• 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:
    The method of producing chlorine and alkali by electrolysis of a solution of alkali metal chloride in electrolyte. A cell with an ion-exchange membrane separating the anode and cathode spaces, characterized in that, in order to increase the current efficiency, a film of fluorinated polymer 0.05-0.5 mm thick is used as the ion-exchange membrane, and the surface layer of the film facing the cathode space contains sulphonic groups connected to a carbon atom to which fluorine atoms are attached, and 40-100% of ion-exchange groups are in the form of M-monosubstituted sulphonamide groups, is 0.1-30% of the membrane thickness.
    公开号:SU1106448A3
    申请号:SU752149415
    申请日:1975-07-02
    公开日:1984-07-30
    发明作者:Рафаэль Ресник Пол；Густав Грот Вальтер
    申请人:Е.И.Дюпон Де Немур Энд Компани (Фирма)；
    IPC主号:
    专利说明:

    9) 4 4; X) The invention relates to electrochemical production, in particular to methods for producing chlorine and alkali by electrolysis of an aqueous solution of an alkali metal chloride. A known method for producing chlorine and alkali by electrolysis of an aqueous solution of an alkaline or alkaline earth metal chloride in an electrolytic cell with an ion-exchange membrane separating the anode and cathode spaces lj. A disadvantage of the known method when using fluorinated ion-exchange membranes, in which the ion-exchange polymer contains additional side chains in the form of sulphuric fluoride compounds, these groups being converted into an ionic form, for example, during hydrolysis with an alkaline material or during treatment with ammonia, the use efficiency is not high enough current and, consequently, increased energy consumption for electrolysis. The aim of the invention is to increase current efficiency. The goal is achieved by the method of producing alkali chlorine by electrolysis of an aqueous solution of alkali metal chloride in an electrolyzer with an ion-exchange membrane separating the anode and cathode spaces, using a film of fluorinated polymer 0.05-0.5 mm thick as the ion-exchange membrane the surface layer of the film, which is connected to the cathode space, contains sulfonyl groups connected to the carbon atom to which fluorine atoms are attached, and 40-100% of the ion-exchange groups are in the form of t - onozameschennyh sulfonamide groups, said layer composition L is 0.1-30% membrane thickness. The polymers are prepared from monomers, which are fluorinated, or from fluorine, replaced by vinyl compounds. The polymers are made of at least two monomers, each of which is derived from one of two groups. The first group is fluorinated vinyl compounds, such as vinyl fluoride, propylene fluoride trichloride, vinyl fluoride, ethylene trifluoride, ethylene chlorotrifluoride, pentafluoroethyl (alkyl vinyl ether), ethylene even, and ethylene fluorofluoride, and mixtures of them. In the case of using copolymers in the electrolysis of brine, it is desirable that the preceding vinyl monomer does not contain hydrogen. The second group is sulphuric monomers containing the previously mentioned group S02C1. . An example of such a monomer introduced for the synthesis of a copolymer is CE2. Auxiliary examples can be represented by the general formula CF-CF R / S.OjF, where R is a bifunctional fluorinated radical containing from 2 to 8 carbon atoms. The particular chemical content or structure of the radical that binds the sulfuryl group with the copolymer chain is not critical, but is such that it must have a fluorine atom bound to the carbon atoms to which the sulfuryl group is bound. If the sulfuryl group binds directly to a chain, then the carbon in the chain must have a fluorine atom bound to it. Other atoms bound to this carbon may be fluorine, chlorine or hydrogen atoms, although in general hydrogen may be eliminated by using a copolymer for ion exchange in the alkali chloride element. The F radical of the above formula may be branched or unbranched, i.e. normally linked, and may also have one or more other bonds. Preferably, the vinyl radical in the group of sufuryl fluorine containing monomers introduced for copolymer synthesis is bound to the RJ group via ether linkages, i.e., the formula of monomer introduced for copolymer synthesis is: CF CFRSO F. The copolymer used in this invention is prepared by universal polymerization, which is designed for the homo- and copolymerization of fluorinated ethylene, in particular, which is used for tetrafluoroethylene. After the formation of the intermediate polymer, the sulfuryl groups are converted to N-monosubstituted sulfonamide groups; when using an ion-exchange polymer, a complex film or laminate is required. Additional sulfuryl groups on one of the surfaces of the film react with the amine and are converted to 1 -substituted sulfonamide groups. Since these groups in the hydrochloric-alkaline element have a high electrical resistance, they then react with the base, transferring to the salt form. The thickness of the N -substituted sulfonamide layer does not seem critical, but usually this thickness is at least about 200 A. For complex film or laminated material t, the thickness of the N -substituted sulfonamide layer may be normal within 0.1-30 % of the thickness of the film or laminate in the chloride-alkaline element. In addition, when using a composite film or shell in an element, it is necessary for the layer with N -substituted sulfonamide groups or their salts to meet with the cathode part of the element in which caustic soda is produced. The polymer is preferably used in the form of a film with a thickness of 0.050, 5 mm. With a smaller film thickness, it has low strength, with an increase in - the electrical resistance increases significantly. Example 1. A 0.5 mm thick film made from a copolymer of tetrafluoroethylene and perfluoro (3,6-dioxa-4-methyl-7-octene sulfonyl) fluoride, having an equivalent weight of 1200, is immersed at room temperature for six hours in N, M-dimethylformamide saturated with anhydrous methylamine. The film is thoroughly washed with water, kept in water overnight and dried. Such a film is used to separate the anon and cathode spaces in the laboratory chlor-alkali element. A sodium chloride aqueous solution placed in the anode compartment and subjected to electrolysis at a current density of 2.0 A / inch. An alkali is obtained in six days with concentrations lying in the range of 18-22 wt.% With a voltage of 4.35-4, 86 V and with current efficiencies of 86-89.5%. Another film. With a thickness of 0.5 mm, from a copolymer of tetrafluoroethylene and perfto (3,6-dioxa-5-methyl-7-octene sulfonyl) fluoride, having an equivalent weight of 1200, is hydrolyzed to the sulfuric acid form and tested in the electrolysis of the brine as described. The alkali is obtained at a concentration of 17% by weight with a voltage of 3.7 V in the cell and a current efficiency of 75%. Example 2. A 0.5 mm thick film made from a copolymer of tetrafluoroethylene and perfluoro (3,6-dioxa-4-methyl-7-octene sulfonyl) fluoride, having an equivalent weight of 1100, is treated on one side with ethylene diamine to turn the surface layer on one side in -beta-aminoethylsulfonamide form. The film is washed with water and treated with a solution of potassium hydroxide to hydrolyze the remaining sulfonyl fluoride groups to potassium sulfonate groups. Such a film is tested in brine electrolysis according to the procedure of Example 1. For 31 days, alkali is obtained with concentrations lying in the range of 26-38 wt.% With a voltage of 3.75-4.98 V in the cell and at current efficiencies of 88- 98%. A similar film of the same copolymer, but not treated with any amine, is hydrolyzed with a solution of potassium hydroxide completely to the potassium sulfonate form and tested in the electrolysis of the brine as described. For 8 days of work, alkali is produced; concentrations lying 9 in the range of 34-40 wt.% when the voltage in the cell is 3.75-4.70 V and current efficiency is 56-79%. PR and M - er 3. A film of a copolymer of tetrafluoroethylene and perfluoro (3,6-diox-4-methyl-7-octene sulfonyl) fluoride with an equivalent weight of 1100, 7 mils thick (180 microns) is treated on one side for 29 min with a mixture of ethylenediamine and water in a ratio / volume.) 18: 1 at. The film is then washed with water, treated for 35 minutes with a 10% solution of acetic acid at room temperature and again washed with water for 40 minutes. As a result of this treatment, the surface layer with a thickness of 1.65 mil (40 μm) on one side of the film turned into the M-beta-aminoethylsulfonamide form. More than 90% of the functional groups in this layer are transferred to substituted sulfonamide groups. The film is then treated with a cadium hydroxide solution in order to transfer, by gvdrolysis, the remaining sulfonyl secondary groups into sulfo groups in which the hydrogen atom is replaced by potassium. The resulting film is used to separate the anodic and cathodic spaces of a small electrolyzer to produce chlorine and alkali, and an aqueous solution of sodium chloride placed in the anode compartment is electrolyzed at a current density of 2.0 A / square inch. During 31 days electrolysis results in electrolysis. caustic soda with a concentration of 26-38 wt.% when the voltage on the electrolyzer is 3.75-4.93 V with a current output of 83-96%. The same film with a thickness of 7 mil {180 µm) from the same copolymer is treated with liquid ammonia for 3.5 hours. In the surface layer with a thickness of 1.2 mil (30 µm), more than 30% of the functional groups are transferred to unsubstituted sulfonamide groups. The film is treated then with a solution of potassium hydroxide in order to transfer, by hydrolysis, the remaining fluoride groups from the sulfonyl group to sulfo groups, B of which the hydrogen atom is replaced by cadmium. The resulting film is tested during brine electrolysis using the method described above. Within 4 days as a result of electrolysis receive caustic soda concentration 20-27 wt.%. The voltage on the electrolyte is 4.22-4.52 V, the TOKV yield is 73-75%. 1 86 Examples 4-6. The procedure of Example 3 is repeated, changing only the thickness of the original gens. The following results were obtained (see table 1). Table {Examples 7-9. The procedure of Example 3 is repeated, changing only the percentage of the total film thickness, which is modified by treatment with ethylenediamine (by adjusting the operation by changing the processing time) and the percentage of mono exchange areas in the treated layer, transformed. in the substituted sulfonamide form (regulation of the operation is carried out by changing the water content in the ethyndiamine). The following results were obtained (see Table 2). Spreadsheets
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING CHLORINE
    AND ALKALI by electrolysis of a solution of alkali metal chloride in an electrolyzer with an ion exchange membrane separating the anode and cathode spaces, characterized in that. that, in order to increase the efficiency of current use, a film of fluorinated polymer with a thickness of 0.05-0.5 mm is used as an ion-exchange membrane, and the surface layer of the film facing the cathode space contains sulfonic groups connected to the carbon atom to which are attached fluorine atoms, and 40-100% of ion-exchange groups are in the form of * M-monosubstituted sulfonamide groups ^^ and this layer is 0.1-30% of the membrane thickness.
    SU_ ,. U 110644S
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    法律状态:
    优先权:
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