• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A method of installing an ion-exchange membrane in an electrolytic cell in which the membrane is expanded by stretching to increase the surface area per unit weight of the membrane and the expanded, stretched membrane is secured to the electrolytic cell or to a part thereof. The stretching is preferably effected at elevated temperature and the expansion produced by stretching may be <<locked>> into the membrane by cooling the expanded, stretched membrane to a lower temperature prior to installation of the membrane in the electrolytic cell.
    公开号:SU1510721A3
    申请号:SU833552566
    申请日:1983-02-16
    公开日:1989-09-23
    发明作者:Джон Смит Питер
    申请人:Империал Кемикал Индастриз Плс (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to methods for installing an ion exchange membrane in an electrolyzer.
    The purpose of the invention is to reduce the voltage on the electrolyzer during electrolysis. by eliminating membrane folding.
    The proposed method of installation in the electrolyzer of the ion-exchange membrane eliminates the formation of folds on the membranes. The goal is achieved due to the fact that the membrane surface is increased by 35-330% by stretching it one and / or two axes at 20-210 ° C and, after stretching, the film is kept at the stretching temperature for 1-3 minutes.
    Stretching the membrane can be accomplished by passing the membrane around and between the rolls, rotating at different peripheral speeds, by applying a tensile force to the opposite frame or machine. The membrane can be stretched along one or two axes; when the membrane is stretched along one axis, hard material strips should be attached to opposite edges of the membrane to prevent the membrane from contracting in the direction perpendicular to the direction of stretching.
    After the stretched and stretched membrane is installed in the electrolyzer and fixed in it, when it comes in contact with the electrolyte, especially at elevated temperatures up to 95 ° C, which takes place in the chlor-alkaline electrolyzer, the fixed part of the elongation or its fraction is released back to not
    C / 4
    315
    the driving condition, which is prevented by its mounting in the electrolyzer. The desire to reduce is compensated by swelling of the membrane when in contact with the electrolyte and, as a result, the membrane remains unwrinkled and tight during use.
    The stretched membrane, as a rule, has a thickness of 0.1 - 2.0 mm. The temperature at which the membrane is stretched depends on the type of membrane and ensures the melting of the membrane polymer. The stretched membrane is subjected to tempering, holding it for 1-3 min in the stretched state at the stretching temperature. After that, the membrane is cooled to room temperature, at which there is no rapid relaxation of stresses in the membrane when removing external products. To reduce the likelihood of damage to the membrane, stretching can be repeated 1-2 times.
    The most corrosive in the production of chlorine and alkali are membranes of a copolymer of tetrafluoroethylene and perfluorovinyl ether with sulfonic or carboxyl ion exchange groups.
    The stretched and stretched membrane is clamped between gaskets or attached to a frame.
    Example 1. A rectangle of 35 x XO cm is cut out from a sheet of a cation-exchange membrane with a thickness of 280 μm, made from a copolymer of tetrafluoroethylene and perfluorovinyl ether containing carbonic acid groups having an ion exchange capacity of 1.3 milliequivalent per gram.
    Strips of elastic PHE-tape are attached to the edges of a sheet 35 cm long, and strips of aluminum are attached to edges 30 cm long. The sheet is then installed in an Orienter Bruck Ner Caro II appliance and heated to 67 C in an oven connected to the appliance.
    Then the sheet is stretched over the aluminum strips at a speed of 1 m / min until the distance between the aluminum strips has increased 1.5 times, while the PVC tape prevent sheet narrowing. Then the sheet, remaining in the device, is removed from the oven and cooled to room temperature in a stream of air.
    The procedure for heating the sheet to 67 ° C and cooling to room temperature
    Jq 15 0
    50
    e Q

    .
    0
    The tours are repeated twice; in the first repetition, the distance between the aluminum strips increases by 2.5 times, and in the second repetition, by 4.2 times compared to the original.
    The resulting film of the cation-exchange membrane is removed from the device. The film is slightly relaxed in the direction of the original sheet size, the film thickness is 80 microns,
    The film of the cation-exchange membrane thus prepared is fixed in the stretched state between a pair of gaskets made of triple ethylene-propylene rubber and installed in an electrolyzer equipped with a 7.5 cm diameter nickel cathode and a titanium mesh anode coated with a mixture of RuG and TiO against 35 65 TiO by weight.
    At the anodic distance, an electrolytic cell is poured with an aqueous solution of 310 g / l NaCl | C pH 8.0, water is introduced into the cathode, after which Nad is electrolyzed at 190 ° C, and the NaCl concentration in the vanodine section during electrolysis is 200 g / l
    Chlorine and depleted NaCl solution are removed from the anode compartment, and hydrogen and an aqueous solution of NaOH (35% by weight) are removed from the cathode compartment. The electrolysis is carried out at a current density of 1 kA / m and at a cell voltage of 3.01 B.
    After operating for 20 days, the electrolyzer opens and the cation exchange membrane is inspected, which is tight and wrinkle-free.
    For comparison, the electrolysis process described above is repeated with a 280 μm thick cathis exchange membrane, i.e. not subjected to stretching. At a current density of 1 kA / m, the voltage is 3.1 V, and the membrane is wrinkled and not stretched.
    PRI mme R 2. The electrolysis of Example 1 is repeated at a current density of 2 kA / m. The voltage is 3.24 V, and the membrane is tight and wrinkle free.
    With the same current density, the voltage on a cell with a membrane thickness of 280 µm and not subjected to stretching is 3.4 V, and the membrane was not stretched and wrinkled.
    Example 3. The electrolysis of example 1 is repeated at the current density
    Barely cooling in primsg e 5 11%, in example 6 10% and in example 7 9% A further increase in tempering time is impractical because shrinkage
    515107216
    3 kA / m, in this case the voltage
    is 3.52 V, and the membrane at
    examination turned out to be tight and without
    wrinkles.
    In comparative electrolysis with non-samples, it does not decrease.
    a pre-stretched membrane thickness of PRie mep 8. Membranes, made of 280 µm, the voltage is 3.7 V, as described in examples 5-7,
    tested in the cell described in example 1, for 30 days, at current density of 3 kA / m, Average
    and when viewed, the membrane was not stretched and wrinkled.
    PRI me R 4. A sample of a cation-exchange membrane measuring 11.5x11.5 cm in size from a copolymer of tetrafluoroethylene and perfluorovinyl ether containing
    ten
    the voltage on the 3.3 V cell. The membranes, which are removed after 30 days from the cell, turned out to be
    the voltage on the Membrane electrolyzer, which extracts 30 days from the electrolyzer,
    sulfonic acid groups in the form of a salt in 15-wrinkled, without folds.
    LIA, glue on the edges of the PVC-tape and clamped in the stretch frame. The membrane is heated before and stretched.
    Example 9. A film of the exchangeable membrane of copolymer of rafluoroethylene and perfluorovinyl ether containing carb groups
    Example 9. A film of a cation exchange membrane made from a copolymer of tetrafluoroethylene and perfluorovinyl ether, containing carboxyl groups along one axis with a velocity
     . , UU CpflVclmclTl it Yllllu IX with vys-- - - i
    0.85 m / min with a coefficient of 2.0. Then, a 20 ”ether, having a thickness of 290 microns, is cooled to room temperature, then pressed by hydraulics and pulled out of the stretching frame.
    This membrane is installed in the electrolyzer of Example 1 and the electrolysis process of Example 2 is carried out, i.e. electrolysis of NaCl solution at a current density of 2 kA / m, during which a solution of NaOH is obtained with a concentration of 25% with an efficiency of 50%. The cell voltage is 2.95 V.
    On examination, the membrane was stretched and wrinkle free.
    For comparison, the electrolysis is carried out with the described membrane, which is not subjected to stretching. The cell operates at a voltage of 3.1 V, and NaOH is obtained with a current efficiency of 57%.
    On examination, it turned out that the membrane was wrinkled and unstretched.
    Example 5. A film of a cation-exchange membrane made of a copolymer of tetrafluoroethylene and perfluorovinyl ether with carboxyl ion-exchange groups, 300 μm thick, is subjected to biaxial stretching at a temperature of: a) 20 ° C; b) c) 210 C.
    Press for 1 min at 220 ° C, and the pressure is 175 kg / sc. The membrane is removed from the press and under-. The temperature of the membrane becomes 215 microns. Due to this, the surface area of the membrane increases by 35%.
    30 Example 10. A film of a cation-exchange membrane 290 µm thick, ka in example 10, is stretched on two axes at 67 ° C due to the application of stretching to opposite sides of the rectangular membrane. After cooling and removal of the stretching force, the membrane thickness was 215 µm, the surface area increased by 35%.
    40
    Example 11. Membranes made as described in examples 9 and 10 are tested in the electrolyzer described in example 1 for 15 days. g is the average cell voltage of 3.41 and 3.32 volts using the membrane in examples 9 and 10, respectively. Average current efficiency is 96%. In 15 days electrolysis
    Example 11. Membranes, made as described in examples 9 and 10, are tested in an electrolyzer, about a sled in example 1, for 15 g 5 the average voltage per electrolyzer is 3.41 and 3.32 V when using a membrane in examples 9 and 1 respectively. The average yield is 96%. In 15 days electrolysis
    The stretching rate is
    0.25 m / min. After stretching the membrane
    Well, incubated for 1 min at a temperature, and the membrane is removed from
    stretch Increase in the area of electrolyzer.
    the surface of the membrane is: a) 43%; Membrane manufactured by
    b) 50%; c) 161%.
    Example s6i7. The membrane stretching process is carried out as in Example 5, except that the tempering time at the stretching temperature is 2 minutes (Example 6) and 3 minutes (Example 7). Shrinkage of pressure specimens, has folds, and the membrane, made by stretching, turned out to be without folds. Consequently, the membrane made by the dissolving of the film possesses the best characteristics, which allow to exclude folding.
    Barely cooling in primsg e 5 11%, in example 6 10% and in example 7 9%. A further increase in vacation time is impractical because shrinkage
    samples is not reduced.
    the voltage on the 3.3 V cell. The membranes, which are removed after 30 days from the cell, turned out to be
     unsweetened, without folds.
    Example 9. A film of a cation-exchange membrane made from a copolymer of tetrafluoroethylene and perfluorovinyl ether, containing the carboxyl group of fPy, UU CpflVclmclTl it Yllllu IX with vys-- - - i
    The ether of 290 microns is compressed with plates of a hydraulic press for 1 min at 220 ° C, and the pressure is 175 kg / s. The membrane is removed from the press and cooled, the membrane thickness becomes 215 microns. As a result, the surface area of the membrane increases by 35%.
    Example 10. A film of a cation-exchange membrane 290 microns thick, as in Example 10, is stretched on two axes at 67 ° C due to the application of tensile force to opposite sides of a rectangular membrane. After cooling and removal of the stretching force, the membrane thickness was 215 µm, the surface area increased by 35%.
    0
    Example 11. Membranes manufactured as described in examples 9 and 10 are tested in the electrolyzer described in example 1 for 15 days, 5 the average voltage on the electrolyzer is 3.41 and 3.32 V using a membrane examples 9 and 10 respectively. Average current efficiency is 96%. In 15 days electrolysis pre5
    compression, has folds, and the membrane, made by stretching, turned out to be without folds. Consequently, the membrane made by stretching the film has the best characteristics to prevent folding.
    权利要求:
    Claims (3)
    [1]
    1. The method of installation in the electrolytic cell of an ion-exchange membrane from a film of a copolymer of tetrafluoroethylene and perfluoro-20 Iil ester with sulfonic or carboxyl ion-exchange groups
    kami, including increasing the surface of the film at elevated temperatures, fixing it in a rigid electrolyzer frame, characterized in that, in order to reduce the voltage on the electrolyzer during electrolysis by eliminating membrane folding, the membrane surface is expanded by stretching the film one and / or two of its axis to increase its surface by 35-330%.
    [2]
    2. The method according to claim 1, characterized by the fact that stretching is carried out at 20-210 ° C.
    [3]
    3. Method according to paragraphs. 1 and 2, that is, by the fact that, after stretching, the film is maintained at a stretching temperature for 1 to 3 minutes.
    Compiled by S. Barabash. Editor N. Yatsola Tehred L. Oliynyk Proofreader S. Cherni
    Order 5831/58
    Circulation 605
    VNIIPI State Committee for Inventions and Discoveries at the State Committee on Science and Technology of the USSR 113035, Moscow, Zh-35, Raushsk nab. 4/5
    Production and publishing plant Patent, Uzhgorod, st. Gagarin, 101
    Subscription
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    引用文献:
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    JPH0142293B2|1982-09-02|1989-09-12|Tokuyama Soda Kk|
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    DK501485A|1984-11-05|1986-05-06|Dow Chemical Co|ELECTROLYTE CELL AND METHOD OF OPERATING THE SAME|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    GB8204574|1982-02-17|
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