CN112323095B - High-strength low-cell-pressure perfluorinated ion exchange membrane for chlor-alkali industry and preparation method thereof - Google Patents
High-strength low-cell-pressure perfluorinated ion exchange membrane for chlor-alkali industry and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-strength low-groove-pressure perfluorinated ion exchange membrane for chlor-alkali industry and a preparation method thereof, belonging to the technical field of perfluorinated ion exchange membranes. The invention relates to a high-strength low-groove-pressure perfluorinated ion exchange membrane for the chlor-alkali industry, which comprises a base membrane consisting of a perfluorinated sulfonic acid resin layer and a perfluorinated carboxylic acid resin layer, wherein a reinforced fiber mesh is embedded into the perfluorinated sulfonic acid resin layer, and gas release coatings are sprayed on the two outer side surfaces of the base membrane; the perfluorosulfonic acid resin layer is internally provided with discontinuous micro-nano pores which are positioned in the perfluorosulfonic acid resin layer and are formed by micro-nano hollow fibers with ion exchange capacity. The high-strength low-tank-pressure perfluorinated ion exchange membrane for the chlor-alkali industry has good electrochemical performance and excellent mechanical strength; the invention also provides a simple and feasible preparation method.
Description
Technical Field
The invention relates to a high-strength low-groove-pressure perfluorinated ion exchange membrane for chlor-alkali industry and a preparation method thereof, belonging to the technical field of perfluorinated ion exchange membranes.
Background
The U.S. DuPont company developed perfluorosulfonic acid resins and their ion exchange membranes in the 60's. It has been found that the perfluorinated ion exchange membrane with a skeleton structure has extraordinary stability, and is most suitable for use in the harsh environment of chlor-alkali electrolysis cells, so that the perfluorinated ion exchange membrane is rapidly and widely applied to the chlor-alkali industry. Inspired by DuPont's perfluorinated ion exchange membranes, Japanese Asahi glass company and Japanese Asahi chemical company have also developed perfluorinated ion exchange resins and ion membranes of similar structures. In 1976, a perfluorocarboxylic acid membrane was used by Asahi Kasei Corp. to replace a perfluorosulfonic acid membrane by DuPont Corp. and thenA carboxylic acid-sulfonic acid composite membrane. In 2009, the polymer materials ltd in the east of Shandong was successfully developed into a domestic chlor-alkali ion membrane, and the experimental device (2.7 m) of yellow Ye chlor-alkali ltd in Cangzhou university group ltd, blue Star (Beijing) chemical machinery ltd, was first introduced2Electrolytic cell) to achieve initial success. Then in the chlor-alkali plant of Shandong Yueye Fluorosilicone materials Co., Ltd, and the chlor-alkali plant F of Zhongji Changzhou chemical industry Co., Ltd2The successful application of the device and the like reveals a new chapter of the chlor-alkali industry in China.
Currently, all commercialized perfluoro ion exchange membranes (chlor-alkali ion membranes) for the chlor-alkali industry are perfluorocarboxylic acid-perfluorosulfonic acid composite membranes, that is, the anode side of the membrane is a perfluorosulfonic acid layer, and the cathode side of the membrane is a perfluorocarboxylic acid layer. The sulfonic acid layer has higher ion permeability and lower cell voltage within the alkali concentration of 20-30 percent, so that the power consumption can be remarkably saved; while the carboxylic acid layer can block OH-And ions permeate and migrate to the anode, so that higher current efficiency is ensured.
In order to achieve high current density and maintain a certain mechanical strength and dimensional stability of the ionic membrane, materials such as fibers, cloth, and fabrics are usually used to enhance the mechanical strength of the ionic membrane and maintain the dimensional stability of the membrane material. European patent EP0875524B1 discloses the reinforcement of dupont Nafion series membranes with glass fibre membranes prepared by means of glass fibre non-woven technology, in which patent documents oxides such as silica are also mentioned. However, the non-woven glass fiber cloth in the patent document is a necessary substrate, which greatly limits the range of use of the film. U.S. Pat. No. 6,430,858 discloses a technique for preparing a fiber-reinforced perfluorosulfonic acid resin by mixing, extruding and transforming a perfluorosulfophthalein fluororesin and polytetrafluoroethylene fibers. The method cannot be used for continuous production due to time consumption in the transformation process, and meanwhile, functional inorganic substances are not used for improving the conductivity of the film. The perfluorinated ion exchange membrane used in the chlor-alkali industry needs to meet the following requirements: excellent electrochemical performance, low membrane voltage, high mechanical strength and dimensional stability. In general, when the ion exchange capacity of the perfluoro ion exchange membrane is increased, the membrane resistance is decreased, but the mechanical strength is decreased.
The latest chlor-alkali ionic membranes typically contain a "sacrificial core". The sacrificial core material is a fiber which is woven with a reinforcing fiber in the process of manufacturing a membrane, can be dissolved away through post-treatment after the membrane is formed, and the original occupied position of the sacrificial core material is changed into a water and ion channel, namely a channel for passing sodium ions on a unit area is increased, so that the membrane voltage is reduced, and the membrane with the sacrificial core material is suitable for a high-density natural circulation tank. CN101773788A discloses a fluorine-containing ion exchange membrane reinforced by a cloth with sacrificial fibers, which comprises a fluorine-containing ion exchange resin base membrane, the cloth with the sacrificial fibers and a hydrophilic coating; the fluorine-containing ion exchange resin base membrane comprises a perfluorocarboxylic acid resin membrane layer with the thickness of 5-10 microns, a perfluorosulfonic acid resin membrane layer with the thickness of 90-120 microns and a perfluorosulfonic acid/carboxylic acid copolymerization or blending resin membrane layer with the thickness of 0-40 microns, wherein the perfluorocarboxylic acid/carboxylic acid copolymerization or blending resin membrane layer is positioned between the perfluorocarboxylic acid membrane layer and the perfluorosulfonic acid membrane layer, and the mesh with sacrificial fibers consists of reinforcing fibers and sacrificial fibers, so that the electrochemical performance of the membrane can be improved, and the resistance of the membrane is effectively reduced. Before the sacrificial fiber is dissolved or chemically degraded, the strength of the membrane and the mechanical strength during initial driving can be ensured, and damage is avoided. After the isoelectric focusing operation is stable, the sacrificial fiber is slowly dissolved and disappears, the resistance of the membrane is naturally reduced, but the strength of the membrane is correspondingly reduced. This is because the sacrificial fibres are continuously and densely distributed in the membrane, and a continuous hole is actually formed in the membrane after the formation of the channels, thus reducing the mechanical strength of the membrane.
The CN103031566A patent introduces a fiber-reinforced perfluorinated ion exchange membrane containing non-continuous nanopores and a preparation method thereof. The authors added discontinuous nanopores in the perfluorosulfonic acid resin layer to provide a perfluorinated ion exchange membrane with better electrochemical properties and mechanical strength, and the nanopores were mainly constructed by adding nano sacrificial fiber materials, such as nano polyester fibers or nano polyamide fibers. However, the added nano sacrificial fiber materials do not have ion exchange capacity, so the authors require that the nano sacrificial fiber materials must be "sacrificed" to form a pore channel when the perfluorinated ion exchange membrane works, but once the pore channel is formed, the perfluorinated ion exchange membrane loses the supporting and reinforcing effect of a part of fibers, and certain loss and reduction of the mechanical strength of the ion membrane are inevitable.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects in the prior art and provide a high-strength low-cell-pressure perfluorinated ion exchange membrane for chlor-alkali industry, which not only has good electrochemical performance, but also has excellent mechanical strength; the invention also provides a simple and feasible preparation method.
The invention relates to a high-strength low-groove-pressure perfluorinated ion exchange membrane for the chlor-alkali industry, which comprises a base membrane consisting of a perfluorinated sulfonic acid resin layer and a perfluorinated carboxylic acid resin layer, wherein a reinforced fiber mesh is embedded into the perfluorinated sulfonic acid resin layer, and gas release coatings are sprayed on the two outer side surfaces of the base membrane; the perfluorosulfonic acid resin layer is internally provided with discontinuous micro-nano pores which are positioned in the perfluorosulfonic acid resin layer and are formed by micro-nano hollow fibers with ion exchange capacity.
The micro-nano hollow fiber is a perfluorinated sulfonic acid ion exchange hollow fiber membrane, and preferably has the outer diameter of 300 nm-20 microns, the length of 10-50 microns and the inner diameter of 20 nm-10 microns.
Preferably, the thickness of the perfluorosulfonic acid resin layer is 80 to 110 μm, the thickness of the perfluorocarboxylic acid resin layer is 8 to 12 μm, and the thickness of the gas release coating on both outer surfaces of the base film is 1 to 5 μm.
The perfluorinated sulfonic acid resin is prepared from the currently disclosed perfluorinated sulfonic acid resin materials, preferably a perfluorinated sulfonic acid resin obtained by copolymerizing tetrafluoroethylene and perfluorinated sulfonyl vinyl ether, and has an exchange capacity of 0.9-1.05 mmol/g.
The perfluorocarboxylic acid resin is prepared from the presently disclosed perfluorocarboxylic acid resin material, preferably a polymer obtained by copolymerizing tetrafluoroethylene and a small amount of perfluorocarboxylic acid ester vinyl ether, and has an ion exchange capacity of 0.88-1.05 mmol/g.
Preferably, the reinforcing fibers are one or more of Polytetrafluoroethylene (PTFE) fibers, polyperfluoroethylpropylene fibers, ion exchange functional fibers (fibers prepared in CN 101003588), polyperfluoropropyl vinyl ether fibers, tetrafluoroethylene-perfluorovinyl ether copolymer fibers, or fluorocarbon polymer fibers.
The gas release coating is formed by a mixture of perfluorinated sulfonic acid resin and nano inorganic oxide, and is specifically formed by coating nano inorganic oxide-lower alcohol dispersion containing perfluorinated sulfonic acid resin on the surface of an ion exchange resin base membrane and then drying.
Preferably, the nano inorganic oxide is ZnO or TiO2Or ZrO2Further, ZrO is preferable2。
The preparation method of the high-strength low-groove-pressure perfluorinated ion exchange membrane for the chlor-alkali industry comprises the following steps:
a. mixing a micro-nano hollow fiber material with ion exchange capacity and perfluorinated sulfonic acid resin powder according to a mass ratio of 1-20: 100, fully mixing, and performing melt extrusion to obtain perfluorosulfonic acid resin master batch containing the micro-nano hollow fiber material; preparing perfluorinated ion exchange resin base membranes from perfluorocarboxylic acid resin and the perfluorinated sulfonic acid resin master batch containing the micro-nano hollow fiber material by a melting coextrusion or multilayer hot pressing composite process;
b. placing a reinforcing fiber mesh cloth on the surface or inside of the perfluorinated sulfonic acid resin layer of the base film by adopting a continuous vacuum composite process to form a reinforced ionic membrane;
c. c, hydrolyzing the reinforced ionic membrane obtained in the step b in a mixed solution of KOH or NaOH aqueous solution and an organic solvent at the temperature of 70-90 ℃ for 30 min-2 h for transformation;
d. spraying the transformed ionic membrane by using a lower alcohol dispersion liquid containing 3-10 wt% of perfluorinated sulfonic acid resin and 5-15 wt% of nano inorganic oxide, and drying to form a gas release coating;
e. and soaking the sprayed film in a sodium hydroxide aqueous solution with the mass fraction of 0.2-2%, and standing and balancing to obtain the water-based paint.
In step c, the organic solvent is ethanol, isopropanol or dimethyl sulfoxide.
In the step c, the mass percentage of KOH or NaOH in the mixed solution is 12-28%, and the mass percentage of the organic solvent is 10-40%. Further preferably, the mass percent of KOH or NaOH in the mixed solution is 15-20%, and the mass percent of the organic solvent is 20-30%.
In step d, the lower alcohol is ethanol, propanol or isopropanol.
The high-strength low-groove-pressure perfluorinated ion exchange membrane prepared by the invention contains discontinuous micro-nano pore canals (also called as channels or cavities) and can be used on the current general chlor-alkali ion membrane electrolysis device. The invention realizes the manufacturing of discontinuous hollow pore canals in the membrane by utilizing the micro-nano hollow fiber material, and comprehensively improves the electrochemical performance and the mechanical performance of the membrane. The micro-nano hollow fiber material has a surface effect, a small-size effect and a macroscopic quantum tunnel effect, and can be prepared by melt extrusion. The ion exchange membrane for the chlor-alkali electrolytic cell with excellent comprehensive performance of mechanical performance and electrochemical performance is obtained by the preferred collocation of resin materials of each layer and the specific combination of process parameters.
Compared with the prior art, the invention has the following beneficial effects:
(1) the high-strength low-groove-pressure perfluorinated ion exchange membrane containing the discontinuous micro-nano pore canals for the chlor-alkali industry, disclosed by the invention, has the advantages that the mechanical strength of the membrane is further improved due to the fact that continuous holes or discontinuous holes formed by sacrificial fibers are avoided, and the membrane is safer and more reliable;
(2) the high-strength low-cell-pressure perfluorinated ion exchange membrane containing the discontinuous micro-nano pores for the chlor-alkali industry disclosed by the invention contains more micro-nano pores, and the micro-nano hollow fiber material has ion exchange capacity, so that the transfer resistance of ions and water is avoided, the cell voltage of the membrane is obviously reduced, and the membrane can save more energy when being used in an electrolytic cell for the chlor-alkali industry;
(3) the high-strength low-groove-pressure perfluorinated ion exchange membrane containing the discontinuous micro-nano pore channels for the chlor-alkali industry does not need to sacrifice the fiber in a longer time because the fiber does not exist in the membrane matrix in the traditional method, thereby obviously shortening the hydrolysis transformation time of the reinforced ion membrane in a mixed solution of KOH or NaOH aqueous solution and an organic solvent, improving the production efficiency and reducing the operation cost.
Drawings
FIG. 1 is a schematic cross-sectional structure diagram of a high-strength low-cell-pressure perfluorinated ion exchange membrane containing discontinuous micro-nano pores and used for chlor-alkali industry;
wherein, 1, a perfluorocarboxylic acid resin layer; 2. a layer of perfluorosulfonic acid resin; 3. a discontinuous micro-nano hollow fiber material; 4. a gas release coating; 5. reinforcing the fibers in the scrim.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
Example 1
The ion exchange capacity of the perfluorosulfonic acid resin in this example was 0.90mmol/g, and it was a powder obtained by copolymerizing tetrafluoroethylene and perfluoro 3, 6-dioxa-4-methyl-7-octenesulfonyl fluoride.
(1) Preparation of resin pellets
Mixing a micro-nano hollow fiber material with the ion exchange capacity and the perfluorinated sulfonic acid resin powder in a mass ratio of 1: 100, and then carrying out melt extrusion granulation to obtain the perfluorosulfonic acid resin granules containing the micro-nano hollow fiber material.
Obtaining powder obtained by copolymerizing tetrafluoroethylene and perfluoro-4, 7-dioxa-5 methyl-8-nonenoic acid methyl ester, and obtaining granules of perfluorocarboxylic acid resin through melt extrusion granulation; the ion exchange capacity was 0.88 mmol/g.
(2) Preparation and enhancement of membranes
Preparing a perfluorinated ion exchange resin base membrane by adopting the perfluorocarboxylic acid resin granules and the perfluorosulfonic acid resin granules containing the micro-nano hollow fiber material through a melting and co-extrusion process; the thickness of the perfluorosulfonic acid resin layer containing the micro-nano hollow fiber material is 80 microns, and the thickness of the perfluorocarboxylic acid resin layer is 12 microns. And then, a PTFE (polytetrafluoroethylene) reinforced mesh is placed inside a perfluorosulfonic acid resin layer in the perfluorinated ion exchange resin base membrane by adopting a continuous vacuum composite process to form a reinforced ionic membrane.
(3) Film transfer and spray coating
The reinforced ionic membrane obtained in the step (2) is added with water in a KOH water-ethanol solution (the mass fraction of KOH in the mixed solution is 20wt percent, and the mass fraction of ethanol is 30wt percent) at 90 DEG CAnd (5) performing transformation after 2h of solution. After drying, the mixture is treated with a mixture containing 3 wt% of perfluorosulfonic acid resin and 5wt% of nano ZrO2-spraying the transformed ionic membrane on both sides by using the ethanol dispersion liquid, and drying to form a gas release coating; the thickness of the gas release coating was 5 μm. And soaking the sprayed membrane in a sodium hydroxide aqueous solution with the mass fraction of 2%, standing and balancing for 4 hours to obtain the high-strength low-tank-pressure perfluorinated ion exchange membrane containing the discontinuous micro-nano pore channels for the chlor-alkali industry. The structure is shown in figure 1.
The ionic membrane prepared by the embodiment has the tensile strength of 39MPa, can be used for an ion exchange membrane in a chlor-alkali ionic membrane electrolytic cell, and is 6.0kA/m2At a current density of (1), the cathode NaOH solution mass ratio concentration is 32%, the anode cell entering brine NaCl concentration is 305g/L, the cell outlet brine NaCl concentration is 205g/L, the cell temperature is 86 +/-1 ℃, the active cathode is tested under the conditions of zero polar distance, the cell voltage is 3.00V, and then the surface resistance of the obtained membrane is 1.54 omega cm by testing according to a standard SJ/T10171.5 method2。
Example 2
The raw materials of the perfluorosulfonic acid resin and the perfluorocarboxylic acid resin powder were the same as in example 1.
(1) Preparation of resin pellets
Mixing a micro-nano hollow fiber material with the ion exchange capacity and the perfluorinated sulfonic acid resin powder in a mass ratio of (10): 100, and then carrying out melt extrusion granulation to obtain the perfluorosulfonic acid resin granules containing the micro-nano hollow fiber material. Pellets of perfluorocarboxylic acid resin were prepared as in example 1.
(2) Preparation and enhancement of membranes
The perfluorocarboxylic acid resin granules and the perfluorosulfonic acid resin granules containing the micro-nano hollow fiber material are adopted to respectively obtain a perfluoroion exchange resin base membrane containing a perfluorocarboxylic acid ion exchange resin membrane and a perfluorosulfonic acid ion exchange resin membrane through melt extrusion; the thickness of the perfluorinated sulfonic acid resin layer containing the micro-nano hollow fiber material is 110 mu m, and the thickness of the perfluorinated carboxylic acid resin layer is 8 mu m. Then, multilayer hot-pressing compounding is adopted, and the PTFE reinforced mesh is arranged inside the perfluorosulfonic acid resin layer to form the reinforced ionic membrane.
(3) Film transfer and spray coating
Hydrolyzing the reinforced ionic membrane obtained in the step (2) in a NaOH water-DMSO solution (a mixed solution of 15wt% of NaOH and 25 wt% of ethanol) at 70 ℃ for 2h for transformation. After drying, the mixture is treated with a mixture containing 5 mass percent of perfluorosulfonic acid resin and 12 mass percent of nano ZrO2-spraying the converted ionic membrane on both sides by using the isopropanol dispersion liquid, and drying to form a gas release coating; the thickness of the gas release coating was 1 μm. And soaking the sprayed membrane in a sodium hydroxide aqueous solution with the mass fraction of 0.2%, standing and balancing for 2 hours to obtain the high-strength low-groove-pressure perfluorinated ion exchange membrane containing the discontinuous micro-nano pore channels for the chlor-alkali industry.
The ionic membrane prepared by the embodiment has the tensile strength of 42MPa, can be used for an ion exchange membrane in a chlor-alkali ionic membrane electrolytic cell, and is 6.0kA/m2At a current density of (1), the cathode NaOH solution mass ratio concentration is 32%, the anode cell entering brine NaCl concentration is 305g/L, the cell outlet brine NaCl concentration is 205g/L, the cell temperature is 86 +/-1 ℃, the active cathode is tested under the conditions of zero polar distance, the cell voltage is 3.02V, and then the surface resistance of the obtained membrane is 1.60 omega cm by testing according to a standard SJ/T10171.5 method2。
Example 3
Step (1), step (2) and step (3) are the same as in example 1. The difference is that the micro-nano hollow fiber material with ion exchange capacity in the step (1) has the outer diameter of 20 microns, the length of 10 microns and the inner diameter of 10 nm.
The ionic membrane prepared by the embodiment has the tensile strength of 39MPa, can be used for an ion exchange membrane in a chlor-alkali ionic membrane electrolytic cell, and is 6.0kA/m2At a current density of (1), the cathode NaOH solution mass ratio concentration is 32%, the anode cell inlet brine NaCl concentration is 305g/L, the cell outlet brine NaCl concentration is 210g/L, the cell temperature is 86 +/-1 ℃, the active cathode is tested under the conditions of zero polar distance, the cell voltage is 3.03V, and then the surface resistance of the obtained membrane is 1.60 omega cm by testing according to a standard SJ/T10171.5 method2。
Example 4
Step (1), step (2) and step (3) are the same as in example 1. Except that in the step (3), 9 percent of perfluorosulfonic acid resin and 8 percent of nano Zr by weight are usedO2And carrying out double-sided spraying on the ion membrane after the rotary drying by using the ethanol dispersion liquid.
The ionic membrane prepared by the embodiment has the tensile strength of 37MPa, can be used for an ion exchange membrane in a chlor-alkali ionic membrane electrolytic cell, and is 6.0kA/m2At a current density of (1), the mass fraction of the cathode NaOH solution is 32%, the NaCl concentration of the brine entering the cell from the anode is 305g/L, the NaCl concentration of the brine leaving the cell is 205g/L, the cell temperature is 86 +/-1 ℃, the active cathode is tested under the condition of zero polar distance, the cell voltage is 3.00V, and then the surface resistance of the obtained membrane is 1.53 omega cm by testing according to a standard SJ/T10171.5 method2。
Example 5
Step (1), step (2) and step (3) are the same as in example 1. Except that in the step (1), the ion exchange capacity of the perfluorosulfonic acid resin is 1.05mmol/g and the ion exchange capacity of the perfluorocarboxylic acid resin is 1.05 mmol/g.
The tensile strength of the ionic membrane prepared by the embodiment is 36MPa, and the ionic membrane can be used for an ion exchange membrane in a chlor-alkali ionic membrane electrolytic cell, and is 6.0kA/m2At a current density of (1), the mass fraction of the cathode NaOH solution is 32%, the NaCl concentration of the anode tank inlet brine is 305g/L, the NaCl concentration of the tank outlet brine is 210g/L, the tank temperature is 86 +/-1 ℃, the active cathode is tested under the conditions of zero polar distance, the tank voltage is 2.97V, and then the surface resistance of the obtained membrane is 1.36 omega cm by testing according to a standard SJ/T10171.5 method2。
Example 6
Step (1), step (2) and step (3) are the same as in example 1. The difference is that in the step (1), the mass ratio of the micro-nano hollow fiber material with ion exchange capacity to the perfluorosulfonic acid resin powder is 20: 100.
the ionic membrane prepared by the embodiment has the tensile strength of 39MPa, can be used for an ion exchange membrane in a chlor-alkali ionic membrane electrolytic cell, and is 6.0kA/m2Under the current density of (1), the mass fraction of a cathode NaOH solution is 32%, the NaCl concentration of brine entering a tank from an anode is 305g/L, the NaCl concentration of brine leaving the tank is 210g/L, the tank temperature is 86 +/-1 ℃, the active cathode is tested under the condition of zero polar distance, the tank voltage is 2.99V, and then the surface resistance of the obtained membrane is tested according to a standard SJ/T10171.5 method1.45Ω·cm2。
Example 7
Step (1), step (2) and step (3) are the same as in example 1. Except that in the step (1), the ion exchange capacity of the perfluorosulfonic acid resin is 0.95mmol/g and the ion exchange capacity of the perfluorocarboxylic acid resin is 1.00 mmol/g.
The ionic membrane prepared by the embodiment has the tensile strength of 37MPa, can be used for an ion exchange membrane in a chlor-alkali ionic membrane electrolytic cell, is tested under the conditions of 32 mass percent concentration of cathode NaOH solution, 305g/L concentration of NaCl of brine entering the cell from the anode, 205g/L concentration of NaCl of brine exiting the cell, 86 +/-1 ℃ of cell temperature, active cathode and zero polar distance under the current density of 6.0kA/m, the cell voltage is 3.01V, and then the surface resistance of the membrane obtained by testing according to a standard SJ/T10171.5 method is 1.58 omega cm2。
Claims (9)
1. A high-strength low-groove-pressure perfluorinated ion exchange membrane for the chlor-alkali industry comprises a base membrane consisting of a perfluorinated sulfonic acid resin layer and a perfluorinated carboxylic acid resin layer, wherein a reinforced fiber mesh is embedded in the perfluorinated sulfonic acid resin layer, and gas release coatings are sprayed on the two outer side surfaces of the base membrane; the perfluorosulfonic acid resin layer contains discontinuous micro-nano pore canals and is characterized in that: the micro-nano pore channel is positioned in the perfluorosulfonic acid resin layer and is formed by micro-nano hollow fibers with ion exchange capacity;
the micro-nano hollow fiber is a perfluorinated sulfonic acid ion exchange hollow fiber membrane, and has an outer diameter of 300 nm-20 microns, a length of 10-50 microns and an inner diameter of 20 nm-10 microns.
2. The high-strength low-cell-pressure perfluorinated ion exchange membrane for the chlor-alkali industry according to claim 1, characterized in that: the thickness of the perfluorosulfonic acid resin layer is 80-110 μm, the thickness of the perfluorocarboxylic acid resin layer is 8-12 μm, and the thickness of the gas release coating on the two outer surfaces of the base film is 1-5 μm.
3. The high-strength low-cell-pressure perfluorinated ion exchange membrane for the chlor-alkali industry according to claim 1, characterized in that: the reinforced fiber is one or more of polytetrafluoroethylene fiber, polyperfluoroethylpropylene fiber, ion exchange functional fiber, polyperfluoropropyl vinyl ether fiber, tetrafluoroethylene-perfluorovinyl ether copolymer fiber or fluorocarbon polymer fiber.
4. The high-strength low-cell-pressure perfluorinated ion exchange membrane for the chlor-alkali industry according to claim 1, characterized in that: the gas release coating is composed of a mixture of perfluorosulfonic acid resin and nano inorganic oxide.
5. The high-strength low-cell-pressure perfluorinated ion exchange membrane for the chlor-alkali industry according to claim 1, characterized in that: the nano inorganic oxide is ZnO or TiO2Or ZrO2。
6. A method for preparing the high-strength low-groove-pressure perfluorinated ion exchange membrane for the chlor-alkali industry according to any of claims 1 to 5, characterized in that: the method comprises the following steps:
mixing a micro-nano hollow fiber material with ion exchange capacity and perfluorinated sulfonic acid resin powder according to a mass ratio of 1-20: 100, obtaining perfluorinated sulfonic acid resin master batch containing micro-nano hollow fiber materials through melt extrusion; preparing perfluorinated ion exchange resin base membranes from perfluorocarboxylic acid resin and the perfluorinated sulfonic acid resin master batch containing the micro-nano hollow fiber material by a melting coextrusion or multilayer hot pressing composite process;
placing a reinforcing fiber mesh cloth on the surface or inside of the perfluorinated sulfonic acid resin layer of the base film by adopting a continuous vacuum composite process to form a reinforced ionic membrane;
c, hydrolyzing the reinforced ionic membrane obtained in the step b in a mixed solution of KOH or NaOH aqueous solution and an organic solvent at the temperature of 70-90 ℃ for 30 min-2 h for transformation;
spraying the transformed ionic membrane by using a lower alcohol dispersion liquid containing 3-10 wt% of perfluorinated sulfonic acid resin and 5-15 wt% of nano inorganic oxide, and drying to form a gas release coating;
and soaking the sprayed film in a sodium hydroxide aqueous solution with the mass fraction of 0.2-2%, and standing and balancing to obtain the water-based paint.
7. The method for preparing the high-strength low-cell-pressure perfluorinated ion exchange membrane for the chlor-alkali industry according to claim 6, characterized in that: in step c, the organic solvent is ethanol, isopropanol or dimethyl sulfoxide.
8. The method for preparing the high-strength low-cell-pressure perfluorinated ion exchange membrane for the chlor-alkali industry according to claim 6, characterized in that: in the step c, the mass percentage of KOH or NaOH in the mixed solution is 12-28%, and the mass percentage of the organic solvent is 10-40%.
9. The method for preparing the high-strength low-cell-pressure perfluorinated ion exchange membrane for the chlor-alkali industry according to claim 6, characterized in that: in step d, the lower alcohol is ethanol, propanol or isopropanol.
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| US3944485A (en) * | 1973-05-23 | 1976-03-16 | California Institute Of Technology | Ion-exchange hollow fibers |
| CN101284216B (en) * | 2008-05-08 | 2011-05-18 | 中国科学技术大学 | Hollow fiber anion-exchange membrane and preparation method thereof |
| CN102978654B (en) * | 2012-12-14 | 2015-03-18 | 山东东岳高分子材料有限公司 | Low-resistance and high-strength ion exchange membrane for chlor-alkali industry and preparation method of low-resistance and high-strength ion exchange membrane |
| CN103031566B (en) * | 2012-12-14 | 2015-03-18 | 山东东岳高分子材料有限公司 | Fiber-reinforced perfluorinated ion exchange membrane containing non-continuous nano-pore canal and preparation method thereof |
| CN103014757B (en) * | 2012-12-14 | 2015-04-22 | 山东东岳高分子材料有限公司 | Hole-containing fiber reinforced ion exchange membrane for chlor-alkali industry and preparation method thereof |
| CN103556178B (en) * | 2013-11-04 | 2016-04-06 | 山东东岳高分子材料有限公司 | For the ion-exchange membrane and preparation method thereof of superhigh-current-density oxygen cathode electrolysis |
| CN104018180B (en) * | 2014-06-06 | 2016-10-05 | 山东东岳高分子材料有限公司 | Zero pole span amberplex and preparation method thereof |
| CN104388978A (en) * | 2014-09-26 | 2015-03-04 | 山东东岳高分子材料有限公司 | Micro-nano pore-containing chlorine-alkali ion membrane preparation method |
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