CN111188063A - Novel low-resistance ion conduction membrane for chlor-alkali industry and preparation method thereof - Google Patents

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

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CN111188063A
CN111188063A CN201911423929.4A CN201911423929A CN111188063A CN 111188063 A CN111188063 A CN 111188063A CN 201911423929 A CN201911423929 A CN 201911423929A CN 111188063 A CN111188063 A CN 111188063A
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perfluorinated
polymer
acid polymer
membrane
perfluorocarboxylic
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CN111188063B (en
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张永明
雷建龙
刘烽
张恒
张振
赵宽
王丽
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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets

Abstract

The invention belongs to the technical field of ion exchange membranes, and particularly relates to a novel 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 perfluoropolymer reinforcing net and a functional surface coating; the functional surface coating is a porous rough structure formed by perfluorinated ionic polymer, and the perfluorinated polymer reinforcing net is formed by compounding and weaving non-woven polymer and protein fiber. According to the novel low-resistance ion-conducting membrane for the 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 perfluorocarboxylic acid layer; a perfluorinated polymer reinforcing net is used as a reinforcing material, so that the membrane resistance is reduced; the usage amount of inorganic oxide or fluorine-containing particles in the traditional coating is reduced, the surface resistance of the composite membrane is reduced, and the rapid transmission of ions is facilitated.

Description

Novel 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 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 low-resistance chlor-alkali ion conduction membrane is developed, 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 the 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 ion conduction membrane for low-resistance chlor-alkali industry. The ion conducting membrane for low resistance chlor-alkali industry shows lower cell voltage and greatly saves electric energy because the separation of metal oxide which does not conduct ions is eliminated. The invention also provides a preparation method thereof.
The novel low-resistance ion-conducting membrane for the chlor-alkali industry consists of a first perfluorocarboxylic acid-perfluorosulfonic acid polymer composite layer, a second perfluorocarboxylic acid-perfluorosulfonic acid polymer composite layer, a perfluoropolymer reinforcing net and a functional surface coating; the functional surface coating is a porous rough structure formed by perfluorinated ionic polymer, and the perfluorinated polymer reinforcing net is formed by compounding and weaving non-woven polymer and protein fiber.
Wherein:
the first perfluorocarboxylic acid-perfluorosulfonic acid polymer composite layer has a thickness of 50 to 250 micrometers, preferably 60 to 150 micrometers; 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 perfluorosulfonic acid polymer to the perfluorocarboxylic 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 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 simultaneously 0.
The first perfluorosulfonic acid-perfluorocarboxylic acid polymer composite layer contains criss-cross hollow tunnels; the distance between two adjacent main fibers in the perfluoropolymer reinforced 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 perfluoropolymer reinforcing web has a porosity of 20-99%, preferably 60-80%, and a thickness of 50-200 microns, preferably 50-100 microns.
The non-woven polymer is one or a combination of more of polytetrafluoroethylene, polyvinylidene fluoride, polyimide or polyether ether ketone, and the like, preferably polytetrafluoroethylene, the porosity is 20-99%, preferably 60-80%, and the thickness is 3-50 microns, preferably 10-40 microns.
The protein fiber is one or more of silk fiber, wool fiber or soybean protein composite fiber.
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 preparation method of the novel ion conduction membrane for low-resistance chlor-alkali industry provided by the invention comprises the following steps:
(1) mixing a perfluorosulfonic acid polymer and a perfluorocarboxylic acid polymer, extruding and granulating to obtain a material A; mixing a perfluorosulfonic acid polymer and a perfluorocarboxylic acid polymer, extruding and granulating to obtain a material B; respectively adding the material A and the material B into co-extrusion equipment, extruding and casting to form a perfluorinated ion exchange membrane base membrane, soaking a perfluorinated polymer reinforcing mesh material into an ultrasonically treated trifluorotrichloroethane solvent for treatment, taking out and drying the perfluorinated polymer reinforcing mesh material, and compounding the perfluorinated ion exchange membrane base membrane with the perfluorinated ion exchange membrane to form a perfluorinated ion exchange membrane precursor;
(2) performing overpressure treatment on the perfluorinated ion exchange membrane precursor prepared in the step (1), then transforming the perfluorinated ion exchange membrane into a perfluorinated ion exchange membrane with an ion exchange function, and simultaneously dissolving and discarding silk in a perfluorinated polymer reinforcing net to form a hollow tunnel structure;
(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 low-resistance ion-conducting membrane for the 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 perfluorocarboxylic acid layer; a perfluorinated polymer reinforcing net is used as a reinforcing material, so that the membrane resistance is reduced; the usage amount of inorganic oxide or fluorine-containing particles in the traditional coating is reduced, the surface resistance of the composite membrane is reduced, and the rapid transmission of ions is facilitated.
(2) According to the novel low-resistance ion conduction membrane for chlor-alkali industry, disclosed by the invention, 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 by preparing the functional surface coating porous structure on the surface of the membrane.
(3) The novel low-resistance ion conduction membrane for chlor-alkali industry is applied to a novel zero polar distance electrolytic cell under a high current density condition to operate, the interior of the novel low-resistance ion conduction membrane is reinforced by a perfluoropolymer reinforcing net, the surface of the novel low-resistance ion conduction membrane has an excellent function of driving bubbles to attach, and the voltage of the electrolytic cell can be effectively reduced.
(4) The novel 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 be attached 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 low-resistance ion conduction membrane for chlor-alkali industry has the advantages of simple and reasonable process, simple and convenient use and easy industrial production.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
The novel low-resistance ion-conducting membrane for alkali chloride industry shown in this embodiment 1 is composed of a first perfluorocarboxylic acid-perfluorosulfonic acid polymer composite layer, a perfluorocarboxylic acid polymer layer, a perfluoropolymer reinforcing mesh, and a functional surface coating; the functional surface coating is a porous rough structure formed by perfluorinated ionic polymer, and the perfluorinated polymer reinforcing net is formed by compounding and weaving polytetrafluoroethylene and silk.
The preparation method of the novel low-resistance ion-conducting membrane for alkali chloride industry described in this embodiment 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: 1, obtaining a material A through melting granulation, then compounding a perfluorinated ion exchange resin base membrane in a coextrusion casting mode by mixing the material A and perfluorocarboxylic acid resin with IEC (international electrotechnical commission) of 0.8mmol/g, wherein the thickness of a perfluorosulfonic acid resin layer containing a small amount of perfluorocarboxylic acid resin is 100 micrometers, the thickness of the perfluorocarboxylic acid resin layer is 7 micrometers, and then soaking a reinforcing material compounded and woven by polytetrafluoroethylene and silk into a trifluorotrichloroethane solvent subjected to ultrasonic treatment for 1.5 hours, wherein the thickness of a porous reinforcing material is 80 micrometers, and the volume ratio of the polytetrafluoroethylene to the silk is 1:1, the porosity of the reinforcing material is 60%, and the reinforcing material is taken out, dried and compounded with a perfluorinated ion exchange resin base membrane to form a perfluorinated 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 15 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 perfluorinated polymer reinforcing net to form a hollow tunnel structure; the distance between two adjacent main fibers in the perfluoropolymer reinforced 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) Mixing ethanol and isopropanol according to a ratio of 1:1, then 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 3%.
(4) Adding zinc oxide particles with the average particle size of 400 nanometers 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 two sides of the perfluorinated ion exchange membrane with the thickness of 210 micrometers prepared in the step (2) by adopting a spraying method, and drying at 150 ℃ for 2 hours to obtain the perfluorinated ion exchange membrane with the thickness of 5 micrometers per square meter.
(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.
Performance detection
The film surface had a roughness Ra value of 375 nm over 10 microns and 5.6 microns over 300 microns, and an adhesion of 68 μ n measured with 3 μ l air bubbles in 250g/l nacl solution.
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 85 ℃ and the current density was 7.0kA/m2After 60 days of electrolysis experiments, the average cell pressure is 2.78V, and the average current efficiency is 99.94%.
The sheet resistance of the resulting film was measured to be 0.81. 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%. An 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 382 nm in the range of 10 μm to 10 μm and a roughness Ra value of 5.5 μm in the range of 240 μm to 300 μm, and the adhesion was measured in a 250g/L NaCl solution using 3. mu.l of air bubbles and found to be 80. mu.l.
Electrolytic testing of sodium chloride solution was carried out under the same conditions as in example 1, with a test temperature of 85 ℃ and a current density of 7.0kA/m2After 60 days of electrolysis experiment, the average cell voltage was 3.03V, the average current efficiency was 99.94%, and the surface resistance was 0.92. omega. cm-2。
Example 2
The ion-conducting membrane for low-resistance chlor-alkali industry shown in this example 2 is composed of a perfluorosulfonic acid polymer layer, a second perfluorocarboxylic acid-perfluorosulfonic acid polymer composite layer, a perfluoropolymer reinforcing mesh and a functional surface coating; the functional surface coating is a porous rough structure formed by perfluorinated ionic polymer, and the perfluorinated polymer reinforcing net is formed by compounding and weaving polytetrafluoroethylene and silk.
The preparation method of the novel low-resistance ion conducting membrane for alkali chloride industry described in this embodiment 2 comprises the following steps:
(1) the method comprises the following steps of (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 in a mass ratio of 1: 100, obtaining a material A through melting granulation, compounding a perfluorinated ion exchange resin base membrane in a coextrusion casting mode by mixing the material A and perfluorinated sulfonic acid resin with IEC (international electrotechnical commission) being 1.0mmol/g, wherein the thickness of the perfluorinated sulfonic acid layer is 70 micrometers, the thickness of a perfluorinated carboxylic acid resin layer containing a small amount of perfluorinated sulfonic acid resin is 10 micrometers, soaking a reinforcing material compounded and woven by polytetrafluoroethylene and silk into a trifluoro trichloroethane solvent subjected to ultrasonic treatment for 1.5 hours, wherein the thickness of the porous reinforcing material is 45 micrometers, the volume ratio of the polytetrafluoroethylene to the silk is 1:1.5, the porosity of the reinforcing material is 30%, taking out, drying, and compounding with the perfluorinated ion exchange resin base membrane to form the perfluorinated ion precursor exchange membrane.
(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 15 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 perfluorinated polymer reinforcing net to form a hollow tunnel structure; the distance between two adjacent main fibers in the perfluoropolymer reinforced net is 0.7 +/-0.1 mm, and the two adjacent main fibers contain 316 hollowed-out tunnels; the diameter of the single tunnel is 5 +/-1 mu m.
(3) Mixing ethanol and isopropanol according to a ratio of 1:1, then adding perfluorinated sulfonic acid resin with the exchange capacity of 1.0mmol/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) Adding zinc oxide particles with the average particle size of 200 nanometers into the perfluorosulfonic acid solution in the step (1), and performing 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 two sides of the 140-micron-thickness perfluorinated ion exchange membrane prepared in the step (2) by adopting a spraying method, and drying the perfluorinated ion exchange membrane at 150 ℃ for 2 hours to obtain the coating with the thickness of 2 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.
Performance detection
The film surface had a roughness Ra value of 165 nm in the range of 10 microns by 10 microns, a roughness Ra value of 1.8 microns in the range of 240 microns by 300 microns, and an adhesion of 89 μ n in a 250g/l nacl solution measured 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 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 2.69V, and the average current efficiency is 99.43%.
The sheet resistance of the resulting film was measured to be 0.61. 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 film surface had a roughness Ra value of 165 nm in the range of 10 microns by 10 microns, a roughness Ra value of 1.8 microns in the range of 240 microns by 300 microns, and an adhesion of 65 μ n measured in a 250g/l nacl solution with 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 was 2.72V, the average current efficiency was 99.52%, and the sheet resistance was 0.63. omega. cm-2。
Example 3
The novel low-resistance ion-conducting membrane for alkali chloride 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 perfluoropolymer reinforcing mesh, and a functional surface coating; the functional surface coating is a porous rough structure formed by perfluorinated ionic polymer, and the perfluorinated polymer reinforcing net is formed by compounding and weaving non-woven polymer and protein fiber.
The preparation method of the novel 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 granulation, and adopting a perfluorinated sulfonic acid resin with IEC (1.0 mmol/g) and a perfluorinated carboxylic acid resin with IEC (0.8 mmol/g) according to a mass ratio of 1: 10 obtaining a material B through melting granulation, wherein the thickness of a perfluorosulfonic acid polymer layer containing a small amount of perfluorocarboxylic acid is 60 microns, the thickness of a perfluorocarboxylic acid resin layer is 15 microns, adding the material A and the material B into co-extrusion equipment respectively, extruding and casting to form a perfluoroion exchange membrane base film, soaking a reinforcing material compounded and woven by polytetrafluoroethylene and silk into a trifluorotrichloroethane solvent subjected to ultrasonic treatment for 1.5 hours, wherein the thickness of a porous reinforcing material is 55 microns, the volume ratio of the polytetrafluoroethylene to the silk is 1:1.5, the porosity of the reinforcing material is 30%, taking out, drying and compounding with the perfluoroion exchange resin base film to form the perfluoroion 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 15 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 perfluorinated polymer reinforcing net to form a hollow tunnel structure; the distance between two adjacent main fibers in the perfluoropolymer reinforced net is 1.3 +/-0.1 mm, and 149 hollowed-out tunnels are arranged in the two adjacent main fibers; the diameter of the single tunnel is 28 +/-2 mu m.
(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) And (3) adding the chopped polyurethane fibers with the average length of 200 micrometers and the diameter of 1 micrometer into the perfluorosulfonic acid solution obtained in the step (3), and performing ball milling for 36 hours to obtain a dispersion solution with the mass fraction of 26%.
(5) And (3) attaching the dispersion liquid obtained in the step (4) to the two side surfaces of the perfluorinated ion exchange membrane with the thickness of 135 micrometers obtained in the step (2) by adopting a transfer printing method, wherein the average thickness of the surface layer is 8 micrometers, and drying the surface layer for 2 hours at 150 ℃.
(6) And (3) carrying out heat treatment on the film containing the coating obtained in the step (5) in a 10% NaOH solution at 80 ℃ for 2 hours.
And (3) 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 1042 nm in the range of 10 microns by 10 microns and a roughness Ra value of 9.6 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 95. mu.l.
Carrying out an electrolytic sodium chloride test on the prepared ion exchange membrane in an electrolytic cell, supplying 290g/L of sodium chloride aqueous solution to an anode chamber, supplying water to a cathode chamber, controlling the concentration of sodium chloride discharged from the anode chamber to be about 190g/L, and controlling the concentration of sodium hydroxide discharged from the cathode chamber to be 32%; the test temperature was 81 ℃ and the current density was 6kA/m2After 30-day electrolysis experiments, the average cell pressure is 2.68V, and the average current efficiency is 99.57%.
The sheet resistance of the resulting film was 0 as measured by the standard SJ/T10171.5 method.42Ω·cm-2。
Example 4
The novel low-resistance ion-conducting membrane for alkali chloride 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 perfluoropolymer reinforcing mesh, and a functional surface coating; the functional surface coating is a porous rough structure formed by perfluorinated ionic polymer, and the perfluorinated polymer reinforcing net is formed by compounding and weaving non-woven polymer and protein fiber.
The preparation method of the novel low-resistance ion conducting membrane for alkali chloride industry described in this embodiment 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 granulation, and adopting a perfluorinated sulfonic acid resin with IEC (1.0 mmol/g) and a perfluorinated carboxylic acid resin with IEC (0.8 mmol/g) according to a mass ratio of 1: 20 obtaining a material B through melting granulation, wherein the thickness of a perfluorosulfonic acid polymer layer containing a small amount of perfluorocarboxylic acid is 50 microns, the thickness of a perfluorocarboxylic acid resin layer is 15 microns, adding the material A and the material B into co-extrusion equipment respectively, extruding and casting to form a perfluoroion exchange membrane base film, soaking a reinforcing material compounded and woven by polytetrafluoroethylene and silk into a trifluorotrichloroethane solvent subjected to ultrasonic treatment for 1.5 hours, wherein the thickness of the porous reinforcing material is 45 microns, the volume ratio of the polytetrafluoroethylene to the silk is 1:1.5, the porosity of the reinforcing material is 30%, taking out, drying and compounding with the perfluoroion exchange resin base film to form the perfluoroion 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 15 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 perfluorinated polymer reinforcing net to form a hollow tunnel structure; the distance between two adjacent main fibers in the perfluoropolymer reinforced net is 1.1 +/-0.1 mm, and 35 hollow tunnels are arranged in the two adjacent main fibers; the diameter of the single tunnel is 45 +/-2 mu m.
(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 a perfluorinated ion exchange membrane with the thickness of 125 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 for roughness Ra value of 995 nm in the range of 10 microns by 10 microns and roughness Ra value of 3.5 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 103. 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 2.6V, and the average current efficiency is 99.62%.
The sheet resistance of the obtained film was measured to be 0.41. omega. cm by the Standard SJ/T10171.5 method-2。
The test data for each example and comparative example are summarized in table 1 below.
Table 1 table comparing test data of examples and comparative examples
Figure BDA0002353063520000091
Figure BDA0002353063520000101

Claims (10)

1. A novel low-resistance ion conduction membrane for chlor-alkali industry 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 perfluoropolymer reinforcing net and a functional surface coating; the functional surface coating is a porous rough structure formed by perfluorinated ionic polymer, and the perfluorinated polymer reinforcing net is formed by compounding and weaving non-woven polymer and protein fiber.
2. The novel 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 50 to 250 micrometers; 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; the perfluorocarboxylic acid polymer has an exchange capacity of 0.5 to 1.5 mmol/g.
3. The novel 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 micrometers; 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; the perfluorocarboxylic acid polymer has an exchange capacity of 0.5 to 1.5 mmol/g.
4. The novel 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 low resistance chlor-alkali industrial ion conductive membrane of claim 1, characterized by: the first perfluorosulfonic acid-perfluorocarboxylic acid polymer composite layer contains criss-cross hollow tunnels; the distance between two adjacent main fibers in the perfluoropolymer reinforced 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 novel low resistance chlor-alkali industrial ion conductive membrane of claim 1, characterized by: the perfluor polymer reinforced net has a porosity of 20-99% and a thickness of 50-200 microns; the non-woven polymer is one or a combination of more of polytetrafluoroethylene, polyvinylidene fluoride, polyimide or polyether ether ketone, and the thickness of the non-woven polymer is 3-50 micrometers.
7. The novel 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.
8. The novel 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 in the functional surface coating is 0.5-1.5 mmol/g, and the perfluorinated ion polymer is one or two of perfluorinated sulfonic acid polymer or perfluorinated phosphoric acid polymer.
9. A method for preparing the novel ion-conducting membrane for low-resistance chlor-alkali industry as defined in claim 1, characterized in that: prepared by the following steps:
(1) mixing perfluorinated sulfonic acid resin and perfluorinated carboxylic acid resin, extruding and granulating to obtain a material A; mixing perfluorinated sulfonic acid resin and perfluorinated carboxylic acid resin, extruding and granulating to obtain a material B; respectively adding the material A and the material B into co-extrusion equipment, extruding and casting to form a perfluorinated ion exchange membrane base membrane, soaking a perfluorinated polymer reinforcing mesh material into a trifluorotrichloroethane solvent for treatment, taking out and drying the perfluorinated polymer reinforcing mesh material, and compounding the perfluorinated ion exchange membrane base membrane with the perfluorinated ion exchange membrane to form a perfluorinated ion exchange membrane precursor;
(2) performing overpressure treatment on the perfluorinated ion exchange membrane precursor prepared in the step (1), then transforming the perfluorinated ion exchange membrane into a perfluorinated ion exchange membrane with an ion exchange function, and simultaneously dissolving and discarding silk in a perfluorinated polymer reinforcing net to form a hollow tunnel structure;
(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 ion-conducting membrane for low-resistance chlor-alkali industry according to claim 9, 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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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111074295A (en) * 2019-12-31 2020-04-28 山东东岳未来氢能材料有限公司 Novel low-resistance ion conduction membrane for chlor-alkali industry and preparation method thereof
CN111074295B (en) * 2019-12-31 2021-07-16 山东东岳高分子材料有限公司 Novel low-resistance ion conduction membrane for chlor-alkali industry and preparation method thereof

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