WO2016013234A1 - Dispositif d'électrolyse - Google Patents

Dispositif d'électrolyse Download PDF

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Publication number
WO2016013234A1
WO2016013234A1 PCT/JP2015/052357 JP2015052357W WO2016013234A1 WO 2016013234 A1 WO2016013234 A1 WO 2016013234A1 JP 2015052357 W JP2015052357 W JP 2015052357W WO 2016013234 A1 WO2016013234 A1 WO 2016013234A1
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Prior art keywords
electrode
electrolysis
flow path
lower electrode
upper electrode
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PCT/JP2015/052357
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English (en)
Japanese (ja)
Inventor
洗　暢俊
坂本　泰宏
信広 林
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シャープ株式会社
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Priority to US15/325,817 priority Critical patent/US20170145571A1/en
Priority to CN201580041222.0A priority patent/CN106661742A/zh
Publication of WO2016013234A1 publication Critical patent/WO2016013234A1/fr

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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
    • 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
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/4618—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water
    • 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
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds 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
    • 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
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C02F2001/46142—Catalytic coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/4618—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water
    • C02F2001/46185—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water only anodic or acidic water, e.g. for oxidizing or sterilizing
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4611—Fluid flow
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/29—Chlorine compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/02—Fluid flow conditions
    • C02F2301/024—Turbulent

Definitions

  • the present invention relates to an electrolytic device, and more particularly to a diaphragmless electrolytic device.
  • Electrolysis is practically used for the production of chemical materials.
  • basic chemical raw materials such as sodium hydroxide (caustic soda), chlorine gas, hydrogen gas, and sodium carbonate (soda ash) are produced by the electrolytic soda method.
  • electrolytic soda sodium hydroxide
  • chlorine gas chlorine gas
  • hydrogen gas hydrogen gas
  • sodium carbonate sodium carbonate
  • electrolytic soda method In addition to industrial applications, there are products that use electrolysis technology in household equipment such as alkali ion water conditioners.
  • An advantage of using the electrolytic technique is that an active substance can be generated from a material that is hardly active and harmless.
  • hypochlorites represented by sodium hypochlorite are used as bleaching agents and disinfectants for treating water and sewage, for treating wastewater, for household kitchens and for laundry.
  • Hypochlorite can be produced by reacting alkali hydroxide obtained by electrolysis of an aqueous solution of an alkali metal chloride such as saline and chlorine gas, or by using an alkali metal chloride in a diaphragm electrolyzer. This is performed by a method of electrolyzing an aqueous solution of the above and producing a hypochlorite aqueous solution in an electrolytic cell.
  • alkali hydroxide obtained by electrolysis of an aqueous solution of an alkali metal chloride such as saline and chlorine gas, or by using an alkali metal chloride in a diaphragm electrolyzer. This is performed by a method of electrolyzing an aqueous solution of the above and producing a hypochlorite aqueous solution in an electrolytic cell.
  • the method of reacting alkali hydroxide with chlorine gas can obtain a highly concentrated hypochlorite aqueous solution, so this method is used when manufacturing for the purpose of selling a hypochlorite aqueous solution. Yes.
  • an electrolytic facility for producing alkali hydroxide and chlorine gas is required, it is carried out in association with production of alkali hydroxide or chlorine gas in a large-scale alkali chloride electrolytic factory such as salt.
  • a method of electrolyzing an aqueous solution such as saline in a diaphragm electrolyzer is a hypochlorite aqueous solution having a concentration that can be directly used for water purification and sterilization using a simple electrolytic facility. Can be generated.
  • hypochlorite aqueous solution uses hypochlorite aqueous solution.
  • electrolytic production of hypochlorite aqueous solution can adjust the current to be applied according to the required amount of hypochlorite aqueous solution, and all the chlorine content effective for sterilization is dissolved in water. It has the feature of being. Therefore, the method of producing a hypochlorous acid aqueous solution by electrolysis has the merit that it is not necessary to store or transport hypochlorite.
  • an anodic reaction such as chemical reaction formulas (1) to (3) proceeds, and a cathode such as chemical reaction formula (4).
  • the reaction is considered to be progressing.
  • 2Cl ⁇ ⁇ Cl 2 + 2e ⁇ (1) Cl 2 + H 2 O ⁇ HCl + HClO (2) H 2 O ⁇ 1 / 2O 2 + 2H + + 2e ⁇ (3) 2H 2 O + 2e ⁇ ⁇ H 2 + 2OH ⁇ (4)
  • aqueous solution becomes strong acidity (pH is 3 or less) the reaction rate of chemical reaction formula (2) will become slow, and chlorine gas may be produced
  • the concentration of the hypochlorite aqueous solution produced by electrolysis is low, the concentration of organic matter contained in the water to be treated will be high, or the sterilization target with a relatively large amount of organic matter will be sufficiently removed. There are cases where disinfection is not possible.
  • a method for producing a high concentration hypochlorite aqueous solution a method of lengthening the time during which the electrolyte stays between the anode and the cathode, and a plurality of electrolytic cells equipped with the anode and the cathode through the partition plate A method using an electrolysis unit installed in a multistage manner is conceivable.
  • FIG. 15 is a diagram schematically showing a conventional electrolysis apparatus 100 that is generally used for products using electrolysis technology.
  • An electrode pair including a first electrode 103 and a second electrode 104 is provided inside a resin casing 101.
  • a wiring 106 (pin) for applying a voltage is connected to the first electrode 103, and a wiring 107 (pin) for applying a voltage is connected to the second electrode 104.
  • one of the pins is welded to the electrode, and the other is threaded so that wiring from the power source can be connected.
  • the shape of the housing 101 can be devised so that liquid leakage can be prevented by using an O ring or the like, but it is omitted because it is not directly related to the present invention.
  • a supply port 108 for supplying the liquid to be processed between the electrodes and a discharge port 109 for discharging the electrolyzed liquid are provided.
  • the electrode pair is installed vertically and the liquid to be treated is supplied from below.
  • the casing 111 includes a water supply port 112 that can be connected to a pipe that can supply water pumped from a water supply or other water source, and a discharge port 113 that discharges electrolytic water.
  • a piping for supplying electrolytic water to the supply destination can be connected to the discharge port 113.
  • a switch 114 for turning on / off the apparatus is provided.
  • an indicator for displaying the operation status and other switches for performing various operations can be provided as appropriate, but they are omitted because they are not directly related to the present invention.
  • FIG. 17 is a diagram schematically showing the internal structure of the electrolyzed water generator 120 of FIG.
  • the water supply port 112 and the discharge port 113 are connected by a pipe 115, and an electromagnetic valve 116 that can be turned ON / OFF as necessary is provided between them.
  • an electromagnetic valve 116 that can be turned ON / OFF as necessary is provided between them.
  • In the middle of the pipe 115 there is a place spatially connected to the outlet of the electrolysis apparatus 100.
  • the inlet of the electrolyzer 100 is spatially connected to the stock solution tank 117 via a tube or the like, and a pump 118 for feeding the stock solution by a specified amount is provided between them.
  • the switch 114 When the switch 114 is turned on, the electromagnetic valve 116 is opened and water is supplied into the generator 120 from the water supply port 112 and discharged from the discharge port 113 through the pipe 115.
  • the pump 118 operates and the stock solution stored in the stock solution tank 117 is supplied to the electrolysis apparatus 100. Electric power is supplied to the electrolyzer 100 from a power source (not shown), and the stock solution is electrolyzed. High-concentration electrolyzed water generated by electrolysis is diluted to an appropriate concentration by water supplied to the pipe 115 and flowing through the pipe 115.
  • the diluted electrolyzed water is sent to the electrolyzed water supply point through a pipe such as a hose connected as appropriate from the discharge port 113.
  • a pipe such as a hose connected as appropriate from the discharge port 113.
  • An electrolyzer for producing hypochlorite having a plurality of bipolar unit electrolyzers wherein an electrolyzer for producing hypochlorite is provided with a cooling chamber at the inflow portion or the outflow portion of the electrolyte of the unit electrolyzer.
  • the electrolysis apparatus described in Patent Document 1 includes a plurality of electrode plates perpendicular to a horizontal plane, and is used so that the liquid to be treated is supplied from below and flows upward. .
  • a molten salt electrolytic cell in which an anode and a cathode are inclined in an electrolytic cell, a generated chlorine gas is transferred upward, and a generated zinc is transferred downward (see Patent Document 2).
  • the conventional electrolysis apparatus has a problem that the production efficiency of the electrolysis product is not sufficiently high.
  • This invention is made
  • the present invention includes an electrolysis unit, and the electrolysis unit includes a fluid flow path to be processed, at least one pair of electrolysis electrodes, an inflow port, and an outflow port, and the electrolysis electrode pair has a vertical direction.
  • An electrolysis apparatus is provided, wherein the electrolysis apparatus is provided so as to flow in a flow path between electrodes from a lower side toward an upper side and to flow out from the outflow port.
  • an electrolysis unit includes a fluid flow path to be processed, at least one pair of electrolysis electrodes, an inflow port, and an outflow port, and the electrolysis electrode pair includes: An upper electrode and a lower electrode arranged so as to face each other, and the fluid flow path to be treated flows through the inter-electrode flow path between the upper electrode and the lower electrode. Since it is provided so as to flow out from the outflow port, it is possible to generate an electrolysis product by electrolyzing the fluid by flowing the fluid through the fluid flow path and applying a voltage to the electrode pair for electrolysis. A fluid containing the product can be produced continuously.
  • the electrode pair for electrolysis is disposed so as to be inclined with respect to the vertical direction, and the fluid flow path to be treated is provided so that the fluid flows through the inter-electrode flow path from the lower side to the upper side. Therefore, the electrolytic product can be efficiently generated. This was verified by experiments conducted by the inventors. The reason why the electrolytic product can be generated efficiently is considered as follows.
  • gas is generated by the electrode reaction in the lower electrode, so that bubbles are generated on the lower electrode, and the bubbles can be floated toward the upper electrode so as to cross the fluid flow direction.
  • the fluid in the vicinity of the lower electrode and the fluid in the vicinity of the upper electrode can be stirred and mixed, and the electrode reaction in the upper electrode can be promoted. Further, since the fluid in the vicinity of the upstream of the lower electrode is promoted to move toward the upper electrode along with the movement of the bubbles, the ratio of the liquid component that has been subjected to the electrolytic treatment is reduced in the fluid in the vicinity of the downstream of the lower electrode. For this reason, the production
  • (A) (b) is a schematic sectional drawing of the electrolyzer of one Embodiment of this invention, (c) demonstrates the overlap of the upper electrode and lower electrode when the electrolyzer is seen from the perpendicular direction A.
  • (D) is a figure for demonstrating the overlap of an upper electrode and a lower electrode at the time of seeing an electrolysis apparatus from the direction B perpendicular
  • (A) (b) is a schematic sectional drawing of the electrolyzer of one Embodiment of this invention, (c) demonstrates the overlap of the upper electrode and lower electrode when the electrolyzer is seen from the perpendicular direction A.
  • (D) is a figure for demonstrating the overlap of an upper electrode and a lower electrode at the time of seeing an electrolysis apparatus from the direction B perpendicular
  • (A) is a schematic sectional drawing of the electrolyzer of one Embodiment of this invention
  • (b) is a figure for demonstrating the overlap of the upper electrode and lower electrode when the electrolyzer is seen from the perpendicular direction A.
  • (C) is a figure for demonstrating the overlap of an upper electrode and a lower electrode at the time of seeing an electrolysis apparatus from the direction B perpendicular
  • FIG. 1 It is a schematic sectional drawing of the electrolysis apparatus produced by the electrolysis experiment.
  • (A) is a schematic cross-sectional view of an electrolyzer according to an embodiment of the present invention, and (b) to (d) are schematic cross-sectional views of components of the electrolyzer.
  • (A) (b) is a schematic sectional drawing of the electrolyzer of one Embodiment of this invention. It is a schematic sectional drawing of the electrolysis apparatus of one Embodiment of this invention.
  • (A) is a schematic cross-sectional view of an electrolyzer according to an embodiment of the present invention, and (b) to (f) are schematic cross-sectional views of components of the electrolyzer.
  • (A) (b) is a schematic block diagram of the electrolyzer of one Embodiment of this invention. It is a schematic block diagram of the electrolysis apparatus of one Embodiment of this invention. It is a graph which shows the measurement result of an electrolysis experiment. It is a figure for demonstrating the flow of the fluid and bubble in a flow path between electrodes.
  • (A)-(c) is a schematic sectional drawing of the electrolysis apparatus produced by the electrolysis experiment.
  • (A) (b) is a schematic sectional drawing of the conventional electrolysis apparatus. It is a schematic perspective view of the conventional electrolyzed water generator. It is the figure which showed typically the internal structure of the conventional electrolyzed water generator. It is a graph which shows the measurement result of an electrolysis experiment. It is a schematic block diagram of the electrolysis apparatus produced by the electrolysis experiment.
  • (A)-(c) is a schematic sectional drawing of the electrolyzer of one Embodiment of this invention.
  • the electrolysis apparatus of the present invention includes an electrolysis unit, and the electrolysis unit includes a fluid flow path to be processed, at least one pair of electrolysis electrodes, an inflow port, and an outflow port, and the electrolysis electrode pair includes: And an upper electrode and a lower electrode that are disposed so as to be inclined with respect to the vertical direction and are opposed to each other, and the fluid flow path includes a fluid that has flowed in from the inflow port.
  • An inter-electrode flow path between the electrode and the lower electrode is provided so as to flow from the lower side to the upper side and to flow out from the outflow port.
  • the electrode pair for electrolysis is preferably arranged so that the inclination angle with respect to the vertical direction is larger than 0 degree and smaller than 50 degrees. According to such a configuration, the electrolysis efficiency of the electrolysis unit can be improved. This was verified by an electrolysis experiment conducted by the present inventors.
  • the fluid flow path to be processed is an upstream bent flow path close to the upstream end of the interelectrode flow path or a downstream bent flow path close to the downstream end of the interelectrode flow path. It is preferable to have.
  • the fluid flow path to be processed has an upstream bent flow path or a downstream bent flow path
  • the gas generated by the electrolytic reaction can be efficiently discharged from the inter-electrode flow path, so that the electrolytic efficiency is reduced due to gas retention. Can be suppressed.
  • the fluid flow path to be treated has the upstream bent flow path, the liquid flow in the fluid flow path to be treated can be disturbed.
  • the upper electrode is provided so as to be an anode and the lower electrode is provided so as to be a cathode. According to such a configuration, bubbles can be generated by the cathodic reaction at the lower electrode, and the electrolysis efficiency can be improved by the stirring / mixing effect of the bubbles.
  • the lower electrode preferably has an electrode surface having a larger area than the electrode surface of the upper electrode.
  • the aqueous solution of the substance having chlorine atoms is electrolyzed to produce hypochlorous acid, and the electrode surface of the upper electrode and the electrode surface of the lower electrode are approximately the same area,
  • chlorine gas bubbles are dissolved / reduced due to the agitation / mixing effect due to bubbles, and the reduction of the electrode effective area due to the bubbles is suppressed.
  • the effective area may be reduced. For this reason, the electrode effective area of the lower electrode becomes relatively small, which becomes a rate-determining factor for the electrolytic reaction, and the area of the upper electrode may not be effectively utilized.
  • the above phenomenon can be mitigated, the electrode area can be used effectively, and the electrolytic efficiency per unit area of the upper electrode can be improved.
  • electrolysis is already performed on the upstream side of the upper electrode in the vicinity.
  • chlorine gas can be efficiently converted into hypochlorous acid.
  • the hydrogen gas generated at the lower electrode can approach the vicinity of the upper electrode even if it floats from the vertical upward direction to the downstream side by the liquid flow rate.
  • the rate of conversion to chlorous acid increases.
  • the electric field wraps around the electrode projecting to the downstream side, or the oxidation of the bubbles directly contacting the electrode causes a slight reduction.
  • An increase in the proportion of chlorine gas converted to chloric acids can be expected.
  • the electrolysis apparatus of the present invention further includes a diluting section, wherein the fluid is an aqueous solution, and the electrode pair for electrolysis is such that hypochlorite ions are generated electrochemically from a chlorine-containing compound contained in the aqueous solution.
  • the aqueous solution at the outlet includes a hypochlorite ion of 4000 ppm or more by weight, and the dilution unit is provided to generate a diluted solution of the aqueous solution including the hypochlorite ion discharged from the outlet.
  • the diluted solution preferably has a pH of 7.5 or less.
  • the electrolysis unit is provided so that hypochlorite ions are generated electrochemically from the chlorine-containing compound, the upper electrode is provided as an anode, and the lower electrode is provided as a cathode. It is preferable to be provided. According to such a configuration, since the hydrogen gas bubbles generated by the cathode reaction at the lower electrode try to move near the upper electrode so as to cross the flow velocity direction, the liquid near the anode and the liquid near the cathode in the electrolysis unit. And stirring can be promoted.
  • D is the surface including the upper electrode
  • E is the surface including the lower electrode
  • the surface C is at the top
  • the surface E is at the bottom
  • the surface D is between the surfaces C and E.
  • the upper electrode and the lower electrode are disposed so as to be positioned. According to such a configuration, bubbles generated in the lower electrode can approach the vicinity of the upper electrode even if the bubbles are caused to flow from the vertically upward direction to the outlet side due to the flow velocity.
  • hypochlorous acid when hypochlorous acid is produced by electrolyzing an aqueous solution of a substance having a chlorine atom, hydrogen gas generated on the downstream side of the lower electrode floats from the vertical upward direction to the downstream side by the liquid flow rate. Since it can approach the upper electrode vicinity which is an anode, the ratio which can convert chlorine gas into hypochlorous acid increases.
  • the upper electrode is curved convexly toward the lower electrode, and the lower electrode is curved concavely toward the upper electrode. Furthermore, the curvature of the upper electrode is preferably smaller than the curvature of the lower electrode. According to such a configuration, bubbles such as chlorine gas generated in the upper electrode as the anode can be discharged from the center portion of the electrode to the end portion, and the reduction of the effective area of the electrode due to the bubbles can be suppressed and the center portion can be suppressed. Electrolytic efficiency can be improved.
  • bubbles such as hydrogen gas generated at the lower electrode which is the cathode
  • the agitation / mixing effect by the bubbles generated at the lower electrode is increased. be able to.
  • hypochlorous acid is produced by electrolysis
  • the conversion of chlorine gas to hypochlorous acid can be promoted by the stirring and mixing effect of the bubbles.
  • the bubbles of chlorine gas can be reduced, so that the reduction of the effective area of the electrode can be further suppressed, and the electrolysis efficiency can be further improved.
  • the bubble moves from the center to the end of the upper electrode to generate a flow velocity vector from the center to the end, and the flow speed at the center is faster than the conventional electrode unit structure. It is possible to suppress variation in the degree of electrolysis between the electrolytic solution flowing in the center and the electrolytic solution flowing in the end due to the slow flow rate. Furthermore, since air bubbles can be reduced in the central portion of the upper electrode compared to the end portion, the electrolytic efficiency is increased in the central portion where the flow velocity tends to be relatively fast. It is possible to suppress variation in the degree of electrolysis of the electrolyte flowing through the.
  • the electrolytic apparatus of the present invention it is preferable that at least a part of the upper electrode is a mesh electrode, and a space is provided on the side opposite to the lower electrode (hereinafter referred to as the back side) of the upper electrode. Furthermore, the electrolysis apparatus of the present invention preferably includes an electrode electrically connected to the upper electrode on at least a part of the wall surface of the space. According to such a configuration, since the bubbles on the upper electrode can be discharged to the back side, the surface of the upper electrode facing the lower electrode can be prevented from being covered with bubbles and the electrode effective area can be suppressed from being reduced. Efficiency can be improved.
  • hypochlorous acid when hypochlorous acid is generated by electrolysis, the hydrogen gas bubbles rising from the lower electrode are relatively less likely to be hindered by the chlorine gas bubbles, and the pH generated easily in the vicinity of the upper electrode is relatively low. Since it can contact a high aqueous solution, chlorine gas can be efficiently converted into hypochlorous acid.
  • it is possible to perform the electrolysis even with the electrode installed on the wall surface via the mesh gap. This can further increase the electrode effective area.
  • the lower electrode is preferably a mesh electrode. According to such a configuration, it is considered that a part of bubbles generated on the surface of the lower electrode grows so as to cover the mesh void as viewed from the upper electrode. As a result, the ratio of the electrode area that is covered with bubbles and becomes ineffective can be reduced as compared with an electrode having a smooth electrode surface. Further, by using a mesh electrode for at least one or both of the upper electrode and the lower electrode, the unevenness of the electrode surface becomes large, and it becomes difficult to make a laminar flow in the channel between the electrodes. As a result, vortex flow and turbulent flow are easily formed in the interelectrode flow path, and separation of bubbles from the electrode can be promoted.
  • hypochlorous acid when hypochlorous acid is generated by electrolysis, chlorine gas microbubbles with a large specific surface area before the bubbles grow large can be detached from the electrode and come into contact with an aqueous solution having a relatively low pH near the upper electrode.
  • the chlorine gas dissolves quickly and can be converted into hypochlorous acid.
  • the stirring of the electrolytic solution is promoted, the chlorine gas is dissolved and converted into hypochlorous acid in the electrolytic unit more efficiently.
  • the bubble guide is preferably a plate-like member separated from the upper electrode and the lower electrode, and the plate-like member is preferably inclined from a position parallel to the upper electrode and the lower electrode.
  • the plate-like member is preferably installed so as to be substantially perpendicular to the upper electrode and the lower electrode.
  • the bubble guide can prevent the bubbles from being combined and becoming larger, so that the solubility of the bubbles is improved.
  • This increases the probability that bubbles generated at the lower electrode come into contact with the electrolyzed liquid in the vicinity of the upper electrode, compared to when there is no bubble guide. Since not only the bubbles but also the electrolyzed water near the upper electrode or the lower electrode is affected by the turbulent flow generated by the bubble guide, the electrolyzed water near the upper electrode or the lower electrode is stirred as well. As a result, the diffusion rate control in the electrolytic reaction is greatly improved, and the dissolution of the bubbles is promoted by mixing and stirring the bubbles. As a result, the electrolytic reaction is comprehensively promoted, so that the electrolytic efficiency is improved.
  • the bubble guide is a columnar member separated from the upper electrode and the lower electrode, and the axis of the column of this member is preferably installed substantially parallel to the upper electrode and the lower electrode. . According to such a configuration, it is possible not to obstruct the movement of the bubbles and the flow of the liquid more than necessary, and it is possible to bring out the stirring effect of the bubbles and the liquid while minimizing the reduction of the effective electrode area. .
  • the electrolysis unit includes a first electrode holder to which the lower electrode is fixed, a second electrode holder to which the upper electrode is fixed, a spacer disposed between the first and second electrode holders,
  • the spacer is preferably provided so that at least a part of the spacer overlaps the upper electrode and the lower electrode when viewed from the direction in which the upper electrode and the lower electrode overlap.
  • the first or second electrode holder has a concave shape at least at the portion for fixing the electrode, and the distance (depth of the concave portion) between the surface for fixing the electrode and the surface of the spacer is larger than the thickness of the electrode for fixing. Things are preferable.
  • the agitation effect of bubbles and liquid can be brought out, and even if the electrode warps or the electrode is loosened for some reason, the possibility of contact between both electrodes is reduced. Can do. Thereby, both the efficiency and safety
  • the distance between the electrodes can be easily changed by changing the thickness of the spacer, it can be easily changed to various specifications according to the purpose, making it easy to share parts such as electrode holders. .
  • a projection is provided which protrudes from a part of the fluid flow path to be processed and from a plane parallel to the surface of the upper electrode or the lower electrode. It is preferable that it exists on the symmetry plane of the structure to form.
  • the flow velocity in the vicinity of the center of the channel between the electrodes, that is, in the vicinity of the center of the electrode is relatively high, so that the time for electrolysis of the electrolyte flowing through that portion is shortened. Since the flow velocity is relatively slow at the other end, the time for electrolysis of the electrolyte flowing through that portion becomes longer. As a result, the electrolytic solution is not electrolyzed uniformly, which causes a concentration unevenness.
  • the electrolysis conditions suitable for the electrolyte flowing through the central portion are set, the electrolyte flowing through the end portion may be electrolyzed more than necessary from the middle, or may not be electrolyzed at all and the area of the electrode may become invalid. If the electrolysis condition is set to an electrolysis condition suitable for the electrolyte flowing through the end portion, the electrolyte flowing through the center becomes insufficiently electrolyzed. In any case, it was not possible to perform electrolysis efficiently, but by providing a protrusion, it was possible to reduce the flow rate at the center and increase the flow rate at the end with a very simple structure. There is an advantage that it is possible to suppress or improve the efficiency of electrolysis.
  • the shape of the fluid flow path to be processed is such that the upper electrode, the lower electrode, the inlet, the outlet, and the upper electrode, the lower electrode, the inlet, the outlet, and the normal direction with respect to the cross section cut by a plane parallel to the electrode surface of the upper electrode or the lower electrode
  • the widths of the upper electrode and the lower electrode are relatively wide, and the widths of the inlet, the outlet, and the projection are relatively narrow. According to such a configuration, the uniformity of the flow rate can be improved, the concentration unevenness can be suppressed, and the electrolysis efficiency can be improved.
  • the cross-sectional area of the flow path near the outflow port is larger than the cross-sectional area of the inter-electrode flow path. According to such a configuration, it is possible to suppress variations in the flow velocity in the vicinity of the outlet and to easily discharge bubbles.
  • a stirring effect and a retention effect can be expected at a location where the cross-sectional area of the flow path becomes large, thereby reducing the chlorine gas to hypochlorous acid. Can be expected to promote conversion. Therefore, improvement in efficiency can be expected.
  • the electrolysis apparatus of the present invention it is preferable to have protrusions on both the upstream side and the downstream side of the interelectrode flow path.
  • the size of the upper and lower electrodes is particularly long in the direction of flow rate, for example, if there is a protrusion on the upstream side and not on the downstream side, the flow rate near the center is high again on the downstream side, and the flow rate is slow at the end A trend arises.
  • by providing protrusions on both the upstream side and the downstream side it is possible to suppress an increase in flow velocity variation.
  • the electrolysis unit includes an upper electrode and a lower electrode, an electrode holder that forms a flow path other than the flow path between the electrodes, and a protrusion, and at least a part of the protrusion includes an upper electrode, It is preferable that it is bonded to the lower electrode, the base material of these electrodes, or a member physically bonded to these electrodes, and also bonded to the electrode holder. According to such a configuration, since the upper electrode or the lower electrode can be fixed to the electrode holder by providing the protrusion, it is not necessary to fix the electrode separately. Therefore, the electrolysis apparatus of the present invention can be realized without complicating the configuration and structure.
  • the protrusion or the member including the protrusion is made of a conductive material, and at least a part of the member made of the conductive material is electrically connected to the upper electrode or the lower electrode. It is preferable.
  • the member made of the conductive material can fix the upper electrode or the lower electrode to the electrode holder or apply a voltage to the upper electrode or the lower electrode. This eliminates the need for a drawing line. Therefore, the configuration and structure are not complicated. Further, there is no need to retrofit electrode terminal lead-out components such as pins as in the conventional electrolysis electrode pair, and the number of components (pins) can be reduced and the number of man-hours for pin mounting can be reduced.
  • the electrolytic device of the present invention since there is no welding process, there is no failure in welding, and repair can be easily performed even if a failure occurs in the electrode terminal parts. If it is welded, it is necessary to peel off the weld and weld a new rod again or replace the entire electrode.
  • it is preferable that at least a portion of the surface of the protruding portion closest to the counter electrode is a nonconductor. According to such a structure, it can suppress that an electrochemical reaction advances on the surface of a projection part.
  • the member having the protrusion is preferably arranged in parallel to the normal direction to the main surface constituting the inter-electrode flow path in the electrode surface, and the electrode holder and the electrode are preferably connected by this member.
  • the first electrode holder to which the lower electrode is fixed and the second electrode holder to which the upper electrode is fixed have substantially the same shape and are arranged so as to be point-symmetric with each other.
  • a spacer is disposed between the first and second electrode holders, and at least a part of the spacer overlaps with the upper electrode and the lower electrode when viewed from the direction in which the upper electrode and the lower electrode overlap. According to such a configuration, even if the electrode warps or the electrode is loosened due to some cause, the possibility of contact of both electrodes can be reduced. Thereby, the safety
  • the spacer overlaps the edge portions of the upper electrode and the lower electrode when viewed from the direction in which the upper electrode and the lower electrode overlap. According to such a configuration, it is possible to suppress the occurrence of electrolysis at the electrode edge where electric field concentration is likely to occur and deterioration is likely to occur. As a result, the electrolysis can be stabilized and electrode wear can be suppressed to extend the life.
  • the electrolysis unit electrolyzes an aqueous solution of a compound containing chlorine atoms to generate hypochlorite ions and / or chlorine molecules corresponding to a concentration of 4000 ppm or more, and dilutes them to adjust pH7. It is preferable to provide the following hypochlorous acid water. In this case, the production efficiency of hypochlorous acid water can be remarkably improved by using the above means.
  • FIGS. 1A and 1B are schematic cross-sectional views of an electrolysis apparatus according to the first embodiment, respectively.
  • FIG. 1C shows the electrolysis apparatus shown in FIG.
  • FIG. 1D is a view of the electrolysis apparatus shown in FIG. 1A viewed from a direction B perpendicular to the main surface of the lower electrode. It is a figure for demonstrating the overlap of the upper electrode and lower electrode at the time.
  • the electrolysis apparatus 15 of the first embodiment includes an electrolysis unit 10, and the electrolysis unit 10 includes a fluid flow path 7 to be processed, at least one pair of electrodes for electrolysis 5, an inflow port 8, and an outflow port 9.
  • the electrode pair 5 for electrolysis is disposed so as to be inclined with respect to the vertical direction and includes an upper electrode 3 and a lower electrode 4 disposed so as to face each other.
  • the fluid flow path 7 to be processed is provided so that the generated electrode reaction proceeds, and the fluid flowing in from the inflow port 8 moves the interelectrode flow path 6 between the upper electrode 3 and the lower electrode 4 upward from the lower side. It is provided so that it may flow out of the flow outlet 9 toward the direction.
  • the plate-like upper electrode 3 and the plate-like lower electrode 4 are fixed to the housing 1 so as to face each other, and the upper electrode 3 and the lower electrode 4 are An interelectrode flow path 6 is formed therebetween.
  • the electrode pair 5 for electrolysis is arranged so as to be inclined with respect to the vertical direction, the upper electrode is the upper electrode 3 and the lower electrode is the lower electrode 4.
  • the electrolysis unit 10 is a device having the fluid flow path 7 to be processed and is a constituent unit of the electrolysis device 15.
  • the electrolysis apparatus 15 is configured by one electrolysis unit 10, but the electrolysis apparatus 15 may be configured by a plurality of electrolysis units 10.
  • the plurality of electrolysis units 10 may be combined so that the fluid flow paths 7 to be processed are in parallel, or may be combined so that the fluid flow paths 7 to be processed are in series.
  • the housing 1 is provided so that the fluid flow path 7 to be processed can be formed together with the upper electrode 3 and the lower electrode 4.
  • a material that is resistant to a fluid flowing in the fluid flow path 7 to be processed and a gas generated secondary by electrolysis can be used.
  • a resin such as a fluororesin, a vinyl chloride resin, a polypropylene resin, or an acrylic resin can be used as the material of the housing 1 in consideration of durability.
  • the housing 1 may have a tubular structure, or may have a structure in which a fluid flow path 7 to be processed is formed by combining a plurality of members. When the housing 1 has a tubular structure, the upper electrode 3 and the lower electrode 4 can be fixed on the inner wall surface of the tubular structure.
  • the fluid flow path 7 to be processed is formed by combining the first member to which the upper electrode 3 is fixed and the second member to which the lower electrode 4 is fixed. Also good.
  • the third member may be sandwiched between the first member and the second member.
  • the member constituting the housing 1 or the housing 1 may be an electrode holder for fixing the upper electrode 3 or the lower electrode 4.
  • the to-be-processed fluid flow path 7 is provided so that the fluid flowing in from the inflow port 8 flows through the interelectrode flow path 6 between the upper electrode 3 and the lower electrode 4 from the lower side to the upper side and flows out from the outflow port 9. It is done.
  • the inflow port 8 can be connected to a tank of electrolytic stock solution via a pump. As a result, the stock electrolyte solution in the tank can be flowed to the fluid flow path 7 to be treated, and electrolytic treatment can be performed.
  • the outflow port 9 can be connected to a tank for storing the fluid after the electrolytic treatment, a liquid feeding pipe to be sent to a location where the fluid after the electrolytic treatment is used, a dilution unit, and the like.
  • the gas generated in the upper electrode 3 or the lower electrode 4 can be efficiently discharged from the interelectrode flow path 6, and the gas is retained. It is possible to suppress a decrease in electrolysis efficiency due to.
  • the inflow port 8 can be provided below the lower end of the interelectrode flow path 6, and the outflow port 9 can be provided above the upper end of the interelectrode flow path 6. As a result, the gas generated in the upper electrode 3 or the lower electrode 4 can be efficiently discharged from the inter-electrode flow path 6, and a reduction in electrolytic efficiency due to gas retention can be suppressed.
  • the to-be-processed fluid flow path 7 includes a part of the housing 1 and the inter-electrode flow path 6. It is desirable that the inner wall surface of the fluid flow path 7 to be processed is composed of the surface of the electrode pair 5 for electrolysis as wide as possible and the surface of the casing 1 as narrow as possible. With such a configuration, the surface of the electrode on which the electrolytic reaction proceeds included in the inner wall surface of the fluid flow path 7 can be widened, and the surface that does not contribute to electrolysis can be reduced as much as possible. If the electrode surface is widened, a sufficient electrolytic reaction can proceed at a low current density, so that the electrode life of the electrode pair 5 for electrolysis can be extended and the electrolysis efficiency can be improved.
  • the internal volume of the electrolysis unit 10 can be reduced even with the same electrolysis capability, so that the starting characteristics of the electrolysis apparatus 15 can be improved.
  • the rise of the electrolyzed water concentration can be improved.
  • the electrode pair 5 for electrolysis is composed of an upper electrode 3 and a lower electrode 4.
  • the electrolysis unit 10 shown in FIG. 1 has one set of electrode pairs 5 for electrolysis, but may have a plurality of electrode pairs 5 for electrolysis.
  • the upper electrode 3 and the lower electrode 4 are disposed so that the main surface (electrode surface) of the upper electrode 3 and the main surface (electrode surface) of the lower electrode 4 face each other. Further, the upper electrode 3 and the lower electrode 4 are provided such that an interelectrode flow path 6 is formed between the main surface of the upper electrode 3 and the main surface of the lower electrode 4.
  • the upper electrode 3 and the lower electrode 4 can be provided so that the main surface of the upper electrode 3 and the main surface of the lower electrode 4 are substantially parallel.
  • the interelectrode flow path 6 becomes a part of the fluid flow path 7 to be processed.
  • the fluid flowing through the interelectrode flow path 6 can be subjected to electrolytic treatment, and a fluid containing an electrolytic product is generated.
  • the upper electrode 3 may be curved in a convex shape toward the lower electrode 4
  • the lower electrode 4 may be curved in a concave shape toward the upper electrode 3.
  • the curvature of the upper electrode 3 may be smaller than the curvature of the lower electrode 4.
  • the upper electrode 3 and the lower electrode 4 are connected to a wiring for applying a potential difference between the electrodes, and this wiring is connected to a power supply device.
  • This wiring may be a conductive member for fixing the upper electrode 3 or the lower electrode 4 to the housing 1.
  • the upper electrode 3 and the lower electrode 4 may be provided so that the upper electrode 3 serves as an anode and the lower electrode 4 serves as a cathode, or may be provided so that the upper electrode 3 serves as a cathode and the lower electrode 4 serves as an anode. .
  • the upper electrode 3 and the lower electrode 4 are provided so that an electrode reaction in which gas is generated in the lower electrode 4 proceeds. Thereby, an electrolysis product can be generated efficiently. Further, when an electrode reaction in which gas is generated in both the upper electrode 3 and the lower electrode 4 proceeds, the upper electrode 3 and the lower electrode 4 can be provided so that the amount of bubbles generated in the lower electrode 4 is increased.
  • the upper electrode 3 and the lower electrode 4 can be fixed to the housing 1.
  • the upper electrode 3 or the lower electrode 4 may be fixed to the housing 1 with a screw member, or may be fixed to the housing 1 with an adhesive. Further, the upper electrode 3 or the lower electrode 4 may be fixed on a plane or a curved surface of the housing 1 or may be fixed in a groove of the housing 1. In the electrolysis apparatus 10 shown in FIG. 1, the upper electrode 3 and the lower electrode 4 are provided in the groove of the housing 1 and are provided so as not to cause a step in the fluid flow path 7 to be processed.
  • the shape of the upper electrode 3 and the lower electrode 4 may be a flat plate shape or a curved plate shape. Further, the upper electrode 3 and the lower electrode 4 may be square or circular. Further, the upper electrode 3 and the lower electrode 4 may have substantially the same shape or different shapes.
  • the upper electrode 3 and the lower electrode 4 included in the electrolysis unit 10 shown in FIG. 1 are plate-shaped and rectangular, and have substantially the same shape. Moreover, the magnitude
  • the upper electrode 3 and the lower electrode 4 may have a mesh structure, a perforated structure, or a porous structure.
  • a space may be provided on the side (back side) opposite to the lower electrode 4 of the upper electrode 3.
  • An auxiliary electrode electrically connected to the upper electrode 3 may be provided on the wall surface of this space. Thereby, bubbles on the electrode surface of the upper electrode 3 can be discharged to the back surface side, and a reduction in effective electrode area can be suppressed. In addition, the electrode reaction can proceed on the auxiliary electrode, and the effective electrode area can be increased.
  • the upper electrode 3 and the lower electrode 4 are formed from a conductive material such as a metal material. Further, insoluble electrodes can be used for the upper electrode 3 and the lower electrode 4.
  • the upper electrode 3 and the lower electrode 4 may have a structure in which a catalyst such as Pt, Pd, Ir, or Ru is supported or coated on the surface thereof. This allows the electrolytic reaction to proceed efficiently.
  • the electrode serving as the cathode is an electrode containing Ti, Pt or other metal
  • the electrode serving as the anode among the upper electrode 3 or the lower electrode 4 is an electrode containing Ir or Ru, Pt or the like Insoluble electrode.
  • the upper electrode 3 and the lower electrode 4 are disposed so as to be inclined with respect to the vertical direction.
  • the upper electrode 3 and the lower electrode 4 are provided so that at least a part of the upper electrode 3 is positioned vertically above the lower electrode 4.
  • the upper electrode 3 and the lower electrode 4 can be arranged such that the inclination angle with respect to the vertical direction is larger than 0 degree and smaller than 50 degrees.
  • this inclination angle can be set to 5 degrees or more and 45 degrees or less, and can be set to 15 degrees or more and 32 degrees or less.
  • the tilt angle is the tilt angle of the surface (main surface, electrode surface) facing the lower electrode 4 of the upper electrode 3 or the tilt angle of the surface (main surface, electrode surface) facing the upper electrode 3 of the lower electrode 4. It is. It is preferable that the inclination angle of the upper electrode 3 and the inclination angle of the lower electrode 4 are substantially the same. As a result, the distance between the electrodes can be made substantially constant, and current concentration can be suppressed from occurring. Thus, by arrange
  • the upper electrode 3 and the lower electrode 4 are arranged so that the inclination angle is ⁇ . Further, as shown in FIG. 1D, the upper electrode 3 and the lower electrode 4 having substantially the same size are substantially overlapped on the entire surface when viewed from the direction B perpendicular to the main surface of the lower electrode 4. The upper electrode 3 and the lower electrode 4 are disposed. Further, as shown in FIG. 1C, the upper electrode 3 and the lower electrode 4 are arranged so that the upper electrode 3 and the lower electrode 4 overlap in the overlapping region 16 when viewed from the vertical direction A.
  • the electrolysis unit 10 is provided so that the fluid to be treated flows from the lower side to the upper side of the interelectrode flow path 6 so that an electrode reaction in which gas (bubbles 11) is generated in the lower electrode 4 proceeds. It has been.
  • bubbles 11 are generated on the lower electrode 4 by the electrode reaction in the lower electrode 4, and the bubbles 11 are formed on the upper electrode 3 so as to cross the fluid flow direction. Can be lifted up.
  • the fluid flow generated by the rising of the bubbles 11 can stir and mix the fluid in the vicinity of the lower electrode 4 and the fluid in the vicinity of the upper electrode 3, and promote the electrode reaction in the upper electrode 3.
  • the fluid near the upstream of the lower electrode 4 is promoted to move toward the upper electrode 3 along with the movement of the bubbles 11, the fluid near the downstream of the lower electrode 4 has a reduced proportion of liquid components that have been subjected to electrolytic treatment. To do. For this reason, the production
  • the electrolytic product produced by the electrode pair 5 for electrolysis can be hypochlorous acid, for example.
  • an aqueous solution of an alkali metal chloride is supplied from the inlet 8 to the fluid flow path 7 (interelectrode flow path 6), and a voltage is applied between the upper electrode 3 and the lower electrode 4 to Electrolytic reactions such as chemical reaction formulas (1) to (4) can be advanced, and a hypochlorite aqueous solution (electrolyzed water) can be produced.
  • a voltage can be applied so that the upper electrode 3 serves as an anode and the lower electrode 4 serves as a cathode.
  • FIGS. 2 (a) and 2 (b) are schematic sectional views of the electrolysis apparatus of the second embodiment, respectively.
  • FIG. 2 (c) is a view of the electrolysis apparatus shown in FIG.
  • FIG. 2D is a diagram for explaining the overlap between the upper electrode and the lower electrode when viewed from the direction B perpendicular to the main surface of the lower electrode. It is a figure for demonstrating the overlap of the upper electrode and lower electrode at the time.
  • the upper electrode 3 and the lower electrode 4 are disposed so that the upper electrode 3 and the lower electrode 4 substantially overlap each other when viewed from the direction B.
  • the upper electrode 3 is disposed so as to be positioned further upward.
  • the upper electrode 3 and the lower electrode 4 overlap in the overlapping region 17 when viewed from the direction B perpendicular to the main surface of the lower electrode 4, but are included in the upper electrode 3.
  • the upper region that does not overlap the lower electrode 4 does not overlap the lower region included in the lower electrode 4.
  • it is the cross section of the electrolysis unit 10 in the direction where the flow-path cross-sectional area of the flow path 6 between electrodes becomes the smallest, Comprising: The surface which does not contain the lower electrode 4 including the upper electrode 3.
  • the electrolyzer 15 of the second embodiment uses the lower electrode 4 as an anode and the upper electrode 3 as a cathode to electrolyze an aqueous solution of a substance having chlorine atoms to generate hypochlorous acid, it is generated at the lower electrode 4 Even if the chlorine gas that floats from the vertical upward direction to the downstream side by the liquid flow rate can approach the vicinity of the upper electrode 3 that is the cathode, the ratio that can be converted to hypochlorous acid increases.
  • FIG. 3A is a schematic cross-sectional view of an electrolysis apparatus according to a third embodiment
  • FIG. 3B is an upper view of the electrolysis apparatus shown in FIG.
  • FIG. 3C is a diagram for explaining the overlap between the electrode and the lower electrode
  • FIG. 3C is an upper electrode when the electrolysis apparatus shown in FIG. 3A is viewed from a direction B perpendicular to the electrode surface of the lower electrode. It is a figure for demonstrating the overlap with a lower electrode. 1 and 2, the electrode surface of the upper electrode 3 and the electrode surface of the lower electrode 4 have substantially the same size, but in the electrolysis device 15 of the third embodiment, The electrode surface of the lower electrode 4 is wider than the electrode surface of the upper electrode 3. Further, as shown in FIG.
  • the upper electrode 3 and the lower electrode 4 have a protrusion length D on the downstream side when the electrolysis apparatus 15 is viewed from the direction B perpendicular to the electrode surface of the lower electrode 4, and an upstream side.
  • the protrusion length is U
  • the lateral protrusion length is S
  • the upper electrode 3 and the lower electrode 4 can be provided so that the entire surface of the upper electrode 3 overlaps the lower electrode 4 when the electrolyzer 15 is viewed from the vertical direction A.
  • the electrode surface of the upper electrode 3 and the electrode surface of the lower electrode 4 are almost the same.
  • the area is the same, in the vicinity of the upper electrode 3, chlorine gas bubbles are dissolved / reduced by the agitation / mixing effect due to the bubbles, and the reduction of the electrode effective area due to the bubbles is suppressed.
  • the effective area of the electrode may be reduced by hydrogen gas bubbles.
  • the electrode effective area of the lower electrode 4 becomes relatively small, which becomes a rate-determining factor for the electrolytic reaction, and the area of the upper electrode 3 may not be used effectively.
  • the above phenomenon can be alleviated, the electrode area can be used effectively, and the electrolytic efficiency per unit area of the upper electrode 3 is improved. be able to.
  • the upstream side of the upper electrode 3 is already present.
  • the chlorine gas can be efficiently converted into hypochlorous acid.
  • the hydrogen gas generated in the lower electrode 4 can approach the vicinity of the upper electrode 3 even if it floats from the vertical upward direction to the downstream side by the amount of the liquid flow velocity.
  • the rate at which can be converted to hypochlorous acid increases.
  • the electric field wraps around the electrode projecting to the downstream side, or oxidation of the bubbles directly contacting the electrode causes An increase in the proportion of chlorine gas converted to chlorous acid can be expected.
  • FIG. 4 is a schematic sectional view of an electrolyzer according to a fourth embodiment.
  • the electrolysis apparatus 15 shown in FIGS. 1 to 3 has the straight fluid flow path 7 to be treated, but in the electrolysis apparatus 15 of the fourth embodiment, the fluid flow path 7 to be treated is an interelectrode flow path. 6 has an upstream bent flow path 25 close to the upstream end, or a downstream bent flow path 26 close to the downstream end of the interelectrode flow path 6.
  • the electrolyzer 15 may have both the upstream bent flow path 25 and the downstream bent flow path 26, or may have either one.
  • At least one of the inflow port 8 or the outflow port 9 can be provided so that the direction of the flow path near the inflow port 8 or the outflow port 9 is non-parallel to the direction of the interelectrode flow path 6.
  • the upstream bent flow path 25 or the downstream bent flow path 26 can be provided. With such a configuration, the liquid flow in the fluid flow path 7 to be processed can be disturbed.
  • the upstream bent flow path 25 in the vicinity of the electrode 5 for electrolysis, the influence of the turbulent flow generated in the bent flow path can be exerted on the interelectrode flow path 6.
  • the downstream bent flow path 26 is preferably provided so that bubbles generated by the electrode pair 5 for electrolysis can float to the outlet 9 by its buoyancy. As a result, the bubbles can be quickly discharged from the fluid flow path 7 to be treated, and a reduction in electrolytic efficiency due to the bubbles remaining can be suppressed.
  • FIG. 6A is a schematic cross-sectional view of an electrolyzer according to a fifth embodiment.
  • FIGS. 6B to 6D are schematic cross-sectional views of components of the electrolysis apparatus according to the fifth embodiment.
  • the electrolysis apparatus 15 of the fifth embodiment has an assembly-type electrolysis unit 10.
  • the electrolysis unit 10 is composed of three parts, two of which are the first electrode holder 31 to which the lower electrode 4 shown in FIG. 6B is fixed and the upper electrode shown in FIG. 6D. 2 is a second electrode holder 32 to which 3 is fixed, and the remaining one is arranged as a spacer 33 between the first and second electrode holders 31 and 32.
  • the spacer 33 overlaps the electrolysis electrode pair 5.
  • Protrusions 35 are provided on the upstream side and the downstream side of the interelectrode flow path 6, respectively.
  • an upstream bent flow path 25 and a downstream bent flow path 26 are provided.
  • the spacer 33 is provided so that the interelectrode flow path 6 is formed between the upper electrode 3 and the lower electrode 4.
  • the first and second electrode holders 31 and 32 have at least a concave portion for fixing the upper electrode 3 or the lower electrode 4, and a surface that fixes the upper electrode 3 or the lower electrode 4 and a surface that contacts the spacer 33.
  • the distance (the depth of the recess) is preferably larger than the thickness of the electrode to be fixed.
  • the stirring effect of bubbles and liquid can be extracted, and the possibility that the upper electrode 3 and the lower electrode 4 will come into contact with each other even if the electrode warps or the electrode is loosened due to any cause is reduced. Can do.
  • security of the electrolyzer 15 can be improved.
  • the material of the metal holders 31 and 32 can be, for example, a resin such as an acrylic resin or a vinyl chloride resin.
  • the bolt 41 for fixing the upper electrode 3 and the bolt 41 for fixing the lower electrode 4 are electrode terminals 45.
  • the material of the bolt 41 can be a metal material, for example, metal titanium.
  • FIG. 7 (a) and 7 (b) are schematic cross-sectional views for explaining the flow of fluid in the electrolysis device 15 as shown in FIG. 6 (a).
  • FIG. 7B is a schematic cross-sectional view of the electrolysis apparatus 15 taken along one-dot chain line FF in FIG.
  • the average velocity V1 at the center is high and the average velocity V2 near the end is low in the flow velocity in the flow path.
  • the amount of chemical change per unit volume due to electrolysis that is, the concentration k of the desired component generated by electrolysis, is substantially proportional to the time t during electrolysis and becomes k ⁇ t if other conditions are constant.
  • the density variation k1 ⁇ k2 L (1 / (V1 ⁇ v) ⁇ 1 / (V2 ⁇ v)), and the density variation becomes small as long as v satisfies V1 ⁇ V2> v.
  • FIG. 8 is a schematic cross-sectional view of an electrolyzer according to a sixth embodiment.
  • the electrolysis unit 10 included in the electrolysis apparatus 15 illustrated in FIG. 8 includes at least an electrode pair 5 for electrolysis and an electrode holder 30 that constitutes a flow path other than the inter-electrode flow path 6 and has a protrusion 35 (see FIG. 8).
  • at least a part of the electrode terminal 45) is bonded to the electrode pair 5 for electrolysis, the base material of the electrode pair 5 for electrolysis, or a member physically bonded to the electrode pair 5 for electrolysis,
  • the electrode holder 30 is also coupled. Such a coupling structure makes it possible to fix the electrode pair 5 for electrolysis to the electrode holder 30.
  • the configuration and structure are not complicated.
  • the above-described coupling structure can reinforce the fixation of the electrolysis electrode pair 5 to the electrode holder 30. Thereby, the reliability of the electrolysis unit 10 can be improved.
  • at least a part of the protrusion 35 or the member (electrode terminal 45 in FIG. 8) coupled to the protrusion 35 is made of a conductive material, and at least a part of the member is electrically connected to the electrode pair 5 for electrolysis. Can be connected.
  • the member having the protrusion 35 can be disposed in the normal direction of the main surface of the surface of the electrode pair 5 for electrolysis that constitutes the fluid flow path 7 to be treated, and can be connected to the electrode holder and the electrode.
  • the protrusion 35 and the electrode terminal 45 can be an integral member.
  • the electrode holder 30 and the electrode pair 5 for electrolysis have a hole suitable for the size of the electrode terminal 45 at a predetermined position.
  • a groove is cut at least at an appropriate position on the opposite side to the protruding portion 35.
  • the electrolysis electrode pair 5 can be fixed to the electrode holder 30 using a nut 42 suitable for this groove, and a voltage can be applied to the electrolysis electrode pair 5 from the outside of the electrode holder 30 through the electrode terminal 45.
  • the occurrence of liquid leakage can be suppressed by using an O-ring 47, a washer 48, and a spring washer 49 as necessary.
  • the metal holder 30 and the electrode terminal are combined. 45 may be joined.
  • the electrode pair 5 for electrolysis can be fixed to the electrode holder 30 without using a nut.
  • the electrode holder 30 and the electrode terminal 45 can be integrally formed.
  • the electrode pair 5 for electrolysis can be fixed to the electrode holder 30 and a voltage can be applied to the electrode pair 5 for electrolysis, so that a separate drawing line for applying a voltage to the electrode pair 5 for electrolysis is necessary. Disappears. Therefore, the configuration and structure are not complicated.
  • the electrolysis electrode pair 5 can be fixed to the electrode holder 30 or a voltage can be applied to the electrolysis electrode pair 5 by a very simple method.
  • the surface of the protrusion 35 at least the portion closest to the counter electrode can be made non-conductive.
  • a nonconductive film can be formed by oxidizing the surface of the protrusion 35.
  • the surface of the protrusion 35 may be coated with a resin or the like.
  • FIG. 9A is a schematic cross-sectional view of an electrolyzer according to a seventh embodiment.
  • FIGS. 9B to 9F are schematic sectional views of components of the electrolysis apparatus according to the seventh embodiment.
  • FIG. 9D is a schematic cross-sectional view of the spacer 33 taken along one-dot chain line GG in FIG. 9C
  • FIG. 9E is a spacer taken along one-dot chain line HH in FIG.
  • the electrolysis device 15 of the seventh embodiment has an assembly-type electrolysis unit 10.
  • the electrolysis unit 10 is composed of three parts, two of which are the first electrode holder 31 to which the lower electrode 4 shown in FIG. 9B is fixed and the upper electrode shown in FIG. 9F.
  • the electrolysis apparatus 15 shown in FIG. 9 the opening 36 of the spacer between electrodes is formed narrower than the electrolysis apparatus 15 shown in FIG.
  • the spacer 33 is disposed so that the spacer 33 overlaps the edge portion of the upper electrode 3 and the edge portion of the lower electrode 4 when viewed from the direction perpendicular to the electrode surface of the lower electrode 4.
  • FIGS. 10A and 10B are schematic configuration diagrams of an electrolysis apparatus according to an eighth embodiment, respectively.
  • the electrolysis apparatus 15 of the eighth embodiment includes the electrolysis unit 10 of the first to seventh embodiments, a stock solution tank 51, and a dilution unit 53.
  • the pipe 57 is indicated by an arrow including the direction in which the fluid in the pipe flows.
  • the electrolyzer 15 shown in FIG. 10A has a configuration that generates a dilute solution by injecting a solution electrolyzed by the electrolysis unit 10 into a pooled water 55 accumulated in a dilution tank 54 that is a dilution unit 53. Yes.
  • 10B has a configuration in which a solution electrolyzed by the electrolysis unit 10 and running water are mixed in the mixing unit 59 that is the dilution unit 53 to generate a diluted solution.
  • 10 (a) and 10 (b) wiring for supplying power to the electrode pair 5 for electrolysis in the electrolysis unit 10 and a liquid feed pump provided as necessary are not shown. According to such a structure, the dilution liquid containing an electrolysis product can be manufactured. Moreover, when producing
  • FIG. 11 is a schematic configuration diagram of an electrolyzer according to a ninth embodiment.
  • the electrolysis apparatus 15 of the ninth embodiment uses the conventional electrolyzed water shown in FIGS. 16 and 17 except that the electrolysis unit 10 is arranged so that the electrode pair 5 for electrolysis is inclined with respect to the vertical direction.
  • the configuration is the same as that of the generator 120.
  • the basic operation of the electrolyzer 15 of the ninth embodiment is the same as that of the conventional electrolyzed water generator 120.
  • the electromagnetic valve 66, the electrolysis unit 10, and the pump 68 are not operated at the same time as the switch 64 is turned on, but the electromagnetic valve 66 is opened at an appropriate timing and water is supplied from the water supply port 62 to the electrolyzer 15.
  • the liquid feed pump 68 is operated at an appropriate timing, and the electrolytic stock solution stored in the stock solution tank 67 is supplied to the electrolysis unit 10. Electric power is supplied to the electrolysis unit 10 from a power source (not shown) at an appropriate timing, and the stock solution is electrolyzed. High-concentration electrolyzed water generated by electrolysis is diluted to an appropriate concentration by water supplied to the pipe 65 and flowing through the pipe 65. The diluted electrolyzed water is sent to the electrolyzed water supply point through a pipe such as a hose connected as appropriate from the discharge port 63.
  • the electromagnetic valve 66 when it is desired to suppress the possibility that high-concentration electrolyzed water is discharged first, it is preferable to turn on the electromagnetic valve 66, the liquid feed pump 68, and the electrolysis unit 10 in this order.
  • a method such as turning on the electrolysis unit 10, the liquid feed pump 68, and the electromagnetic valve 66 in this order can be used. Even when the operation is stopped, when it is desired to rinse with electrolyzed water after using electrolyzed water, the electrolysis unit 10 and the liquid feed pump 68 are turned off, and the electromagnetic valve 66 is turned on for a specified time. It becomes possible to rinse.
  • the liquid feed pump 68 is turned on for a while after the electrolysis unit 10 is turned off to electrolyze the high concentration electrolyzed water in the electrolysis unit 10. It is also possible to dilute or almost replace with the stock solution. In this case, it is desirable that the electromagnetic valve 66 is also turned on. Needless to say, since the undiluted solution and water are necessary, it is of course desirable to design so as not to perform such an operation when frequently used repeatedly.
  • Experimental example 1 An electrolysis apparatus as shown in FIG. 1 was produced, and an electrolysis experiment was performed by changing the inclination angle of the electrolysis electrode pair 5 with respect to the vertical direction.
  • iridium oxide is sintered to an electrode made of a 1 mm thick titanium plate having a long side of 8 cm and a short side of 3 cm (referred to as a Ti electrode) and a 1 mm thick titanium plate having a long side of 8 cm and a short side of 3 cm.
  • An electrode coated by the method (referred to as an Ir-coated Ti electrode) was used.
  • the electrolytic electrode pair 5 was fixed to the acrylic resin casing 1 so that the Ti electrode and the Ir-coated Ti electrode were substantially parallel and the distance between the electrodes was in the range of 1 mm to 5 mm, thereby producing an electrolytic device. Further, the power supply device and the electrode pair 5 for electrolysis were connected so that the Ti electrode became a cathode and the Ir-coated Ti electrode became an anode. An electrolyzer produced by changing the installation angle so that the inclination angle of the electrode pair 5 for electrolysis with respect to the vertical direction is about ⁇ 50 degrees to about +50 degrees is installed, and 3 to 4% A sodium chloride aqueous solution was supplied from the lower side at a constant flow rate.
  • the tilt angle is 0 degree, and when the electrode pair for electrolysis is tilted so that the Ir-coated Ti electrode (anode) is on the upper side, the tilt angle is a positive angle, When the electrode pair for electrolysis is tilted so that the Ir-coated Ti electrode is on the lower side, the tilt angle is a negative angle. Then, a constant current of 5 A was supplied to the electrode pair 5 for electrolysis by the power supply device, and the sodium chloride aqueous solution was subjected to electrolytic treatment. The applied voltage was between about 4 and 5V. Moreover, the effective chlorine concentration (mg / L) of the aqueous solution after electrolytic treatment was measured.
  • the measurement result of the effective chlorine concentration is shown in FIG. According to this result, it was possible to increase the effective chlorine concentration of the aqueous solution after the electrolytic treatment by tilting the electrode pair 5 for electrolysis so that the Ir-coated Ti electrode as the anode is on the upper side. Specifically, when the electrode pair 5 for electrolysis is tilted in a range from about 5 degrees to about 45 degrees, the effective chlorine concentration is improved by about 5% compared to when the electrode pair 5 for electrolysis is set to be vertical. Moreover, when the electrode pair 5 for electrolysis was tilted in the range of about 15 degrees to about 32 degrees, the effective chlorine concentration was improved by about 10% compared to when the electrode pair 5 for electrolysis was made vertical.
  • the electrolyzer When the inclination of the electrode pair 5 for electrolysis was too large, the effective chlorine concentration was reduced to about the same as the effective chlorine concentration at the vertical (0 degree) at about 50 degrees. Therefore, it is preferable to install the electrolyzer so that the inclination angle of the electrolysis electrode pair 5 with respect to the vertical direction is larger than 0 degree and smaller than 50 degrees, and the inclination angle of the electrolysis electrode pair 5 is preferably 5 degrees to It is preferable to install the electrolyzer so as to be 45 degrees (about 5% improvement), more preferably 15 degrees to 32 degrees.
  • the effective chlorine concentration of the aqueous solution after the electrolytic treatment is increased by arranging the electrode pair 5 for electrolysis so that a part of the Ir-coated Ti electrode serving as the anode is positioned vertically above the Ti electrode serving as the cathode. It was found that the electrolysis efficiency could be improved.
  • the vertical (0 degree) may be the best angle depending on the electrolysis conditions
  • it is preferable that the anode is tilted to some extent so that the anode is upward.
  • the tilt is set in advance so that the effective chlorine concentration decreases little or increases when tilted to the same degree from the vertical (0 degree) to the anode side and the cathode side.
  • the optimum inclination changes depending on the structure of the electrolyzer, the composition of the aqueous solution to be electrolyzed, the amount of liquid to be fed, the electrolysis conditions, and the like, but as described above, vibration, vibration, inclination, etc. occur in a practical environment.
  • vibration, vibration, inclination, etc. occur in a practical environment.
  • a highly transparent acrylic resin was used for the casing 1 in order to observe the state of bubbles.
  • various aqueous solutions supplied to the electrolysis apparatus various electrolyzed substances generated by electrolysis, and generated gases
  • various materials can be used for the housing 1 if it is resistant to the above, and polypropylene or the like can also be used if the desired reliability can be ensured.
  • a vinyl chloride resin is generally the most preferable material for the housing 1 in terms of high resistance, workability, and low cost.
  • the aqueous solution near the cathode is promoted to move toward the anode along with the movement of the bubbles, so the aqueous solution near the cathode is effective for electrolysis because the proportion of the liquid component that has undergone electrolysis decreases.
  • FIG. 13 is a schematic diagram of the interelectrode flow path when the inclination angle of the electrode pair for electrolysis is 0 degree.
  • the direction of the aqueous solution flowing from the bottom to the top in the interelectrode flow path coincides with the direction in which bubbles generated by the electrolytic reaction on the electrode surface rise from the bottom to the top. . Therefore, as indicated by the arrows in FIG. 13, the aqueous solution and bubbles closer to the cathode and the aqueous solution and bubbles closer to the anode flow through the inter-electrode flow path in a relatively difficult state to be mixed.
  • the bubbles generated in the inclined inter-electrode flow path that is, in the aqueous solution having the slanting flux, act as a force to move upward by buoyancy.
  • the moving direction of the bubbles is not parallel to the direction in which the aqueous solution flows, and moves in the direction from the lower electrode (cathode) to the upper electrode (anode) in the upward direction from the direction of the aqueous solution flow.
  • the aqueous solution is also moved in the direction from the lower electrode (cathode) to the upper electrode (anode) as the bubble moves. This causes a flow in which the aqueous solution near the cathode moves to the vicinity of the anode.
  • the anode side product and the cathode side product are well mixed.
  • Bubbles generated at the anode, which is the lower electrode are chlorine gas and oxygen gas as in the chemical reaction formulas (1) and (3), but the chlorine gas is converted into water as in the chemical reaction formula (2). Almost dissolves to produce hypochlorous acid. Therefore, the amount of bubbles generated at the cathode as the lower electrode is smaller than the bubbles of H 2 gas generated at the cathode as the upper electrode. For this reason, the stirring effect by the bubble which generate
  • the inclination angle of the electrode pair for electrolysis is set to 0 degree, and the upper end of the Ir-coated Ti electrode as the anode 21 is set to the upper end of the Ti electrode as the cathode 22 as shown in FIG.
  • a sodium chloride aqueous solution was supplied from the lower side to the fluid flow path 7 to be treated of these electrolyzers, and a constant current of 5 A was supplied between the cathode 22 and the anode 21 to conduct an electrolysis experiment.
  • FIG. 14A when no bubbles are generated, the stirring and mixing effect due to the bubbles cannot be expected. Also, when bubbles are generated, if the amount of bubbles is the same on both sides, it can be considered that which electrode is placed upward is almost equivalent in terms of the effect of the bubbles.
  • the appearance is different. In the case of this experiment, the chlorine gas mainly generated from the anode 21 dissolves well in the aqueous solution, so the amount of bubbles is small, and the amount of bubbles in the cathode 22 where hydrogen gas is generated is larger.
  • FIGS. 14B and 14C schematically show this state.
  • Experimental example 2 As shown in FIG. 1, a “vertical” type electrolysis unit 10 having an inflow port 8 and an outflow port 9 in the flow direction of the inter-electrode flow channel 6 and upstream so that the outflow port 9 faces upward as shown in FIG.
  • the “lateral (up)” type electrolysis unit 10 provided with the side bent flow path 25 and the downstream bent flow path 26, and the upstream bent flow path 25 so that the outlet 9 faces downward as shown in FIG.
  • a “side-out (lower)” type electrolysis unit 10 provided with a downstream-side bent flow path 26 was produced, and an electrolysis experiment was conducted.
  • the electrolysis apparatus 15 was installed so that the inclination angle of the electrode pair 5 for electrolysis with respect to the vertical direction was about 23 degrees and about 45 degrees, and 3-4% sodium chloride aqueous solution was added to the fluid flow path 7 to be treated. Supplying at a constant flow rate from the lower side, electrolytic treatment was performed by the electrode pair 5 for electrolysis. Moreover, the effective chlorine concentration (ppm) of the aqueous solution after electrolytic treatment was measured. The other conditions are the same as in Experimental Example 1. The results of the electrolysis experiment are shown in Table 1. From Table 1, it is apparent that the electrolysis efficiency of the “horizontal (up)” type electrolyzer is high.
  • the reason for this is not clear, but it is more likely that the upstream flow path close to the upstream end of the interelectrode flow path is bent to some extent or the downstream flow path close to the downstream end is bent to some extent. Or the flow of bubbles may be randomized to improve electrolysis efficiency. If it is preferable that the flow of bubbles after the fluid bends be smooth, it is conceivable that the outlet-side channel, particularly the outlet-side channel, is in the vertical direction as shown in FIG. Considering the ease of mass production, a modification example in which the pipe portion 70 is set in the vertical direction as shown in FIGS. 20B and 20C is also conceivable.
  • FIG. 6A An electrolysis unit 10 as shown in FIG. 6A was prepared and an electrolysis experiment was conducted.
  • the produced electrolysis unit 10 is composed of three parts as shown in FIGS. 6B to 6D, and two of them are electrode holders 31 and 32 having the same shape and arranged so as to be point-symmetric with each other. The remaining one is a spacer 33, which is disposed between the two electrode holders, and at least a part of the spacer 33 overlaps the electrolysis electrode pair 5 when viewed from the direction in which the electrolysis electrode pair 5 overlaps. Further, in the produced electrolytic unit 10, a titanium bolt 41 having a protrusion 35 was used.
  • the electrode holders 31 and 32 and the spacer 33 were made of acrylic resin.
  • the upper electrode 3 serving as an anode an insoluble electrode for producing sodium hypochlorite manufactured by Daiso Engineering was used.
  • the lower electrode 4 serving as the cathode a Nilaco titanium plate was used.
  • the thickness of the spacer 33 was adjusted, and three members were assembled so that the distance between the electrodes was in the range of 1 mm to 5 mm.
  • the electrode holder or the like made of acrylic resin since the electrode holder or the like made of acrylic resin is used, the inside of the electrolysis unit 10 can be observed. However, it was made of acrylic that does not transmit short-wavelength light, especially UV. This is to minimize the influence of light. Therefore, it is preferable to use a material that does not transmit light at all in an actual product.
  • the electrode holders 31 and 32 and the spacer 33 were fixed using bolts 41 and nuts 42, and a washer, a spring washer and an O-ring (not shown). Although it can be disassembled in this experimental example, from the viewpoint of long-term reliability, it is preferable to prevent the electrolytic solution from leaking from the adhesive surface of the electrolytic unit 10 with a strong adhesive or the like. Further, by using a gasket having high chemical resistance and high airtightness as the spacer 33, it is possible to perform both thickness adjustment and sealing. Furthermore, in order to reduce the cost by mass production, the electrolytic unit 10 can be produced at a time by integral molding. For comparison, an electrolysis unit not provided with the protrusion 35 was also produced and an electrolysis experiment was conducted. Other configurations are the same as those of the electrolysis unit 10 described above.
  • Electrolysis was carried out while feeding a 3 to 4% NaCl aqueous solution at a rate of 5 to 80 ml / min to the fluid flow path 7 of the produced electrolysis unit 10, and the electrolysis unit 10 provided with the protrusions 35 was The electrolytic treatment could be performed with higher electrolysis efficiency than the electrolysis unit not provided with the protrusion 35.
  • Experimental Example 4 An electrolysis unit 10 as shown in FIG. 9A was prepared and an electrolysis experiment was conducted.
  • the produced electrolysis unit 10 is composed of components as shown in FIGS. 9B to 9F, and the size of the opening of the spacer 33 is narrower than that of the electrolysis unit 10 shown in FIG.
  • the spacer 33 is arranged so that the spacer 33 overlaps the edge portion of the upper electrode 3 and the edge portion of the lower electrode 4.
  • the electrolysis efficiency was not so different from that of Experimental Example 3.
  • the electrolysis unit 10 having the configuration of FIG.
  • the concentration of hypochlorous acid produced was high and the concentration fluctuation was small. Accordingly, the configuration shown in FIG. 9 dramatically improves the electrolysis efficiency and the stability of the generated substance concentration.
  • the reason for this is considered to be that, by adopting the configuration as shown in FIG. 9, the electrolytic reaction proceeds relatively uniformly in the electrode pair 5 for electrolysis and stirring is performed relatively uniformly.
  • the fluid flow path 7 to be treated is configured as shown in FIG. 9, the effect of stirring and uniformizing the fluid to be treated can be obtained even in a place other than the inter-electrode flow path 6. It is thought that the nature improved.
  • the manufactured diluted solution has a pH in the region of 6 to 8, and the hypochlorous acid concentration is 1000 ppm.
  • the chlorine gas concentration near the surface of the diluted solution was 0.5 ppm or less. Therefore, in the electrolysis apparatus 15 of this experimental example, the release of chlorine gas could be significantly suppressed as compared with the comparative example.
  • the chlorine gas generated by electrolysis can be efficiently dissolved in the aqueous solution in the electrolysis apparatus 15 of this experimental example, the time required for the hypochlorous acid concentration of the diluted solution to exceed 1000 ppm is significantly shortened.
  • Experimental Example 6 An electrolysis apparatus as shown in FIG. 19 was prepared, and an electrolysis experiment was performed by changing the inclination angle of the electrolysis electrode pair 5 with respect to the vertical direction in the same manner as in Experimental Example 1.
  • iridium oxide is sintered to an electrode made of a 1 mm thick titanium plate having a long side of 5 cm and a short side of 1 cm (referred to as a Ti electrode), and a 1 mm thick titanium plate having a long side of 5 cm and a short side of 1 cm.
  • An electrode coated by the method (referred to as an Ir-coated Ti electrode) was used.
  • the electrolytic electrode pair 5 was fixed to the acrylic resin casing 1 so that the Ti electrode and the Ir-coated Ti electrode were substantially parallel and the distance between the electrodes was in the range of 1 mm to 5 mm, thereby producing an electrolytic device. Further, the power supply device 72 and the electrode pair 5 for electrolysis were connected so that the Ti electrode became a cathode and the Ir-coated Ti electrode became an anode.
  • the electrode as in Experimental Example 1 forms a part of the flow path, and is not in the form of a closed flow path electrolysis unit in which the fluid to be processed is supplied in a substantially constant direction.
  • the so-called electrolytic cell 74 was installed with the installation angle changed so that the inclination angle of the electrode pair 5 for electrolysis with respect to the vertical direction was about ⁇ 60 degrees to about +60 degrees.
  • the electrolytic cell 74 was charged with 3 to 4% sodium chloride aqueous solution.
  • the tilt angle is 0 degree
  • the electrode pair 5 for electrolysis is tilted so that the Ir-coated Ti electrode (anode) is on the upper side, the tilt angle is a positive angle.
  • the tilt angle is a negative angle.
  • a constant current of 1 A was supplied to the electrode pair 5 for electrolysis by the power supply device 72 to electrolyze the sodium chloride aqueous solution.
  • the applied voltage was between about 4 and 5V.
  • the effective chlorine concentration (mg / L) of the aqueous solution after electrolytic treatment was measured.
  • the effective chlorine concentration of the aqueous solution after the electrolytic treatment could be increased by inclining the electrode pair 5 for electrolysis so that the Ir-covered Ti electrode as the anode was on the lower side, contrary to Experimental Example 1.
  • the electrolysis electrode pair 5 is tilted within a range of at least about ⁇ 60 degrees, the effective chlorine concentration is improved as compared with the case where the electrolysis electrode pair 5 is vertical.
  • the electrolysis electrode pair 5 is tilted in the range of about ⁇ 20 degrees to about ⁇ 45 degrees, the effective chlorine concentration is improved by about 5% compared to the case where the electrolysis electrode pair 5 is vertical.
  • the electrolysis electrode pair 5 is preferably installed so that the inclination angle of the electrolysis electrode pair 5 with respect to the vertical direction is larger than 0 degree and smaller than 60 degrees, and the inclination angle of the electrolysis electrode pair 5 is preferably It is preferable to install the electrode pair 5 for electrolysis in the electrolytic cell 74 so as to be 20 to 45 degrees (about 5% improvement).
  • the effective chlorine concentration of the aqueous solution after the electrolytic treatment is increased by arranging the electrode pair 5 for electrolysis so that a part of the Ir-coated Ti electrode serving as the anode is positioned vertically below the Ti electrode serving as the cathode. It was found that the electrolysis efficiency could be improved. There are cases where the short side is horizontal and the long side is horizontal as the direction of the electrode pair 5 for electrolysis. In both cases, the electrolysis efficiency is better when the electrode pair 5 is inclined so that the cathode side is up. Was good.
  • the electrolysis electrode pair 5 is inclined and disposed so that a part of the electrode anode is positioned vertically below the cathode. Efficiency is improved. The reason for this difference is not clear, but the following hypothesis can be considered.
  • H 2 is generated as in Experimental Example 1. Since the generated H 2 is relatively difficult to dissolve, most of it becomes bubbles.
  • the open area of the batch-type electrolytic cell 74 is large, particularly including the side surface, since the confinement effect is small, the average time for the presence of H 2 bubbles between the electrodes is shortened.
  • the efficiency of electrolysis is improved because the fresh electrolyte is naturally supplied by replacing the bubbles of 2 . Further, since the amount of the electrolyte to be naturally supplied is not particularly limited, the electrolyzed concentration between the electrodes, here, the concentration of hypochlorous acid is kept at a relatively low concentration. Chlorine gas generated at the anode and not converted into hypochlorous acid rises by buoyancy and moves to the cathode side. At this time, the alkali solution near the cathode is slower in moving speed than H 2 and chlorine gas bubbles, so the chance of contact with the chlorine gas moving from the anode side increases, and the chlorine gas hypochlorous acid. Conversion to etc. is promoted.
  • the generated H 2 bubbles move toward the anode side due to the buoyancy, and the H 2 bubbles are filled between the electrodes, and in some cases, adhere to and stay on the anode side, and the anode becomes the electrolyte.
  • the contact area is significantly reduced.
  • the angle was 80 degrees or more, most of the anode surface was covered with H 2 bubbles, and the electrolytic efficiency was remarkably reduced. As described above, it is considered that the electrolytic efficiency is lowered due to a decrease in the amount of the electrolyte between the electrodes, a reduction in the effective electrode area due to bubbles, an inhibition of the inflow of fresh electrolyte, and the like.
  • the aqueous solution near the anode and the chlorine gas generated at the anode flow out from between the electrodes to the open surface such as the side surface so as to be pushed out by H 2 bubbles, the aqueous solution near the cathode Stirring with the aqueous solution in the vicinity of the anode is not promoted, and conversion of chlorine gas to hypochlorous acid is not promoted. In some cases, chlorine gas is released from the electrolyte as it is into the space. Conceivable.
  • the difference is that the bubbles of H 2 are held between the electrodes regardless of the inclination, and the supply amount of the electrolyte is limited.
  • the closed electrolysis unit in such a state when the cathode side is turned up, the desorption of H 2 from the cathode is delayed, so that the effective electrode area of the cathode is reduced due to the coating effect of H 2 and the electrolyte near the cathode surface approaches. It is thought that the electrolysis efficiency is lowered because it is hindered.
  • the concentration of the electrolyzed substance that is, the concentration of hypochlorous acid in this experimental example
  • the electrolysis efficiency decreases.
  • at least part of the chlorine gas generated at the anode is not converted into hypochlorous acid in the electrolysis unit, but is discharged from the outlet, and even converted into hypochlorous acid by contact with water after the dilution section.
  • the increase in the concentration of hypochlorous acid in the electrolysis unit is suppressed and the electrolysis efficiency is improved.
  • the conditions for improving the electrolytic efficiency differ depending on the case.
  • the electrolysis unit includes an inlet of the substance to be electrolyzed and an outlet of the substance generated by electrolysis and the unelectrolyzed substance, and (iii) means for forcibly supplying the substance to be electrolyzed from the inlet or forced from the outlet
  • it is considered to be a structure having a means for sucking a substance generated by electrolysis and a non-electrolytic substance, or both.
  • the pump is pumped into the inlet, or the pump is sucked from the outlet, or the dilution part and its surroundings are sucked from the outlet as a structure in which a venturi effect is generated, or a tank is provided. It is possible to use a method such as providing it above and feeding it by gravity. It is preferable to provide a pump that can realize liquid feeding most stably. If a certain degree of variation is allowed, it is preferable to provide a structure that uses the Venturi effect or gravity without using a pump, because the energy for operating the pump becomes unnecessary, which saves energy and reduces pump costs. Of course, any combination or all of the pump, the venturi effect and gravity can be used. For example, in Experimental Example 1, a structure in which a tube pump is used to supply a constant amount as much as possible is employed.
  • the electrode pair for electrolysis When the electrode pair for electrolysis is provided in an electrolyzed material that is substantially stored, and there is no means for forcibly supplying or sucking the electrolyzed material between the electrodes, the anode is positioned below the cathode. Thus, it is considered that the electrode pair is preferably inclined. In the case of this structure, the electrolyte is passively supplied as the bubbles rise. In addition, chlorine gas that has not been converted to hypochlorous acid is easily released into the gas phase in a shorter time than a closed electrolysis unit. The closed-system electrolysis unit suppresses the release to the gas phase because the amount of the supplied electrolyte is limited, so that it is reduced to hypochlorous acid by the confinement effect in the electrolysis unit and the stirring effect by H 2 bubbles.
  • Electrode holder 31 First electrode holder 32: Second electrode holder 33: Spacer 35: Projection 36: Opening of spacer 37: Groove of electrode holder 41: Bolt 42: Nut 43: Bolt hole 45: Electrode terminal 47: O Ring 48: Washer 49: Spring washer 51: Electrolysis stock solution tank 52: Electrolysis stock solution 53: Dilution section 54: Dilution tank 55: Reservoir water 57: Piping 9: Mixing unit 61: Housing 62: Water supply port 63: Discharge port 64: Switch 65: Piping 66: Solenoi

Abstract

L'invention concerne un dispositif d'électrolyse caractérisé en ce que : le dispositif est pourvu d'une unité d'électrolyse ; l'unité d'électrolyse est pourvue d'un trajet d'écoulement pour un fluide devant être traité, d'au moins une paire d'électrodes d'électrolyse, d'une ouverture d'entrée, et d'une ouverture de sortie ; la paire d'électrodes d'électrolyse est disposée de manière à être inclinée par rapport à la direction verticale et comprend une électrode supérieure et une électrode inférieure disposées de façon à se trouver en face l'une de l'autre ; et le trajet d'écoulement pour le fluide devant être traité est fourni de telle sorte que le fluide s'écoulant à partir de l'ouverture d'entrée s'écoule d'un côté inférieur à un côté supérieur d'un trajet d'écoulement inter-électrodes entre l'électrode supérieure et l'électrode inférieure et s'écoule hors de l'ouverture de sortie.
PCT/JP2015/052357 2014-07-25 2015-01-28 Dispositif d'électrolyse WO2016013234A1 (fr)

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