WO2015184568A1 - Novel ion-conducting membrane and preparation method therefor - Google Patents

Novel ion-conducting membrane and preparation method therefor Download PDF

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WO2015184568A1
WO2015184568A1 PCT/CN2014/000652 CN2014000652W WO2015184568A1 WO 2015184568 A1 WO2015184568 A1 WO 2015184568A1 CN 2014000652 W CN2014000652 W CN 2014000652W WO 2015184568 A1 WO2015184568 A1 WO 2015184568A1
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ion exchange
resin
perfluoro
acid resin
microparticles
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PCT/CN2014/000652
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French (fr)
Chinese (zh)
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王婧
张永明
杨淼昆
张恒
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山东东岳高分子材料有限公司
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Publication of WO2015184568A1 publication Critical patent/WO2015184568A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20Manufacture of shaped structures of ion-exchange resins
    • C08J5/22Films, membranes or diaphragms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/34Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/46Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00Diaphragms; Spacing elements
    • C25B13/04Diaphragms; Spacing elements characterised by the material
    • C25B13/08Diaphragms; Spacing elements characterised by the material based on organic materials

Definitions

  • the invention belongs to the technical field of ion membranes, and in particular relates to a novel ion conducting membrane and a preparation method thereof.
  • the air bubbles block the current channel, which reduces the effective electrolysis area of the film, resulting in uneven current distribution on the film surface, and the local polarization is significantly increased.
  • the membrane resistance and the cell voltage are sharply increased, and the electrolysis power consumption is remarkably increased.
  • the adhered hydrogen bubbles are quickly released from the hydrophilic surface, and a modification method of the hydrophilic coating on the surface of the ion film is developed.
  • a modification method of the hydrophilic coating on the surface of the ion film is developed.
  • the hydrophilicity of the membrane surface is significantly increased, and the anti-foaming ability is remarkably improved.
  • the ionic membrane modified by the hydrophilic coating can be closely attached to the electrode and greatly reduce the cell voltage, and is currently widely used in the zero-pole ion membrane electrolysis process.
  • the hydrophilic coating modification process needs to be covered by the inorganic component and the special binder, and covered on the surface of the ion membrane by electrolytic deposition method, particle embedding method, etc.
  • the coating process is specifically introduced by patent CA2446448 and CA2444585. Although the modification method is remarkable, the process is relatively complicated. In addition, since the ionic membrane undergoes continuous scouring caused by continuous scouring and turbulence of the lye flow during the electrolysis operation, the hydrophilic coating attached to the surface of the ionic membrane gradually falls off, and the anti-foaming function is gradually reduced to ineffective.
  • Patent No. 4502931 mentions that the surface of the ion film is subjected to surface roughening modification by ion etching, but the method is not easy to implement in a large area, and the anti-foaming ability is not high, when the distance between the electrodes is reduced to a certain extent, The cell pressure is still greater than 3.5V and the current efficiency is less than 90%.
  • a new type of ion-conducting membrane which has a long-term effective hydrophilic degassing function, and can continuously provide good anti-foaming effect and reduce the cell voltage in the most advanced electrolyzer and electrolysis process. It is very important to improve current efficiency and reduce power consumption.
  • the object of the present invention is to provide a novel ion conducting membrane which can be stabilized for the chlor-alkali industry. Efficiently processing a wide range of alkali metal chloride solutions, suitable for operation in a zero-pole electrolysis cell under a new high current density condition, and having excellent product purity index; the invention also provides a preparation method thereof, and the process is simple and reasonable Easy to industrialize production.
  • the novel ion-conducting membrane of the present invention comprises a surface layer of a perfluoro ion exchange resin base membrane, a porous reinforcing material, and a mixture of fine particles of perfluoro ion exchange resin and inorganic compound particles.
  • the perfluoro ion exchange resin base film is composed of a resin layer mainly composed of a perfluorosulfonic acid resin and a resin layer mainly composed of a perfluorocarboxylic acid resin, and a resin layer mainly composed of a perfluorosulfonic acid resin.
  • the thickness of the resin is 30-300 micrometers, preferably 50-150 micrometers.
  • the resin layer mainly composed of perfluorosulfonic acid resin has a small fixed ion content, and the repulsive force to the hydroxide is weak, and the thickness is not too thin;
  • the resin layer mainly composed of a fluorocarboxylic acid resin has a thickness of 2 to 30 ⁇ m, preferably 7 to 18 ⁇ m, and the resin layer mainly composed of a perfluorocarboxylic acid resin has a large electric resistance and the thickness is not excessively large.
  • the resin layer mainly composed of perfluorosulfonic acid resin is obtained by blending or copolymerizing a perfluorosulfonic acid resin and a perfluorocarboxylic acid resin in a mass ratio of 100:0.1 to 100:10; the mass ratio thereof is preferably 100:0.5. -100:5.
  • the presence of a small amount of perfluorocarboxylic acid resin in a resin layer mainly composed of perfluorosulfonic acid resin can play a key transition role, so that the water and ion permeability gradient in the membrane is weakened, and the flux of the ion membrane is stabilized. Sex plays a key role while preventing stripping between different layers.
  • the resin layer mainly composed of a perfluorocarboxylic acid resin is obtained by blending or copolymerizing a perfluorocarboxylic acid resin and a perfluorosulfonic acid resin in a mass ratio of 100:0.1 to 100:10, preferably 100:0.5-100:5. .
  • the presence of a small amount of perfluorosulfonic acid resin in a resin layer mainly composed of a perfluorocarboxylic acid resin can also play a key transition role as described in the above paragraph.
  • the perfluorosulfonic acid resin has an exchange capacity of 0.8 to 1.5 mmol/g, preferably 0.9 to 1.1 mmol/g; and the perfluorocarboxylic acid resin has an exchange capacity of 0.8 to 1.2 mmol/g, preferably 0.85 to 1.0 mmol/ Gram.
  • the exchange capacity of the two resins should be matched, and the difference should not be too large.
  • the surface layer thickness of the perfluoro ion exchange resin microparticles mixed with the inorganic compound particles is between 200 nm and 100 ⁇ m, preferably between 200 nm and 2 ⁇ m.
  • the mass ratio of the perfluoro ion exchange resin microparticles to the inorganic compound particles in the surface layer is from 1:100 to 100:1.
  • the surface layer is formed by mixing the perfluoro ion exchange resin microparticles with the inorganic compound particles.
  • the introduction of the inorganic chemical particles not only reduces the manufacturing cost of the coating, but also improves the anti-impurity performance of the film, and the inorganic compound particles are small in the coating. ,Evenly distributed.
  • the perfluoro ion exchange resin microparticles are a mixture of one or two of perfluorocarboxylic acid resin microparticles or perfluorosulfonic acid carboxylic acid copolymer resin microparticles and perfluorosulfonic acid resin microparticles; wherein: perfluorosulfonic acid
  • the mass percentage of the resin microparticles is from 95% to 50% of the mixture.
  • the perfluoro ion exchange resin microparticles are obtained by grinding the resin pellets once in a low temperature crushing device and then grinding them in a cryogenic device. The particles have an irregular appearance and defoaming of the surface layer. Has an excellent effect.
  • the microparticle size ranges from 20 nm to 10 microns, preferably from 50 to 300 nm. Particle size When it is too low, the particles tend to agglomerate and block the ion channel; when the particle size is too high, the particles formed on the surface of the film are too prominent, and are easily detached under external force.
  • the perfluoro ion exchange resin microparticles in the surface layer have a particle size ranging from 20 nm to 10 ⁇ m, and the ion exchange capacity of the perfluoro ion exchange resin microparticles is from 0.01 to 1.5 mmol/g, preferably from 0.3 to 1.0 m.
  • Molar/g when the ion exchange capacity is too high, there will be a certain degree of swelling in the hydroalcoholic solution, thereby destroying the irregular shape of the broken microparticles, and the volume will be enlarged, the porosity will be seriously reduced, and the ion channel will be blocked. It is not easy to be broken; if the ion exchange capacity is too low, it will affect the ion permeability of the film to some extent.
  • the inorganic compound particles in the surface layer are selected from one or any of oxides, hydroxides, nitrides of Group IV-A, Group IV-B, Group VB, iron, cobalt, nickel, chromium, manganese or boron. a mixture of several kinds, preferably one or more of zirconium oxide, cerium oxide, tin oxide, iron oxide, titanium oxide, silicon oxide, zirconium hydroxide or zirconium nitride, the inorganic compound particles having a particle size ranging from 20 nm to 10 nm Between microns.
  • the porous reinforcing material is a polytetrafluoroethylene non-woven fabric, and the fiber boundary is overlapped or fused together, and the porous reinforcing material has a thickness of between 1 and 200 micrometers, preferably 10 to 50 micrometers; to improve mechanical strength, using existing The technology can be prepared.
  • the polytetrafluoroethylene nonwoven fabric has a porosity of between 20 and 99%, preferably between 50 and 85%. If the porosity is too low, it will cause the cell pressure to rise.
  • novel ion conducting membrane of the present invention comprises the following preparation steps:
  • the perfluoro ion exchange membrane precursor prepared in the step (1) is converted into a perfluoro ion exchange membrane having an ion exchange function.
  • Step (1) The porous reinforcing material is soaked in a fluorocarbon solvent for ultrasonic treatment for 1-2 hours, taken out and dried, and then combined with a perfluoro ion exchange resin base film. Since the wetting of the polytetrafluoroethylene nonwoven fabric is very difficult, if it is directly combined with the base film without treatment, the resin matrix cannot completely fill the voids of the nonwoven fabric, thereby forming a non-compact space inside the film body, not only It is easy to deposit impurities, and it can also form a space barrier and increase resistance.
  • Porous reinforcing material in fluorocarbon solvent After immersion for 1-2 hours, the impregnation of the resin matrix is very easy, and the two can form a good and tight bond, which not only increases the mechanical strength, but also has little effect on the membrane resistance due to the high open porosity of the nonwoven fabric.
  • the fluorocarbon solvent according to the step (1) is selected from the group consisting of trifluorotrichloroethane (F-113) or trifluorotrichloroethane mixed with other solvents; the other solvents are anhydrous ethanol, propanol, methanol, acetone.
  • the surfactant may be selected from commercially available anionic, cationic, amphoteric or nonionic surfactants.
  • Step (2) is to use the perfluoro ion exchange membrane precursor prepared in the step (1) at a temperature of 10 to 200 ° C under a pressure of 20 to 100 tons at a rate of 1 to 50 m / min.
  • the press is subjected to an overpressure treatment, and after the overpressure treatment, the perfluoro ion exchange membrane precursor is immersed in a mixed aqueous solution of 15 wt% dimethyl sulfoxide and 20 wt% NaOH, and converted into a perfluoro ion exchange membrane having ion exchange function. .
  • the overpressure treatment further increases the compactness of the nonwoven fabric and the base film
  • the overpressure treatment also improves the physical structure of the nonwoven fabric and the base film to some extent, and the microfibrillation and base film of the nonwoven fabric.
  • the thermo-induced crystal structure is refined, which will effectively improve the ion transport effect.
  • the perfluoro ion exchange resin microparticles in the step (3) are obtained by grinding the resin pellets once in a low temperature crushing apparatus and then grinding them in a cryogenic apparatus.
  • the obtained perfluoro ion exchange resin microparticles and inorganic compound particles each have an irregular appearance and have an excellent effect on surface defoaming desorption.
  • Step (4) attaching the dispersion to the surface of the perfluorinated ion exchange membrane obtained in the step (2), and the adhesion method is various, including: spraying, brushing, roll coating, dipping, transfer, spin coating, etc., preferably spraying, Roll coating.
  • the process operation can be carried out according to the prior art.
  • the present invention has the following advantages:
  • the present invention replaces the inorganic oxide coating in the existing product with a surface layer obtained by mixing fine particles of perfluoro ion exchange resin with inorganic compound particles, due to the chemical chemistry of the perfluoro ion exchange resin microparticles and the base film material.
  • the structure is the same, with good compatibility and adhesion, so that it can ensure good degassing effect throughout the life of the new ion-conducting membrane, and the degassing effect is much better than the inorganic oxide coating.
  • the surface layer formed by mixing the perfluoro ion exchange resin microparticles with the inorganic compound particles has an ion exchange function due to the presence of the perfluoro ion exchange resin microparticles, which is beneficial to the reduction of the ion conductive membrane cell voltage and the sheet resistance.
  • the introduction of inorganic chemical particles not only reduces the cost of coating production, but also improves the anti-impurity properties of the film.
  • the polytetrafluoroethylene non-woven fabric is compounded with the base film after solvent treatment, and adopts an overpressure process to greatly improve the anti-impurity performance of the ion-conducting membrane while obtaining excellent electrochemical performance and mechanical properties.
  • the present invention provides an ion-conducting membrane for electrolytically preparing sodium chloride/potassium chloride to prepare chlorine gas and sodium hydroxide/potassium hydroxide, and the introduction of the polytetrafluoroethylene nonwoven fabric improves the purity of the product.
  • the purity of the chlorine gas obtained by electrolysis is ⁇ 99.5%
  • the purity of hydrogen is ⁇ 99.9%
  • the salt in the alkali is ⁇ 5ppm.
  • the ion-conducting membrane of the present invention is suitable for electrolysis of a base of 30-35% concentration, whereas the ion-conducting membrane of the prior art is generally only suitable for electrolysis of a base of 30-32% concentration.
  • the ion-conducting membrane of the present invention can be used for the chlor-alkali industry to stably and efficiently treat a wide range of alkali metal chloride solutions, and exhibits an unexpected effect in terms of impurity tolerance, and is suitable for a novel high current.
  • the cell voltage is significantly reduced while increasing product purity.
  • the cell pressure is below 2.75V.
  • the present invention also provides a preparation method thereof, which is simple and reasonable in process and easy to industrialize.
  • the sulfonic acid resin-based resin layer has a perfluorosulfonic acid resin and a perfluorocarboxylic acid resin in a mass ratio of 100:0.5, and a perfluorocarboxylic acid resin and a perfluorosulfonic acid in a resin layer mainly composed of a perfluorosulfonic acid resin.
  • the resin mass ratio was 100:1, wherein the resin layer mainly composed of a perfluorosulfonic acid resin was 130 ⁇ m, and the thickness of the resin layer mainly composed of a perfluorosulfonic acid resin was 10 ⁇ m. Then, the porous reinforcing material polytetrafluoroethylene nonwoven fabric was immersed in a trifluorotrichloroethane solvent in an ultrasonic processor for 1.5 hours, wherein the thickness of the non-woven fabric was 40 micrometers, and the porosity was 75%.
  • the perfluoro ion exchange resin base film is compounded, a porous reinforcing material is introduced between the film forming rolls, and the porous reinforcing material is pressed into the film body under the action of the pressure between the rolls to form a perfluoro ion exchange film precursor.
  • the perfluoro ion exchange membrane precursor prepared in the step (1) is subjected to an overpressure treatment at a temperature of 200 ° C under a pressure of 60 tons at a speed of 1 m/min using an overpressure press. After the pressure treatment, the perfluoro ion exchange membrane precursor was immersed in a mixed aqueous solution containing 15 wt% of dimethyl sulfoxide and 20 wt% of NaOH at 85 ° C for 80 minutes to be converted into a perfluoro ion exchange membrane having an ion exchange function.
  • the perfluoro ion exchange resin microparticles are a mixture of perfluorocarboxylic acid resin microparticles and perfluorosulfonic acid resin microparticles; the perfluorosulfonic acid resin microparticles comprise 50% by mass of the mixture.
  • the surface layer has a thickness of 200 nm and is dried to form a finished product.
  • the prepared ion exchange membrane is subjected to an electrolysis test of an aqueous solution of sodium chloride in an electrolytic cell, and a 300 g/L aqueous solution of sodium chloride is supplied to the anode chamber, and water is supplied to the cathode chamber to ensure that the concentration of sodium chloride discharged from the anode chamber is 200g / L, the concentration of sodium hydroxide discharged from the cathode chamber is 33%; the test temperature is 90 ° C, the current density is 7.5kA / m 2 , after 23 days of electrolysis experiments, the average cell pressure is 2.76V, the average current efficiency is 99.7%.
  • the sheet resistance of the obtained film was 1.0 ⁇ cm -2 according to the standard SJ/T 10171.5 method, and the abrasion loss of the film obtained by ASTM standard D1044-99 was 2.7 mg.
  • the purity of the electrolyzed products was determined to be 99.7% purity of chlorine gas, 99.9% purity of hydrogen, and 3 ppm of salt in alkali.
  • An ion exchange membrane having an ion exchange function was prepared in the same manner as in Example 1, and then a dispersion liquid was prepared in the same manner except that the perfluoro ion exchange resin and the inorganic compound mixed microparticles in the dispersion were replaced with The inorganic oxide particles having an average particle diameter of 50 nm were homogenized in a ball mill to form a dispersion having a content of 15% by weight.
  • An ion exchange membrane having an inorganic oxide coating adhered to both sides was obtained in the same manner as in Example 1.
  • the electrolysis test of the sodium chloride solution was carried out under the same conditions as in Example 1. After 23 days of electrolysis experiments, the average cell pressure was 2.91 V, the average current efficiency was 96.3%, and the sheet resistance was 2.4 ⁇ cm -2 . The wear loss is 12 mg. Thereafter, 15 g of inorganic Ca and Mg impurities were added to the aqueous sodium chloride solution, and an electrolysis experiment was carried out for 140 days under the same conditions as described above. The average cell pressure was stabilized at 3.15 V, and the average current efficiency was 95.9%.
  • An ion exchange membrane having an ion exchange function was prepared in the same manner as in Example 1 except that the porous reinforcing material was not immersed in a fluorocarbon solvent before being compounded with the perfluoro ion exchange resin base film, and thereafter Overpressure treatment with an overpressure press.
  • a fine particle dispersion of a perfluoro ion exchange resin and an inorganic compound was prepared in the same manner and homogenized in a ball mill to form a dispersion having a content of 15% by weight.
  • the ion exchange membrane product was obtained in the same manner as in Example 1.
  • the electrolysis test of the sodium chloride solution was carried out under the same conditions as in Example 1. After 23 days of electrolysis, the average cell pressure was 2.84 V, the average current efficiency was 99.1%, and the sheet resistance was 1.7 ⁇ cm -2 . Thereafter, 15 g of inorganic Ca and Mg impurities were added to the aqueous sodium chloride solution, and an electrolysis experiment was carried out for 40 days under the same conditions as described above. The average cell pressure was stabilized at 2.93 V, and the average current efficiency was 97.4%. The purity of the tested products was 98.4% for chlorine, 98.5% for hydrogen, and 15 ppm for alkali.
  • the sulfonic acid resin-based resin layer has a perfluorosulfonic acid resin and a perfluorocarboxylic acid resin in a mass ratio of 100:2, and a perfluorocarboxylic acid resin and a perfluorosulfonic acid in a resin layer mainly composed of a perfluorosulfonic acid resin.
  • the resin mass ratio was 100:0.5, wherein the resin layer mainly composed of a perfluorosulfonic acid resin was 150 ⁇ m, and the thickness of the resin layer mainly composed of a perfluorosulfonic acid resin was 7 ⁇ m. Then, the porous reinforcing material polytetrafluoroethylene non-woven fabric is immersed in a mixed solvent of trifluorotrichloroethane and absolute ethanol in an ultrasonic processor for 2 hours, wherein the non-woven fabric has a thickness of 50 ⁇ m and a porosity of 70%.
  • the perfluoro ion exchange membrane precursor prepared in the step (1) is subjected to an overpressure treatment at a temperature of 180 ° C at a pressure of 100 ton at a speed of 25 m/min using an overpressure press. After the pressure treatment, the perfluoro ion exchange membrane precursor was immersed in a mixed aqueous solution containing 15 wt% of dimethyl sulfoxide and 20 wt% of NaOH at 85 ° C for 80 minutes to be converted into a perfluoro ion exchange membrane having an ion exchange function.
  • the mixed mass ratio of the perfluoro ion exchange resin microparticles to the inorganic compound particles zirconium hydroxide is 1:1.
  • the perfluoro ion exchange resin microparticles are a mixture of perfluorocarboxylic acid resin microparticles, perfluorosulfonic acid carboxylic acid copolymer resin microparticles and perfluorosulfonic acid resin microparticles; perfluorosulfonic acid resin microparticles by mass percentage of the mixture 75%.
  • the dispersion is adhered to both sides of the perfluoro ion exchange membrane obtained in the step (2) by a roll coating method, and the surface layer has a thickness of about 500 nm, and is dried to form a finished product.
  • the prepared ion exchange membrane is subjected to an electrolysis test of an aqueous solution of sodium chloride in an electrolytic cell, and a 300 g/L aqueous solution of sodium chloride is supplied to the anode chamber, and water is supplied to the cathode chamber to ensure that the concentration of sodium chloride discharged from the anode chamber is 200g / L, the concentration of sodium hydroxide discharged from the cathode chamber is 34%; the test temperature is 90 ° C, the current density is 6.5kA / m 2 , after 23 days of electrolysis experiments, the average cell pressure is 2.72V, the average current efficiency is 99.8%.
  • the sheet resistance of the obtained film was measured to 1.0 ⁇ cm -2 according to the standard SJ/T 10171.5 method, and the abrasion loss of the film obtained by ASTM standard D1044-99 was 2.8 mg.
  • the purity of the electrolysis products was determined to be 99.5% purity of chlorine gas, 99.9% purity of hydrogen gas, and 4 ppm salt in alkali.
  • sulfonic acid resin-based resin layer has a perfluorosulfonic acid resin and a perfluorocarboxylic acid resin in a mass ratio of 100:5, and a perfluorocarboxylic acid resin and a perfluorosulfonic acid in a resin layer mainly composed of a perfluorosulfonic acid resin.
  • the resin mass ratio was 100:2.5, wherein the resin layer mainly composed of a perfluorosulfonic acid resin was 80 ⁇ m, and the thickness of the resin layer mainly composed of a perfluorosulfonic acid resin was 10 ⁇ m. Then, the porous reinforcing material polytetrafluoroethylene non-woven fabric is immersed in a mixed solvent of trifluorotrichloroethane and propanol in an ultrasonic processor for 2 hours, wherein the non-woven fabric has a thickness of 10 ⁇ m and a porosity of 50%.
  • the perfluoro ion exchange membrane precursor prepared in the step (1) is subjected to an overpressure treatment at a temperature of 140 ° C under a pressure of 80 tons at a speed of 30 m / min. After the pressure treatment, the perfluoro ion exchange membrane precursor was immersed in a mixed aqueous solution containing 15 wt% of dimethyl sulfoxide and 20 wt% of NaOH at 85 ° C for 80 minutes to be converted into a perfluoro ion exchange membrane having an ion exchange function.
  • the mixed mass ratio of the perfluoro ion exchange resin microparticles to the inorganic compound particles tin oxide is 1:50.
  • the perfluoro ion exchange resin microparticles are a mixture of a perfluorosulfonic acid carboxylic acid copolymer resin micro and a perfluorosulfonic acid resin microparticle; wherein: the perfluorosulfonic acid resin microparticles account for 65% by mass of the mixture.
  • the dispersion is adhered to both sides of the perfluoro ion exchange membrane obtained in the step (2), and the surface layer has a thickness of about 1000 nm, and is dried to form a finished product.
  • the prepared ion exchange membrane is subjected to an electrolysis test of an aqueous solution of sodium chloride in an electrolytic cell, and a 300 g/L aqueous solution of sodium chloride is supplied to the anode chamber, and water is supplied to the cathode chamber to ensure that the concentration of sodium chloride discharged from the anode chamber is 200g / L, the concentration of sodium hydroxide discharged from the cathode chamber is 30%; the test temperature is 90 ° C, the current density is 7.5kA / m 2 , after 23 days of electrolysis experiments, the average cell pressure is 2.75V, the average current efficiency is 99.8%.
  • the sheet resistance of the obtained film was measured to 1.2 ⁇ cm -2 according to the standard SJ/T 10171.5 method, and the abrasion loss of the film obtained by ASTM standard D1044-99 was 2.7 mg.
  • the purity of the electrolysis products is determined to be 99.8% purity of chlorine gas, 99.9% purity of hydrogen gas, and 3 ppm salt in alkali.
  • the sulfonic acid resin-based resin layer has a perfluorosulfonic acid resin and a perfluorocarboxylic acid resin in a mass ratio of 100:2.5, and a perfluorocarboxylic acid resin and a perfluorosulfonic acid in a resin layer mainly composed of a perfluorosulfonic acid resin.
  • the resin mass ratio was 100:5, wherein the resin layer mainly composed of perfluorosulfonic acid resin was 75 ⁇ m, and the thickness of the resin layer mainly composed of perfluorosulfonic acid resin was 15 ⁇ m. Then, the porous reinforcing material polytetrafluoroethylene non-woven fabric is immersed in a mixed solvent of trifluorotrichloroethane and methanol in an ultrasonic processor for 1 hour, wherein the non-woven fabric has a thickness of 50 ⁇ m and a porosity of 85%.
  • the perfluoro ion exchange membrane precursor prepared in the step (1) is subjected to an overpressure treatment at a temperature of 10 ° C at a temperature of 10 ° C at a speed of 50 m/min using an overpressure press. After the pressure treatment, the perfluoro ion exchange membrane precursor was immersed in a mixed aqueous solution containing 15 wt% of dimethyl sulfoxide and 20 wt% of NaOH at 85 ° C for 80 minutes to be converted into a perfluoro ion exchange membrane having an ion exchange function.
  • the mixed mass ratio of the perfluoro ion exchange resin microparticles to the inorganic compound particles cerium oxide is 100:1.
  • the perfluoro ion exchange resin microparticles are a mixture of perfluorocarboxylic acid resin microparticles and perfluorosulfonic acid resin microparticles; the perfluorosulfonic acid resin microparticles account for 80% by mass of the mixture.
  • the dispersion is adhered to both sides of the perfluoro ion exchange membrane obtained in the step (2) by a spraying method, and the surface layer has a thickness of about 1500 nm, and is dried to form a finished product.
  • the prepared ion exchange membrane is subjected to an electrolysis test of an aqueous solution of sodium chloride in an electrolytic cell, and a 300 g/L aqueous solution of sodium chloride is supplied to the anode chamber, and water is supplied to the cathode chamber to ensure that the concentration of sodium chloride discharged from the anode chamber is 200g / L, the concentration of sodium hydroxide discharged from the cathode chamber is 30%; the test temperature is 90 ° C, the current density is 6.5kA / m 2 , after 23 days of electrolysis experiments, the average cell pressure is 2.71V, the average current efficiency is 99.7%.
  • the sheet resistance of the obtained film was measured to 1.2 ⁇ cm -2 according to the standard SJ/T 10171.5 method, and the abrasion loss of the film obtained by ASTM standard D1044-99 was 2.7 mg.
  • the purity of the electrolyzed products was determined to be 99.8% purity of chlorine gas, 100% purity of hydrogen, and 4 ppm of salt in alkali.
  • sulfonic acid resin-based resin layer has a perfluorosulfonic acid resin and a perfluorocarboxylic acid resin in a mass ratio of 100:0.5, and a perfluorocarboxylic acid resin and a perfluorosulfonic acid in a resin layer mainly composed of a perfluorosulfonic acid resin.
  • the resin mass ratio was 100:2.5, wherein the resin layer mainly composed of a perfluorosulfonic acid resin was 50 ⁇ m, and the thickness of the resin layer mainly composed of a perfluorosulfonic acid resin was 18 ⁇ m. Then, the porous reinforcing material polytetrafluoroethylene non-woven fabric is immersed in a mixed solvent of trifluorotrichloroethane and acetone in an ultrasonic processor for 1.5 hours, wherein the non-woven fabric has a thickness of 10 ⁇ m and a porosity of 70%.
  • the perfluoro ion exchange membrane precursor prepared in the step (1) is subjected to an overpressure treatment at a temperature of 200 ° C under a pressure of 20 tons at a speed of 1 m/min. After the pressure treatment, the perfluoro ion exchange membrane precursor was immersed in a mixed aqueous solution containing 15 wt% of dimethyl sulfoxide and 20 wt% of NaOH at 85 ° C for 80 minutes to be converted into a perfluoro ion exchange membrane having an ion exchange function.
  • the mixed mass ratio of the perfluoro ion exchange resin microparticles to the inorganic compound particles zirconium nitride is 50:1.
  • the perfluoro ion exchange resin microparticles are perfluorocarboxylic acid resin microparticles, perfluorosulfonic acid carboxylic acid copolymer resin microparticles a mixture with microparticles of perfluorosulfonic acid resin; the percentage by mass of the perfluorosulfonic acid resin microparticles is 85% of the mixture.
  • the dispersion is adhered to both sides of the perfluoro ion exchange membrane obtained in the step (2) by a spraying method, and the surface layer has a thickness of about 2 ⁇ m, and is dried to form a finished product.
  • the prepared ion exchange membrane is subjected to an electrolysis test of an aqueous solution of sodium chloride in an electrolytic cell, and a 300 g/L aqueous solution of sodium chloride is supplied to the anode chamber, and water is supplied to the cathode chamber to ensure that the concentration of sodium chloride discharged from the anode chamber is 200g / L, the concentration of sodium hydroxide discharged from the cathode chamber is 33%; the test temperature is 90 ° C, the current density is 5.5kA / m 2 , after 23 days of electrolysis experiments, the average cell pressure is 2.70V, the average current efficiency is 99.8%.
  • the sheet resistance of the obtained film was 1.1 ⁇ cm -2 according to the standard SJ/T 10171.5 method, and the abrasion loss of the film obtained by ASTM standard D1044-99 was 2.6 mg.
  • the purity of the electrolyzed products was determined to be 99.7% purity of chlorine gas, 99.9% purity of hydrogen, and 3 ppm of salt in alkali.

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Abstract

The present invention belongs to the technical field of ion membranes, and specifically relates to a novel ion-conducting membrane, consisting of a perfluorinated ion exchange resin base membrane, a porous reinforcing material and a surface layer made by mixing perfluorinated ion exchange resin microparticles and inorganic compound particles. The inorganic compound particles are selected from one or a mixture of any of oxides, hydroxides and nitrides of group IV-A elements, group IV-B elements, group V-B elements, iron, cobalt, nickel, chromium, manganese and boron. The perfluorinated ion exchange resin microparticles are a mixture of one or both of perfluorinated carboxylic acid resin microparticles and perfluorinated sulphonic acid carboxylic acid copolymer resin microparticles and perfluorinated sulphonic acid resin microparticles. The present invention is used in the chlor-alkali industry, and stably and effectively treats alkali metal chloride solutions having a wide range of concentrations. The present invention is suitable for operating in a zero pole distance electrolyser under novel high current density conditions, and product purity is high. Also provided is a preparation method for the novel ion-conducting membrane. The preparation method has a simple and reasonable process, and facilitates industrial production.

Description

新型离子传导膜及其制备方法Novel ion conductive membrane and preparation method thereof 技术领域Technical field
本发明属于离子膜技术领域,具体涉及一种新型离子传导膜及其制备方法。The invention belongs to the technical field of ion membranes, and in particular relates to a novel ion conducting membrane and a preparation method thereof.
背景技术Background technique
近年来,在离子膜法氯碱生产中,为实现在高电流密度、低槽电压、与碱液浓度高的条件下进行电解,以达到提高生产率与降低电耗的目的,其关键在于缩短离子膜与电极间的距离,以降低其槽电压,使窄极距型的离子膜电解工艺达到实用化。随着技术的不断进步,零极距电解槽已得到广泛应用,但当电极间的距离减少到小于2mm时,由于膜与阴极紧贴,而使膜面上粘附的氢气泡难于释放,故在面向阴极的膜面上积聚了大量的氢气泡。气泡阻碍了电流通道,使膜的有效电解面积减少,导致膜面上电流分布不均,局部极化作用明显增加。由此,反而使膜电阻与槽电压急剧增大,其电解电耗显著升高。In recent years, in the production of ionic membrane chlor-alkali, in order to achieve electrolysis under conditions of high current density, low cell voltage, and high lye concentration, in order to achieve productivity and reduce power consumption, the key is to shorten the ion membrane. The distance between the electrodes and the electrodes is used to lower the cell voltage, and the narrow-electrode type ion-exchange membrane electrolysis process is put into practical use. With the continuous advancement of technology, the zero-pole electrolysis cell has been widely used, but when the distance between the electrodes is reduced to less than 2 mm, since the film and the cathode are in close contact, the hydrogen bubbles adhered on the film surface are difficult to release, so A large amount of hydrogen bubbles accumulate on the membrane surface facing the cathode. The air bubbles block the current channel, which reduces the effective electrolysis area of the film, resulting in uneven current distribution on the film surface, and the local polarization is significantly increased. As a result, the membrane resistance and the cell voltage are sharply increased, and the electrolysis power consumption is remarkably increased.
为克服气泡效应所带来的缺点,使粘附的氢气泡从亲水性小的膜面上快速释放出去,开发了离子膜表面亲水涂层的改性方法。在膜表面覆盖一种气体和液体都能渗透的多孔型、无电催化活性的非电极涂层后,使膜面亲水性明显增加,抗起泡能力显著提高。亲水涂层改性后的离子膜,可以与电极紧贴,极大降低槽电压,目前被广泛应用于零极距型离子膜电解工艺。亲水涂层改性工艺需要由无机物组分与特种粘结剂混配后,通过电解沉积法、粒子埋入法等覆盖在离子膜表面,专利CA2446448和CA2444585对涂层工艺进行了具体介绍;此种改性方法虽然效果显著,但工艺相对复杂。此外,由于离子膜在电解运行过程中会经历碱液流的不断冲刷和湍流造成的不断震荡,附着在离子膜表面的亲水涂层会逐渐脱落,防起泡功能逐渐降低至无效。In order to overcome the shortcomings caused by the bubble effect, the adhered hydrogen bubbles are quickly released from the hydrophilic surface, and a modification method of the hydrophilic coating on the surface of the ion film is developed. When the surface of the membrane is covered with a porous, electrocatalytically active non-electrode coating capable of permeating both gas and liquid, the hydrophilicity of the membrane surface is significantly increased, and the anti-foaming ability is remarkably improved. The ionic membrane modified by the hydrophilic coating can be closely attached to the electrode and greatly reduce the cell voltage, and is currently widely used in the zero-pole ion membrane electrolysis process. The hydrophilic coating modification process needs to be covered by the inorganic component and the special binder, and covered on the surface of the ion membrane by electrolytic deposition method, particle embedding method, etc. The coating process is specifically introduced by patent CA2446448 and CA2444585. Although the modification method is remarkable, the process is relatively complicated. In addition, since the ionic membrane undergoes continuous scouring caused by continuous scouring and turbulence of the lye flow during the electrolysis operation, the hydrophilic coating attached to the surface of the ionic membrane gradually falls off, and the anti-foaming function is gradually reduced to ineffective.
专利US 4502931提到将离子膜表面采用离子刻蚀的方法进行表面粗糙化改性,但该方法不仅不易大面积实施,且抗起泡能力不高,当极间距离减少到一定程度时,其槽压仍大于3.5V,且电流效率低于90%。Patent No. 4502931 mentions that the surface of the ion film is subjected to surface roughening modification by ion etching, but the method is not easy to implement in a large area, and the anti-foaming ability is not high, when the distance between the electrodes is reduced to a certain extent, The cell pressure is still greater than 3.5V and the current efficiency is less than 90%.
因此,开发一种新型的新型离子传导膜,其表面具有长期有效的亲水脱气功能,且能够在最先进的电解槽及电解工艺过程中持续提供良好的抗起泡效果、降低槽电压、提高电流效率,并能降低电耗,具有非常重要的意义。Therefore, a new type of ion-conducting membrane has been developed, which has a long-term effective hydrophilic degassing function, and can continuously provide good anti-foaming effect and reduce the cell voltage in the most advanced electrolyzer and electrolysis process. It is very important to improve current efficiency and reduce power consumption.
发明内容Summary of the invention
针对现有技术的不足,本发明的目的是提供一种新型离子传导膜,用于氯碱工业可以稳 定高效地处理宽范围浓度的碱金属氯化物溶液,适合在新型高电流密度条件下的零极距电解槽中运行,具有十分优异的产品纯度指标;本发明还提供其制备方法,工艺简单合理,易于工业化生产。In view of the deficiencies of the prior art, the object of the present invention is to provide a novel ion conducting membrane which can be stabilized for the chlor-alkali industry. Efficiently processing a wide range of alkali metal chloride solutions, suitable for operation in a zero-pole electrolysis cell under a new high current density condition, and having excellent product purity index; the invention also provides a preparation method thereof, and the process is simple and reasonable Easy to industrialize production.
本发明所述的新型离子传导膜,由全氟离子交换树脂基膜、多孔增强材料和全氟离子交换树脂微颗粒与无机化合物颗粒混合而成的表面层组成。The novel ion-conducting membrane of the present invention comprises a surface layer of a perfluoro ion exchange resin base membrane, a porous reinforcing material, and a mixture of fine particles of perfluoro ion exchange resin and inorganic compound particles.
其中:所述的全氟离子交换树脂基膜是由以全氟磺酸树脂为主的树脂层和以全氟羧酸树脂为主的树脂层组成,以全氟磺酸树脂为主的树脂层厚度为30-300微米,优选50-150微米,以全氟磺酸树脂为主的树脂层膜内固定离子含量较少,且对氢氧根的排斥力较弱,厚度不宜过薄;以全氟羧酸树脂为主的树脂层厚度为2-30微米,优选7-18微米,以全氟羧酸树脂为主的树脂层膜电阻较大,厚度不宜过大。Wherein: the perfluoro ion exchange resin base film is composed of a resin layer mainly composed of a perfluorosulfonic acid resin and a resin layer mainly composed of a perfluorocarboxylic acid resin, and a resin layer mainly composed of a perfluorosulfonic acid resin. The thickness of the resin is 30-300 micrometers, preferably 50-150 micrometers. The resin layer mainly composed of perfluorosulfonic acid resin has a small fixed ion content, and the repulsive force to the hydroxide is weak, and the thickness is not too thin; The resin layer mainly composed of a fluorocarboxylic acid resin has a thickness of 2 to 30 μm, preferably 7 to 18 μm, and the resin layer mainly composed of a perfluorocarboxylic acid resin has a large electric resistance and the thickness is not excessively large.
以全氟磺酸树脂为主的树脂层是以质量比为100∶0.1-100∶10的全氟磺酸树脂和全氟羧酸树脂共混或共聚而成;其质量比优选为100∶0.5-100∶5。全氟羧酸树脂在以全氟磺酸树脂为主的树脂层中的少量存在却能起到关键的过渡作用,使得膜中的水和离子的透过梯度减弱,对离子膜的通量稳定性起到关键作用,同时可防止不同膜层间的剥离。The resin layer mainly composed of perfluorosulfonic acid resin is obtained by blending or copolymerizing a perfluorosulfonic acid resin and a perfluorocarboxylic acid resin in a mass ratio of 100:0.1 to 100:10; the mass ratio thereof is preferably 100:0.5. -100:5. The presence of a small amount of perfluorocarboxylic acid resin in a resin layer mainly composed of perfluorosulfonic acid resin can play a key transition role, so that the water and ion permeability gradient in the membrane is weakened, and the flux of the ion membrane is stabilized. Sex plays a key role while preventing stripping between different layers.
以全氟羧酸树脂为主的树脂层是以质量比为100∶0.1-100∶10的全氟羧酸树脂和全氟磺酸树脂共混或共聚而成,优选100∶0.5-100∶5。全氟磺酸树脂在以全氟羧酸树脂为主的树脂层中的少量存在也能起到上段所述的关键过渡作用。The resin layer mainly composed of a perfluorocarboxylic acid resin is obtained by blending or copolymerizing a perfluorocarboxylic acid resin and a perfluorosulfonic acid resin in a mass ratio of 100:0.1 to 100:10, preferably 100:0.5-100:5. . The presence of a small amount of perfluorosulfonic acid resin in a resin layer mainly composed of a perfluorocarboxylic acid resin can also play a key transition role as described in the above paragraph.
全氟磺酸树脂的交换容量为0.8-1.5毫摩尔/克,优选0.9-1.1毫摩尔/克;全氟羧酸树脂的交换容量为0.8-1.2毫摩尔/克,优选0.85-1.0毫摩尔/克。两种树脂的交换容量要相匹配,差值不宜太大。The perfluorosulfonic acid resin has an exchange capacity of 0.8 to 1.5 mmol/g, preferably 0.9 to 1.1 mmol/g; and the perfluorocarboxylic acid resin has an exchange capacity of 0.8 to 1.2 mmol/g, preferably 0.85 to 1.0 mmol/ Gram. The exchange capacity of the two resins should be matched, and the difference should not be too large.
全氟离子交换树脂微颗粒与无机化合物颗粒混合而成的表面层厚度为200纳米-100微米之间,优选200纳米-2微米。表面层中全氟离子交换树脂微颗粒与无机化合物颗粒的质量比为1∶100-100∶1。表面层是由全氟离子交换树脂微颗粒与无机化合物颗粒混合而成,无机化学物颗粒的引入不仅降低了涂层制作成本,而且提高了膜的抗杂质性能,无机化合物颗粒在涂层中少量、均匀分布。全氟离子交换树脂微颗粒为全氟羧酸树脂微颗粒或全氟磺酸羧酸共聚树脂微颗粒中的一种或两种与全氟磺酸树脂微颗粒的混合物;其中:全氟磺酸树脂微颗粒的质量百分比占混合物的95%-50%。全氟离子交换树脂微颗粒是由树脂粒料在低温破碎装置中一次粉碎后,再在深冷装置中进行研磨得到的,颗粒均具备不规则的表观形貌,对于表层起泡的脱附具有优异的效果。微颗粒粒径范围为20纳米-10微米之间,优选50-300纳米。粒径 过低时,颗粒容易团聚,堵塞离子通道;粒径过高时,在膜表面形成的微粒凸起过于明显,容易在外力刮擦下脱离。The surface layer thickness of the perfluoro ion exchange resin microparticles mixed with the inorganic compound particles is between 200 nm and 100 μm, preferably between 200 nm and 2 μm. The mass ratio of the perfluoro ion exchange resin microparticles to the inorganic compound particles in the surface layer is from 1:100 to 100:1. The surface layer is formed by mixing the perfluoro ion exchange resin microparticles with the inorganic compound particles. The introduction of the inorganic chemical particles not only reduces the manufacturing cost of the coating, but also improves the anti-impurity performance of the film, and the inorganic compound particles are small in the coating. ,Evenly distributed. The perfluoro ion exchange resin microparticles are a mixture of one or two of perfluorocarboxylic acid resin microparticles or perfluorosulfonic acid carboxylic acid copolymer resin microparticles and perfluorosulfonic acid resin microparticles; wherein: perfluorosulfonic acid The mass percentage of the resin microparticles is from 95% to 50% of the mixture. The perfluoro ion exchange resin microparticles are obtained by grinding the resin pellets once in a low temperature crushing device and then grinding them in a cryogenic device. The particles have an irregular appearance and defoaming of the surface layer. Has an excellent effect. The microparticle size ranges from 20 nm to 10 microns, preferably from 50 to 300 nm. Particle size When it is too low, the particles tend to agglomerate and block the ion channel; when the particle size is too high, the particles formed on the surface of the film are too prominent, and are easily detached under external force.
表面层中的全氟离子交换树脂微颗粒,粒径范围为20纳米-10微米之间,全氟离子交换树脂微颗粒的离子交换容量介于0.01-1.5毫摩尔/克,优选0.3-1.0毫摩尔/克,离子交换容量过高时,在水醇溶液中会有一定的溶胀度,从而破坏破碎微颗粒自有的不规则形貌,且会体积膨大,严重降低孔隙率,阻塞离子通道,且不易破碎;离子交换容量过低又会一定程度影响膜的离子透过性。表面层中的无机化合物颗粒选自IV-A族、IV-B族、V-B族、铁、钴、镍、铬、锰或硼元素的氧化物、氢氧化物、氮化物中的一种或任意几种的混合物,优选氧化锆、氧化锶、氧化锡、氧化铁、氧化钛、氧化硅、氢氧化锆或氮化锆中的一种或几种,无机化合物颗粒粒径范围为20纳米-10微米之间。The perfluoro ion exchange resin microparticles in the surface layer have a particle size ranging from 20 nm to 10 μm, and the ion exchange capacity of the perfluoro ion exchange resin microparticles is from 0.01 to 1.5 mmol/g, preferably from 0.3 to 1.0 m. Molar/g, when the ion exchange capacity is too high, there will be a certain degree of swelling in the hydroalcoholic solution, thereby destroying the irregular shape of the broken microparticles, and the volume will be enlarged, the porosity will be seriously reduced, and the ion channel will be blocked. It is not easy to be broken; if the ion exchange capacity is too low, it will affect the ion permeability of the film to some extent. The inorganic compound particles in the surface layer are selected from one or any of oxides, hydroxides, nitrides of Group IV-A, Group IV-B, Group VB, iron, cobalt, nickel, chromium, manganese or boron. a mixture of several kinds, preferably one or more of zirconium oxide, cerium oxide, tin oxide, iron oxide, titanium oxide, silicon oxide, zirconium hydroxide or zirconium nitride, the inorganic compound particles having a particle size ranging from 20 nm to 10 nm Between microns.
多孔增强材料为聚四氟乙烯无纺布,纤维交界处是搭接或融合在一起,多孔增强材料厚度介于1-200微米之间,优选10-50微米;以提高机械强度,采用现有技术制备即可。所述的聚四氟乙烯无纺布孔隙率介于20-99%之间,优选50-85%。孔隙率如果过低,否则会导致槽压升高。The porous reinforcing material is a polytetrafluoroethylene non-woven fabric, and the fiber boundary is overlapped or fused together, and the porous reinforcing material has a thickness of between 1 and 200 micrometers, preferably 10 to 50 micrometers; to improve mechanical strength, using existing The technology can be prepared. The polytetrafluoroethylene nonwoven fabric has a porosity of between 20 and 99%, preferably between 50 and 85%. If the porosity is too low, it will cause the cell pressure to rise.
本发明所述的新型离子传导膜,包括以下制备步骤:The novel ion conducting membrane of the present invention comprises the following preparation steps:
(1)通过螺杆式挤出机共挤出的方式熔融流延成全氟离子交换树脂基膜,再将多孔增强材料浸泡在氟碳类溶剂中,超声处理1-2小时,取出干燥后再与全氟离子交换树脂基膜进行复合,在膜成型压辊间引入多孔增强材料,在辊间压力的作用下将多孔增强材料压入全氟离子交换树脂基膜中,从而获得全氟离子交换膜前体。(1) melt-casting into a perfluoro ion exchange resin base film by co-extrusion by a screw extruder, and then immersing the porous reinforcing material in a fluorocarbon solvent, sonicating for 1-2 hours, taking out and drying, and then The perfluoro ion exchange resin base film is composited, a porous reinforcing material is introduced between the film forming rolls, and the porous reinforcing material is pressed into the perfluoro ion exchange resin base film under the pressure between the rolls to obtain a perfluoro ion exchange membrane. Precursor.
(2)将步骤(1)中制得的全氟离子交换膜前体转化为具有离子交换功能的全氟离子交换膜。(2) The perfluoro ion exchange membrane precursor prepared in the step (1) is converted into a perfluoro ion exchange membrane having an ion exchange function.
(3)将水和乙醇按照1∶1重量比配成混合液,加入全氟离子交换树脂微颗粒与无机化合物颗粒混合物,在球磨机中均一化处理,形成分散液。(3) Water and ethanol are mixed in a ratio of 1:1 by weight, and a mixture of perfluoro ion exchange resin microparticles and inorganic compound particles is added and homogenized in a ball mill to form a dispersion.
(4)将(3)中的分散液附着在步骤(2)得到的全氟离子交换膜表面,经干燥后形成成品。(4) The dispersion in (3) is adhered to the surface of the perfluoro ion exchange membrane obtained in the step (2), and dried to form a finished product.
其中:步骤(1)将多孔增强材料浸泡在氟碳类溶剂中超声处理1-2小时,取出干燥后再与全氟离子交换树脂基膜进行复合。由于对聚四氟乙烯无纺布的浸润是十分困难的,若不经过处理直接与基膜进行复合,树脂基体无法完全填满无纺布的空隙,从而形成膜体内部的不密实空间,不仅容易沉积杂质,还能形成空间阻隔,增加阻力。多孔增强材料在氟碳类溶剂 中浸泡1-2小时之后,树脂基体的浸润十分容易,二者能够形成良好、紧密的结合,不仅增加了力学强度,且由于无纺布开孔率高,对膜体阻力的影响微乎其微。Wherein: Step (1) The porous reinforcing material is soaked in a fluorocarbon solvent for ultrasonic treatment for 1-2 hours, taken out and dried, and then combined with a perfluoro ion exchange resin base film. Since the wetting of the polytetrafluoroethylene nonwoven fabric is very difficult, if it is directly combined with the base film without treatment, the resin matrix cannot completely fill the voids of the nonwoven fabric, thereby forming a non-compact space inside the film body, not only It is easy to deposit impurities, and it can also form a space barrier and increase resistance. Porous reinforcing material in fluorocarbon solvent After immersion for 1-2 hours, the impregnation of the resin matrix is very easy, and the two can form a good and tight bond, which not only increases the mechanical strength, but also has little effect on the membrane resistance due to the high open porosity of the nonwoven fabric.
步骤(1)所述的氟碳类溶剂选自:三氟三氯乙烷(F-113)或者三氟三氯乙烷与其它溶剂混合;其它溶剂为无水乙醇、丙醇、甲醇、丙酮、二氯甲烷或表面活性剂水溶液中的一种或几种。表面活性剂选自市购的阴离子型、阳离子型、两性型或非离子型表面活性剂即可。The fluorocarbon solvent according to the step (1) is selected from the group consisting of trifluorotrichloroethane (F-113) or trifluorotrichloroethane mixed with other solvents; the other solvents are anhydrous ethanol, propanol, methanol, acetone. One or more of methylene chloride or an aqueous solution of a surfactant. The surfactant may be selected from commercially available anionic, cationic, amphoteric or nonionic surfactants.
步骤(2)为将步骤(1)中制得的全氟离子交换膜前体在10-200℃的温度下,于20-100吨的压力下,以1-50米/分的速度使用超压机进行超压处理,超压处理后,将全氟离子交换膜前体浸渍于15wt%二甲基亚砜和20wt%NaOH的混合水溶液中,转化为具有离子交换功能的全氟离子交换膜。其中:超压处理进一步增加了无纺布与基膜的结合密实度,同时超压处理还一定程度上改善了无纺布和基膜的物理结构形态,无纺布的微纤化和基膜的热压致结晶结构细致化,会有效提高离子传递效果。Step (2) is to use the perfluoro ion exchange membrane precursor prepared in the step (1) at a temperature of 10 to 200 ° C under a pressure of 20 to 100 tons at a rate of 1 to 50 m / min. The press is subjected to an overpressure treatment, and after the overpressure treatment, the perfluoro ion exchange membrane precursor is immersed in a mixed aqueous solution of 15 wt% dimethyl sulfoxide and 20 wt% NaOH, and converted into a perfluoro ion exchange membrane having ion exchange function. . Among them: the overpressure treatment further increases the compactness of the nonwoven fabric and the base film, and the overpressure treatment also improves the physical structure of the nonwoven fabric and the base film to some extent, and the microfibrillation and base film of the nonwoven fabric. The thermo-induced crystal structure is refined, which will effectively improve the ion transport effect.
步骤(3)中全氟离子交换树脂微颗粒是由树脂粒料在低温破碎装置中一次粉碎后,再在深冷装置中进行研磨得到的。得到的全氟离子交换树脂微颗粒与无机化合物颗粒均具备不规则的表观形貌,对于表层起泡的脱附具有优异的效果。The perfluoro ion exchange resin microparticles in the step (3) are obtained by grinding the resin pellets once in a low temperature crushing apparatus and then grinding them in a cryogenic apparatus. The obtained perfluoro ion exchange resin microparticles and inorganic compound particles each have an irregular appearance and have an excellent effect on surface defoaming desorption.
步骤(4)将分散液附着在步骤(2)得到的全氟离子交换膜表面,附着方式很多种,包括:喷涂、刷涂、辊涂、浸渍、转印、旋涂等方法,优选喷涂、辊涂。工艺操作均按现有技术即可。Step (4) attaching the dispersion to the surface of the perfluorinated ion exchange membrane obtained in the step (2), and the adhesion method is various, including: spraying, brushing, roll coating, dipping, transfer, spin coating, etc., preferably spraying, Roll coating. The process operation can be carried out according to the prior art.
综上所述,本发明具有以下优点:In summary, the present invention has the following advantages:
(1)本发明用由全氟离子交换树脂微颗粒与无机化合物颗粒混合而成的表面层替代了现有产品中的无机氧化物涂层,由于全氟离子交换树脂微颗粒与基膜材质化学结构相同,具有良好的相容性和粘接性,因此可以保证在新型离子传导膜的整个寿命期间保持良好的脱气效果,且脱气效果远优于无机氧化物涂层。(1) The present invention replaces the inorganic oxide coating in the existing product with a surface layer obtained by mixing fine particles of perfluoro ion exchange resin with inorganic compound particles, due to the chemical chemistry of the perfluoro ion exchange resin microparticles and the base film material. The structure is the same, with good compatibility and adhesion, so that it can ensure good degassing effect throughout the life of the new ion-conducting membrane, and the degassing effect is much better than the inorganic oxide coating.
(2)由全氟离子交换树脂微颗粒与无机化合物颗粒混合而成的表面层因全氟离子交换树脂微颗粒的存在而具有离子交换功能,有益于离子传导膜槽电压和面电阻的降低。无机化学物颗粒的引入不仅降低了涂层制作成本,而且提高了膜的抗杂质性能。(2) The surface layer formed by mixing the perfluoro ion exchange resin microparticles with the inorganic compound particles has an ion exchange function due to the presence of the perfluoro ion exchange resin microparticles, which is beneficial to the reduction of the ion conductive membrane cell voltage and the sheet resistance. The introduction of inorganic chemical particles not only reduces the cost of coating production, but also improves the anti-impurity properties of the film.
(3)聚四氟乙烯无纺布经过溶剂处理后与基膜复合,并采用了超压工艺,在获得优异的电化学性能和力学性能的同时,大大提高了离子传导膜的抗杂质性能。(3) The polytetrafluoroethylene non-woven fabric is compounded with the base film after solvent treatment, and adopts an overpressure process to greatly improve the anti-impurity performance of the ion-conducting membrane while obtaining excellent electrochemical performance and mechanical properties.
(4)本发明提供的是一种用于电解氯化钠/氯化钾制备氯气和氢氧化钠/氢氧化钾的离子传导膜,聚四氟乙烯无纺布的引入提高了产品的纯度,电解得到的氯气纯度≥99.5%、氢气纯度≥99.9%、碱中含盐≤5ppm。 (4) The present invention provides an ion-conducting membrane for electrolytically preparing sodium chloride/potassium chloride to prepare chlorine gas and sodium hydroxide/potassium hydroxide, and the introduction of the polytetrafluoroethylene nonwoven fabric improves the purity of the product. The purity of the chlorine gas obtained by electrolysis is ≥99.5%, the purity of hydrogen is ≥99.9%, and the salt in the alkali is ≤5ppm.
(5)本发明离子传导膜适合于30-35%浓度碱的电解,而现有技术中离子传导膜一般只适合于30-32%浓度碱的电解。(5) The ion-conducting membrane of the present invention is suitable for electrolysis of a base of 30-35% concentration, whereas the ion-conducting membrane of the prior art is generally only suitable for electrolysis of a base of 30-32% concentration.
(6)本发明所述的离子传导膜用于氯碱工业可以稳定高效地处理宽范围浓度的碱金属氯化物溶液,且在杂质耐受性方面表现出出乎意料的效果,适合在新型高电流密度条件下的零极距电解槽中运行,在提高产品纯度的同时,槽电压显著降低,在高于5.5KA/m2的电流密度下,槽压低于2.75V。(6) The ion-conducting membrane of the present invention can be used for the chlor-alkali industry to stably and efficiently treat a wide range of alkali metal chloride solutions, and exhibits an unexpected effect in terms of impurity tolerance, and is suitable for a novel high current. In the zero-pole electrolysis cell operating under density conditions, the cell voltage is significantly reduced while increasing product purity. At current densities above 5.5 kA/m 2 , the cell pressure is below 2.75V.
(7)本发明还提供其制备方法,工艺简单合理,易于工业化生产。(7) The present invention also provides a preparation method thereof, which is simple and reasonable in process and easy to industrialize.
具体实施方式detailed description
下面结合实施例对本发明做进一步说明。The present invention will be further described below in conjunction with the embodiments.
实施例1Example 1
(1)选取IEC=1.1mmol/g的全氟磺酸树脂和IEC=1.0mmol/g的全氟羧酸树脂通过共挤出流延的方式复合成全氟离子交换树脂基膜,在以全氟磺酸树脂为主的树脂层中全氟磺酸树脂和全氟羧酸树脂质量比为100∶0.5,在以全氟磺酸树脂为主的树脂层中全氟羧酸树脂和全氟磺酸树脂质量比为100∶1,其中以全氟磺酸树脂为主的树脂层厚度为130微米,以全氟磺酸树脂为主的树脂层厚度为10微米。再将多孔增强材料聚四氟乙烯无纺布浸泡在超声处理器中的三氟三氯乙烷溶剂中处理1.5小时,其中无纺布厚度为40微米,孔隙率为75%,取出干燥后再与全氟离子交换树脂基膜进行复合,在膜成型压辊间引入多孔增强材料,在辊间压力的作用下将多孔增强材料压入膜体当中,从而形成全氟离子交换膜前体。(1) Selecting a perfluorosulfonic acid resin with IEC=1.1 mmol/g and a perfluorocarboxylic acid resin with IEC=1.0 mmol/g to form a perfluoro ion exchange resin base film by co-extrusion casting, in the form of perfluoro The sulfonic acid resin-based resin layer has a perfluorosulfonic acid resin and a perfluorocarboxylic acid resin in a mass ratio of 100:0.5, and a perfluorocarboxylic acid resin and a perfluorosulfonic acid in a resin layer mainly composed of a perfluorosulfonic acid resin. The resin mass ratio was 100:1, wherein the resin layer mainly composed of a perfluorosulfonic acid resin was 130 μm, and the thickness of the resin layer mainly composed of a perfluorosulfonic acid resin was 10 μm. Then, the porous reinforcing material polytetrafluoroethylene nonwoven fabric was immersed in a trifluorotrichloroethane solvent in an ultrasonic processor for 1.5 hours, wherein the thickness of the non-woven fabric was 40 micrometers, and the porosity was 75%. The perfluoro ion exchange resin base film is compounded, a porous reinforcing material is introduced between the film forming rolls, and the porous reinforcing material is pressed into the film body under the action of the pressure between the rolls to form a perfluoro ion exchange film precursor.
(2)将步骤(1)中制得的全氟离子交换膜前体在200℃的温度下,于60吨的压力下,以1米/分的速度使用超压机进行超压处理,超压处理后,将全氟离子交换膜前体浸没于85℃下含有15wt%二甲基亚砜和20wt%NaOH的混合水溶液中80分钟,转化为具备离子交换功能的全氟离子交换膜。(2) The perfluoro ion exchange membrane precursor prepared in the step (1) is subjected to an overpressure treatment at a temperature of 200 ° C under a pressure of 60 tons at a speed of 1 m/min using an overpressure press. After the pressure treatment, the perfluoro ion exchange membrane precursor was immersed in a mixed aqueous solution containing 15 wt% of dimethyl sulfoxide and 20 wt% of NaOH at 85 ° C for 80 minutes to be converted into a perfluoro ion exchange membrane having an ion exchange function.
(3)将水和乙醇按照1∶1的重量比配成混合液,加入IEC=1.0mmol/g、平均粒径为50纳米、具有不规则多面体形貌的全氟离子交换树脂微颗粒与平均粒径为20纳米的无机化合物颗粒均匀混合物(全氟离子交换树脂微颗粒和无机化合物颗粒均是由树脂粒料在低温破碎装置中一次粉碎后,再在深冷装置中进行研磨得到的),在球磨机中均一化处理,形成含量为15wt%的分散液;其中:全氟离子交换树脂微颗粒与无机化合物颗粒氧化钛的混合质量比例为1∶100。全氟离子交换树脂微颗粒为全氟羧酸树脂微颗粒与全氟磺酸树脂微颗粒的混合物;全氟磺酸树脂微颗粒的质量百分比占混合物的50%。(3) Mixing water and ethanol in a weight ratio of 1:1, adding PF=1.0 mmol/g, average particle size of 50 nm, perfluoro ion exchange resin microparticles with average polyhedral morphology and average a uniform mixture of inorganic compound particles having a particle diameter of 20 nm (perfluoro ion exchange resin microparticles and inorganic compound particles are obtained by grinding the resin pellets once in a low temperature crushing device and then grinding in a cryogenic apparatus) The mixture was homogenized in a ball mill to form a dispersion having a content of 15% by weight; wherein: the mixed mass ratio of the perfluoro ion exchange resin microparticles to the inorganic compound particulate titanium oxide was 1:100. The perfluoro ion exchange resin microparticles are a mixture of perfluorocarboxylic acid resin microparticles and perfluorosulfonic acid resin microparticles; the perfluorosulfonic acid resin microparticles comprise 50% by mass of the mixture.
(4)采用喷涂的方法,将分散液附着在步骤(2)得到的全氟离子交换膜两侧表面,表 面层厚度为200纳米,经干燥后形成成品。(4) using a spraying method, attaching the dispersion to both sides of the perfluoro ion exchange membrane obtained in the step (2), The surface layer has a thickness of 200 nm and is dried to form a finished product.
性能测试:Performance Testing:
将制备得到的离子交换膜在电解槽内进行氯化钠水溶液的电解测试,将300g/L的氯化钠水溶液供给阳极室,将水供给阴极室,保证从阳极室排出的氯化钠浓度为200g/L,从阴极室排出的氢氧化钠浓度为33%;测试温度为90℃,电流密度为7.5kA/m2,经过23天的电解实验,平均槽压为2.76V,平均电流效率为99.7%。The prepared ion exchange membrane is subjected to an electrolysis test of an aqueous solution of sodium chloride in an electrolytic cell, and a 300 g/L aqueous solution of sodium chloride is supplied to the anode chamber, and water is supplied to the cathode chamber to ensure that the concentration of sodium chloride discharged from the anode chamber is 200g / L, the concentration of sodium hydroxide discharged from the cathode chamber is 33%; the test temperature is 90 ° C, the current density is 7.5kA / m 2 , after 23 days of electrolysis experiments, the average cell pressure is 2.76V, the average current efficiency is 99.7%.
之后,向供给氯化钠水溶液中加入无机物Ca、Mg杂质15ppb,在上述相同的条件下进行140天的电解实验,平均槽压稳定在2.77V,平均电流效率为99.7%。Thereafter, 15 g of inorganic Ca and Mg impurities were added to the aqueous sodium chloride solution, and an electrolysis experiment was carried out for 140 days under the same conditions as described above. The average cell pressure was stabilized at 2.77 V, and the average current efficiency was 99.7%.
按照标准SJ/T 10171.5方法测试所得膜的面电阻为1.0Ω·cm-2,采用ASTM标准D1044-99测试所得膜的磨耗损失为2.7mg。The sheet resistance of the obtained film was 1.0 Ω·cm -2 according to the standard SJ/T 10171.5 method, and the abrasion loss of the film obtained by ASTM standard D1044-99 was 2.7 mg.
按照标准的电解产品检测标准,检测电解产品纯度分别为,氯气纯度99.7%,氢气纯度99.9%,碱中含盐3ppm。According to the standard electrolysis product testing standards, the purity of the electrolyzed products was determined to be 99.7% purity of chlorine gas, 99.9% purity of hydrogen, and 3 ppm of salt in alkali.
比较例1Comparative example 1
采用与实施例1相同的方法制备具备离子交换功能的离子交换膜,之后按照同样的方法制备分散液,所不同的是,将分散液中的全氟离子交换树脂与无机化合物混合微颗粒替换为平均粒径为50纳米无机氧化物颗粒,在球磨机中均一化处理,形成含量为15wt%的分散液。采用与实施例1同样的操作得到两侧附着有无机氧化物涂层的离子交换膜。An ion exchange membrane having an ion exchange function was prepared in the same manner as in Example 1, and then a dispersion liquid was prepared in the same manner except that the perfluoro ion exchange resin and the inorganic compound mixed microparticles in the dispersion were replaced with The inorganic oxide particles having an average particle diameter of 50 nm were homogenized in a ball mill to form a dispersion having a content of 15% by weight. An ion exchange membrane having an inorganic oxide coating adhered to both sides was obtained in the same manner as in Example 1.
在与实施例1相同的条件下进行氯化钠溶液的电解测试,经过23天的电解实验,平均槽压为2.91V,平均电流效率为96.3%,面电阻为2.4Ω·cm-2,膜的磨耗损失为12mg。之后,向供给氯化钠水溶液中加入无机物Ca、Mg杂质15ppb,在上述相同的条件下进行140天的电解实验,平均槽压稳定在3.15V,平均电流效率为95.9%。The electrolysis test of the sodium chloride solution was carried out under the same conditions as in Example 1. After 23 days of electrolysis experiments, the average cell pressure was 2.91 V, the average current efficiency was 96.3%, and the sheet resistance was 2.4 Ω·cm -2 . The wear loss is 12 mg. Thereafter, 15 g of inorganic Ca and Mg impurities were added to the aqueous sodium chloride solution, and an electrolysis experiment was carried out for 140 days under the same conditions as described above. The average cell pressure was stabilized at 3.15 V, and the average current efficiency was 95.9%.
比较例2Comparative example 2
采用与实施例1相同的方法制备具备离子交换功能的离子交换膜,所不同的是,多孔增强材料在与全氟离子交换树脂基膜进行复合之前未采用氟碳溶剂浸泡处理,且之后也未用超压机超压处理。按照同样的方法制备全氟离子交换树脂与无机化合物混合微颗粒分散液,在球磨机中均一化处理,形成含量为15wt%的分散液。采用与实施例1同样的操作得到离子交换膜成品。An ion exchange membrane having an ion exchange function was prepared in the same manner as in Example 1 except that the porous reinforcing material was not immersed in a fluorocarbon solvent before being compounded with the perfluoro ion exchange resin base film, and thereafter Overpressure treatment with an overpressure press. A fine particle dispersion of a perfluoro ion exchange resin and an inorganic compound was prepared in the same manner and homogenized in a ball mill to form a dispersion having a content of 15% by weight. The ion exchange membrane product was obtained in the same manner as in Example 1.
在与实施例1相同的条件下进行氯化钠溶液的电解测试,经过23天的电解实验,平均槽压为2.84V,平均电流效率为99.1%,面电阻为1.7Ω·cm-2。之后,向供给氯化钠水溶液中加入无机物Ca、Mg杂质15ppb,在上述相同的条件下进行40天的电解实验,平均槽压稳定 在2.93V,平均电流效率为97.4%。检测产品纯度分别为,氯气纯度98.4%,氢气纯度98.5%,碱中含盐15ppm。The electrolysis test of the sodium chloride solution was carried out under the same conditions as in Example 1. After 23 days of electrolysis, the average cell pressure was 2.84 V, the average current efficiency was 99.1%, and the sheet resistance was 1.7 Ω·cm -2 . Thereafter, 15 g of inorganic Ca and Mg impurities were added to the aqueous sodium chloride solution, and an electrolysis experiment was carried out for 40 days under the same conditions as described above. The average cell pressure was stabilized at 2.93 V, and the average current efficiency was 97.4%. The purity of the tested products was 98.4% for chlorine, 98.5% for hydrogen, and 15 ppm for alkali.
实施例2Example 2
(1)选取IEC=0.95mmol/g的全氟磺酸树脂和IEC=0.85mmol/g的全氟羧酸树脂通过共挤出流延的方式复合成全氟离子交换树脂基膜,在以全氟磺酸树脂为主的树脂层中全氟磺酸树脂和全氟羧酸树脂质量比为100∶2,在以全氟磺酸树脂为主的树脂层中全氟羧酸树脂和全氟磺酸树脂质量比为100∶0.5,其中以全氟磺酸树脂为主的树脂层厚度为150微米,以全氟磺酸树脂为主的树脂层厚度为7微米。再将多孔增强材料聚四氟乙烯无纺布浸泡在超声处理器中的三氟三氯乙烷与无水乙醇混合溶剂中处理2小时,其中无纺布厚度为50微米,孔隙率为70%,取出干燥后再与全氟离子交换树脂基膜进行复合,在膜成型压辊间引入多孔增强材料,在辊间压力的作用下将多孔增强材料压入膜体当中,从而形成全氟离子交换膜前体。(1) Selecting a perfluorosulfonic acid resin with IEC=0.95mmol/g and a perfluorocarboxylic acid resin with IEC=0.85mmol/g to form a perfluoro ion exchange resin base film by co-extrusion casting, in the form of perfluoro The sulfonic acid resin-based resin layer has a perfluorosulfonic acid resin and a perfluorocarboxylic acid resin in a mass ratio of 100:2, and a perfluorocarboxylic acid resin and a perfluorosulfonic acid in a resin layer mainly composed of a perfluorosulfonic acid resin. The resin mass ratio was 100:0.5, wherein the resin layer mainly composed of a perfluorosulfonic acid resin was 150 μm, and the thickness of the resin layer mainly composed of a perfluorosulfonic acid resin was 7 μm. Then, the porous reinforcing material polytetrafluoroethylene non-woven fabric is immersed in a mixed solvent of trifluorotrichloroethane and absolute ethanol in an ultrasonic processor for 2 hours, wherein the non-woven fabric has a thickness of 50 μm and a porosity of 70%. After taking out and drying, it is combined with the perfluoro ion exchange resin base film, and a porous reinforcing material is introduced between the film forming rolls, and the porous reinforcing material is pressed into the film body under the action of the pressure between the rolls to form a perfluoro ion exchange. Film precursor.
(2)将步骤(1)中制得的全氟离子交换膜前体在180℃的温度下,于100吨的压力下,以25米/分的速度使用超压机进行超压处理,超压处理后,将全氟离子交换膜前体浸没于85℃下含有15wt%二甲基亚砜和20wt%NaOH的混合水溶液中80分钟,转化为具备离子交换功能的全氟离子交换膜。(2) The perfluoro ion exchange membrane precursor prepared in the step (1) is subjected to an overpressure treatment at a temperature of 180 ° C at a pressure of 100 ton at a speed of 25 m/min using an overpressure press. After the pressure treatment, the perfluoro ion exchange membrane precursor was immersed in a mixed aqueous solution containing 15 wt% of dimethyl sulfoxide and 20 wt% of NaOH at 85 ° C for 80 minutes to be converted into a perfluoro ion exchange membrane having an ion exchange function.
(3)将水和乙醇按照1∶1的重量比配成混合液,加入IEC=0.85mmol/g、平均粒径为60纳米、具有不规则多面体形貌的全氟离子交换树脂微颗粒与平均粒径为100纳米的无机化合物颗粒均匀混合物(全氟离子交换树脂微颗粒和无机化合物颗粒均是由树脂粒料在低温破碎装置中一次粉碎后,再在深冷装置中进行研磨得到的),在球磨机中均一化处理,形成含量为15wt%的分散液。其中,全氟离子交换树脂微颗粒与无机化合物颗粒氢氧化锆的混合质量比例为1∶1。全氟离子交换树脂微颗粒为全氟羧酸树脂微颗粒、全氟磺酸羧酸共聚树脂微颗粒与全氟磺酸树脂微颗粒的混合物;全氟磺酸树脂微颗粒的质量百分比占混合物的75%。(3) Mixing water and ethanol in a weight ratio of 1:1, adding PF=0.85mmol/g, an average particle size of 60 nm, and having a polyhedral ion exchange resin microparticle and average with irregular polyhedral morphology a uniform mixture of inorganic compound particles having a particle diameter of 100 nm (perfluoride ion exchange resin microparticles and inorganic compound particles are obtained by grinding the resin pellets once in a low temperature crushing device and then grinding in a cryogenic apparatus) The mixture was homogenized in a ball mill to form a dispersion having a content of 15% by weight. Wherein, the mixed mass ratio of the perfluoro ion exchange resin microparticles to the inorganic compound particles zirconium hydroxide is 1:1. The perfluoro ion exchange resin microparticles are a mixture of perfluorocarboxylic acid resin microparticles, perfluorosulfonic acid carboxylic acid copolymer resin microparticles and perfluorosulfonic acid resin microparticles; perfluorosulfonic acid resin microparticles by mass percentage of the mixture 75%.
(4)采用辊涂的方法,将分散液附着在步骤(2)得到的全氟离子交换膜两侧表面,表面层厚度约为500纳米,经干燥后形成成品。(4) The dispersion is adhered to both sides of the perfluoro ion exchange membrane obtained in the step (2) by a roll coating method, and the surface layer has a thickness of about 500 nm, and is dried to form a finished product.
性能测试:Performance Testing:
将制备得到的离子交换膜在电解槽内进行氯化钠水溶液的电解测试,将300g/L的氯化钠水溶液供给阳极室,将水供给阴极室,保证从阳极室排出的氯化钠浓度为200g/L,从阴极室排出的氢氧化钠浓度为34%;测试温度为90℃,电流密度为6.5kA/m2,经过23天的电解实验,平均槽压为2.72V,平均电流效率为99.8%。The prepared ion exchange membrane is subjected to an electrolysis test of an aqueous solution of sodium chloride in an electrolytic cell, and a 300 g/L aqueous solution of sodium chloride is supplied to the anode chamber, and water is supplied to the cathode chamber to ensure that the concentration of sodium chloride discharged from the anode chamber is 200g / L, the concentration of sodium hydroxide discharged from the cathode chamber is 34%; the test temperature is 90 ° C, the current density is 6.5kA / m 2 , after 23 days of electrolysis experiments, the average cell pressure is 2.72V, the average current efficiency is 99.8%.
之后,向供给氯化钠水溶液中加入无机物Ca、Mg杂质15ppb,在上述相同的条件下 进行140天的电解实验,平均槽压稳定在2.72V,平均电流效率为99.7%。Thereafter, an inorganic Ca and Mg impurities of 15 ppb were added to the aqueous sodium chloride solution, under the same conditions as above. After 140 days of electrolysis experiments, the average cell pressure was stabilized at 2.72V and the average current efficiency was 99.7%.
按照标准SJ/T 10171.5方法测试所得膜的面电阻为1.0Ω·cm-2,采用ASTM标准D1044-99测试所得膜的磨耗损失为2.8mg。The sheet resistance of the obtained film was measured to 1.0 Ω·cm -2 according to the standard SJ/T 10171.5 method, and the abrasion loss of the film obtained by ASTM standard D1044-99 was 2.8 mg.
按照标准的电解产品检测标准,检测电解产品纯度分别为,氯气纯度99.5%,氢气纯度99.9%,碱中含盐4ppm。According to the standard electrolysis product testing standards, the purity of the electrolysis products was determined to be 99.5% purity of chlorine gas, 99.9% purity of hydrogen gas, and 4 ppm salt in alkali.
实施例3Example 3
(1)选取IEC=1.0mmol/g的全氟磺酸树脂和IEC=0.95mmol/g的全氟羧酸树脂通过共挤出流延的方式复合成全氟离子交换树脂基膜,在以全氟磺酸树脂为主的树脂层中全氟磺酸树脂和全氟羧酸树脂质量比为100∶5,在以全氟磺酸树脂为主的树脂层中全氟羧酸树脂和全氟磺酸树脂质量比为100∶2.5,其中以全氟磺酸树脂为主的树脂层厚度为80微米,以全氟磺酸树脂为主的树脂层厚度为10微米。再将多孔增强材料聚四氟乙烯无纺布浸泡在超声处理器中的三氟三氯乙烷与丙醇混合溶剂中处理2小时,其中无纺布厚度为10微米,孔隙率为50%,取出干燥后再与全氟离子交换树脂基膜进行复合,在膜成型压辊间引入多孔增强材料,在辊间压力的作用下将多孔增强材料压入膜体当中,从而形成全氟离子交换膜前体。(1) Selecting a perfluorosulfonic acid resin with IEC=1.0 mmol/g and a perfluorocarboxylic acid resin with IEC=0.95 mmol/g to form a perfluoro ion exchange resin base film by co-extrusion casting, in the form of perfluoro The sulfonic acid resin-based resin layer has a perfluorosulfonic acid resin and a perfluorocarboxylic acid resin in a mass ratio of 100:5, and a perfluorocarboxylic acid resin and a perfluorosulfonic acid in a resin layer mainly composed of a perfluorosulfonic acid resin. The resin mass ratio was 100:2.5, wherein the resin layer mainly composed of a perfluorosulfonic acid resin was 80 μm, and the thickness of the resin layer mainly composed of a perfluorosulfonic acid resin was 10 μm. Then, the porous reinforcing material polytetrafluoroethylene non-woven fabric is immersed in a mixed solvent of trifluorotrichloroethane and propanol in an ultrasonic processor for 2 hours, wherein the non-woven fabric has a thickness of 10 μm and a porosity of 50%. After being taken out and dried, it is combined with the perfluoro ion exchange resin base film, a porous reinforcing material is introduced between the film forming rolls, and the porous reinforcing material is pressed into the film body under the action of the pressure between the rolls to form a perfluoro ion exchange film. Precursor.
(2)将步骤(1)中制得的全氟离子交换膜前体在140℃的温度下,于80吨的压力下,以30米/分的速度使用超压机进行超压处理,超压处理后,将全氟离子交换膜前体浸没于85℃下含有15wt%二甲基亚砜和20wt%NaOH的混合水溶液中80分钟,转化为具备离子交换功能的全氟离子交换膜。(2) The perfluoro ion exchange membrane precursor prepared in the step (1) is subjected to an overpressure treatment at a temperature of 140 ° C under a pressure of 80 tons at a speed of 30 m / min. After the pressure treatment, the perfluoro ion exchange membrane precursor was immersed in a mixed aqueous solution containing 15 wt% of dimethyl sulfoxide and 20 wt% of NaOH at 85 ° C for 80 minutes to be converted into a perfluoro ion exchange membrane having an ion exchange function.
(3)将水和乙醇按照1∶1的重量比配成混合液,加入IEC=0.75mmol/g、平均粒径为150纳米、具有不规则多面体形貌的全氟离子交换树脂微颗粒与平均粒径为200纳米的无机化合物颗粒的均匀混合物(全氟离子交换树脂微颗粒和无机化合物颗粒均是由树脂粒料在低温破碎装置中一次粉碎后,再在深冷装置中进行研磨得到的),在球磨机中均一化处理,形成含量为15wt%的分散液。其中,全氟离子交换树脂微颗粒与无机化合物颗粒氧化锡的混合质量比例为1∶50。全氟离子交换树脂微颗粒为全氟磺酸羧酸共聚树脂微与全氟磺酸树脂微颗粒的混合物;其中:全氟磺酸树脂微颗粒的质量百分比占混合物的65%。(3) Mixing water and ethanol in a weight ratio of 1:1, adding PF=0.75 mmol/g, an average particle size of 150 nm, and having a polyhedral ion exchange resin microparticle and average with an irregular polyhedral morphology A homogeneous mixture of inorganic compound particles having a particle diameter of 200 nm (perfluoro ion exchange resin microparticles and inorganic compound particles are obtained by grinding the resin pellets once in a low temperature crushing device and then grinding in a cryogenic apparatus) It was homogenized in a ball mill to form a dispersion having a content of 15% by weight. Wherein, the mixed mass ratio of the perfluoro ion exchange resin microparticles to the inorganic compound particles tin oxide is 1:50. The perfluoro ion exchange resin microparticles are a mixture of a perfluorosulfonic acid carboxylic acid copolymer resin micro and a perfluorosulfonic acid resin microparticle; wherein: the perfluorosulfonic acid resin microparticles account for 65% by mass of the mixture.
(4)采用刷涂的方法,将分散液附着在步骤(2)得到的全氟离子交换膜两侧表面,表面层厚度约为1000纳米,经干燥后形成成品。(4) Using a brushing method, the dispersion is adhered to both sides of the perfluoro ion exchange membrane obtained in the step (2), and the surface layer has a thickness of about 1000 nm, and is dried to form a finished product.
性能测试:Performance Testing:
将制备得到的离子交换膜在电解槽内进行氯化钠水溶液的电解测试,将300g/L的氯化钠水溶液供给阳极室,将水供给阴极室,保证从阳极室排出的氯化钠浓度为200g/L,从 阴极室排出的氢氧化钠浓度为30%;测试温度为90℃,电流密度为7.5kA/m2,经过23天的电解实验,平均槽压为2.75V,平均电流效率为99.8%。The prepared ion exchange membrane is subjected to an electrolysis test of an aqueous solution of sodium chloride in an electrolytic cell, and a 300 g/L aqueous solution of sodium chloride is supplied to the anode chamber, and water is supplied to the cathode chamber to ensure that the concentration of sodium chloride discharged from the anode chamber is 200g / L, the concentration of sodium hydroxide discharged from the cathode chamber is 30%; the test temperature is 90 ° C, the current density is 7.5kA / m 2 , after 23 days of electrolysis experiments, the average cell pressure is 2.75V, the average current efficiency is 99.8%.
之后,向供给氯化钠水溶液中加入无机物Ca、Mg杂质15ppb,在上述相同的条件下进行140天的电解实验,平均槽压稳定在2.75V,平均电流效率为99.8%。Thereafter, 15 g of inorganic Ca and Mg impurities were added to the aqueous sodium chloride solution, and an electrolysis experiment was carried out for 140 days under the same conditions as described above. The average cell pressure was stabilized at 2.75 V, and the average current efficiency was 99.8%.
按照标准SJ/T 10171.5方法测试所得膜的面电阻为1.2Ω·cm-2,采用ASTM标准D1044-99测试所得膜的磨耗损失为2.7mg。The sheet resistance of the obtained film was measured to 1.2 Ω·cm -2 according to the standard SJ/T 10171.5 method, and the abrasion loss of the film obtained by ASTM standard D1044-99 was 2.7 mg.
按照标准的电解产品检测标准,检测电解产品纯度分别为,氯气纯度99.8%,氢气纯度99.9%,碱中含盐3ppm。According to the standard electrolysis product testing standards, the purity of the electrolysis products is determined to be 99.8% purity of chlorine gas, 99.9% purity of hydrogen gas, and 3 ppm salt in alkali.
实施例4Example 4
(1)选取IEC=0.9mmol/g的全氟磺酸树脂和IEC=0.85mmol/g的全氟羧酸树脂通过共挤出流延的方式复合成全氟离子交换树脂基膜,在以全氟磺酸树脂为主的树脂层中全氟磺酸树脂和全氟羧酸树脂质量比为100∶2.5,在以全氟磺酸树脂为主的树脂层中全氟羧酸树脂和全氟磺酸树脂质量比为100∶5,其中以全氟磺酸树脂为主的树脂层厚度为75微米,以全氟磺酸树脂为主的树脂层厚度为15微米。再将多孔增强材料聚四氟乙烯无纺布浸泡在超声处理器中的三氟三氯乙烷与甲醇混合溶剂中处理1小时,其中无纺布厚度为50微米,孔隙率为85%,取出干燥后再与全氟离子交换树脂基膜进行复合,在膜成型压辊间引入多孔增强材料,在辊间压力的作用下将多孔增强材料压入膜体当中,从而形成全氟离子交换膜前体。(1) Selecting a perfluorosulfonic acid resin with IEC=0.9 mmol/g and a perfluorocarboxylic acid resin with IEC=0.85 mmol/g to form a perfluoro ion exchange resin base film by co-extrusion casting, in the form of perfluoro The sulfonic acid resin-based resin layer has a perfluorosulfonic acid resin and a perfluorocarboxylic acid resin in a mass ratio of 100:2.5, and a perfluorocarboxylic acid resin and a perfluorosulfonic acid in a resin layer mainly composed of a perfluorosulfonic acid resin. The resin mass ratio was 100:5, wherein the resin layer mainly composed of perfluorosulfonic acid resin was 75 μm, and the thickness of the resin layer mainly composed of perfluorosulfonic acid resin was 15 μm. Then, the porous reinforcing material polytetrafluoroethylene non-woven fabric is immersed in a mixed solvent of trifluorotrichloroethane and methanol in an ultrasonic processor for 1 hour, wherein the non-woven fabric has a thickness of 50 μm and a porosity of 85%. After drying, it is compounded with the perfluoro ion exchange resin base film, and a porous reinforcing material is introduced between the film forming rolls, and the porous reinforcing material is pressed into the film body under the action of the pressure between the rolls to form a perfluoro ion exchange film. body.
(2)将步骤(1)中制得的全氟离子交换膜前体在10℃的温度下,于40吨的压力下,以50米/分的速度使用超压机进行超压处理,超压处理后,将全氟离子交换膜前体浸没于85℃下含有15wt%二甲基亚砜和20wt%NaOH的混合水溶液中80分钟,转化为具备离子交换功能的全氟离子交换膜。(2) The perfluoro ion exchange membrane precursor prepared in the step (1) is subjected to an overpressure treatment at a temperature of 10 ° C at a temperature of 10 ° C at a speed of 50 m/min using an overpressure press. After the pressure treatment, the perfluoro ion exchange membrane precursor was immersed in a mixed aqueous solution containing 15 wt% of dimethyl sulfoxide and 20 wt% of NaOH at 85 ° C for 80 minutes to be converted into a perfluoro ion exchange membrane having an ion exchange function.
(3)将水和乙醇按照1∶1的重量比配成混合液,加入IEC=0.55mmol/g、平均粒径为200纳米、具有不规则多面体形貌的全氟离子交换树脂微颗粒与平均粒径为300纳米的无机化合物颗粒的均匀混合物(全氟离子交换树脂微颗粒和无机化合物颗粒均是由树脂粒料在低温破碎装置中一次粉碎后,再在深冷装置中进行研磨得到的),在球磨机中均一化处理,形成含量为15wt%的分散液。其中:全氟离子交换树脂微颗粒与无机化合物颗粒氧化锶的混合质量比例为100∶1。全氟离子交换树脂微颗粒为全氟羧酸树脂微颗粒与全氟磺酸树脂微颗粒的混合物;全氟磺酸树脂微颗粒的质量百分比占混合物的80%。(3) Mixing water and ethanol in a weight ratio of 1:1, adding PF = 0.55 mmol/g, an average particle size of 200 nm, and having a polyhedral ion exchange resin microparticle and average with an irregular polyhedral morphology A homogeneous mixture of inorganic compound particles having a particle diameter of 300 nm (perfluoro ion exchange resin microparticles and inorganic compound particles are obtained by grinding the resin pellets once in a low temperature crushing device and then grinding in a cryogenic apparatus) It was homogenized in a ball mill to form a dispersion having a content of 15% by weight. Wherein: the mixed mass ratio of the perfluoro ion exchange resin microparticles to the inorganic compound particles cerium oxide is 100:1. The perfluoro ion exchange resin microparticles are a mixture of perfluorocarboxylic acid resin microparticles and perfluorosulfonic acid resin microparticles; the perfluorosulfonic acid resin microparticles account for 80% by mass of the mixture.
(4)采用喷涂的方法,将分散液附着在步骤(2)得到的全氟离子交换膜两侧表面,表面层厚度约为1500纳米,经干燥后形成成品。 (4) The dispersion is adhered to both sides of the perfluoro ion exchange membrane obtained in the step (2) by a spraying method, and the surface layer has a thickness of about 1500 nm, and is dried to form a finished product.
性能测试:Performance Testing:
将制备得到的离子交换膜在电解槽内进行氯化钠水溶液的电解测试,将300g/L的氯化钠水溶液供给阳极室,将水供给阴极室,保证从阳极室排出的氯化钠浓度为200g/L,从阴极室排出的氢氧化钠浓度为30%;测试温度为90℃,电流密度为6.5kA/m2,经过23天的电解实验,平均槽压为2.71V,平均电流效率为99.7%。The prepared ion exchange membrane is subjected to an electrolysis test of an aqueous solution of sodium chloride in an electrolytic cell, and a 300 g/L aqueous solution of sodium chloride is supplied to the anode chamber, and water is supplied to the cathode chamber to ensure that the concentration of sodium chloride discharged from the anode chamber is 200g / L, the concentration of sodium hydroxide discharged from the cathode chamber is 30%; the test temperature is 90 ° C, the current density is 6.5kA / m 2 , after 23 days of electrolysis experiments, the average cell pressure is 2.71V, the average current efficiency is 99.7%.
之后,向供给氯化钠水溶液中加入无机物Ca、Mg杂质15ppb,在上述相同的条件下进行140天的电解实验,平均槽压稳定在2.71V,平均电流效率为99.7%。Thereafter, 15 g of inorganic Ca and Mg impurities were added to the aqueous sodium chloride solution, and an electrolysis experiment was carried out for 140 days under the same conditions as described above. The average cell pressure was stabilized at 2.71 V, and the average current efficiency was 99.7%.
按照标准SJ/T 10171.5方法测试所得膜的面电阻为1.2Ω·cm-2,采用ASTM标准D1044-99测试所得膜的磨耗损失为2.7mg。The sheet resistance of the obtained film was measured to 1.2 Ω·cm -2 according to the standard SJ/T 10171.5 method, and the abrasion loss of the film obtained by ASTM standard D1044-99 was 2.7 mg.
按照标准的电解产品检测标准,检测电解产品纯度分别为,氯气纯度99.8%,氢气纯度100%,碱中含盐4ppm。According to the standard electrolysis product testing standards, the purity of the electrolyzed products was determined to be 99.8% purity of chlorine gas, 100% purity of hydrogen, and 4 ppm of salt in alkali.
实施例5Example 5
(1)选取IEC=1.0mmol/g的全氟磺酸树脂和IEC=0.95mmol/g的全氟羧酸树脂通过共挤出流延的方式复合成全氟离子交换树脂基膜,在以全氟磺酸树脂为主的树脂层中全氟磺酸树脂和全氟羧酸树脂质量比为100∶0.5,在以全氟磺酸树脂为主的树脂层中全氟羧酸树脂和全氟磺酸树脂质量比为100∶2.5,其中以全氟磺酸树脂为主的树脂层厚度为50微米,以全氟磺酸树脂为主的树脂层厚度为18微米。再将多孔增强材料聚四氟乙烯无纺布浸泡在超声处理器中的三氟三氯乙烷与丙酮混合溶剂中处理1.5小时,其中无纺布厚度为10微米,孔隙率为70%,取出干燥后再与全氟离子交换树脂基膜进行复合,在膜成型压辊间引入多孔增强材料,在辊间压力的作用下将多孔增强材料压入膜体当中,从而形成全氟离子交换膜前体。(1) Selecting a perfluorosulfonic acid resin with IEC=1.0 mmol/g and a perfluorocarboxylic acid resin with IEC=0.95 mmol/g to form a perfluoro ion exchange resin base film by co-extrusion casting, in the form of perfluoro The sulfonic acid resin-based resin layer has a perfluorosulfonic acid resin and a perfluorocarboxylic acid resin in a mass ratio of 100:0.5, and a perfluorocarboxylic acid resin and a perfluorosulfonic acid in a resin layer mainly composed of a perfluorosulfonic acid resin. The resin mass ratio was 100:2.5, wherein the resin layer mainly composed of a perfluorosulfonic acid resin was 50 μm, and the thickness of the resin layer mainly composed of a perfluorosulfonic acid resin was 18 μm. Then, the porous reinforcing material polytetrafluoroethylene non-woven fabric is immersed in a mixed solvent of trifluorotrichloroethane and acetone in an ultrasonic processor for 1.5 hours, wherein the non-woven fabric has a thickness of 10 μm and a porosity of 70%. After drying, it is compounded with the perfluoro ion exchange resin base film, and a porous reinforcing material is introduced between the film forming rolls, and the porous reinforcing material is pressed into the film body under the action of the pressure between the rolls to form a perfluoro ion exchange film. body.
(2)将步骤(1)中制得的全氟离子交换膜前体在200℃的温度下,于20吨的压力下,以1米/分的速度使用超压机进行超压处理,超压处理后,将全氟离子交换膜前体浸没于85℃下含有15wt%二甲基亚砜和20wt%NaOH的混合水溶液中80分钟,转化为具备离子交换功能的全氟离子交换膜。(2) The perfluoro ion exchange membrane precursor prepared in the step (1) is subjected to an overpressure treatment at a temperature of 200 ° C under a pressure of 20 tons at a speed of 1 m/min. After the pressure treatment, the perfluoro ion exchange membrane precursor was immersed in a mixed aqueous solution containing 15 wt% of dimethyl sulfoxide and 20 wt% of NaOH at 85 ° C for 80 minutes to be converted into a perfluoro ion exchange membrane having an ion exchange function.
(3)将水和乙醇按照1∶1的重量比配成混合液,加入IEC=0.3mmol/g、平均粒径为300纳米、具有不规则多面体形貌的全氟离子交换树脂微颗粒与平均粒径为500纳米的无机化合物颗粒的均匀混合物(全氟离子交换树脂微颗粒和无机化合物颗粒是由树脂粒料在低温破碎装置中一次粉碎后,再在深冷装置中进行研磨得到的),在球磨机中均一化处理,形成含量为15wt%的分散液。其中,全氟离子交换树脂微颗粒与无机化合物颗粒氮化锆的混合质量比例为50∶1。全氟离子交换树脂微颗粒为全氟羧酸树脂微颗粒、全氟磺酸羧酸共聚树脂微颗粒 与全氟磺酸树脂微颗粒的混合物;全氟磺酸树脂微颗粒的质量百分比占混合物的85%。(3) Mixing water and ethanol in a weight ratio of 1:1, adding PF=0.3 mmol/g, average particle size of 300 nm, perfluoro ion exchange resin microparticles with average polyhedral morphology and average a homogeneous mixture of inorganic compound particles having a particle diameter of 500 nm (perfluoro ion exchange resin microparticles and inorganic compound particles are obtained by grinding the resin pellets once in a low temperature crushing device and then grinding in a cryogenic apparatus), The mixture was homogenized in a ball mill to form a dispersion having a content of 15% by weight. Wherein, the mixed mass ratio of the perfluoro ion exchange resin microparticles to the inorganic compound particles zirconium nitride is 50:1. The perfluoro ion exchange resin microparticles are perfluorocarboxylic acid resin microparticles, perfluorosulfonic acid carboxylic acid copolymer resin microparticles a mixture with microparticles of perfluorosulfonic acid resin; the percentage by mass of the perfluorosulfonic acid resin microparticles is 85% of the mixture.
(4)采用喷涂的方法,将分散液附着在步骤(2)得到的全氟离子交换膜两侧表面,表面层厚度约为2微米,经干燥后形成成品。(4) The dispersion is adhered to both sides of the perfluoro ion exchange membrane obtained in the step (2) by a spraying method, and the surface layer has a thickness of about 2 μm, and is dried to form a finished product.
性能测试:Performance Testing:
将制备得到的离子交换膜在电解槽内进行氯化钠水溶液的电解测试,将300g/L的氯化钠水溶液供给阳极室,将水供给阴极室,保证从阳极室排出的氯化钠浓度为200g/L,从阴极室排出的氢氧化钠浓度为33%;测试温度为90℃,电流密度为5.5kA/m2,经过23天的电解实验,平均槽压为2.70V,平均电流效率为99.8%。The prepared ion exchange membrane is subjected to an electrolysis test of an aqueous solution of sodium chloride in an electrolytic cell, and a 300 g/L aqueous solution of sodium chloride is supplied to the anode chamber, and water is supplied to the cathode chamber to ensure that the concentration of sodium chloride discharged from the anode chamber is 200g / L, the concentration of sodium hydroxide discharged from the cathode chamber is 33%; the test temperature is 90 ° C, the current density is 5.5kA / m 2 , after 23 days of electrolysis experiments, the average cell pressure is 2.70V, the average current efficiency is 99.8%.
之后,向供给氯化钠水溶液中加入无机物Ca、Mg杂质15ppb,在上述相同的条件下进行140天的电解实验,平均槽压稳定在2.71V,平均电流效率为99.7%。Thereafter, 15 g of inorganic Ca and Mg impurities were added to the aqueous sodium chloride solution, and an electrolysis experiment was carried out for 140 days under the same conditions as described above. The average cell pressure was stabilized at 2.71 V, and the average current efficiency was 99.7%.
按照标准SJ/T 10171.5方法测试所得膜的面电阻为1.1Ω·cm-2,采用ASTM标准D1044-99测试所得膜的磨耗损失为2.6mg。The sheet resistance of the obtained film was 1.1 Ω·cm -2 according to the standard SJ/T 10171.5 method, and the abrasion loss of the film obtained by ASTM standard D1044-99 was 2.6 mg.
按照标准的电解产品检测标准,检测电解产品纯度分别为,氯气纯度99.7%,氢气纯度99.9%,碱中含盐3ppm。 According to the standard electrolysis product testing standards, the purity of the electrolyzed products was determined to be 99.7% purity of chlorine gas, 99.9% purity of hydrogen, and 3 ppm of salt in alkali.

Claims (10)

  1. 一种新型离子传导膜,其特征在于:由全氟离子交换树脂基膜、多孔增强材料和全氟离子交换树脂微颗粒与无机化合物颗粒混合而成的表面层组成。A novel ion-conducting membrane characterized by comprising a perfluoro ion exchange resin base film, a porous reinforcing material, and a surface layer of a mixture of fine particles of perfluoro ion exchange resin and inorganic compound particles.
  2. 根据权利要求1所述的新型离子传导膜,其特征在于:所述的全氟离子交换树脂基膜是由以全氟磺酸树脂为主的树脂层和以全氟羧酸树脂为主的树脂层组成,以全氟磺酸树脂为主的树脂层厚度为30-300微米,以全氟羧酸树脂为主的树脂层厚度为2-30微米;以全氟磺酸树脂为主的树脂层是以质量比为100∶0.1-100∶10的全氟磺酸树脂和全氟羧酸树脂共混或共聚而成;以全氟羧酸树脂为主的树脂层是以质量比为100∶0.1-100∶10的全氟羧酸树脂和全氟磺酸树脂共混或共聚而成。The novel ion-conducting membrane according to claim 1, wherein said perfluoro ion exchange resin base film is a resin layer mainly composed of a perfluorosulfonic acid resin and a resin mainly composed of a perfluorocarboxylic acid resin. The layer composition is a perfluorosulfonic acid resin-based resin layer having a thickness of 30 to 300 μm, a perfluorocarboxylic resin-based resin layer having a thickness of 2 to 30 μm, and a perfluorosulfonic acid resin-based resin layer. It is a blend or copolymerization of a perfluorosulfonic acid resin and a perfluorocarboxylic acid resin in a mass ratio of 100:0.1-100:10; the resin layer mainly composed of a perfluorocarboxylic acid resin is a mass ratio of 100:0.1. A -100:10 perfluorocarboxylic acid resin and a perfluorosulfonic acid resin are blended or copolymerized.
  3. 根据权利要求2所述的新型离子传导膜,其特征在于:全氟磺酸树脂的交换容量为0.8-1.5毫摩尔/克,全氟羧酸树脂的交换容量为0.8-1.2毫摩尔/克。The novel ion-conducting membrane according to claim 2, wherein the perfluorosulfonic acid resin has an exchange capacity of 0.8 to 1.5 mmol/g, and the perfluorocarboxylic acid resin has an exchange capacity of 0.8 to 1.2 mmol/g.
  4. 根据权利要求1所述的新型离子传导膜,其特征在于:全氟离子交换树脂微颗粒与无机化合物颗粒混合而成的表面层厚度为200纳米-100微米之间,表面层中全氟离子交换树脂微颗粒与无机化合物颗粒的质量比为1∶100-100∶1。The novel ion-conducting membrane according to claim 1, wherein the surface layer of the perfluoro ion exchange resin microparticles mixed with the inorganic compound particles has a thickness of from 200 nm to 100 μm, and the perfluoro ion exchange in the surface layer The mass ratio of the resin microparticles to the inorganic compound particles is from 1:100 to 100:1.
  5. 根据权利要求1所述的新型离子传导膜,其特征在于:无机化合物颗粒选自IV-A族、IV-B族、V-B族、铁、钴、镍、铬、锰或硼元素的氧化物、氢氧化物、氮化物中的一种或任意几种的混合物。The novel ion-conducting membrane according to claim 1, wherein the inorganic compound particles are selected from the group consisting of oxides of Group IV-A, Group IV-B, Group VB, iron, cobalt, nickel, chromium, manganese or boron, One or a mixture of any of a hydroxide and a nitride.
  6. 根据权利要求1所述的新型离子传导膜,其特征在于:全氟离子交换树脂微颗粒为全氟羧酸树脂微颗粒或全氟磺酸羧酸共聚树脂微颗粒中的一种或两种与全氟磺酸树脂微颗粒的混合物;其中:全氟磺酸树脂微颗粒的质量百分比占混合物的95%-50%。The novel ion-conducting membrane according to claim 1, wherein the perfluoro ion exchange resin microparticles are one or both of perfluorocarboxylic acid resin microparticles or perfluorosulfonic acid carboxylic acid copolymer resin microparticles. a mixture of perfluorosulfonic acid resin microparticles; wherein: the perfluorosulfonic acid resin microparticles comprise 95% to 50% by mass of the mixture.
  7. 根据权利要求1、5或6所述的新型离子传导膜,其特征在于:表面层中的全氟离子交换树脂微颗粒,粒径范围为20纳米-10微米之间,全氟离子交换树脂微颗粒的离子交换容量介于0.01-1.5毫摩尔/克;表面层中的无机化合物颗粒粒径范围为20纳米-10微米之间。The novel ion-conducting membrane according to claim 1, 5 or 6, wherein the perfluoro ion exchange resin microparticles in the surface layer have a particle size ranging from 20 nm to 10 μm, and the perfluoro ion exchange resin is micro. The ion exchange capacity of the particles is between 0.01 and 1.5 mmol/g; the inorganic compound particles in the surface layer have a particle size ranging from 20 nm to 10 microns.
  8. 根据权利要求1所述的新型离子传导膜,其特征在于:多孔增强材料为聚四氟乙烯无纺布,纤维交界处是搭接或融合在一起,多孔增强材料厚度介于1-200微米之间;聚四氟乙烯无纺布孔隙率介于20-99%之间。The novel ion-conducting membrane according to claim 1, wherein the porous reinforcing material is a polytetrafluoroethylene nonwoven fabric, and the fiber boundary is overlapped or fused, and the porous reinforcing material has a thickness of 1 to 200 μm. The polytetrafluoroethylene nonwoven fabric has a porosity of between 20 and 99%.
  9. 一种权利要求1所述的新型离子传导膜的制备方法,其特征在于:包括以下步骤:A method for preparing a novel ion-conducting membrane according to claim 1, comprising the steps of:
    (1)通过螺杆式挤出机共挤出的方式熔融流延成全氟离子交换树脂基膜,再将多孔增强材料浸泡在氟碳类溶剂中,超声处理1-2小时,取出干燥后再与全氟离子交换树脂基膜进行 复合,在膜成型压辊间引入多孔增强材料,在辊间压力的作用下将多孔增强材料压入全氟离子交换树脂基膜中,从而获得全氟离子交换膜前体;(1) melt-casting into a perfluoro ion exchange resin base film by co-extrusion by a screw extruder, and then immersing the porous reinforcing material in a fluorocarbon solvent, sonicating for 1-2 hours, taking out and drying, and then Perfluoro ion exchange resin base film Compounding, introducing a porous reinforcing material between the film forming press rolls, pressing the porous reinforcing material into the perfluoro ion exchange resin base film under the action of the pressure between the rolls, thereby obtaining a perfluoro ion exchange film precursor;
    (2)将步骤(1)中制得的全氟离子交换膜前体转化为具有离子交换功能的全氟离子交换膜;(2) converting the perfluoro ion exchange membrane precursor prepared in the step (1) into a perfluoro ion exchange membrane having an ion exchange function;
    (3)将水和乙醇按照1∶1重量比配成混合液,加入全氟离子交换树脂微颗粒与无机化合物颗粒混合物,在球磨机中均一化处理,形成分散液;(3) mixing water and ethanol in a weight ratio of 1:1, adding a mixture of perfluoro ion exchange resin microparticles and inorganic compound particles, and homogenizing in a ball mill to form a dispersion;
    (4)将(3)中的分散液附着在步骤(2)得到的全氟离子交换膜表面,经干燥后形成成品。(4) The dispersion in (3) is adhered to the surface of the perfluoro ion exchange membrane obtained in the step (2), and dried to form a finished product.
  10. 根据权利要求9所述的新型离子传导膜的制备方法,其特征在于:步骤(3)中全氟离子交换树脂微颗粒是由树脂粒料在低温破碎装置中一次粉碎后,再在深冷装置中进行研磨得到的。 The method for preparing a novel ion-conducting membrane according to claim 9, wherein the perfluoro ion exchange resin microparticles in the step (3) are pulverized by the resin pellets in the low-temperature crushing device, and then in the cryogenic device. Grinded in.
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