Method of producing two-ply catione-exchange membrane

专利摘要:
A cation exchange membrane of a fluorocarbon polymer containing pendant carboxylic acid and/or carboxylate groups, preferably having, at a predetermined ratio, pendant carboxylic acid and/or carboxylate groups, and pendant sulfonic acid and/or sulfonate groups uniformly distributed therein, is produced by contacting with a reducing agent a fluorocarbon polymer containing pendant groups of the formula: wherein X is a fluorine atom, a chlorine atom, a hydrogen atom, M or OM in which M represents a hydrogen atom, a metal atom or an ammonium group, and m is as defined above, and forming the treated polymer into a film or sheet. A double-layer type composite cation exchange membrane can be produced by laminating the above-mentioned membrane having pendant carboxylic acid and/or carboxylate groups and pendant sulfonic acid and/or sulfonate groups on a membrane made from the same fluorocarbon polymer containing pendant sulfonic acid and/or sulfonate groups. Since both membranes are based on the same kind of polymer, the risk of peeling-off at the interface of the two layers is reduced while exhibiting high current efficiency and low electrolytic voltage. The membrane is especially suitable for electrolysis of sodium chloride to produce caustic soda and chlorine.
公开号:SU1491342A3
申请号:SU813356855
申请日:1981-11-27
公开日:1989-06-30
发明作者:Хане Тосиоки；Охмура Юкити
申请人:Асахи Касеи Когио Кабусики Кайся (Фирма)；
IPC主号:

专利说明:

The invention relates to the technology of producing fluorocarbon cation exchange membranes and can be used in electrolytic processes for the production of chlorine and alkali.
The purpose of the invention is to increase the lifetime of the membranes in the electrolysis process without deterioration of the electrochemical properties.
Examples of specific embodiments of the method.
Example 1. In a 1000 ml stainless steel autoclave with a volume of 1000 ml.
d 290 g of CF5r CFCFcCFO (CFe), SOjFj, 580 g of 1-hlrr-2,2-dichlorotri6 ethane and 0.04 g of perfluoropropionyl peroxide. After introducing gaseous nitrogen into the apparatus, copolymerization is carried out at
 and under pressure of tetrafluoroethylene, 3.4 kg / cm. At the end of the copolymerization (by this time, 90.7 g of tetrafluoroethylene is introduced) 140 g of polymer (polymer A) are obtained.
From part of the polymer A thus obtained under pressure and when a film is formed. The film is washed in an alkaline solution to determine its ion exchange capacity of 0.7 meq / g (equivalent weight (VO) of the dry resin is 1408).
The remaining polymer A in the form of porosity is hydrolyzed in a mixture consisting of 1 part by volume. water 6 n. potassium peroxide solution and 1 vol. methanol, for 5 hours. The polymer obtained is washed with water, dried, immersed in a mixture (1: 1 by weight of phos (law
WITH
with
4 to
 CM
pentachloride and phosphorous oxychloride and heated to 120 ° C;
living at this temperature for AO hours. After that, the polymer is washed with carbon tetrachloride and immersed in a mixture consisting of 1 part by volume, of hydroiodic acid with a concentration of 57% by weight, and of 1 part by volume. glacial acetic acid and then held at 100 hours. The polymer obtained is immersed in a mixture consisting of 4 parts by volume. 1 and. hydrochloric acid and 96 ob.h. methanol, incubated at 60 ° C for 16 h and npoNti with water until the wash water is neutral.
The sulfur content in the resulting polymer is reduced to 0.11 wt.% Compared to 2.27 wt., 7, in the starting polymer, the content of carboxyl groups is 95%. The polymer obtained is plasticized in a roller mixer and molded under pressure to obtain a film with a thickness of about 100 microns (film A). In the full reflection spectrum of film A, there is a strong absorption band at 1800 cm, characteristic of the carboxylate group, and a weak absorption band at 1470 cm, characteristic of the fluorosulfonyl group,
The procedures described are repeated with the difference that the pressure of the loaded tetrafluoroethylene is reduced to 2.1 kg / cm (g), to obtain a polymer having an ion exchange capacity of 0.86 meq / g (EV 1163, polymer B). Polymer B is heat pressed to produce a film approximately 100 microns thick (film B). Film A is layered on film B to form a two-layer membrane.
The two-layer membrane is immersed in a mixture (1: 1 by volume) 6 n. peroxide and methanol and maintained at for 16 hours. Next, the membrane is immersed in an aqueous solution of caustic soda at a concentration of 0.1%, which is held at rest for 16 hours. The resulting membrane is used as a diaphragm during the electrolysis of sodium chloride.
The current efficiency and voltage in the electrolysis are measured as follows.
Elb strolizer has a working area of 0.06 dm C2 cm "3 cm and consists of an anode and cathode section
to
20
25
thirty
J5
91342
lenii, separated by a cation-exchange membrane, with film A facing the cathode. Use a metal anode with a stable size; The iron plate serves as the cathode. In the anode compartment, a saturated aqueous solution of sodium chloride is circulated with the addition of hydrochloric acid to maintain a pH of 3. In the cathode compartment there is 6.5 n. an aqueous solution of caustic soda at a concentration of this solution is kept constant by adding water. In such conditions, an electric current with a density of 40 A / dm passes between the electrodes. The current efficiency (current efficiency) is calculated by dividing the amount of caustic soda produced in the cathode compartment in an hour by the theoretical value calculated from the electrical charge that has passed during this time. The following results were obtained: Current flow time, h 24 720
Current efficiency,% 96 96 Voltage in the electrolyzer, B 3.6 3.6 Example 2 (comparative). The procedures are repeated as in example 1, except that instead of the CFe compound, the GHGHATS (CP5) x50,, G
CFj use compound
35
CFc CFOCFgCFO (CF) COOCH to get CF
nor a polymer having an ion exchange capacity of 0.70 meq / g (polymer C). Polymer C is heat pressed to obtain a film with a thickness of 40 µm (film C).
Film C was deposited on film B prepared in accordance with Example 1 at 260 ° C to form a two-layer membrane. The bilayer membrane is saponified in an aqueous alkaline solution and immersed under heating in .0.1 n. caustic soda solution as described in example 1.
Electrolysis is carried out similarly to example 1 with a film C located on the side of the cathode. Got the following results:
Flow time
current h24 720
current efficiency,%
96
3.7
90
Voltage and
electrolyzer, B 3,7 4,1 Example 3, Polymer L, containing fluoride-sulfonyl side groups, prepared according to example 1 (in the form of powder), immersed in a mixture (1: 1 by volume) 6 n. an aqueous solution of potassium peroxide and methanol and heated to saponification for 4 hours. The polymer obtained is washed with water, dried and submerged in a mixture (1: 1 by weight) of phosphorous pentachloride and phosphorous oxychloride, where it is held for AO hours. The polymer is then washed with carbon tetrachloride and immersed in a mixture consisting of 1 about aqueous solution of hydrobromic acid with a concentration of 47 wt.% and from 1 ob.h. glacial acetic acid, where it is heated to 85 ° C for 120 hours. The polymer obtained is immersed in a mixture of 4 parts by volume. sulfuric acid concentration of 98 wt.% and from 96 ob.h. methanol, maintained at 60 ° C for 16 h and washed with water until the wash water is neutral.
The sulfur content in the resulting polymer is reduced to 0.23 wt.% By weight (content, carboxyl groups is 90%). This polymer is plasticized in a roller mixer at and molded under pressure to produce a film about 40 microns thick (film A).
The resulting film was applied to film B made in accordance with Example I, and washed with alkali as in Example 1. The electrolysis was carried out as in Example 1 with film A located in the cathode compartment. The results are shown below. Flow time
1491342
0.07 wt.%. The resultant polymer is 1-ruled into a mixture of ich 4 ob.h. concentrated sulfuric acid and
96 ob.ch. methanol, heated at 60 ° C for 16 h and washed with methanol, in accordance with example I, into a film with a thickness of about 30 μm (film D).
Similarly to the described example 1, a polymer E is obtained having an ion-exchange capacity of 0.95 meq / g (EV 1050). The resulting polymer is formed into a film with a thickness of about 100 microns (film E). The foam D is laminated to the film E by compressing to form a two-layer membrane. This bilayer membrane is immersed in a mixture of O: 1 by volume) 6 n. caustic soda and methanol and heated at 72 ° C for 16 h. Then the membrane is immersed in 0.1 n. an aqueous solution of caustic soda and heated at 16 h.
The electrolysis, in which the alkali concentration in the cathode chamber was set to 10 n., Is carried out under the conditions of example I, with the D film of the two-layer MeNjCpaHbi directed towards the cathode. The results are shown below.
Current passing time, h24720
Current efficiency,% 95.5 95.0 Voltage at cell terminals, V, 3.52 3.53
Example 5. Carried out analogously to example 1, with the addition of
that the pressure of the loaded tetrafluoroethylene is changed so as to obtain a polymer having an exchange capacity of 0.83 meq / g (EV 1200). The polymer is processed in accordance with Example 1,
resulting in a film thickness of about 30 microns (film F), having a sulfur content of 0.08 weight ..
24
720
93
3.5
92.5 3.5
50
current h
Current efficiency,%
Voltage in the electrolyzer, V
Example 4. Carried out analogously to example 1, except that the pressure of the loaded tetra- 55 results are given below, the fluoroethy- lene is changed so that the half-time
chit polymer having an ion exchange current, h
capacity 0.77 mEq / g (EW 1300). Soder-Efficiency The sulfur loading in the polymer is%
The film f is laminated onto under compression for a semi-layered membrane. The membrane is in accordance with Example 4 and subjected to a dilution, with the F membrane of two membranes being directed to the side
24
93
50
 55 The results are shown below.
Film f is laminated to tineHxy E under compression to form a two-layer membrane. The membrane is hydrolyzed according to example 4 and is subjected to electrolysis, with the F film of the double-layer membrane being directed towards the cathode.
others
24
93
720 92.6
Element voltage, V
3.41
3.40
Example 6 (comparative). The procedures of Example 1 are repeated, except that the pressure of the loaded tetrafluoroethylene is changed so as to obtain a polymer having an exchange capacity of 0.49 meq / g (EW 2040). The polymer is treated according to Example 1, obtaining a 30 μm thick film having a sulfur content of 0.13% by weight (Film G).
Film G is laminated to film E at 260 ° C by compression to form a two-layer membrane. The membrane is hydrolyzed analogously to example 4 and subjected to electrolysis, with the film G being directed towards the cathode. From the very beginning of the passage of current, there is an increase in voltage over time at the terminals of the cell. After 24 hours, the voltage at the terminals of the cell exceeds 5 V. Then the passage of current has stopped.
0
five
0

权利要求:
Claims (1)
[1]
Invention Formula
A method for producing a bilayer exchange membrane by hot-forming films of fluorocarbon copolymers containing sulfonyl fluoride groups with equivalent weights differing by at least 150 units, combining the films and subsequent hydrolysis of the membrane, characterized in that increase the lifetime of the membrane in electrolysis processes while maintaining the electrochemical properties; two copolymers with equivalent weights of 1200-1408 and 1050-1163, respectively, are used as fluorocarbon copolymers rusting O (CF (i) 50qY) side groups, the first of these copolymers being processed at the molding stage with a reducing agent with conversion of 90-95% of sulfonylfluoride groups to carboxyl and esterification with methanol in the presence of mineral acid.

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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JP55168554A|JPS6411663B2|1980-11-29|1980-11-29|

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