• 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:
    PURPOSE:To make it possible to electrolyze alkali halide at high temp. and low voltage by electrolyzing an aq. soln. of alkali halide in a cell divided into cathodic and anodic chambers by a cation exchange membrane and pressurized to above atmospheric press. so as to produce pressurized halogen gas and H2 and to facilitate recoverying waste heat from the product gases.
    公开号:SU1750435A3
    申请号:SU772500804
    申请日:1977-07-04
    公开日:1992-07-23
    发明作者:Огава Синсаку；Есида Мунео
    申请人:Асахи Касеи Когио Кабусики Кайся (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the field of electrochemical production, in particular to the electrolysis of an aqueous solution of sodium chloride.
    The purpose of the invention is to reduce energy consumption.
    Example 1. A perfluorosulfonic acid membrane N eff l 315 membrane consisting of two layers, one layer 0.1 mm thick, having an equivalent weight of 1100 g with ion-exchange sulfonic acid groups, and a second layer with an equivalent weight of 1500 g are installed in the electrolyzer.
    The anode is a 60% porous titanium anode coated with a mixture of ruthenium, titanium and zirconium oxides, and porous iron is used as the cathode. The cell is bipolar, the distance between the main sheet of the bipolar cell and the anode is 45 mm, the same distance between the cathode and the main sheet, the main sheet
    made of iron and titanium. 74 bipolar electrodes are placed in the cell.
    An aqueous solution of sodium chloride from the tank is fed in parallel streams into each anode chamber of the electrolyzer at a rate of 600 l / h, and sodium chloride is fed at the same rate into the cathode chambers.
    The product outlet from the electrolysis cell chambers is carried out in the vapor-liquid state, and the pressure in the chambers is regulated by making holes in the outlet nozzle.
    The process is conducted at a current density of 40 A / dm, the electrolysis voltage, temperature and pressure in the cathode chamber are interconnected, as shown in the graph (drawing). As can be seen from the graph, the electrolysis voltage has its minimum at approximately 85 ° C. with a pressure equal to atmospheric, but with increasing pressure in
    h ate about
    | B
    SL5 SP
     WITH
    In the electrolysis bath, the temperature Tc, at which the electrolysis voltage becomes minimal, increases. Points for Tc corresponding to different pressures P in the electrolysis bath will give line A-A. In a similar way, when the current density changes at 20.40 and 60 A / dm2, the corresponding A-A curves are determined. The specified parameters are related to each other by the empirical formula:
    Re-Pn2 About 0.000535 (TS - 56)
    In the drawing, a pressure higher than 1 eta or equal to 1 eta, especially to the left of line A-A, indicates an area of critical gas partial pressure or higher at which a reduction in energy consumption is achieved.
    In the proposed method, due to the increased pressure in the chambers in the anode space, chlorine will dissolve, but due to the use of a cation-exchange membrane, the quality of sodium hydroxide does not deteriorate.
    When the cell is under increased pressure, the gas shielding the surface of the membrane is removed from it. Since the electrical resistance of the membrane and solution decreases when the temperature rises, the electrolysis voltage can be reduced. But sometimes the temperature of the electrolysis rises, and the pressure is maintained at a certain level, the voltage on the cell first decreases. However, there is a critical electrolysis temperature Tc, at which the voltage becomes minimal when the temperature passes through a certain critical value, the electrolysis voltage begins to increase sharply. It has been found that there is a critical pressure PC at which or above which the electrolysis voltage varies slightly. If the pressure is too high, the strength of the membrane may be impaired; therefore, it is important to determine the pressure that allows the process to proceed without destroying the membrane. As a result of the research, an empirical formula was found:
    1-5 (Ps-Pn2o},
    where PC-PHI about k CTC - T0);
    P is the pressure in the electrolyzer chambers;
    PHZ is the partial pressure of water vapor in the chambers;
    Рс - critical pressure in the cells of the electrolyzer;
    T is the temperature in the electrolyzer;
    Tc is the critical temperature in the electrolyzer;
    T0 - constant, equal to 56 ± 5 ° С; I — current density, A / dm2;
    k is a coefficient equal to 0.000535,
    (ata / ° C) (A / dm2).
    The constant k depends on the electrolyte used, its concentration, the design of the electrolyzer, the amount of circulating fluid, etc. The value of k is typically 0.00054 ± 0.0002. the practical range of f is 10-100 A / dm.
    The membrane is located between the cathode and the anode, therefore both chlorine and hydrogen can
    to shield the surface of the electrodes and the membrane, in this case it is necessary to take into account the partial pressure of chlorine and hydrogen.
    To prevent rupture of the membrane, it is necessary to maintain the pressure difference in the cathode and anode chambers of 0.5 or lower. In addition, when the process is conducted at high temperature and high current density, the temperature in the membrane rises due to the heat released by
    in a layer with lower electrical conductivity, and this increase is so significant that a boiling phenomenon is observed in the membrane, with water bubbles forming at the interface of the membrane, which can lead to rupture of the membrane. For example, if electrolysis takes place at a temperature of 85 ° C, which is about 20 ° C below the boiling point of the electrolyte, a cation-exchange membrane is formed
    water bubbles at a current density of 30 A / dm. In accordance with the invention, when the gas partial pressure in the electrolytic cell is maintained not so high compared with the critical gas partial pressure, which is determined by the electrolysis temperature and current density in accordance with the formula, the boiling effect in the membrane is completely eliminated.
    Critical partial pressure means pressure at which no significant decrease in voltage is observed during subsequent pressure generation in the electrolyzer at a constant temperature.
    electrolysis. Therefore, the concept of critical partial pressure can be defined as a graphical dependence of stress on pressure at a constant temperature.
    When electrolyzing a solution of sodium chloride with ion exchange membranes, the higher the pressure, the lower the voltage. However, if the pressure exceeds 5 at.
    no significant voltage change occurs.
    One of the advantages of the invention is that the heat generated in the cell can be used at elevated electrolysis temperatures. The heat generated is usually removed with cold water, it is more advantageous to use this heat as a heat source for the concentration of sodium hydroxide. If it is possible to increase the temperature of the electrolysis above 85 ° C without increasing the voltage of the electrolysis, the heat generated can be used to concentrate the aqueous solution of sodium hydroxide. During the process, the voltage on the electrolyzer is 3.98 V, while in the known voltage it is 4.61 V.
    权利要求:
    Claims (1)
    [1]
    The invention The method of electrolysis of an aqueous solution of sodium chloride in a cell with a two-layer cation-exchange membrane with poluche0
    five
    0
    Chlorine in the anode chamber and in the cathode - alkali, characterized in that, in order to reduce energy consumption, the layer of cation-exchange membrane with higher electrical conductivity is turned to the anode, and with less to the cathode and electrolysis is carried out while maintaining a pressure of 1-5 at the cathode chambers and the partial pressure of gas in each chamber, determined by the formula:
    1-5 ()
    where (Pc-PH2 o) - It I Pe-To).
    Рс - critical pressure in the upper part of the electrolyzer;
    Рн2 о is the partial pressure of water vapor in the upper part of the electrolyzer;
    Tc is the critical temperature;
    That 56 ± 5 ° С is a constant;
    I is the current density;
    K - coefficient equal to O, 000535 ± 0.0002.
    类似技术:
    公开号 | 公开日 | 专利标题
    SU1750435A3|1992-07-23|Method of electrolysis of aqueous solution of sodium chloride
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    KR830002163B1|1983-10-17|Chlorine-Alkaline Electrolyzer
    CA1153982A|1983-09-20|Electrolytic production of alkali metalhypohalite and apparatus therefor
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    RU2062307C1|1996-06-20|Electrolytic cell to produce chlorine and alkali
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    FI82078B|1990-09-28|ELEKTROKEMISKT AVLAEGSNANDE AV HYPOKLORITER UR KLORATCELLOESNINGAR.
    US4127457A|1978-11-28|Method of reducing chlorate formation in a chlor-alkali electrolytic cell
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    US4360412A|1982-11-23|Treatment of permionic membrane
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    JPS5591989A|1980-07-11|Electrolysis method
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    JPS56123386A|1981-09-28|Method and apparatus for electrolysis of salt
    SU1542419A3|1990-02-07|Electrolyzer for producing chlorine and alkali
    SU729283A1|1980-04-25|Method of chlorine and caustic soda production
    JPH05339771A|1993-12-21|Diaphragm for sodium chloride electrolysis and method for electrolyzing sodium chloride
    JPS5629681A|1981-03-25|Electrolysis of aqueous alkali chloride solution
    同族专利:
    公开号 | 公开日
    SE7707733L|1978-01-06|
    NL168569B|1981-11-16|
    DE2729589C2|1988-04-14|
    SE433623B|1984-06-04|
    IT1104768B|1985-10-28|
    US4105515A|1978-08-08|
    BR7704391A|1978-05-16|
    FR2357661A1|1978-02-03|
    JPS5643116B2|1981-10-09|
    GB1547062A|1979-06-06|
    JPS534796A|1978-01-17|
    NL168569C|1985-07-16|
    DE2729589A1|1978-01-12|
    FR2357661B1|1980-01-18|
    CA1115234A|1981-12-29|
    NL7707440A|1978-01-09|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US1377722A|1918-03-09|1921-05-10|Marconi Guglielmo|Electric accumulator|
    US3017338A|1958-03-03|1962-01-16|Diamond Alkali Co|Electrolytic process and apparatus|
    US3321388A|1962-08-09|1967-05-23|Asahi Denka Kogyo Kk|Process for coordinated operation of diaphragm and mercury cathode electrolytic cells|
    US3382167A|1964-04-01|1968-05-07|Trw Inc|High pressure electrolytic cell module|
    US3274082A|1965-06-01|1966-09-20|Chlormetals Inc|Gas removal from electrolytic cells|
    GB1149416A|1967-03-16|1969-04-23|Ici Ltd|Manufacture of chlorine and caustic alkali in diaphragm cells|
    US3652431A|1970-03-12|1972-03-28|Julian Louis Reynolds|Method of operating an electrolysis cell for the production of gases under hydrostatic pressure|
    BE790369A|1971-10-21|1973-04-20|Diamond Shamrock Corp|METHOD AND APPARATUS FOR THE PREPARATION OF HYDROXIDES FROM HIGH PURE ALKALINE METALS IN AN ELECTROLYTIC TANK.|
    DE2214920A1|1972-03-27|1973-10-11|J Louis Reynolds|Electrolyzer - for producing gases under hydrostatic press|
    US3864226A|1972-10-19|1975-02-04|Du Pont|Process for electrolyzing aqueous sodium or potassium ion solutions|
    DE2503652A1|1974-02-04|1975-08-07|Diamond Shamrock Corp|CELL FOR CHLORAL CALCIUM ELECTROLYSIS|
    JPS50120493A|1974-03-09|1975-09-20|
    US3893897A|1974-04-12|1975-07-08|Ppg Industries Inc|Method of operating electrolytic diaphragm cells having horizontal electrodes|
    JPS5232865B2|1974-12-10|1977-08-24|US4204920A|1978-12-06|1980-05-27|Allied Chemical Corporation|Electrolytic production of chlorine and caustic soda|
    US4370209A|1979-02-23|1983-01-25|Ppg Industries, Inc.|Electrolytic process including recovery and condensation of high pressure chlorine gas|
    DE2914870A1|1979-04-12|1980-10-30|Hoechst Ag|METHOD FOR CHLORINE AND COOLING THE ANOLYTE OF ALKALI HALOGENIDE ELECTROLYSIS|
    US4313812A|1980-03-10|1982-02-02|Olin Corporation|Membrane electrode pack cells designed for medium pressure operation|
    US4390408A|1980-06-06|1983-06-28|Olin Corporation|Membrane electrode pack cells designed for medium pressure operation|
    DE3144599A1|1981-11-10|1983-05-19|Hoechst Ag, 6230 Frankfurt|"SAFETY DEVICE FOR PRESSURE ELECTROLYSIS|
    US4488946A|1983-03-07|1984-12-18|The Dow Chemical Company|Unitary central cell element for filter press electrolysis cell structure and use thereof in the electrolysis of sodium chloride|
    US4568434A|1983-03-07|1986-02-04|The Dow Chemical Company|Unitary central cell element for filter press electrolysis cell structure employing a zero gap configuration and process utilizing said cell|
    US4560452A|1983-03-07|1985-12-24|The Dow Chemical Company|Unitary central cell element for depolarized, filter press electrolysis cells and process using said element|
    US4673479A|1983-03-07|1987-06-16|The Dow Chemical Company|Fabricated electrochemical cell|
    US4572770A|1983-05-31|1986-02-25|The Dow Chemical Company|Preparation and use of electrodes in the electrolysis of alkali halides|
    GB8821927D0|1988-09-19|1988-10-19|Ici Plc|Process for cooling gaseous chlorine|
    EP0505899B1|1991-03-18|1997-06-25|Asahi Kasei Kogyo Kabushiki Kaisha|A bipolar, filter press type electrolytic cell|
    DE10138215A1|2001-08-03|2003-02-20|Bayer Ag|Process for the electrochemical production of chlorine from aqueous solutions of hydrogen chloride|
    US8178059B2|2007-12-05|2012-05-15|Ch2M Hill Engineers, Inc.|Systems and methods for supplying chlorine to and recovering chlorine from a polysilicon plant|
    US8317994B2|2008-08-07|2012-11-27|Westlake Vinyl Corporation|Method of concentrating an aqueous caustic alkali using a catholyte heat recovery evaporator|
    US20110186462A1|2009-12-07|2011-08-04|Activated Environmental Solutions Inc.|Microcidal composition|
    DE102011005133A1|2011-03-04|2012-09-06|Bayer Materialscience Aktiengesellschaft|Method for operating an oxygen-consuming electrode|
    US8562810B2|2011-07-26|2013-10-22|Ecolab Usa Inc.|On site generation of alkalinity boost for ware washing applications|
    JP5996399B2|2012-11-27|2016-09-21|株式会社東芝|Method for recovering platinum group elements|
    JP6438741B2|2014-11-07|2018-12-19|旭化成株式会社|Electrical insulation method for electrolysis system|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP7889576A|JPS5643116B2|1976-07-05|1976-07-05|
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