℃ in a closed reaction kettle to obtain a uniform perfluorinated sulfonic acid solution with the mass fraction of 15%.
(4) Adding potassium carbonate particles with the average particle size of 1 mu m into the perfluorosulfonic acid solution obtained in the step (3), 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 (2) to the two side surfaces of the perfluorinated ion exchange membrane with the thickness of 85 micrometers by adopting a brush coating method, wherein the average thickness of the surface layer is 4 micrometers, and drying at 150 ℃ for 2 hours.
(6) And (4) treating the film containing the coating obtained in the step (3) in a 10% HCl solution for 1 hour at normal temperature.
Performance testing
The hydrophobic bubble coating with the ion conduction function has the pore volume accounting for 30 percent of the volume of the coating.
The film surface was tested to have a roughness Ra value of 878 nm in the range of 10 microns by 10 microns and a roughness Ra value of 3.6 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 82. mu.l.
Carrying out an electrolysis test on a potassium chloride aqueous solution in an electrolytic cell by using the prepared ion exchange membrane, supplying 300g/L of the potassium chloride aqueous solution to an anode chamber, supplying water to a cathode chamber, and ensuring that the concentration of potassium chloride discharged from the anode chamber is 205g/L and the concentration of potassium hydroxide discharged from the cathode chamber is 34%; the test temperature was 82 ℃ and the current density was 5.5kA/m2After 35 days of electrolysis experiments, the average cell pressure is 2.52V, and the average current efficiency is 99.8%.
The sheet resistance of the resulting film was measured to be 0.44. omega. cm by the standard SJ/T10171.5 method-2。
Summary of test data for examples 1-4 and comparative examples 1-3:
table 1 table comparing test data of examples and comparative examples
Figure BDA0002353065010000091
Figure BDA0002353065010000101

Claims (10)

1. A novel ultra-thin low resistance chlor-alkali industrial ion conduction membrane is characterized in that: the composite material consists of a first perfluorocarboxylic acid-perfluorosulfonic acid polymer composite layer, a second perfluorocarboxylic acid-perfluorosulfonic acid polymer composite layer, a porous non-woven polymer layer and a functional surface coating; wherein the functional surface coating is a porous rough structure composed of perfluorinated ionic polymer.
2. The novel ultra-thin low resistance chlor-alkali industrial ion conductive membrane of claim 1, characterized by: the thickness of the first perfluorocarboxylic acid-perfluorosulfonic acid polymer composite layer is 10-80 microns, the mass ratio of the perfluorocarboxylic acid polymer to the perfluorosulfonic acid polymer is 0-40%, the exchange capacity of the perfluorosulfonic acid polymer is 0.6-1.5 mmol/g, and the exchange capacity of the perfluorocarboxylic acid polymer is 0.5-1.5 mmol/g.
3. The novel ultra-thin low resistance chlor-alkali industrial ion conductive membrane of claim 1, characterized by: the thickness of the second perfluorocarboxylic acid-perfluorosulfonic acid polymer composite layer is 1-20 microns, the mass ratio of the perfluorosulfonic acid polymer to the perfluorocarboxylic acid polymer is 0-40%, the exchange capacity of the perfluorosulfonic acid polymer is 0.6-1.5 mmol/g, and the exchange capacity of the perfluorocarboxylic acid polymer is 0.5-1.5 mmol/g.
4. The novel ultra-thin low resistance chlor-alkali industrial ion conductive membrane of claim 1, characterized by: the mass ratio of the perfluorocarboxylic acid polymer in the first perfluorocarboxylic acid-perfluorosulfonic acid polymer composite layer to the perfluorosulfonic acid polymer and the mass ratio of the perfluorosulfonic acid polymer in the second perfluorocarboxylic acid-perfluorosulfonic acid polymer composite layer to the perfluorocarboxylic acid polymer cannot be both 0.
5. The novel ultra-thin low resistance chlor-alkali industrial ion conductive membrane of claim 1, characterized by: the porous non-woven polymer layer is made of one or a combination of more of polytetrafluoroethylene, polyvinylidene fluoride, polyimide or polyether ether ketone, the porosity is 20-99%, and the thickness is 3-50 microns.
6. The novel ultra-thin low resistance chlor-alkali industrial ion conductive membrane of claim 1, characterized by: the inner part and the surface of the functional surface coating are porous rough structures, and the thickness of the coating is 0.01-30 mu m; the roughness Ra value in the range of 10 micrometers to 10 micrometers is 10 nanometers to 5 micrometers, and the roughness Ra value in the range of 240 micrometers to 300 micrometers is 300 nanometers to 10 micrometers.
7. The novel ultra-thin low resistance chlor-alkali industrial ion conductive membrane of claim 1, characterized by: the volume of the coating hole of the functional surface accounts for 5 to 95 percent of the volume fraction of the coating; the exchange capacity of the perfluorinated ion polymer is 0.5-1.5 mmol/g; the perfluoroionomer is one or both of a perfluorosulfonic acid polymer or a perfluorophosphoric acid polymer.
8. The novel ultra-thin low resistance chlor-alkali industrial ion conductive membrane of claim 1, characterized by: the adhesion force of 3 microliter volume bubbles and the coating is 0-400 micro-newtons in a 0-300 g/L saline water environment of the functional surface coating; at 25 ℃, in 250g/L saline environment, the contact angle of 5 microliter bubbles is more than or equal to 130 degrees.
9. The preparation method of the novel ultrathin low-resistance ion-conducting membrane for alkali chloride industry, which is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing and extruding a perfluorosulfonic acid polymer and a perfluorocarboxylic acid polymer for granulation, using the mixture as a material A, and dissolving the material A in a polar solution to prepare a perfluorosulfonic acid-perfluorocarboxylic acid resin solution; mixing a perfluorosulfonic acid polymer and a perfluorocarboxylic acid polymer into a material B to prepare a second perfluorosulfonic acid-perfluorocarboxylic acid composite membrane; soaking the porous non-woven polymer layer material into a trifluoro-trichloroethane solvent subjected to ultrasonic treatment for treatment, taking out and drying for later use, spraying a perfluorosulfonic acid-perfluorocarboxylic acid resin solution on the upper surface and the lower surface of the porous non-woven polymer, drying, and compounding with a second perfluorosulfonic acid-perfluorocarboxylic acid composite membrane to form 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 transforming the perfluorinated ion exchange membrane 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 pore-forming agents 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 the perfluorinated ion exchange membrane prepared in the step (2) in a coating mode, and etching the surface to form a porous rough structure.
10. The method for preparing the novel ultra-thin low-resistance ion-conducting membrane for alkali chloride industry according to claim 9, is characterized in that: in the step (1), the mass ratio of the perfluorocarboxylic acid polymer in the material A to the perfluorosulfonic acid polymer is 0-40%, the mass ratio of the perfluorosulfonic acid polymer in the material B to the perfluorocarboxylic acid polymer is 0-40%, and the mass ratios of the perfluorocarboxylic acid polymer and the perfluorosulfonic acid polymer are not 0 at the same time; the perfluorinated ionic polymer in the step (3) is one or two of perfluorinated sulfonic acid polymer or perfluorinated phosphoric acid polymer; 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.
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