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Carbon-nanotube-modified high-current-density perfluorinated ion exchange membrane and preparation method thereof

A carbon nanotube modification, perfluorinated ion technology, applied in the direction of diaphragm, electrolysis process, electrolysis components, etc., can solve problems such as strength reduction, and achieve the effect of reducing cell voltage, increasing strength, and reducing transmission resistance

Active Publication Date: 2014-02-05
SHANDONG DONGYUE POLYMER MATERIAL
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The solution to this problem is to reduce the thickness of the ionic membrane itself, but simply reducing the thickness of the ionic membrane will easily lead to a decrease in the strength of the membrane. A new type of membrane suitable for ultra-high current density (6-8kA / m 2 Even higher) The chlor-alkali membrane of the electrolysis process makes it have good electrochemical performance and mechanical strength at the same time, and has important industrial value

Method used

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  • Carbon-nanotube-modified high-current-density perfluorinated ion exchange membrane and preparation method thereof
  • Carbon-nanotube-modified high-current-density perfluorinated ion exchange membrane and preparation method thereof
  • Carbon-nanotube-modified high-current-density perfluorinated ion exchange membrane and preparation method thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0046] (1) Preparation of resin pellets

[0047] Perfluorosulfonic acid resin is obtained by in situ polymerization of tetrafluoroethylene and perfluoro 3,6-dioxa-4-methyl-7-octenesulfonyl fluoride in the presence of fluorinated modified single-walled carbon nanotubes The powder has an ion exchange capacity of 0.98mmol / g, and the single-walled carbon nanotubes are (6,6)-type single-walled tubes with a length of 5-15 microns and a mass content of 4.3%. The perfluorocarboxylic acid resin used is a powder obtained by copolymerization of tetrafluoroethylene and perfluoro 4,7-dioxa-5methyl-8-nonenoic acid methyl ester, and the ion exchange capacity is 0.94mmol / g. The perfluorosulfonic acid resin powder and the perfluorocarboxylic acid resin powder are melt-extruded and granulated to obtain respective pellets.

[0048] (2) Membrane preparation and reinforcement

[0049] Using the above-mentioned perfluorocarboxylic acid resin pellets and perfluorosulfonic acid resin pellets contai...

Embodiment 2

[0054] (1) Preparation of resin pellets

[0055] Perfluorosulfonic acid resin is a powder obtained by copolymerization of tetrafluoroethylene, hexafluoropropylene and perfluoro 3,6-dioxa-4-methyl-7-octenesulfonyl fluoride, and its ion exchange capacity is 1.08mmol / g , the (9,9) type, single-walled carbon nanotubes with a length of about 40 microns and the above-mentioned perfluorosulfonic acid resin powder (mass ratio 10:100) were thoroughly mixed, and then melted and extruded to obtain full carbon nanotube-containing carbon nanotubes. Pellets of fluorosulfonic acid resin. The perfluorocarboxylic acid resin used is the powder obtained by the copolymerization of tetrafluoroethylene and perfluoro-4,7-dioxa-5-methyl-8-nonenoate methyl ester, the ion exchange capacity is 0.95mmol / g, and it is melt-extruded Go out and granulate to obtain the pellet of perfluorocarboxylic acid resin.

[0056] (2) Membrane preparation and reinforcement

[0057] Using the above-mentioned perfluoroc...

Embodiment 3

[0062] Step (1), step (2) and step (3) are the same as in Example 1, except that the carbon nanotubes in step (1) are (12,0) single-walled carbon nanotubes.

[0063] The prepared ion membrane tensile strength of the present embodiment is 32MPa, can be used for the ion exchange membrane in the chlor-alkali ion membrane electrolyzer, at 6.5kA / m 2 Under the current density, the mass ratio concentration of the cathode NaOH solution is 32%, the concentration of the anode brine entering the tank is 305g / L, the concentration of the brine leaving the tank is 212g / L, the tank temperature is 85-87°C, the active cathode is under the conditions of 1mm pole distance Test, the cell voltage is 3.10-3.13V, and the current efficiency is 96.9%.

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Abstract

The invention relates to a carbon-nanotube-modified high-current-density perfluorinated ion exchange membrane and a preparation method thereof. According to the membrane, a carbon-nanotube-containing perfluorosulfonic acid ion exchange resin layer and a perfluorocarboxylic acid ion exchange resin layer constitute a basal membrane, a reinforcing mesh is arranged to the surface or inside of the basal membrane, and a 3-12-micrometer gas release coating is respectively coated on two side surfaces of the basal membrane, wherein the perfluorosulfonic acid resin layer contains 0.1-10 wt% of carbon nanotubes, the thickness of the perfluorosulfonic acid resin layer is 80-150 micrometers, and the thickness of the perfluorocarboxylic acid resin layer is 8-15 micrometers. The membrane can be prepared by a melt coextrusion or multilayer hot-press compounding technique. The membrane can be as an ion exchange membrane in chlor-alkali industry, is especially suitable for a superhigh-current-density electrolysis technique, and has favorable mechanical properties and electrochemical properties.

Description

technical field [0001] The invention relates to a perfluorinated ion exchange membrane modified by carbon nanotubes for chlor-alkali industry and a preparation method thereof, belonging to the field of polymer separation membrane materials. Background technique [0002] DuPont of the United States developed perfluorosulfonic acid resin and its ion exchange membrane in the 1960s. It was quickly found that this perfluorinated ion exchange membrane with a skeleton structure has extraordinary stability and is most suitable for use in the harsh environment of chlor-alkali electrolyzers, so it has been widely used in the chlor-alkali industry. Inspired by DuPont's perfluorinated ion-exchange membrane, Japan's Asahi Glass Company and Japan's Asahi Kasei Corporation have also successively developed perfluorinated ion-exchange resins and ion-exchange membranes with similar structures. In 1976, Asahi Kasei Corporation of Japan replaced DuPont's perfluorosulfonic acid membrane with a ...

Claims

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Application Information

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IPC IPC(8): C25B13/08C25B13/02C25B1/46
Inventor 王学军王婧
Owner SHANDONG DONGYUE POLYMER MATERIAL
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