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WO2018180726A1 - Procédé de fabrication d'hydroxyde de sodium et/ou de chlore et cellule d'électrolyse d'eau salée à deux chambres - Google Patents

Procédé de fabrication d'hydroxyde de sodium et/ou de chlore et cellule d'électrolyse d'eau salée à deux chambres Download PDF

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Publication number
WO2018180726A1
WO2018180726A1 PCT/JP2018/010870 JP2018010870W WO2018180726A1 WO 2018180726 A1 WO2018180726 A1 WO 2018180726A1 JP 2018010870 W JP2018010870 W JP 2018010870W WO 2018180726 A1 WO2018180726 A1 WO 2018180726A1
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Prior art keywords
chamber
cathode
anode
cathode chamber
humidification
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PCT/JP2018/010870
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English (en)
Japanese (ja)
Inventor
忠義 白川
智典 井筒
刑部　次功
大助 廣田
Original Assignee
株式会社カネカ
東亞合成株式会社
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Application filed by 株式会社カネカ, 東亞合成株式会社 filed Critical 株式会社カネカ
Priority to EP18776655.5A priority Critical patent/EP3608444B1/fr
Priority to CN201880022309.7A priority patent/CN110520555B/zh
Priority to JP2019509359A priority patent/JP7061997B2/ja
Publication of WO2018180726A1 publication Critical patent/WO2018180726A1/fr
Priority to US16/587,369 priority patent/US20200024758A1/en

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded

Definitions

  • the present invention relates to a method for producing sodium hydroxide and / or chlorine, and a two-chamber saline electrolyzer.
  • Patent Document 2 also discloses supplying a moist oxygen-containing gas to the cathode compartment. Specifically, the oxygen-containing gas is provided by bubbling oxygen into water heated to 80 ° C. It is described that a gas is prepared and introduced into the cathode compartment.
  • Patent Documents 1 and 2 require energy for heating water to 80 ° C. or 90 ° C. Furthermore, in Patent Document 1, when the temperature of the electrolytic cell becomes too high, the anolyte is circulated through an external heat exchanger, and the temperature of the anolyte is lowered using cooling water or the like, and cooling water is prepared. Energy is also needed.
  • the present invention provides an oxygen cathode method in which the water is efficiently supplied by supplying moisture to the cathode chamber and suppressing overheating of the electrolytic cell without requiring extra energy other than that required for the electrolytic reaction.
  • An object is to provide a method capable of producing sodium oxide and / or chlorine.
  • a two-chamber saline electrolyzer having at least one unit cell having an anode chamber with an anode and a cathode chamber with a gas diffusion cathode sandwiched between ion exchange membranes is used in the anode chamber.
  • the unit cell further includes a humidification chamber that generates a humidified oxygen-containing gas to be supplied to the cathode chamber,
  • the humidifying chamber is adjacent to the anode chamber or cathode chamber in the unit cell or the anode chamber or cathode chamber of an adjacent unit cell so that heat can be exchanged, and water vapor is generated by heat from the anode chamber or cathode chamber.
  • the humidification chamber is adjacent to the cathode chamber, and the humidified oxygen-containing gas generated in the humidification chamber is removed from the humidification chamber through the opening provided in the partition between the humidification chamber and the cathode chamber.
  • a two-chamber type saline electrolyzer having one or more unit cells each having an anode chamber and a cathode chamber with an ion exchange membrane interposed therebetween,
  • the anode chamber has a built-in anode and is provided with a raw material salt water supply port and an electrolyzed salt water discharge port and a chlorine discharge port, and
  • the cathode chamber has a gas diffusion cathode and is a humidified oxygen-containing gas.
  • the unit cell further includes a humidification chamber that generates an oxygen-containing gas to be supplied to the cathode chamber,
  • the humidifying chamber is adjacent to the anode chamber or the cathode chamber in the unit cell, or to the anode chamber or the cathode chamber of an adjacent unit cell so that heat exchange is possible, and is provided with an oxygen-containing gas supply port.
  • Legal saline electrolyzer
  • the humidification chamber is adjacent to the anode chamber or the cathode chamber so that heat exchange is possible, the oxygen-containing gas can be humidified using the heat of the anode chamber or the cathode chamber, and the electrolytic cell is overheated. Can be prevented.
  • FIG. 1 is a schematic cross-sectional view showing an example of a unit cell.
  • FIG. 2 is a schematic cross-sectional view showing an example of the shape of the opening for supplying the humidified oxygen-containing gas.
  • FIG. 3 is a schematic cross-sectional view illustrating an example of a unit cell including a connection pipe that supplies a humidified oxygen-containing gas.
  • FIG. 4 is a schematic cross-sectional view showing an example of a monopolar electrolytic cell.
  • FIG. 5 is a schematic cross-sectional view showing an example of a bipolar electrolytic cell.
  • FIG. 1 is a diagram showing an example of a unit cell in the electrolytic cell of the present invention.
  • the unit cell 1 has an anode chamber 3 and a cathode chamber 4 with an ion exchange membrane 2 interposed therebetween.
  • This anode chamber 3 is provided with an anode 3a in close contact with the side of the anode chamber of the ion exchange membrane 2, and the anode chamber 3 is provided with a supply port 3b for the raw material saline solution at the lower part thereof. And a chlorine discharge port 3c at the top thereof.
  • the cathode chamber 4 includes a liquid holding layer 4b in close contact with the side of the cathode chamber of the ion exchange membrane 2, a gas diffusion cathode 4a, and a gas diffusion cathode support 4c and a cushioning material 4d as necessary. .
  • the unit cell 1 of the present invention includes a humidification chamber 5 separated from the cathode chamber 4 by a partition wall 6, and the humidification chamber 5 can exchange heat with the cathode chamber 4.
  • the partition wall 6 in the illustrated example has a planar shape as shown in FIG. 2A, and the upper portion of the partition wall 6 has an opening 7 throughout. For this reason, the humidified oxygen-containing gas can be supplied from the humidification chamber 5 to the cathode chamber 4.
  • the cathode chamber 4 is also provided with a pressure equalizing line 4e for making the water surface height of the humidifying chamber constant.
  • the pressure equalizing line 4e is not essential if the same function can be performed by other means.
  • the water in the humidification chamber may or may not be circulated to the outside.
  • a line for passing water from the outside to the humidification chamber and discharging hot water can be separately provided (not shown).
  • the flow rate and temperature of the water can be set as appropriate so that the temperature of the water in the humidification chamber satisfies a predetermined condition (for example, 80 ° C. or higher). Even if the water is passed through, it is preferable from the viewpoint of energy efficiency that the temperature is set to a predetermined temperature using only the heat of the electrolytic reaction.
  • raw material saline is supplied to the anode chamber 3 from the raw salt water supply port 3b, and oxygen-containing gas is bubbled from the oxygen-containing gas supply port 5a into the water stored in the humidifying chamber 5,
  • oxygen-containing gas oxygen concentration is, for example, 90% or more, preferably 93% or more
  • chlorine is generated in the anode 3a.
  • Sodium hydroxide is formed in 4a.
  • the electrolytic reaction of the saline solution proceeds and the heat generated at the cathode is transmitted to the humidification chamber 5 so that the temperature of the water stored in the humidification chamber 5 can be raised, and the vaporization of the water in the humidification chamber is promoted.
  • the oxygen-containing gas is subsequently supplied to the humidification chamber 5 by bubbling or the like, an oxygen-containing gas containing an amount of water vapor approximately equal to the amount saturated at the temperature of the water in the humidification chamber can be generated. Therefore, the humidification efficiency of the oxygen-containing gas can be increased without using extra external energy other than the energy required for the electrolytic reaction.
  • oxygen-containing gas containing high-concentration water vapor is supplied to each unit cell from a humidifier provided outside the electrolytic cell as disclosed in Patent Document 1, moisture is supplied through a pipe in the middle of supply.
  • the degree of moisture condensation may vary from unit cell to unit cell, and the water supply amount varies from unit cell to unit cell.
  • each unit cell has a humidifying chamber, a sufficient amount of water can be supplied to each unit cell without variation.
  • the heat of the cathode chamber to the humidification chamber, it is possible to prevent overheating of the unit cell, that is, overheating of the electrolytic cell, without requiring extra energy for cooling.
  • the humidification chamber 5 is adjacent to the cathode chamber 4 in the unit cell 1, but may be adjacent to the anode chamber 3 in the unit cell 1 (in this way, the humidification chamber 5).
  • the unit cell having the respective chambers in the order of the anode chamber 3 and the cathode chamber 4 is hereinafter referred to as a B-type unit cell, and the unit cell having the respective chambers in the order of the anode chamber 3, the cathode chamber 4 and the humidifying chamber 5 Hereinafter referred to as A-type unit cell).
  • the humidification chamber 5 can be heated by using the heat to increase the steam generation efficiency. It is. As will be described later, a plurality of B-type unit cells may be used side by side. In such a case, the humidifying chamber 5 may be adjacent to the cathode chamber 4 of the adjacent unit cell. In that case, the steam generation efficiency in the humidification chamber 5 can be increased by the exothermic reaction in the cathode chamber 4 of the adjacent unit cell.
  • the sodium hydroxide produced in the cathode chamber 4 is a sodium hydroxide aqueous solution having a concentration of about 32.0 to 34.0% due to electroosmotic water from the anode chamber 3 and moisture in the oxygen-containing gas sent to the cathode chamber. Thus, it flows under the cathode chamber under its own weight and is discharged together with the exhaust gas of the oxygen-containing gas from the electrolysis reaction product discharge port 4g.
  • the concentration of the sodium hydroxide aqueous solution does not become too high, and damage to the gas diffusion cathode 4a and the ion exchange membrane 2 can be prevented. .
  • the partition 6 in the unit cell 1 may have various shapes of openings 7 as long as the oxygen-containing gas humidified from the humidification chamber 5 to the cathode chamber 4 can flow through the upper part of the partition 6. .
  • a plurality of openings may be provided in the upper part of the partition wall 6.
  • the opening provided in the upper part of the partition wall 6 may extend over the entire upper surface of the partition wall 6 as shown in FIG. 2A, or may be a part of the upper surface as shown in FIG. Good.
  • the number of openings is not particularly limited, and may be one or plural, and the shape of the openings is not particularly limited.
  • the partition wall 6 may not have the opening 7 as long as the humidified oxygen-containing gas can be circulated from the humidifying chamber 5 to the cathode chamber 4.
  • a humidified oxygen-containing gas may be supplied to the cathode chamber 4 through an external flow path such as the communication pipe 8.
  • the unit cell 1 in FIG. 3 is the same as the unit cell shown in FIG. 1 except that it has a connecting pipe 8 instead of the opening 7 in FIG.
  • the humidified oxygen-containing gas is supplied from the humidifying chamber 5 to the cathode chamber 4 by connecting the humidifying chamber 5 and the cathode chamber 4 with the connecting pipe 8 as described above. This is possible.
  • an opening 7 is formed between the humidifying chamber 5 and the cathode chamber 4 of the adjacent unit cell, or connected by a connecting pipe 8 so as to be adjacent to the humidifying chamber 5.
  • the oxygen-containing gas may be supplied to the cathode chamber 4 of the unit cell.
  • the anode 3a is not particularly limited as long as it is an insoluble anode used for brine electrolysis.
  • An expanded metal composed of a metal such as titanium, or a base having a mesh structure such as fine mesh coated with a metal oxide including a ruthenium oxide, titanium oxide, iridium oxide, or platinum group metal oxide. Can be used.
  • the ion exchange membrane 2 is not particularly limited as long as it can be used for saline electrolysis, and examples thereof include a perfluorocarbon type cation exchange membrane having carboxylic acid and / or sulfonic acid as an ion exchange group.
  • the gas diffusion cathode 4a is not particularly limited as long as it is used for saline electrolysis by the oxygen cathode method.
  • a metal mesh material, carbon cloth and / or hydrophobic resin is used as a base material
  • a reaction layer on which a hydrophilic catalyst is supported can be used on one surface
  • a sheet-like electrode having a three-layer structure in which a water-repellent gas diffusion layer is bonded to the other surface can be used.
  • the catalyst include silver, platinum, gold, metal oxide, and carbon.
  • the gas diffusion cathode may be permeable to liquid or may not be permeable to liquid.
  • the cathode chamber 4 no current can flow unless there is a liquid between the ion exchange membrane 2 and the gas diffusion cathode 4 a. If the ion exchange membrane 2 and the gas diffusion cathode 4a are in close contact with each other, it is possible to hold the liquid between them by capillarity, but in order to hold the liquid more reliably, the ion exchange membrane 2 and the gas diffusion cathode It is preferable that the liquid holding layer 4b exists between 4a.
  • the liquid holding layer 4b can uniformly hold a liquid such as an aqueous sodium hydroxide solution between the ion exchange membrane 2 and the gas diffusion cathode 4a, and can prevent an increase in current density and an increase in voltage.
  • the liquid holding layer is required to have hydrophilicity and corrosion resistance because it needs to hold a sodium hydroxide aqueous solution (concentration is about 30% and temperature is about 80 to 90 ° C.) generated by an electrolytic reaction. Therefore, a porous structure made of a carbon material such as carbon fiber or a resin is preferably used.
  • the advantage of the two-chamber method is that the anode, the ion exchange membrane and the cathode are in contact with each other, and the electric resistance between the electrodes is small, so that the electrolysis voltage can be reduced.
  • the cushion material 4d is accommodated in a compressed state to generate a reaction force on the cushion material, and the reaction force is used to make the gas diffusion cathode 4a. It is preferable to adhere to the ion exchange membrane 2.
  • a liquid pressure due to a saline solution acts on the anode chamber with the ion exchange membrane as a boundary, and a gas pressure acts on the cathode chamber.
  • the reaction force of the cushion material is designed according to the differential pressure between the fluid pressure and the gas pressure, but the fluid pressure increases as the depth of the saline solution increases. By making it larger, it is possible to equalize the pressure applied to the ion exchange membrane and the anode.
  • a cushioning material 4d it is possible to use a coil material or a woven mat material.
  • the coil has elasticity in the diametrical direction, and a reaction force is generated in this direction. Therefore, the coil axis can be used in parallel with the back plate of the cathode gas chamber, and the coil diameter, coil system, and laying density can be reduced. By adjusting, the reaction force of the cushion material may be made larger in the lower part than in the upper part.
  • the woven mat material can be a demister mesh woven knitted metal wire, and the cushion material can be adjusted by adjusting the wire diameter, the number of wires to be bundled, and the number of mat layers laminated. It is sufficient to make the reaction force of the lower part larger than the upper part.
  • a gas diffusion cathode support 4c can be interposed between the cushion material 4d and the gas diffusion cathode 4a as necessary.
  • the gas diffusion cathode support 4c can receive the reaction force of the cushion material 4d, make it uniform, and transmit it to the gas diffusion cathode 4a, the liquid holding layer 4b, and the ion exchange membrane 2.
  • a mesh material such as a wire mesh may be used as the gas diffusion cathode support 4c.
  • both the cushioning material 4d and the gas diffusion cathode support 4c are accommodated in the cathode chamber, and the cathode chamber has a high corrosion environment in which high-concentration oxygen and a high-concentration sodium hydroxide aqueous solution exist at high temperatures. Therefore, it is preferable to use Ni or a Ni alloy having a Ni content of 20% by weight or more, or a silver alloy plated with Ni.
  • the wall surface constituting the anode chamber 3 As a material for the wall surface constituting the anode chamber 3, it is preferable to use Ti or a Ti alloy having a Ti content of 20% by weight or more. Moreover, as a material of the wall surface which comprises the cathode chamber 4 and the humidification chamber 5, it is preferable to use Ni or Ni alloy whose Ni content is 20 weight% or more, and also what plated this with silver.
  • the electrolytic cell may be configured by arranging a plurality of the above-described unit cells (A type unit cell or B type unit cell, preferably A type unit cell).
  • each unit cell may be a monopolar electrolytic cell electrically connected in parallel, or each unit cell may be a bipolar electrolytic cell electrically connected in series, A bipolar electrolytic cell is preferred.
  • FIG. 4 is a schematic cross-sectional view showing an example of a monopolar electrolytic cell in which three A-type unit cells 1 having openings 7 are arranged.
  • the A-type unit cells arranged in the order of the anode chamber 3, the cathode chamber 4, and the humidifying chamber 5 are arranged in the normal order (the anode chamber 3, the cathode chamber 4, and the humidifying chamber 5 in this order).
  • the normal order in order of humidification chamber 5, cathode chamber 4 and anode chamber 3
  • normal order, reverse order, etc. a plurality (three in the illustrated example) are arranged while alternately reversing the order of the chambers in the unit cell. .
  • the anode of each unit cell is connected in parallel to an external power supply, and the cathode is also connected in parallel to the external power supply.
  • 9 is a water storage tank for adjusting the water surface height of the humidification chamber. Even in such an example, the heat of the cathode chamber 4 is transmitted to the humidification chamber 5, and the oxygen-containing gas can be humidified efficiently.
  • the humidifying chamber 5 of one unit cell (1) is adjacent to the humidifying chamber 5 of the adjacent unit cell (2). Sometimes. In such a case, both unit cells (1) and (2) may share one humidification chamber 5.
  • FIG. 5 is a schematic cross-sectional view showing an example of a bipolar electrolytic cell in which four A-type unit cells having openings 7 are arranged.
  • the unit cell 1 having the anode chamber 3 and the cathode chamber 4 having the humidifying chamber 5 therein repeats the order of the anode chamber 3, the cathode chamber 4, and the humidifying chamber 5.
  • a large number (four in the illustrated example) are arranged, and the anode 3a in one unit cell (1) can be electrically connected to the cathode 4a in the adjacent unit cell (2) ( The cathode 4a at one end and the anode 3a at the other end are connected to an external power source, so that the unit cells are connected in series.
  • the raw material salt water supply ports 3b of each unit cell, the electrolyzed salt water and chlorine discharge ports 3c, the oxygen-containing gas supply ports 5a, the water supply ports 5b, and the electrolysis reaction product discharge ports 4g The pressure equalization lines 4e are connected to each other by piping, and the water supply port 5b and the pressure equalization line 4e are connected to the water storage tank 9.
  • the mechanism of the electrolytic reaction in each unit cell of the bipolar electrolytic cell 20 is the same as that of the unit cell described above. However, by arranging the unit cells, one humidifying chamber 5 can be used as a cathode chamber in the same unit cell. 4 is adjacent to the anode chamber 3 in the adjacent unit cell.
  • the humidification chamber 5 can be humidified using both the heat generated by the electrolytic reaction of the anode chamber 3 and the heat generated by the electrolytic reaction of the cathode chamber 4, and the thermal efficiency during humidification can be further increased. Further, since the heat of the anode chamber 3 is transferred to the humidification chamber 5, the anode chamber 3 can also be cooled.
  • Example 1 As shown in FIG. 5, five unit cells having the structure shown in FIG. 1 (but not having a gas diffusion cathode support) are arranged so that the anode chamber, the cathode chamber, and the humidifying chamber are repeated in this order. Specifically, it was connected in series to assemble a bipolar two-chamber saline electrolyzer.
  • the anode is DSE manufactured by Permerek Electrode Co., Ltd. (insoluble metal coated with a Pt group metal or its oxide as a main component on a metal substrate), and the cathode is a gas-liquid permeable carbon-silver electrode (GDE2013) manufactured by Permerek Electrode Co. ), 4403D manufactured by Asahi Kasei Chemicals Co., Ltd. for the ion exchange membrane, a carbon fiber woven fabric having a thickness of 0.45 mm for the liquid holding layer, and a spiral nickel wire after silver plating for the cushioning material.
  • GDE2013 gas-liquid permeable carbon-s
  • a saline solution having a concentration of 218 g / L and a temperature of 53.8 ° C. is supplied to the anode chamber at a rate of 183 L / m 2 / h, and water is stored in the humidifying chamber, and the temperature is 25 ° C. and the concentration is 93.0. %, 1.5 times the required theoretical amount of oxygen-containing gas (corresponding to “oxygen-containing gas supplied to the electrolytic cell” shown in Table 1 below) was bubbled into the water in the humidification chamber. Since the temperature of the humidification chamber is 84.0 ° C., the temperature of the humidified oxygen-containing gas is about 84.0 ° C. when supplied to the cathode chamber. Electrolysis was performed at a current density of 5.65 kA / m 2 , and various values were measured after 10 days.
  • Comparative Example 1 The unit cell does not have a humidifying chamber, but the other materials such as the anode, cathode, ion exchange membrane, etc., and the size of the cathode chamber, anode chamber, etc. are the same as in Example 1, but the anode cell, cathode Five sheets were arranged so that the order of the chambers was repeated, and electrically connected in series to assemble a bipolar type conventional two-chamber saline electrolyzer (not shown).
  • a saline solution having a concentration of 219 g / L and a temperature of 51.4 ° C. was supplied to the anode chamber at a rate of 183 L / m 2 / h.
  • the cathode chamber of each unit cell is connected to one humidifier provided outside the electrolytic cell.
  • the oxygen-containing gas having a concentration of 93.0% and 1.5 times the required theoretical amount of oxygen-containing gas is connected.
  • a humidified oxygen-containing gas was generated by bubbling in water (25 ° C.) in a humidifier, and the humidified oxygen-containing gas was supplied to the cathode chamber at the same temperature. Electrolysis was performed at a current density of 5.65 kA / m 2 , and various values were measured after 10 days.
  • Comparative Example 1 does not have a humidifying chamber in the unit cell and supplies an oxygen-containing gas humidified from an external humidifier.
  • Oxygen-containing gas and “oxygen-containing gas supplied to the cathode chamber” mean the same thing (the same applies to Comparative Examples 2 to 4 below).
  • Comparative Example 2 The water temperature of the external humidifier in Comparative Example 1 was set to 84 ° C., and the humidified oxygen-containing gas generated at 84 ° C. was supplied to the cathode chamber as it was (heat input to the humidifier was about 5.2 MJ / m 2 / h) Except that, various values at the time of 10 days were measured in the same manner as in Comparative Example 1.
  • Comparative Example 3 In the same configuration as that of Comparative Example 2, the temperature of the humidified oxygen-containing gas is prevented from decreasing by keeping the surroundings of the pipe connecting the humidifier and the cathode chamber of each unit cell intensified. The value was measured. The heat input to the humidifier was about 5.2 MJ / m 2 / h, as in Comparative Example 2.
  • Example 2 Various values after operating the same electrolytic cell as in Example 1 for 300 days were measured.
  • Comparative Example 4 Various values after operating the same electrolytic cell as Comparative Example 1 for 300 days were measured.
  • Tables 1 and 2 show the average value of the five unit cells and the difference between the value of each unit cell and the average value for the concentration of the aqueous sodium hydroxide solution and the current efficiency.
  • Example 1 the temperature of the humidification chamber is equal to the temperature of the anode chamber due to the reaction heat of the electrolytic reaction, and the concentration of the generated aqueous sodium hydroxide solution is not too high at 32.2%. It can be seen that a sufficient amount of water vapor can be supplied (Table 1). Moreover, since the dispersion
  • Example 2 in which Example 1 was operated for a long period of time, a good current efficiency of 96.3% was exhibited even after 300 days had passed, and the other results were as good as those in Example 1. Is obtained. Further, in Example 2, since a sufficient amount of water vapor can be supplied, the generated sodium hydroxide concentration can be kept low, and damage to the gas diffusion cathode is suppressed, so that the gas after 300 days has elapsed since the operation of the electrolytic cell. The change in the voltage of the diffusion cathode was as small as 45 mV as an average value of the five unit cells. In addition, the change of the voltage of the gas diffusion cathode in each unit cell was 78 mV, 15 mV, 45 mV, 33 mV, and 54 mV, respectively.
  • Comparative Example 2 is an example in which the temperature of the external humidifier is changed to 84 ° C. in order to increase the water vapor pressure in the oxygen-containing gas, and energy for increasing the water temperature in the external humidifier is required.
  • the average value of the concentration of the generated aqueous sodium hydroxide solution is 32.2%, and on average, a sufficient amount of water vapor can be supplied.
  • both the sodium hydroxide concentration and the current efficiency are obtained.
  • the variation for each unit cell is large. This is presumably because moisture was condensed during the introduction of the humidified oxygen-containing gas from the external humidifier to the cathode chamber of each unit cell, and the degree of condensation differed for each unit cell.
  • a high-temperature oxygen-containing gas is supplied from the outside of the electrolytic cell, and it is necessary to make the supply saline solution to the anode low in order to prevent overheating of the electrolytic cell (supply in Example 1)
  • the temperature of the salt solution is 53.8 ° C., which is a general temperature range in a salt electrolysis factory, whereas the temperature of the salt solution supplied in Comparative Example 2 is 47.0 ° C.) Extra energy for is needed.
  • Comparative Example 3 is an example in which heat insulation is strengthened on the pipe from the external humidifier in Comparative Example 2, and, like Comparative Example 2, energy for heating in the external humidifier is required.
  • Comparative Example 3 as a result of suppressing the condensation of water in the piping, the variation in the generated sodium hydroxide concentration and current efficiency from cell to cell was suppressed. Extra energy for is needed.
  • Comparative Example 4 is an example in which the electrolytic cell was operated for 300 days under the same conditions as Comparative Example 1, and the change in the voltage of the gas diffusion cathode after 300 days from the operation of the electrolytic cell was the average value of five unit cells. It was 108 mV, which was much higher than that of Example 2, and the current efficiency was 96.0%, which was lower than that of Example 2.
  • the sodium hydroxide aqueous solution concentration produced in Comparative Example 4 is 34.6%, which is 2% higher than the sodium hydroxide aqueous solution concentration of 32.2% in Examples 1 and 2. Therefore, it is considered that the gas diffusion cathode is damaged. Note that changes in the voltage of the gas diffusion cathode in each unit cell were 123 mV, 66 mV, 114 mV, 108 mV, and 129 mV, respectively.

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  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

L'invention concerne un procédé de fabrication d'hydroxyde de sodium et/ou de chlore dans lequel, dans un procédé à deux chambres pour un procédé d'électrode négative à oxygène, de l'eau est introduite dans les chambres d'électrode négative et une surchauffe de la cellule électrolytique est évitée sans nécessiter d'énergie supplémentaire. La présente invention consiste en un procédé de fabrication d'hydroxyde de sodium et/ou de chlore par électrolyse d'eau salée, à l'aide d'une cellule d'électrolyse d'eau salée à deux chambres ayant une ou plusieurs cellules unitaires pourvues d'une chambre d'électrode positive, comprenant une électrode positive, et une chambre d'électrode négative, comprenant une électrode négative à diffusion de gaz, une membrane échangeuse d'ions étant placée entre lesdites chambres. Le procédé est caractérisé en ce que les cellules unitaires comprennent également une chambre d'humidification pour générer un gaz qui comprend de l'oxygène auquel de l'humidité est ajoutée pour l'alimentation de la chambre d'électrode négative ; la chambre d'humidification est adjacente à la chambre d'électrode positive ou à la chambre d'électrode négative à l'intérieur de la cellule unitaire ou dans une cellule unitaire adjacente, de telle sorte qu'un échange de chaleur est possible, et elle ajoute de l'humidité au gaz contenant de l'oxygène par génération de vapeur d'eau au moyen de la chaleur provenant de la chambre d'électrode positive ou de la chambre d'électrode négative.
PCT/JP2018/010870 2017-03-30 2018-03-19 Procédé de fabrication d'hydroxyde de sodium et/ou de chlore et cellule d'électrolyse d'eau salée à deux chambres WO2018180726A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP18776655.5A EP3608444B1 (fr) 2017-03-30 2018-03-19 Procédé de fabrication d'hydroxyde de sodium et/ou de chlore et cellule d'électrolyse d'eau salée à deux chambres
CN201880022309.7A CN110520555B (zh) 2017-03-30 2018-03-19 氢氧化钠和/或氯的制造方法、以及二室法型食盐水电解槽
JP2019509359A JP7061997B2 (ja) 2017-03-30 2018-03-19 水酸化ナトリウム及び／又は塩素の製造方法、並びに２室法型食塩水電解槽
US16/587,369 US20200024758A1 (en) 2017-03-30 2019-09-30 Method for producing sodium hydroxide and/or chlorine, and two-chamber type electrolytic cell for saltwater

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-068057 2017-03-30
JP2017068057 2017-03-30

Related Child Applications (3)

Application Number Title Priority Date Filing Date
US16/086,495 A-371-Of-International US10750060B2 (en) 2016-03-31 2017-03-17 Camera module, method of manufacturing camera module, imaging apparatus, and electronic apparatus
US16/587,369 Continuation US20200024758A1 (en) 2017-03-30 2019-09-30 Method for producing sodium hydroxide and/or chlorine, and two-chamber type electrolytic cell for saltwater
US16/923,914 Continuation US11595551B2 (en) 2016-03-31 2020-07-08 Camera module, method of manufacturing camera module, imaging apparatus, and electronic apparatus

Publications (1)

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WO2018180726A1 true WO2018180726A1 (fr) 2018-10-04

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US (1) US20200024758A1 (fr)
EP (1) EP3608444B1 (fr)
JP (1) JP7061997B2 (fr)
CN (1) CN110520555B (fr)
WO (1) WO2018180726A1 (fr)

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KR102607849B1 (ko) * 2022-01-03 2023-11-30 한국세라믹기술원 마이크로파 가열을 이용한 수산화나트륨의 제조방법

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US20200024758A1 (en) 2020-01-23
CN110520555A (zh) 2019-11-29
EP3608444B1 (fr) 2025-01-01
CN110520555B (zh) 2021-10-15
EP3608444A1 (fr) 2020-02-12
JPWO2018180726A1 (ja) 2020-02-06
JP7061997B2 (ja) 2022-05-02

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