CN-121972007-A - Bipolar membrane electrodialysis device for preparing perfluorinated sulfonic acid resin solution and preparation method

CN121972007ACN 121972007 ACN121972007 ACN 121972007ACN-121972007-A

Abstract

The application belongs to the technical field of preparation of perfluorinated sulfonic acid resin, and particularly relates to a bipolar membrane electrodialysis device for preparing perfluorinated sulfonic acid resin solution and a preparation method thereof. The device comprises an electrolytic tank, an anode plate arranged at one end of the electrolytic tank, a cathode plate arranged at the other end of the electrolytic tank, an anode chamber, a bipolar membrane assembly and a cathode chamber, wherein the anode chamber, the bipolar membrane assembly and the cathode chamber are arranged between the anode plate and the cathode plate, the anode chamber and the cathode chamber are connected in series, and the bipolar membrane assembly comprises a bipolar membrane, an acid chamber, a cation exchange membrane and an alkali chamber. The preparation method of the perfluorinated sulfonic acid resin solution firstly uses a bipolar membrane electrodialysis device to transform and prepare the perfluorinated sulfonic acid resin solution, and utilizes bipolar membranes to directly dissociate water to generate H + and OH Compared with the traditional method, the conversion rate and the yield of the method are improved greatly, the time cost and the labor cost are saved greatly, and no pollutant emission can be realized.

Inventors

ZHOU CHAOYI
PAN DANDAN
XU RAN
LI DAN
XIA FENGJIE
LIU HAO
ZHOU MINGZHENG
TANG HAOLIN

Assignees

国家电投集团氢能科技发展有限公司
武汉绿动氢能能源技术有限公司

Dates

Publication Date: 20260505
Application Date: 20260211

Claims (10)

1. The bipolar membrane electrodialysis device for preparing the perfluorinated sulfonic acid resin solution is characterized by comprising an electrolytic tank, an anode plate arranged at one end of the electrolytic tank, a cathode plate arranged at the other end of the electrolytic tank, and an anode chamber, a bipolar membrane assembly and a cathode chamber which are arranged between the anode plate and the cathode plate, wherein the anode chamber and the cathode chamber are connected in series; The bipolar membrane assembly includes a bipolar membrane, an acid compartment, a cation exchange membrane, and a base compartment.
2. The bipolar membrane electrodialysis device according to claim 1, wherein said anode plate and said cathode plate are each coated titanium electrodes, preferably said coated titanium electrodes comprise titanium plates and titanium plates coated with a noble metal oxide coating, more preferably said noble metal of said noble metal oxide comprises one or more of ruthenium (Ru), iridium (Ir) and platinum (Pt); and/or the bipolar membrane comprises a cation exchange layer, an anion exchange layer, and an intermediate catalytic layer between the cation exchange layer and the anion exchange layer; the cation exchange layer comprises a high molecular polymer material containing a negative fixed charge functional group, preferably, the negative fixed charge functional group comprises one or more of a sulfonic acid group, a phosphoric acid group and a carboxylic acid group, preferably, the high molecular polymer in the high molecular polymer material containing the negative fixed charge functional group comprises one or more of polystyrene, polyphenyl ether, sodium alginate, modified chitosan, polyvinyl chloride and polyether ether ketone; the anion exchange layer comprises a high molecular polymer material containing fixed positive charge functional groups, preferably, the fixed positive charge functional groups comprise one or more of quaternary ammonium groups, tertiary ammonium groups and secondary ammonium groups, and preferably, the high molecular polymer in the high molecular polymer material containing the fixed positive charge functional groups comprises one or more of polystyrene, polysulfone and polyvinylidene fluoride; The intermediate catalytic layer comprises a polymer matrix network and a catalytic active component, wherein the polymer matrix network comprises one or more of polyvinyl alcohol, polyacrylonitrile and polysulfone, and the catalytic active component comprises one or more of ferric hydroxide (Fe (OH) 3 ), chromium hydroxide (Cr (OH) 3 ), aluminum hydroxide (Al (OH) 3 ), silicon dioxide (SiO 2 ), titanium dioxide (TiO 2 ) and zirconium dioxide (ZrO 2 ); And/or the cation exchange membrane comprises a high polymer material containing a negative fixed charge functional group, preferably the negative fixed charge functional group comprises one or more of a sulfonic acid group, a phosphoric acid group and a carboxylic acid group, and preferably the high polymer in the high polymer material containing the negative fixed charge functional group comprises one or more of tetrafluoroethylene-perfluorovinyl ether copolymer, polystyrene, polyphenyl ether, sodium alginate, modified chitosan, polyvinyl chloride and polyether ether ketone.
3. The bipolar membrane electrodialysis device for producing a perfluorosulfonic acid resin solution according to claim 1, wherein the number of the membrane modules is 1 or more, and a plurality of the membrane modules are connected in series.
4. A method for preparing a perfluorosulfonic acid resin solution using the bipolar membrane electrodialysis apparatus according to any one of claims 1-3, comprising the steps of: Adding salt solution into the anode chamber and the cathode chamber of the bipolar membrane electrodialysis device, adding perfluorosulfonate resin solution into the acid chamber, adding water into the alkali chamber, and introducing direct current to cause hydrolysis reaction in the electrolytic cell to obtain perfluorosulfonate resin solution.
5. The method for preparing a perfluorosulfonic acid resin solution using a bipolar membrane electrodialysis apparatus according to claim 4, wherein the mass concentration of the salt solution is 2% -8%; And/or, the salt solution comprises a sodium sulfate solution; and/or the mass concentration of the perfluorosulfonate resin solution is 1% -30%.
6. The method for preparing a perfluorosulfonic acid resin solution using a bipolar membrane electrodialysis apparatus according to claim 4, wherein the perfluorosulfonic acid salt resin solution has a viscosity of 2.0-100.0 mpa.s.
7. The method for preparing a perfluorosulfonic acid resin solution using a bipolar membrane electrodialysis apparatus according to claim 4, wherein the perfluorosulfonate resin in the perfluorosulfonate resin solution has a particle size of 50-500nm; And/or the solvent adopted by the perfluorosulfonate resin solution comprises one or more of water, methanol, ethanol, isopropanol, n-propanol and n-butanol.
8. The method for preparing a perfluorosulfonic acid resin solution according to claim 4, wherein the current density of the hydrolysis reaction is 10-100mA/cm 2 and the temperature is 10-60 ℃.
9. The method for producing a perfluorosulfonic acid resin solution using a bipolar membrane electrodialysis apparatus according to claim 4, wherein the linear flow rates of the solution flows in the anode compartment, the cathode compartment, the acid compartment and the base compartment are each independently 0.1 to 10cm/s.
10. The method for producing a perfluorosulfonic acid resin solution using a bipolar membrane electrodialysis apparatus according to claim 4, wherein the energization is stopped while the concentration of the solution in the base compartment is maintained during the hydrolysis reaction, and the perfluorosulfonic acid resin solution flows out of the acid compartment.

Description

Bipolar membrane electrodialysis device for preparing perfluorinated sulfonic acid resin solution and preparation method Technical Field The application belongs to the technical field of preparation of perfluorinated sulfonic acid resin, and particularly relates to a bipolar membrane electrodialysis device for preparing perfluorinated sulfonic acid resin solution and a preparation method thereof. Background The perfluorosulfonic acid proton exchange membrane is a solid polymer electrolyte, has the advantages of high conductivity, high mechanical strength, good chemical stability and thermal stability, and the like, and is widely applied to the fields of fuel cells, water electrolysis hydrogen production, chlor-alkali industry, energy storage batteries, gas sensors, and the like. The perfluorinated sulfonic acid resin solution is a key material for producing perfluorinated sulfonic acid proton exchange membranes, and the preparation process of the perfluorinated sulfonic acid resin solution not only affects the performance of the proton exchange membranes, but also directly affects the production efficiency and cost of the proton exchange membranes. The traditional process for preparing the perfluorosulfonic acid resin solution comprises the steps of immersing perfluorosulfonate resin powder in high-concentration acid solution for multiple times for acidification, converting the perfluorosulfonic acid resin into perfluorosulfonic acid resin, washing the perfluorosulfonic acid resin powder with deionized water for multiple times to remove residual acid solution and salt-type byproducts, and drying the perfluorosulfonic acid resin powder. And dissolving and dispersing the washed and dried perfluorinated sulfonic acid resin in an aqueous alcohol low-boiling point solvent to obtain a perfluorinated sulfonic acid resin solution. The traditional preparation method of the perfluorosulfonic acid resin solution has the following problems that the transformation efficiency is low because the perfluorosulfonate resin is subjected to acidification and transformation under the powder state, the transformation needs to be subjected to repeated impregnation and acidification by high-concentration acid liquor and then is subjected to repeated washing by deionized water to remove residual acid liquor and byproducts, a large amount of waste acid and waste water are generated in the preparation process, the process is complicated, the time and labor are long, the cost is high, the perfluorosulfonic acid resin can be slightly dissolved in the deionized water, the resin loss is caused in the washing process, the yield in the transformation and washing processes is low, and the preparation cost of the resin is increased. Disclosure of Invention The application provides a bipolar membrane electrodialysis device for preparing a perfluorinated sulfonic acid resin solution and a preparation method thereof, and aims to solve the problems that the existing perfluorinated sulfonic acid resin solution is complex in preparation process, generates a large amount of waste acid and waste water, and is low in yield and high in cost. The application provides a bipolar membrane electrodialysis device for preparing a perfluorosulfonic acid resin solution, which comprises an electrolytic tank, an anode plate arranged at one end of the electrolytic tank, a cathode plate arranged at the other end of the electrolytic tank, and an anode chamber, a bipolar membrane assembly and a cathode chamber arranged between the anode plate and the cathode plate, wherein the anode chamber and the cathode chamber are connected in series; The bipolar membrane assembly includes a bipolar membrane, an acid compartment, a cation exchange membrane, and a base compartment. According to some embodiments of the bipolar membrane electrodialysis device for producing perfluorosulfonic acid resin solutions of the application, the anode plate and the cathode plate are both coated titanium electrodes, preferably the coated titanium electrodes comprise a titanium plate and a titanium plate coated with a noble metal oxide coating, more preferably the noble metal in the noble metal oxide comprises one or more of ruthenium (Ru), iridium (Ir), and platinum (Pt). According to some embodiments of the bipolar membrane electrodialysis apparatus for producing perfluorosulfonic acid resin solutions of the application, the bipolar membrane comprises a cation exchange layer, an anion exchange layer, and an intermediate catalytic layer positioned between the cation exchange layer and the anion exchange layer. The cation exchange layer faces to one side of the cathode, the anion exchange layer faces to one side of the anode, and the middle catalytic layer is tightly clamped between the cation exchange layer and the anion exchange layer. The cation exchange layer comprises a high molecular polymer material containing a negative fixed charge functional group, preferably, the negative fixed charg