• 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:
    1497749 Brine electrolysis in diaphragm cells ASAHI KASEI KOGYO KK 4 March 1975 [7 March 1974] 17596/77 Divided out of 1497748 Heading C7B NaCl solution is electrolyzed supplied to the anode chamber of a cell divided by a non-porous cation-exchange membrane comprising a fluorocarbon polymer having carboxylic and sulphonic acid groups, preferably a (co) polymer having pendant-SO 3 H groups and a perfluorovinyl (co)polymer having pendant-COOH groups. The latter (co)polymer may be of a perfluorocarbon vinyl ether of Formula CF 2 =CF-O-(CF 2 ) n -X with or without a perfluorocarbon sulphonyl fluoride of Formula FSO 2 CFRg CF 2 O (CFY CF 2 O) m CF= CF 2 , or a perfluoroacrylic acid of Formula CF 2 =CFCOZ, and tetrafluoroethylene with or without CF 2 =CF-OR f , where X is -CN -COF, -COOH, -CONH 2 or alkyl derivatives thereof, Z is F, alkoxy, amino or OH group, Rg is F or a perfluoroalkyl(C 1-10 ) group and R f is a perfluoroalkyl (C 1-3 )group. The membrane may be obtained by impregnating or coating the (co) polymer having pendant -SO 3 H groups with CF 2 = CF-O-(CF 2 ) m -X, followed by polymerization. Both the NaCI and NaOH product solutions may be recycled. The cathode may be a mesh or rod of Ni (compound) plated iron coated with Ru oxide. Specification no. 1401290 is referred to.
    公开号:SU1313352A3
    申请号:SU823381954
    申请日:1982-01-08
    公开日:1987-05-23
    发明作者:Секо Маоми
    申请人:Асахи Касеи Когио Кабусики Кайся (Фирма)；
    IPC主号:
    专利说明:

    eleven
    The invention relates to new cation-exchange membranes used in the electrolysis of sodium chloride.
    The aim of the invention is to increase the current utilization factor.
    Example 1. From a copolymer of per- (2-fluorosulfonyl-ethoxy) -propyl vinyl ether with tetrafluoroethylene, a membrane of thickness 12 12 mm is smelted, which is then subjected to hydrolysis to form a cation-exchange membrane with an exchange capacity of 0.88 mg-eq. / g dry mixture in terms of sulfonic acid groups.
    The perfluorosulfonic acid type cation exchange membrane is impregnated with a perfluoroacrylic acid solution and then polymerized to obtain a perfluorovinyl ether type cation exchange membrane, which contains perfluoro sulfonic acid units along with acrylic acid perfluoro acid units.
    This cation-exchange membrane contains 0.75 mEq / g of dry resin of sulphonic acid groups and 1.1 mg X hekv / g of dry resin of carboxyl acid groups.
    This cation exchange membrane, having an effective area of 100 dm, is used to separate the electrolytic cell into the anode and cathode chambers. The 50 units of such electrolytic cells are connected in a sequential manner so that the corresponding adjacent electrodes constitute a bipolar system, and systems of 50 electrolytic cells are obtained.
    The constituted CHCTBMJ-electrolytic cells are used for electrolysis by loading an aqueous solution of sodium chloride through the feed system into the anode chamber of each of the cells.
    The electrolysis is carried out, the current passing through the chambers is 5,000 A. In this case, the amount of solution entering the anode chamber is maintained at 11.515 cells / h of water, while the aqueous solution of sodium hydroxide from the outlet line of the cathode chamber is 35.5 % returns to cycle.
    In the given example of the electrolyzer, the current efficiency in the calculation
    22
    at the outlet of the cathode chamber, sodium hydroxide is 95.8%.
    PRI me R 2 (comparative). The 2- (2-fluorophosphonyl-ethoxy) perfluoro-propyl vinyl ether ester copolymer is formed into a membrane 0.12 mm thick, which is then hydrolyzed to obtain
    cation exchange membrane, holding 0.90 mg Eq / g of dry resin sulfonic groups.
    The process of electrolysis is carried out as in Example 1, using 50 sheets of the obtained cation-exchange membrane, passing a current of 5000 A successively through 50 electrolytic cells. As a result, the current efficiency in obtaining Sodium hydroxide, having a concentration of 35.1%, is 55.7% and the amount of NaCl in NaOH is 2000 ppm. The specific electrical conductivity of said membrane is 11, as measured in 0.1 n. NaOH at 25 ° C.
    The conductivity of the membrane is measured by the following method.
    The membrane is fully translated into
    SOjNa form and then brought to a state of equilibrium., Immersing it for 10 hours at a normal temperature in O, 1 n. NaOH aqueous solution.
    carried out continuously. Then, the membrane resistance to electricity in a solvent is measured, and an alternating current with a frequency of 1000 Hz is passed, the temperature of 25 ° C being maintained in solution. and then the specific electrical conduit is calculated; 1, based on the thickness and effective area of the membrane.
    PRI me R 3 (comparative). From copolymer J1; similar to Example 2, mer.1 brane 0.12 mm thick was smelted, which was then subjected to hydrolysis to obtain a cation-exchange membrane containing 0.65 mg, eq / g of a dry resin of sulphonic acid: groups.
    An example of Example 2j is carried out. A copy of the memorandum is given. As a result, the current efficiency in the production of hydrolysis and iujutz concentration 35) 1%. is 73%. The electrical conductivity of said membrane is 4.5 mm to
    IC / cm according to measurements in O, 1 n. NaOH aqueous solution at 25 C.
    PRI me 4, the cation-exchange membrane is made by melting a ternary polymer containing per- (2-fluorosulfonyl ethoxy) -propyl vinyl ether}, tetrafluoroethylene and methylperfluoro-6-oxa-7-octenoate in the form of a membrane strengthened with a network material, consisting of Teflon, followed by hydrolysis.
    This cation-exchange membrane contains sulphonic acid groups in the amount of 0.71 mg Evc / g of dry resin and carboxyl acid groups in the amount of 1.5 mg eq / g of dry resin.
    Electrolysis is carried out as in Example 1, using 50 layers of the cation-exchange membrane indicated, having an extruder pressed in a hot condition.
    However, the effective area of 100 dm using the same electrolytic cell system, however, introduces an aqueous solution of sodium chloride at a concentration of 305 g / l into the cathode chamber, which is recycled at a feed rate of 12.820 kg / h, while continuously introducing water into the solution in such a quantity that the concentration of sodium hydroxide in the indicated coating is turned into
    and hydrolyzed, pion-exchange membrane with a thickness of 0.01 mm. Manufactured by kim cation exchange
    25 contains 0.83 mg.eq.v / g of carboxylic acidic acid. The electrolysis of the membrane is carried out, so that the side of the membrane is
    the withdrawn solution would be maintained at 31.1%. In this case, the amount of water is maintained at 767.65 kg / h, the electrolysis is carried out, the current of 5000 A passes through 50 units of electrical cells in succession. As a result, the amount of chlorine formed in the anode chamber is 311 kg / h, the amount of 31 The 1% sodium hydroxide solution discharged from the cathode chamber is 1127.4 kg / h, and the amount of hydrogen from the cathode chamber is 9325 g / h.
    In this case, the electrolysis current efficiency of 94%.
    Example 5. A membrane produced according to Example 2 is impregnated with methyl perfluoro-5-oxa-6-heptoatom and polymerized and then hydrolyzed to obtain a cation-exchange membrane with an exchange capacity of 0.77 mg, eq / g of dry resin in terms of sulfonic acid groups and with an exchange capacity of 0.42 mg y-eq / g in terms of carboxylic acid groups.
    55
    Electrolysis is carried out as in Example 1 using the cation-exchange membrane. As a result, the current efficiency in producing sodium hydroxide with a concentration of 35.0% is 96.2%, and the amount of NaCl in NaOH is 150 ppm. The specific electrical conductivity of the membrane is 13.2 mm.h / cm and the voltage drop across the cell is no different from the voltage drop in Example 2.
    Example 6: A solution of a terpolymer consisting of methylperfluoro-6-hydroxy-7-octenoate, perfluoromethylvinyl ether and tetrafluoroethylene was applied to one of the sides of the membrane prepared according to Example 2.
    After evaporation of the solvent, the ampoule is turned into
    and hydrolyzed to obtain a cation-exchange membrane coated with a thickness of 0.01 mm. The cation-exchange membrane produced in this way contains 0.83 mg.eq./g dry resin of carboxyl acid groups. Electrolysis is carried out using the indicated membrane, positioning it so that the side of the membrane with
    the side
    the cathode as in Example 1. As a result, the current efficiency in producing sodium hydroxide with a concentration of 35.5% is 97.1%.
    EXAMPLE 7 From a terpolymer composed of 2- (2-fluorosulfonyloxy-propyl vinyl ether of tetrafluoroethylene and perfluoro-6-oxa-7-octenes) ylfluoride perfluoro, is melted
    a 0.12 mm thick membrane, which is then subjected to hydrolysis, to obtain a cation exchange resin containing 0.43 mg eq / g of dry resin of sulfo acid groups and 0.70 mg eq / g of dry
    gum carboxyl acid groups.
    Electrolysis is carried out using 50 sheets of the indicated cation-exchange membrane having an effective area of 100 dm, similarly to example 1 and using the same apparatus, passing a current of 5000 A in succession through 50 units of an electrolytic cell. Sodium hydroxide with a concentration of 35.6% is 98.8%, and the electrical conductivity of the membrane is 9.0 mm.h / cm.
    ExampleB A four-component copolymer consisting of perfluoro-2- (2-fluorosulfonyl-ethoxy) -propylene vinyl ether, ethylene tetrafluoro, perfluoro-3-oxa-b-heptenoyl fluoride and perfluoropropylperfluorine vinyl ether, melted a membrane, and a membrane. After hardening the membrane with teflon fiber, it is subjected to hydrolysis to obtain a cation exchange resin containing 0.84 mg.eq./g dry resin of sulfonic acid groups and 1.20 mg. Equp / g of dry resin of carboxylic acid groups.
    Electrolysis is carried out using the specified cation-exchange membrane as in Example 1. As a result, the current efficiency in preparing sodium hydroxide with a concentration of 36.0% is 98.4%.
    EXAMPLE 9 A reinforced polytetrafluoroethylene (PTFE) membrane was made by using a copolymer containing a sulphonyl group, which was prepared in Example 1. First, from a 2- (2-fluorocon-Lfonylethoxy) propyl vinyl ether ester copolymer and tetrafluoroethylene is formed into a membrane with a thickness of 0.12 mm, after which reinforcing material PTFE is introduced into this membrane and then hydrolysis is carried out. This membrane is characterized by an exchange capacity of 0.88 mg eq / g of dry resin in terms of sulphonic acid groups.
    This perfluoroacrylic acid solution is impregnated with a perfluoroacrylic acid solution and then polymerized, resulting in a cation exchange membrane in which perfluoroacrylic acid units are present in a mixture with perfluorosulfonic acid units.
    These cation-exchange membranes contain 0.77 MG EKV / G dry resin.
    groups of SULFO ACID and 1.25 MG EQ / H
    dry resin carboxylic acid groups
    When using a cation-exchange membrane in electrolysis is similar
    Example 1, except that the sodium hydroxide concentration in the solution exiting the cathode space is maintained at 36%, the current utilization factor is.
    Example 10. A membrane reinforced with a mesh material consisting of PTFE using
    calling the membrane as in example 2, after which hydrolysis is carried out.
    This membrane is impregnated with methylperfluoro-5-hydroxy-6-heptanoate, which is then polymerized and hydrolyzed to produce a cation-exchange membrane having an exchange capacity equal to 0.80 mg-eq / g dry resin and an exchange capacity equal in terms of the carboxylic acid group of 0.41 MG EKV / G dry resin.
    When using this cation-exchange membrane, electrolysis is carried out similarly to Example 1. The current utilization factor for producing sodium hydroxide with a concentration of 35.5% is 95.5%.
    Example 11. A membrane reinforced with a mesh material consisting of PTFE using a membrane similar to that shown in Example 2 was made, followed by hydrolysis.
    With a solution of a three-component copolymer similar to that used in Example 6, 3 dichloroperfluorobutane is coated on one side of a perfluorosulfonic acid type membrane. After evaporation of the solvent, the membrane is hot pressed and then hydrolyzed to obtain a cation exchange membrane with a coating thickness of 0.01 mm. The cation-exchange membrane thus obtained contains 0.84 mg-eq / g of dry resin in terms of sulfonic acid groups and 0.05 mg-eq / g of dry resin in terms of carboxylic acid groups.
    When using this membrane, electrolysis is carried out analogously to example 1, when turning the side of the membrane with coated :: cathode. The current utilization factor for producing sodium hydroxide with a concentration of 34.0% is 96.3%.
    Example 12. From a ternary copolymer comprising perfluoro 2- (2-fluorosulfonyloxy) propyl vinyl ether, tetrafluoroethylene and perfluoro-6-oxa-7-octeno acid fluoride, obtained in Example 7,
    55 molded membrane thickness of 0.12 mm.
    PTFE reinforcing material is introduced into this membrane, followed by hydrolysis.
    713
    This cation exchange membrane contains 0.43 mg.eq./g dry resin based on sulfonic acid groups and 0.70 mg.eq./g dry resin based on carboxylic acid groups. When using a cation-exchange membrane in electrolysis as in Example 1, the current utilization factor for producing sodium hydroxide with a concentration of 34.5% is 97.8%.
    权利要求:
    Claims (7)
    [1]
    1. A cation-exchange membrane for use in the electrolysis of sodium chloride, made in the form of a film of perfluorinated polymer containing ion-exchange groups reinforced with polytetrafluoroethylene fibers, characterized in that, in order to increase the current efficiency, a polymer or mixture of polymers is used as a perfluorinated polymer containing carboxyl and sulphonic acid groups with an exchange capacity for carboxyl groups of 0.05-1.5 mG eq / g at an equivalent ratio of carboxyl to sulfo group PP equal to 0.06-2.1: 1, based on monomers selected from the group including perfluoroacrylic acid, perfluorospropylvinylether), perfluoro (methylvinyl ether), perfluoro 2- (2-fluorosulfonylethoxy) Compiled by V.Mkrtychan Editor N. Lazarenko Tehred M. Khodanych Proofreader N. Korol
     - - --- - - - - - - - ---- - --i-- - -i - - .. „-
    Order 1984/59 Circulation 438Subscription
    VNIISH State Committee of the USSR
    for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5
    Production and printing company, Uzhgorod, Projecto st., 4
    133528
    propyl vinyl ether, perfluoro-6-oxa-7-octenoylfluoride, methylperfluoro-5-oxa-6-heptenoate, methylperfluoro-6-oxa-7-octenoate, tetrafluoroethylene. five
    [2]
    2. A membrane according to claim 1, characterized in that it has a thickness of 0.1-0.15 mm.
    [3]
    3. A membrane according to claim 1, characterized in that the carboxyl groups are located on the same surface of the film.
    [4]
    4. The membrane according to claim 1, characterized in that it is made of a polymer containing COOM groups 0 (CP2) 4-4, where AND represents hydrogen or alkali metal, and OCFj groups.
    [5]
    5. Membrane on p; 1, characterized in that it is made of a mixture of two polymers, one of which contains sulphonic acid groups and the other contains carboxyl.
    [6]
    6. The membrane according to PP, 1 and 5, which is made from a mixture of polymers, one of which is a copolymer with SO, M groups, and the other is poly- (perfluoroacrylic) acid.
    [7]
    7. Membrane on PP, 1 and 5, about the fact that she
    made from a mixture of polymers, one of which is a copolymer with GCF CF SO, M groups, and the other a copolymer containing groups 0 (CP2) .g-4 COOM.
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    公开号 | 公开日
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    NL168568C|1987-11-16|
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    申请号 | 申请日 | 专利标题
    JP2571874A|JPS551351B2|1974-03-07|1974-03-07|
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