• 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 for producing an alkali metal hydroxide by electrolysis in an electrolytic cell comprising an anode compartment and a cathode compartment, which comprises supplying an alkali metal chloride to the anode compartment and water or a dilute alkali metal hydroxide to the cathode compartment, wherein a fluorine-containing cation exchange membrane comprising a first outer layer of a perfluorocarbon polymer having -SO₃M groups (wherein M is an alkali metal) with a thickness of at least 5 µm, and a second layer of a perfluorocarbon polymer having -CO₂M groups (wherein M is an alkali metal) and a water content of from 2 to 7% by weight in a 45 wt% NaOH aqueous solution with a thickness of at least 5 µm, the water content of the first layer being higher than that of the second layer, is disposed with the first layer facing the cathode compartment.
    公开号:SU1727534A3
    申请号:SU864028662
    申请日:1986-12-12
    公开日:1992-04-15
    发明作者:Мияке Харухиса；Канеко Исаму；Ватакабе Ацуси
    申请人:Асаки Гласс Компани Лтд.(Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a method for preparing an alkali metal hydroxide solution, in particular, to a method for producing a relatively high concentration of alkali metal hydroxide using ion-exchange membrane technology.
    The purpose of the invention is to reduce the voltage on the cell and ensure the stability of the current efficiency over time.
    Example 1: To obtain a laminate, a film of a copolymer / CF2 CF2 / CF2 CFOCF2CF2CF2C02CH3. having an ion exchange capacity of 1.44 meq / r of dry rubber and a thickness of 200 μm, compress
    when heated with a CF2 CF2 / CF2 CFOCF2CF2CF2C02CH3 copolymer film having an ion exchange capacity of 1.25 meq / g of dry resin and a thickness of 20 μm. In addition, a mixture containing methyl cellulose with 30% by weight Zr02 with a particle size of 5 μm, water, cyclohexanol and cyclohexane is triturated to form a paste. The paste is applied to a Maylar film, dried and a porous Zr02 layer is obtained, having a thickness of 10 µm and a density of Zr02 particles located on the surface of the film, equal to 1 mg and 1 cm of the surface. The porous ZrOa layer is then transferred onto the side, described layered membrane,
    VI
    to
    vj SL CJ 4

    WITH
    having an ion exchange capacity of 1.44 meq / g of dry resin, is compressed when heated and then subjected to hydrolysis in 25% NaOH at 70 ° C for 16 hours. Then 7% by weight ethanol solution of CF2 CF2 / CF2 CFOCF2CF copolymer (CF3) OCF2CF2S03H with an ion exchange capacity of 1.1 meq / g of dry resin is poured onto the surface containing a polymer with carboxyl groups, having an ion exchange capacity of 1.25 meq / g of dry resin, dried in air at 60 ° C and a coating layer having a thickness of 6 μm is obtained . This layered membrane is soaked for 16 hours in 25% by weight of NaOH.
    To the thus obtained membrane, from the side containing a polymer with carboxyl groups and an ion exchange capacity of 1.44 meq / g of dry resin coated with a porous layer of Zr02, pressing the cathode side presses the anode obtained from the solid solution of ruthenium oxide, iridium oxide and titanium oxide on the perforated titanium metal (small hole diameter 4 mm, large hole diameter 8 mm) with low chlorine overvoltage, resulting in the membrane and the anode coming into close contact with each other, and on the side with a polymer containing sulfate acid groups and having an ion exchange capacity of 1.1 meq / g of dry resin, place the cathode obtained by treating a SUS 304 metal with a hole (small hole diameter 4 mm, large diameter 8 mm) with a pickling aqueous solution containing 52 wt.% hydroxide sodium at 150 ° C for 52 hours, and having low hydrogen overvoltage, the cathode being placed in such a way that the distance from the membrane to the cathode is maintained at 2 mm. The electrolysis is then carried out at 90 ° C and a current density of 30 A / dm, feeding 5N sodium chloride aqueous solution into the anode chamber and water into the cathode chamber, maintaining the sodium chloride concentration in the anode chamber of 3.5 wt.% And the sodium hydroxide concentration. in the cathode chamber, equal to 45 wt.%, as a result, sodium hydroxide is obtained in a concentration of 45 wt.% with a current efficiency of 92% and a voltage across cells of 3.7 V. During continuous hydrolysis for 40 hours, no decrease in current efficiency is noted . The membrane is then removed from the electrolytic cell and disturbances such as salt deposition in the membrane are checked.
    Example 2: One side of a CF2 CF2 / CF2 CFOCF2CF2CF2C02CH3 copolymer film having an ion exchange capacity of 1.17 meq / g of dry resin with a thickness of 200 µm is treated to remove chlorine bubbles.
    using Zr02 particles as in example 1, then hydrolysis is carried out in 25 May% sodium hydroxide solution at 90 ° C for 16 h. Then on the other side
    5 was treated to remove chlorine bubbles, an 8% ethanolic solution of a CF2 CF2 / CF2 CFOCF2CF2S03NH4 copolymer was poured, having an ion exchange capacity of 1.0 meq / g of dry resin,
    0 dried in air at 60 ° C and receive a covering layer thickness of 8 μm. This membrane is soaked in a 25 wt.% Solution of sodium hydroxide at 90 ° C for 16 h and then placed in an electrolytic
    5 cell so that the sulfonic acid polymer layer is facing the cathode side. Using an electrolytic cell, electrolysis of an aqueous solution of sodium chloride is carried out analogously to example 1 and
    0, sodium hydroxide is obtained in a concentration of 45% by weight with a current efficiency of 93% and a voltage of 4.3 V.
    Comparative example. CF2 CF2 / CF2 Copolymer Membrane
    5 CFOCF2CF (CF3) OCF2CF2S02F, having an ion exchange capacity of 0.91 meq / g of dry resin with a thickness of 220 µm, is treated to remove chlorine bubbles in the same manner as in Example 1, and then subjected to hydrolysis in
    0 30% dimethyl sulfoxide / 11% KOH at 90 ° C for 20 minutes and soaked in 2% sodium hydroxide solution at room temperature for 2 hours. The membrane thus obtained is placed in an electrolytic cell, having a membrane treated side for removing chlorine bubbles to the anode. The electrolysis of an aqueous solution of sodium chloride is carried out analogously to example 1, obtaining
    0 sodium hydroxide in a concentration of 45 wt.% With a current efficiency of 70% and a voltage across the cell of 3.9 V.
    EXAMPLE 3 One side of a CF2 CF2 / GF2 CFOCF2CF2C02CH3 copolymer film, having a ion exchange capacity of 1.38 meq / g of dry resin with a thickness of 200 µm, is treated to remove chlorine bubbles in the same manner as in Example 1, then hydrolyzed film in a 25 wt.% solution of sodium hydroxide at
    0 to 70 ° C for 1 bh. Thereafter, an 8% ethanol solution of a CF2 CF2 / CF2 copolymer CFO CFCF2CF2CF2S03H copolymer having
    5 ion-exchange capacity of 1.0 mEq / g of dry resin, dried in air at 60 ° C and get the covering layer with a thickness of 11 μm. This membrane is soaked in a 25 wt.% Solution of sodium hydroxide for 16 hours at
    73 ° C and placed in an electrolytic
    cell sulphonic acid polymer layer to the cathode chamber. The electrolysis of an aqueous solution of sodium chloride is carried out analogously to example 1 and sodium hydroxide is obtained in a concentration of 45% by weight with a current efficiency of 93% and a voltage across the cell of 3.7 V.
    PRI me R 4. A porous polytetrafluoroethylene film having a pore diameter of 2 μm, a porosity of 70%, a Harle number of 5, and a thickness of 120 μm are layered on a CF2 CF2 CPO CPO (CP2) copolymer film having Ion exchange capacity of 1.25 meq / g of dry resin. Thickness of 40 microns and get a two-layer membrane thickness of 150 microns.
    Then an ethanol solution of CFa CF2 / CF2 -CFOCF2CFCF30 (CF2) 2S03H copolymer A (copolymer A) having an ion exchange capacity of 1.1 mEq / g of dry resin is poured onto the film of the indicated bilayer membrane, dried, and a three-layer membrane coated with copolymer A coated with a thickness of 7 microns.
    Then, with a solution containing copolymer A and zirconyl chloride, the porous structure of the three-layer membrane is impregnated, dried and the inner wall of the porous structure coated with a mixture of copolymer A and zirconyl chloride is obtained, thus obtaining a three-layer membrane with hydrophilic inner walls of the porous structure.
    Then, a ZrCte suspension with a particle size of 5 µm in the solution of copolymer A is sprayed onto the side with the porous structure and onto the side of the three-layer membrane with copolymer A, and a multilayer membrane coated with fine ZrOa particles is obtained.
    The multilayer membrane thus obtained is soaked in sodium hydroxide solution, and then placed in an electrolytic cell so that the anode, having a low chlorine overvoltage, is in contact with the porous polytetrafluoroethylene layer, and the cathode, which has a low overvoltage on hydrogen, is in contact with the polytetrafluoroethylene porous layer, and the cathode, which has a low overvoltage on hydrogen, is in contact with polytetrafluoroethylene and has a cathode that has low overvoltage in hydrogen and finds hydrogen in the polytetrafluoroethylene layer. in contact with the side containing copolymer A. Then electrolysis is carried out at 90 ° C with a current density of 30 A / dm, maintaining a sodium hydroxide concentration in the cathode chamber of 45% by weight, with a current efficiency of 93.0% and for example On a cell of 3.04 V.
    Example 5: A multilayer membrane was prepared as in Example 4, however, the thickness of the copolymer A coating in this case is 20 microns. The electrolysis is carried out analogously to example 4 with
    current efficiency 95.01% and a cell voltage of 3.05 V.
    PRI me R 6, a multilayer membrane is prepared analogously to example 4, but instead
    watering the ethanol solution of copolymer A is carried out by watering the ethanol solution with a mixture of ZrO2 particles having a size of 5 µm / copolymer A 4/6, to obtain a layer of ZrOa particles having a thickness of 30 µm. Electrolysis is carried out in a similar manner with a current efficiency of 95.0% and a voltage of 3.05 V. The continuous operation for 60 days shows no changes.
    5 Example 7. A mixture of methylcellulose containing 30% by weight of Zr02 with a particle size of 5 µm, water, cyclohexanol, and cyclohexane is triturated to form a paste. The paste is applied on
    0 Maylar-film, dried and get a porous layer of Zr02 with a thickness of 10 microns with a concentration of Zr02 particles equal to 1 mg per 1 cm of the film surface. Then, the porous Zr02 layer is pressed by pressing with heating on
    5 one side of CF2 CF2 / CF2 СРО (СР2) ЗС02СНз copolymer film having an ion exchange capacity of 1.32 meq / g of dry resin with a thickness of 20 μm. The membrane is hydrolyzed by soaking it in 25 wt.% NaOH.
    0 for 16h
    The anode obtained by applying a solid solution of ruthenium oxide, iridium oxide and
    5 titanium oxide perforated titanium metal (small hole diameter 4 mm, large diameter 8 mm) and having low chlorine overvoltage, and on the opposite side of the membrane at a distance of
    0 2 mm from it have a cathode, obtained by etching a perforated metal SUS 304 small hole diameter 4 mm, large diameter 8 mm) in an aqueous solution containing 52 wt.% Sodium hydroxide,
    5 at 150 ° C for 52 h and having low hydrogen overvoltage. Then electrolysis is carried out at 90 ° C and a current density of 30 A / dm2, feeding 5 N. an aqueous solution of sodium chloride in the anode chamber and water in
    0 cathode chamber, maintaining 3.5 N. the concentration of sodium chloride in the anode chamber and 45 wt.% The concentration of sodium hydroxide in the cathode chamber. Sodium hydroxide is obtained in a concentration of 45% by weight with
    5 current efficiency of 95% and a voltage on the cell of 3.5 V. During continuous operation for 3 months, a decrease in current efficiency is not observed. The membrane is removed from the electrolytic cell and set to no impairment, such as precipitation.
    salts in the membrane. In a 45 wt.% Solution of sodium hydroxide, the water content in the membranes used for the layer with carboxyl groups and the layer with sulfonic groups is 3.2 and 16.6%, respectively.
    Comparative example. One side of the film of the CPz CF2 / CF2 CPO (CP2) cS02CH3 copolymer having an ion exchange capacity of 1.25 meq / g of dry resin with a thickness of 250 µm is treated to remove chlorine bubbles in the same manner as in Example 7, and then subjected to film hydrolysis in 25 wt.% sodium hydroxide solution at 90 ° C for 16 hours. Then, as in Example 7, electrolysis is carried out with an initial current efficiency of 92%, an initial voltage on the cell of 3.9 V and a sodium hydroxide concentration of 45% by weight, 1 month current efficiency drops to 87%. The same membrane is used for electrolysis with a concentration of sodium hydroxide of 48 wt.%, With the initial current efficiency being 88%, and the voltage at the cell is 4.0 V.
    Comparative example. The electrolysis is carried out analogously to example 7, however, a sulfonic acid polymer layer with a thickness of 2 µm is used, with the initial current efficiency being 92%, and after a month it drops to 89%.
    Example The electrolysis is carried out analogously to example 7, but during electrolysis, sodium hydroxide is used equal to 50% by weight, the current efficiency being 95%, and the cell voltage is 3.6 V.
    PRI me R 9. Electrolysis is carried out analogously to example 7, however, using a CF2 CF2 / CF2 CPO (CP2) 3C02CH3 film of copolymer having an ion exchange capacity of 1.25 meq / g of dry resin and a thickness of 100 µm, and the thickness of the covering layer from CF2 CF2 / CF2 CFOCF2CF (CF3) 0 (CF2) 2S03H copolymer, having an ion exchange capacity of 1.1 meq / g of dry resin, is 10 µm, while the current efficiency is 94%, the voltage across the cell is 3.6 V. Content water in the carboxylic acid layer upon contact of the membrane with a 45 wt.% solution of sodium hydroxide is 3.1%.
    PRI me R 10. CF2 CF2 / CF2 CPO (CP2) 2C02CH3 copolymer films with an ion exchange capacity of 1.38 meq / g of dry resin and a thickness of 200 µm were applied to one side of the copolymer CF2 CF2 / CF2 CPO (CP2) 250zN, having an ion exchange capacity of 1.4 meq / g of dry resin, and dried to obtain a coating layer of 50 μm.
    The membrane is hydrolyzed on 25 May. % sodium hydroxide solution at 70 ° C for 16 hours and then placed in the electrolytic cell with a sulfonic acid polymer layer to the cathode. Then electrolysis is carried out as in Example 7. In addition, 5 N sodium chloride solution containing zirconium at a concentration of 10 is fed to the initial electrolysis step for 5 hours.
    0 ppm to deposit a layer of fine particles of zirconium oxide on the anode side of the membrane. Sodium hydroxide is obtained at a concentration of 45% by weight with a current efficiency of 95% and voltage across the cell.
    5 3.8 V. On contact with a 45 wt.% Solution of sodium hydroxide, the water content in the carboxyl-containing and sulfonic acid layers of the membrane is 3.5 and 20%, respectively.
    0 EXAMPLE 11. CF2 CF2 / CF2 CPO (CP2) cS02CH3 copolymer having an ion exchange capacity of 1.32 meq / g of dry resin, and CF2 CF2 / CF2 copolymer CFOCF2CF (CF3) 0; CF2) 2S02F having ion-exchange capacity 1.1
    5 mEq / g of dry resin, extruded together and get a two-layer membrane with layer thicknesses of 170 and 30 microns, respectively. The membrane is hydrolyzed in an aqueous solution containing 15 wt.% KOH at 50 ° C for 40 hours and then placed in an electrolytic cell with a sulfonic acid layer to the cathode. Then electrolysis is carried out as in Example 7 with a current efficiency of 93%. Upon contact of the membrane with 45 wt.%
    5 NaOH, the water content in the carboxylic and sulfonic acid layers is 4.4 and 13.5%, respectively.
    Example 2. Get the layered material of the film obtained from the copolymer
    0 CF2 CF2 / CF2 CFOCF2CF (CF3) 0 (CF2) 2S02F,
    having an ion exchange capacity of 0.93
    mEq / g of dry resin and a thickness of 200 microns and
    CF2 CF2 / CF2 copolymer films
    CPCRP2CP (CPP) 0 (CP2) zC02CH3, having
    5, an ion exchange capacity of 0.93 meq / g of dry resin and a thickness of 20 µm and a surface with a sulfonic acid polymer layer are treated to remove chlorine bubbles in the same manner as in Example 7. The membrane is hydrolyzed
    0 in 11% KOH / 30% dimethyl sulfoxide at 90 ° C for 20 minutes and soaked in 2% NaOH at room temperature, then dried. Then on the surface with the carboxylic polymer layer is poured
    A 5 ethanol solution of CF2 CF2 / CF2 CFOCF2CF (CF3) 0 (CF2) 2S03H copolymer having an ion exchange capacity of 1.1 meq / g of dry resin is dried and a covering layer of 30 μm is obtained. Spray is applied to this coating layer.
    suspension containing 84.5 May. % ethanol, 13.0 wt.% ZrOa, 2.5 wt.% copolymer CF2 CF2 / CF2 CPCPP CPP (CPP) 0 (CP2) 230ZH having an ion exchange capacity of 1.1 meq / g of dry resin and a small amount of non-ionic surfactant Triton X-100 compounds, ZrOa precipitation in the amount of 2 g / m2. This membrane is soaked in 25 wt.% NaOH at 90 ° C for 16 hours and placed in an electrolytic cell with the side treated to remove chlorine bubbles to the anode. Then electrolysis is carried out as in Example 7 and sodium hydroxide is obtained at a concentration of 43% by weight with a current efficiency of 94% and a voltage of 3.4 Å cell. The water content in the carboxylic acid layer of the membrane is 4.5 when in contact with 45% by weight NaOH. %
    权利要求:
    Claims (4)
    [1]
    Comparative example. A CF2 CF2 / CF2 CPO (CP2) ZSO3-CH3 copolymer film having an ion exchange capacity of 1.25 meq / g of dry resin and a thickness of 250 µm is applied to one side of the CF2 CF2 / CF2 -CFOCF2CF (CF3 ) 0 (CF2) 2S03H, having an ion exchange capacity of 1.1 meq / g of dry resin and a thickness of 20 μm. In both cases, electrolysis was carried out as in Example 7 for 3 months with a sodium hydroxide concentration of 45% by weight. Each membrane is removed from the electrolytic cell. A membrane having a sulfonic acid polymer layer is soaked in a mixture of hot water and ethanol, after which the sulfonic acid polymer layer is removed with filter paper. Then each membrane is kept in water for 50 hours at 90 ° C, periodically exchanged water, and dried. The ion exchange capacity of the surface on the cathode side of the carboxylic acid layer of each membrane is determined by measuring the fluorescence intensity of sodium in x-rays and compared with the result obtained for a similarly treated but not used electrolysis membrane. The results indicate that the ion-exchange capacity of the anode surface of the membrane having a sulfonic acid polymer layer 20 microns thick does not differ from the capacity before electrolysis, and the ion-exchange capacity of the surface on the cathode side of the membrane that does not have a sulfonic acid polymer layer drops to 1.0 meq / g dry resin. Claim 1. Method for preparing alkali metal hydroxide solution by electrolysis
    solution of alkali metal chloride in an electrochemical cell divided by a multilayer cation-exchange membrane made of perforated
    polymer to the anode and cathode chambers with an anode and cathode placed in them, respectively, including the introduction of an alkali metal chloride solution into the anode chamber and water or diluted
    alkali metal hydroxide solution in the cathode chamber, characterized in that, in order to reduce the cell voltage and ensure the stability of the current output over time, the electrolysis is carried out using a membrane made of a perforated polymer layer with sulfonic ionic groups, exchange capacity 0 , 93-1.4 meq / g dry resin with a thickness of 10-100 µm and from a layer of perfluorinated polymer with carboxyl ionic groups with an exchange capacity of 0.93-1.44 meq / g of dry resin with water content in the layers upon contact with 45 wt. .% solution oh alkali metal hydroxide
    13.5–20 and 3.2–4.5 wt.%, respectively, and a porous nonconducting layer of 10–30 zirconia particles is applied to the outer surface of the layer with carboxyl ionic groups.
    μm with a particle concentration of 1-2 mg / cm and a particle size of 5 μm, the membrane is installed in the cell so that the layer with sulfonic and ionic groups faces the cathode, and the concentration of alkali metal hydroxide solution in the cathode chamber is maintained at 42–50 wt%
    [2]
    2. A method according to claim 1, characterized in that a membrane is used which, between layers with carboxyl, sulfonic acid and ionic groups, further comprises a polymer layer with carboxyl ionic groups with an exchange capacity of 1.17-1.25 meq / g dry resin 20 microns.
    [3]
    3. A method according to claim 1, characterized in that a membrane is used which, between the polymer layer with carboxyl ionic groups and the layer of zirconia particles, contains an additional porous layer of polytetrafluoroethylene with a pore diameter of 2 microns, a porosity of 30-95% and a thickness of 120 microns.
    [4]
    4. A method according to claim 1, characterized in that the layer of zirconia particles is
    applied to both external sides of the membrane.
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    同族专利:
    公开号 | 公开日
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    引用文献:
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    JP5113892B2|2010-04-30|2013-01-09|アクアエコス株式会社|Membrane-electrode assembly, electrolytic cell using the same, ozone water production apparatus, ozone water production method, sterilization method, and waste water / waste liquid treatment method|
    JP5842919B2|2011-09-02|2016-01-13|旭硝子株式会社|Method for producing organic compound having sulfo group, method for producing liquid composition, and method for hydrolyzing organic compound having fluorosulfonyl group|
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    JP6515922B2|2014-04-21|2019-05-22|Ａｇｃ株式会社|Cation exchange membrane and method for producing potassium hydroxide aqueous solution|
    JP2018059163A|2016-10-06|2018-04-12|旭化成株式会社|Cation exchange membrane and electrolytic tank|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP27916485|1985-12-13|
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