WO2016013234A1

WO2016013234A1 - Electrolysis device

Info

Publication number: WO2016013234A1
Application number: PCT/JP2015/052357
Authority: WO
Inventors: 洗　暢俊; 坂本　泰宏; 信広林
Original assignee: シャープ株式会社
Priority date: 2014-07-25
Filing date: 2015-01-28
Publication date: 2016-01-28
Also published as: US20170145571A1; JP5887385B2; JP2016029204A; CN106661742A

Abstract

This electrolysis device is characterized in that: the device is provided with an electrolysis unit; the electrolysis unit is provided with a flow path for a fluid to be processed, at least one electrolysis electrode pair, an inflow opening, and an outflow opening; the electrolysis electrode pair is disposed so as to be inclined to the vertical direction and includes an upper electrode and a lower electrode disposed so as to face each other; and the flow path for the fluid to be processed is provided such that fluid flowing in from the inflow opening flows from a lower side to an upper side of an inter-electrode flow path between the upper electrode and lower electrode and flows out of the outflow opening.

Description

Electrolyzer

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. For example, 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. 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. For example, 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.

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. However, since 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.
In contrast, 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. For this reason, this method is utilized in the field which uses hypochlorite aqueous solution. Moreover, the 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. For this reason, even in factories where liquid chlorine storage facilities have been used so far and chlorine gas has been used, or in the factories where concentrated hypochlorite aqueous solutions have been stored and hypochlorite aqueous solutions have been used, Production of hypochlorite aqueous solution by decomposition is performed.

In the method of producing hypochlorite by electrolysis of an aqueous solution of alkali metal chloride, 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)
In addition, when 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 | generated by a reverse reaction.

However, if 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. As 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. However, if the residence time is lengthened, the production amount per unit time is reduced, and if a multistage electrode is used, the productivity is lowered and the price is increased. Also, in these methods, a large amount of hydrogen gas is generated and the contact area between the electrolyte and the electrode is reduced due to the adhesion of bubbles, the production efficiency of the electrolytic product is reduced by shielding the electric field, etc. There is a problem such as a variation in the density.
Since an acidic aqueous solution having a small hydrogen ion index (pH) has sterilizing properties, it is conceivable to produce a hypochlorite aqueous solution having a relatively low hypochlorite concentration and a low pH. This makes it possible to produce a hypochlorite aqueous solution having sufficient sterilization properties while suppressing necessary power consumption. However, an acidic hypochlorite aqueous solution has a drawback that chlorine gas is easily generated in addition to hydrogen gas.

A conventional apparatus for producing a hypochlorite aqueous solution by electrolysis will be described with reference to FIGS.
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. Typically, one of the pins is welded to the electrode, and the other is threaded so that wiring from the power source can be connected. As appropriate, 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. Usually, the electrode pair is installed vertically and the liquid to be treated is supplied from below.

With such a configuration, when gas is generated by the electrolytic reaction and bubbles are generated on the electrode surface, the bubbles can be easily removed from the electrode surface by the buoyancy of the bubbles and the flow of the liquid to be processed. It is possible to suppress a decrease in the electrode surface where the progress of. However, in such a configuration, the flow rate of the electrolyte near the center of the inter-electrode flow path is high, and the flow rate of the electrolyte near the end is slow. For this reason, there is a problem in that the time for electrolysis varies depending on the flow path, and the production efficiency of the electrolysis product decreases.

As an example of the applied product of the electrolysis apparatus, it is desired that the electrolysis apparatus is made as compact as possible and used in the electrolyzed water generator 120 as shown in FIG. 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. In addition, 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. 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.

Next, the basic operation of the electrolyzed water generator 120 will be described. 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. In addition, 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. When the switch 114 is turned off, the power supply to the solenoid valve 116, the pump 118, and the electrolyzer 100 is cut off and the operation is stopped.

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. Is known (see Patent Document 1). In this method, it is possible to prevent the generated bubbles from rising and accumulating in the upper part of the electrolysis unit and the electrode upper area from being immersed in the electrolytic solution, thereby reducing the electrode effective area. The electrolysis apparatus described in Patent Document 1 (referred to as an electrolytic cell 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. .
There is also known 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).

Japanese Patent Laid-Open No. 6-200393 JP 2003-328173 A

However, the conventional electrolysis apparatus has a problem that the production efficiency of the electrolysis product is not sufficiently high.
This invention is made | formed in view of such a situation, and provides the electrolyzer which can produce | generate an electrolysis product efficiently.

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 upper electrode and a lower electrode arranged so as to be inclined with respect to each other, and the fluid flow path to be treated includes a fluid that flows in from the inlet and the upper electrode and the lower electrode. 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.

According to the present invention, an electrolysis unit is provided, 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: 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.
According to the present invention, 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.
In the electrolysis apparatus of the present invention, 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. By the fluid flow generated by the rising of the bubbles, 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 | generation efficiency of an electrolysis product can be made high.

(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 | vertical to the main surface of a lower electrode. (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 | vertical to the main surface of a lower electrode. (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 | vertical to the main surface of a lower electrode. It is a schematic sectional drawing of the electrolysis apparatus of one Embodiment of this invention. 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.

In the electrolysis apparatus of the present invention, 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.
In the electrolysis apparatus of the present invention, 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.
Since 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.
In addition, since 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. By providing the bent channel near the electrodes, the influence of the turbulent flow generated in the bent channel extends to the inter-electrode channel. As a result, a sufficient stirring effect can be provided from the vicinity of the inlet of the inter-electrode flow path where there are not so many bubbles, so that the diffusion of the substance near the electrode surface can be promoted and the electrolysis efficiency can be improved.
In addition, since the fluid flow path to be processed has the downstream bent flow path, even if there is a gas that cannot be sufficiently dissolved in the inter-electrode flow path, stirring can be performed again in the bent flow path. For example, when electrolyzing an aqueous solution of a substance having a chlorine atom to produce hypochlorous acid, depending on conditions, chlorine gas may not be sufficiently dissolved in the aqueous solution, and the production efficiency of hypochlorous acid may be reduced. With such a configuration, dissolution of chlorine gas in an aqueous solution and conversion to hypochlorous acid can be promoted, so that substantial electrolytic efficiency can be improved.

In the electrolysis apparatus of the present invention, it is preferable that 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.
In the electrolytic apparatus of the present invention, the lower electrode preferably has an electrode surface having a larger area than the electrode surface of the upper electrode.
When the lower electrode is the cathode and the upper electrode is the anode, 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, In the vicinity of the upper electrode, 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.
By increasing the area of the electrode surface of the lower electrode compared to the upper electrode, 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. .
Further, with the above configuration, when hydrogen gas bubbles generated upstream of the lower electrode reach the vicinity of the upper electrode that works as a vertically upward anode, electrolysis is already performed on the upstream side of the upper electrode in the vicinity. In addition, since it can come into contact with an aqueous solution having a lowered pH, chlorine gas can be efficiently converted into hypochlorous acid.
Further, with the above configuration, 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. In particular, when hydrogen gas is generated frequently, even if the downstream side of the upper electrode is blocked by air bubbles and the electric field is shielded, 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.
According to such a configuration, electrolyzed water containing hypochlorite ions, suppressing release of chlorine gas, and having a pH of 7.5 or less can be produced with high electrolysis efficiency.
In the electrolysis apparatus of the present invention, 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. In addition, as the hydrogen gas bubbles move to the vicinity of the anode, alkaline water near the cathode is carried to the vicinity of the anode, and the chlorine gas generated by the anodic reaction comes into contact with the aqueous solution close to the alkali. Conversion to chloric acids and the like can be promoted.

In the electrolysis apparatus of the present invention, the cross section of the electrolysis unit in the direction in which the cross-sectional area of the inter-electrode flow path becomes the smallest, and the surface including the upper electrode and not including the lower electrode is defined as C, both the upper electrode and the lower electrode. Where D is the surface including the upper electrode, and E is the surface including the lower electrode, the surface C is at the top, the surface E is at the bottom, and the surface D is between the surfaces C and E. It is preferable that 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. For example, 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.

In the electrolysis apparatus of the present invention, it is preferable that 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. In addition, since bubbles such as hydrogen gas generated at the lower electrode, which is the cathode, can quickly move to the vicinity of the upper electrode without being obstructed by bubbles such as chlorine gas, the agitation / mixing effect by the bubbles generated at the lower electrode is increased. be able to. When 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. As a result, 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.
In addition, 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.

In 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. In addition, 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. In addition, by adopting the above-described configuration, 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.

In the electrolysis apparatus of the present invention, 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. In addition, 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. In addition, since the stirring of the electrolytic solution is promoted, the chlorine gas is dissolved and converted into hypochlorous acid in the electrolytic unit more efficiently.

In the electrolysis apparatus of the present invention, it is preferable to provide a bubble guide between the upper electrode and the lower electrode. 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.
According to such a configuration, after a part of the bubbles generated on the surface of the lower electrode rises to the middle, the path is directly or indirectly on the liquid flow changed by the bubble guide or indirectly by the bubble guide. Be changed. This makes the bubble trajectory more complex than when there is no bubble guide. Further, the electrolyte solution is stirred by the turbulent flow generated behind the bubble guide. In addition, 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.

In the electrolytic apparatus of the present invention, 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. .
In the electrolysis apparatus according to the present invention, 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. Further, 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.
According to such a configuration, 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 | security of an electrolyzer can be improved. In addition, since 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. .

In the electrolysis apparatus of the present invention, 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.
In the conventional structure, 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.
Also, if 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.

In the electrolytic apparatus of the present invention, 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 When the projections are projected, it is preferable that 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.
In the electrolysis apparatus of the present invention, it is preferable that 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. In addition, for example, in the production of hypochlorous acid, even if unconverted chlorine gas is generated, 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.

In 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.
When 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. In such a case, by providing protrusions on both the upstream side and the downstream side, it is possible to suppress an increase in flow velocity variation.
In the electrolysis apparatus of the present invention, 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.

In the electrolytic device of the present invention, at least a part of 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.
According to such a configuration, 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. As another method of drawing out the electrode terminals, there is a method in which ears for terminals are attached to the electrodes in advance. However, a wasteful material is generated in the punching, and a retrofitting process is generated in the retrofitting. In addition, it is difficult to use an inexpensive O-ring for sealing the leakage of the electrolyte from the drawer, but according to the present invention, such waste and processes do not occur. Furthermore, there is a method of drawing out the electrode terminal on the back side of the electrode, but in the conventional electrode, a rod is welded on the back side. Although it is possible to employ welding in the present invention, the electrodes can be fixed and the electrode terminals can be pulled out without using welding. Accordingly, 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.
In the electrolytic device of the present invention, 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.
In the electrolysis apparatus of the present invention, 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.
Thereby, it is possible to fix the upper electrode or the lower electrode to the electrode holder and to apply a voltage to the upper electrode and the lower electrode by a very simple method.

In the electrolysis apparatus of the present invention, 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. Preferably, 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 | security of an electrolysis apparatus can be improved. In addition, since 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. .
In the electrolysis apparatus of the present invention, it is preferable that 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.
In the electrolysis apparatus of the present invention, 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.

Hereinafter, an embodiment of the present invention will be described with reference to the drawings. The configurations shown in the drawings and the following description are merely examples, and the scope of the present invention is not limited to those shown in the drawings and the following description.

First Embodiment 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.

In the electrolysis apparatus 15 (electrolysis unit 10) of the first embodiment, 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. When 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. In FIG. 1, 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. As the material of the housing 1, 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. Specifically, 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. When the housing 1 has a structure in which a plurality of members are combined, 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. In this case, the third member may be sandwiched between the first member and the second member. Further, 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. Moreover, 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.
Further, since the fluid flows from the lower side to the upper side of the interelectrode flow path 6, 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. Further, 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. Further, if the surface that does not contribute to electrolysis is narrowed, 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. When producing electrolyzed water by the electrolyzer 15, 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. With such a configuration, by applying a voltage between the upper electrode 3 and the lower electrode 4, the fluid flowing through the interelectrode flow path 6 can be subjected to electrolytic treatment, and a fluid containing an electrolytic product is generated. Can do.
Further, the upper electrode 3 may be curved in a convex shape toward the lower electrode 4, and the lower electrode 4 may be curved in a concave shape toward the upper electrode 3. Furthermore, 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 | size of the upper electrode 3 and the lower electrode 4 can be made into 8 cm of long sides, and 3 cm of short sides, for example.
The upper electrode 3 and the lower electrode 4 may have a mesh structure, a perforated structure, or a porous structure.
Further, when at least a part of the upper electrode 3 has a mesh structure or a perforated 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. Further, 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.
For example, of the upper electrode 3 and the lower electrode 4, the electrode serving as the cathode is an electrode containing Ti, Pt or other metal, and 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 (electrolytic electrode pair 5) 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.
Further, 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. Moreover, 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 | positioning the electrode pair 5 for electrolysis, electrolysis efficiency can be improved.

In the electrolysis unit 10 shown in FIG. 1, the upper electrode 3 and the lower electrode 4 are arranged so that the inclination angle is θ. 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.
In such an electrolysis unit 10, as shown in FIG. 1B, 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. Further, since 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 | generation efficiency of an electrolysis product can be made high.

The electrolytic product produced by the electrode pair 5 for electrolysis can be hypochlorous acid, for example. In this case, 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.
In this case, a voltage can be applied so that the upper electrode 3 serves as an anode and the lower electrode 4 serves as a cathode. As a result, H ₂ gas bubbles can be generated on the lower electrode 4, and the aqueous solution can be stirred and mixed by the rising of the bubbles, thereby improving the generation efficiency of hypochlorous acid. Moreover, since it can suppress that the aqueous solution of the anode vicinity becomes strong acidity, the reaction rate of said chemical reaction formula (2) can be made quick. For this reason, the production | generation efficiency of hypochlorous acid can be improved.

Second Embodiment 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.
In the electrolysis apparatus shown in FIG. 1, 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. In the electrolysis apparatus 15 of the form, the upper electrode 3 is disposed so as to be positioned further upward. Specifically, as shown in FIG. 2D, 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.
Moreover, in the electrolysis apparatus 15 of 2nd Embodiment, 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. When C is a surface including both the upper electrode 3 and the lower electrode 4 and D is a surface including the lower electrode but not the upper electrode 3, the surface C is at the top and the surface E is at the bottom. The upper electrode 3 and the lower electrode 4 are arranged so that the surface D is located between the surface C and the surface E.
With such a configuration, the overlapping region 16 where the upper electrode 3 and the lower electrode 4 overlap when viewed from the vertical direction A as shown in FIG.

In such an electrolysis unit 10, as shown in FIG. 2B, bubbles 11 are generated by the electrode reaction in the lower electrode 4, and the bubbles 11 are floated toward the upper electrode 3 so as to cross the fluid flow direction. Can do. In addition, since the overlapping region 16 is wide as shown in FIG. 2C, the probability that the bubbles 11 generated in the lower electrode 4 rise and approach the upper electrode 3 can be increased. Moreover, even if the bubble 11 generated by the lower electrode 4 floats due to the flow of the fluid flow path 7 to be processed, the bubble 11 can be brought close to the upper electrode 3 with high probability. For this reason, the stirring / mixing effect by the bubbles 11 can be increased, and the electrode reaction in the upper electrode 3 can be more effectively promoted. For this reason, the production | generation efficiency of an electrolysis product can be made high.

For example, when 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.

Third Embodiment FIG. 3A is a schematic cross-sectional view of an electrolysis apparatus according to a third embodiment, and 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, and 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. 3C, 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. When the protrusion length is U and the lateral protrusion length is S, it can be provided so as to satisfy D> U ≧ S. 3B, 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.

For example, when the lower electrode 4 is used as a cathode and the upper electrode 3 is used as an anode and an aqueous solution of a substance having chlorine atoms is electrolyzed to generate hypochlorous acid, the electrode surface of the upper electrode 3 and the electrode surface of the lower electrode 4 are almost the same. When 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. In some cases, the effective area of the electrode may be reduced by hydrogen gas bubbles. For this reason, 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.
By increasing the area of the electrode surface of the lower electrode 4 as compared with the upper electrode 3, 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.
Further, with the above configuration, when the hydrogen gas bubbles generated on the upstream side of the lower electrode 4 reach the vicinity of the upper electrode 3 acting as the vertically upper anode, in the vicinity thereof, the upstream side of the upper electrode 3 is already present. Since it is possible to come into contact with the aqueous solution having a lowered pH, the chlorine gas can be efficiently converted into hypochlorous acid.
Further, with the above configuration, 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. In particular, when the generation of hydrogen gas is large, even if the downstream side of the upper electrode 3 is blocked by air bubbles and the electric field is shielded, 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.

Fourth Embodiment 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.
For example, 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. . Thus, 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.
By providing 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. As a result, a sufficient stirring effect can be provided from the vicinity of the entrance where there are not so many bubbles, so that the diffusion of the substance in the vicinity of the electrode surface can be promoted and the electrolysis efficiency can be improved.
Further, by providing the downstream bent flow path 26, even if there is a gas that cannot be sufficiently dissolved in the interelectrode flow path 6, stirring can be performed again in the bent flow path. For example, when electrolyzing an aqueous solution of a substance having a chlorine atom to produce hypochlorous acid, depending on the conditions, chlorine gas may not sufficiently dissolve and the production efficiency of hypochlorous acid may be reduced. By making it a structure, dissolution of chlorine gas and conversion to hypochlorous acid can be promoted, so that substantial electrolytic efficiency can be improved.
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.

Fifth Embodiment 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. In the fifth embodiment, 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. Further, when viewed from the direction in which the electrolysis electrode pair 5 overlaps, at least a part of 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. Further, 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. As a result, 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. Thereby, both the electrolysis efficiency and safety | security of the electrolyzer 15 can be improved. Moreover, since the distance between the upper electrode 3 and the lower electrode 4 can be easily changed by changing the thickness of the spacer 33, it can be easily changed to various specifications according to the purpose. It is easy to share parts. 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.
In the electrolysis apparatus 15 shown in FIG. 6A, 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.

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.
In general, it is known that 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. Further, 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. Therefore, if the shape of the electrode is substantially rectangular and the length in the average flow velocity direction is substantially the same length L at the center and the end, t = L / V, and therefore k∝L / V. Therefore, the generated concentration of the desired component in the aqueous solution flowing through the central portion is k1∝L / V1, and the end portion is k2∝L / V2. / V1-1 / V2).
As shown in FIGS. 7A and 7B, when the protrusion 35 is provided upstream of the interelectrode flow path 6, the protrusion 35 can end the obstacle and the fluid from the central portion against the movement of the liquid in the flow path. Guide to the department. For this reason, the amount of fluid flowing per unit cross-sectional area is small in the central portion and large in the end portions. Therefore, considering a simplified system, the average flow velocity flowing through the center is V1−v, and the average flow velocity flowing through the ends is V2−v (v> 0). At this time, 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.

Sixth Embodiment 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). 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. For this reason, the configuration and structure are not complicated. In addition, 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.
Further, 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.
In addition, 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.

For example, 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. In the electrode terminal 45, 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.
Further, for example, by providing a groove of a female screw structure in the hole of the electrode holder 30 and providing a groove of a screw structure in the electrode terminal 45 and combining the female screw structure and the male screw structure, the metal holder 30 and the electrode terminal are combined. 45 may be joined. With such a structure, the electrode pair 5 for electrolysis can be fixed to the electrode holder 30 without using a nut.
As another method, for example, the electrode holder 30 and the electrode terminal 45 can be integrally formed.

With such a structure, 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. In addition, 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.
Of the surface of the protrusion 35, at least the portion closest to the counter electrode can be made non-conductive. For example, a nonconductive film can be formed by oxidizing the surface of the protrusion 35. Further, the surface of the protrusion 35 may be coated with a resin or the like. As a result, it is possible to suppress the electrochemical reaction from proceeding on the surface of the protrusion 35, and it is possible to suppress the generation of unnecessary components and the fluctuation in the generation concentration.

Seventh Embodiment 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, and FIG. 9E is a spacer taken along one-dot chain line HH in FIG. FIG.
The electrolysis device 15 of the seventh embodiment has an assembly-type electrolysis unit 10. In the seventh embodiment, 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. 2 is a second electrode holder 32 to which 3 is fixed, and the remaining one is a spacer 33 shown in FIGS. 9C to 9E, which is disposed between the first and

second electrode holders

31 and 32. Moreover, in 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. Further, 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. As a result, it is possible to suppress the electrolytic reaction from proceeding at the electrode edge where electric field concentration is likely to occur and deterioration is likely to occur. As a result, the electrolytic treatment can be performed stably, and electrode wear can be suppressed and the life of the electrode pair 5 for electrolysis can be extended.

Eighth Embodiment 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. The electrolysis device 15 shown in FIG. 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 | generating hypochlorous acid by electrolyzing the aqueous solution of the substance which has a chlorine atom, the dilution liquid by which discharge | release of chlorine gas was suppressed can be produced | generated.

Ninth Embodiment 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.
In the electrolyzer 15, desirably, 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. And is discharged from the discharge port 63 through the pipe 65. Moreover, 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.
When the switch 64 is turned OFF, power supply to the electromagnetic valve 66, the liquid feed pump 68, and the electrolysis unit 10 is interrupted at an appropriate timing, and the operation of the electrolysis device 15 is stopped.
Actually, after providing various interlocks, the electromagnetic valve is first opened, and then the stock solution remaining in the electrolysis unit 10 during the previous operation is electrolyzed and then the stock solution supply is started. Set the optimal sequence.

For example, 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.
On the other hand, when it is desired to increase the rise of the electrolytic water concentration, 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.
When it is desired to avoid the high concentration electrolyzed water from staying in the electrolysis unit 10, 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. For the electrode pair 5 for electrolysis, 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. When the electrode pair for electrolysis is vertical, 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. 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. Further, 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 same experiment was conducted using various electrode materials for chlorine generation, using aqueous solutions containing chlorides, such as sodium chloride aqueous solution, hydrochloric acid, or a mixture of both, or changing the amount of aqueous solution fed. Even when the electrolysis conditions (voltage and current amount) were changed, the same tendency was shown. In some cases, the effective chlorine concentration at the time of vertical (0 degree) and the best inclination (from 0 degree to about 50 degrees) may be the same within the range of measurement error. However, when the cathode side is tilted upward, the effective chlorine concentration clearly decreases and tends to decrease by about 10% at about 23 degrees and about 20% at about 45 degrees as in FIG. there were. Therefore, although it is assumed that 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 reason is that not only the assembly tolerance when the electrolysis apparatus is incorporated into various devices, but also when the incorporated devices are actually used, they are not always used in a strictly horizontal place. Therefore, it is preferable that 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. In view of this, for example, in the case of an assumed usage mode, when a margin of 5 degrees is seen, it is preferable to install with the best inclination in the range of 5 degrees to 45 degrees. Typically, it is expected to be in the range of 20 to 30 degrees, but in order to take advantage of the fact that the height of the apparatus incorporating the electrolyzer can be reduced, it can be used at an angle of 45 degrees.
In this experimental example, a highly transparent acrylic resin was used for the casing 1 in order to observe the state of bubbles. However, various aqueous solutions supplied to the electrolysis apparatus, various electrolyzed substances generated by electrolysis, and generated gases It is needless to say that 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. When a chlorine-based aqueous solution or gas is generated as in this experimental example, a vinyl chloride resin is generally the most preferable material for the housing 1 in terms of high resistance, workability, and low cost.

The reason why the electrolysis efficiency is improved by inclining and arranging the electrode pair 5 for electrolysis so that a part of the anode is positioned vertically above the cathode is not clear, but the following hypothesis can be considered.
At the cathode, it is considered that the electrode reaction as shown in the chemical reaction formula (4) proceeds to generate H ₂ . Since the generated H ₂ is relatively difficult to dissolve, most of it becomes bubbles. Since the cathode is positioned vertically below the anode due to the inclination of the electrode pair 5 for electrolysis, it is considered that the H ₂ bubbles float away from the cathode by the buoyancy and move to the vicinity of the anode. For this reason, since bubbles generated at the cathode try to move across the flow rate direction of the aqueous solution, stirring of the aqueous solution near the cathode and the aqueous solution near the anode is promoted. Also, since the H ₂ bubbles move to the vicinity of the anode, the alkaline solution near the cathode is also transported to the vicinity of the anode, so that the conversion of chlorine gas to hypochlorous acid or the like as shown in the chemical reaction formula (2) is possible. Promoted. In addition, 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. To work.

FIG. 13 is a schematic diagram of the interelectrode flow path when the inclination angle of the electrode pair for electrolysis is 0 degree. When the electrode pair for electrolysis is installed at an inclination angle of 0 °, 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.

Even when the electrode pair for electrolysis is disposed so as to be inclined with respect to the vertical direction so that the anode becomes the upper electrode, it is considered that the aqueous solution flows as in FIG. However, the situation is greatly different when electrolysis is performed, especially when bubbles are generated.
When bubbles rise in the aqueous solution from the cathode toward the anode, if the velocity vectors of the bubbles and the aqueous solution are different, they become resistance to each other and exchange momentum. In a typical example, if there are bubbles in still water, the bubbles move upward due to buoyancy, but it is well known that a water flow is also generated as dragged by the movement.
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. For this reason, 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. At this time, 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. As a result, the anode side product and the cathode side product are well mixed.

Next, consider a case where the electrode pair for electrolysis is tilted so that the cathode becomes the upper electrode, that is, a negative tilt angle in the graph of FIG. 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). Easily 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 | occur | produced in the lower electrode is few. Further, a relatively large amount of bubbles generated at the cathode as the upper electrode move along the cathode surface. For this reason, the area of the surface of the cathode covered with bubbles is increased, and the contact between the cathode and the aqueous solution is hindered to lower the electrolysis efficiency. For this reason, it is thought to work against electrolysis.
In this experimental example, it was preferable to use the anode as the upper electrode, but according to this hypothesis, depending on what is to be electrolyzed, the electrode with a relatively large number of bubbles generated is used as the lower electrode, It can be seen that electrolysis efficiency can be improved by using the electrode with relatively few bubbles as the upper electrode.

Next, in order to confirm this hypothesis, 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. Then, an electrolyzer that was shifted 1 cm above the upper end and an electrolyzer where the upper end of the cathode 22 was shifted 1 cm higher than the upper end of the anode 21 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. Other experimental conditions and measurement methods are the same as in the above electrolysis experiment.
In an electrolysis experiment using an electrolysis apparatus in which the anode 21 was shifted upward, the effective chlorine concentration (mg / L) of the aqueous solution after the electrolysis treatment was about 65 mg / L. Moreover, in the electrolysis experiment using the electrolyzer in which the cathode 22 was shifted upward, the effective chlorine concentration (mg / L) of the aqueous solution after the electrolysis treatment was about 60 mg / L. As described above, in the experiment using the electrolysis apparatus in which the anode 21 was shifted upward, the electrolytic reaction product was obtained with about 10% higher efficiency than the experiment using the electrolysis apparatus in which the cathode 22 was shifted upward.

As shown in 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.
However, when using the anode 21 and the cathode 22 with different amounts of bubbles generated as in this experiment, 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. When the anode 21 is shifted upward as shown in FIG. 14B, it is expected that when the amount of bubbles generated at the cathode 22 is sufficiently large, the bubbles move to the vicinity of the anode, and the aqueous solution can be stirred and mixed. Is done.
In the case where the cathode 22 is shifted upward as shown in FIG. 14C, the bubbles generated at the cathode 22 cannot move to the vicinity of the anode, and at least compared with FIG. Expected to have little effect of mixing. When the effect of stirring and mixing is small, the aqueous solution that has been subjected to the electrolytic treatment on the lower side of the anode rises along the electrode surface of the anode, so that it is expected that the electrolytic efficiency is lowered on the upper side of the anode. When the stirring and mixing effect is large, a fresh stock solution is supplied to the anode surface, so that the electrolysis efficiency is expected to be improved. Therefore, the effect of stirring and mixing the aqueous solution by bubbles and the experimental results are qualitatively matched.
Therefore, in this experiment, it was preferable to shift the anode 21 to the upper side. However, according to this hypothesis, depending on what is to be electrolyzed, the electrode with a relatively large number of bubbles generated is placed downward and generated. It can be seen that the electrolytic efficiency can be improved by placing the electrode having relatively few bubbles upward.

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.
In the electrolysis experiment, 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.

Experimental example 3
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. As the upper electrode 3 serving as an anode, an insoluble electrode for producing sodium hypochlorite manufactured by Daiso Engineering was used. As the lower electrode 4 serving as the cathode, a Nilaco titanium plate was used. In addition, 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. In this experimental example, 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.
When the solution to be electrolyzed was a sodium chloride aqueous solution, the electrolysis efficiency was not so different from that of Experimental Example 3. However, in the case where the electrolyte was made acidic by adding hydrochloric acid to the sodium chloride aqueous solution, 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. Moreover, since 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.

Experimental Example 5
Using an electrolysis apparatus 15 as shown in FIGS. 10 (a) and 10 (b), a diluted solution containing an electrolysis product was manufactured. As the electrolytic stock solution 52, a 3 to 4% NaCl aqueous solution was used, and electrolytic treatment was performed using the electrolytic unit 10 as shown in FIG. 6 (a) under the condition of theoretically generating 4000 ppm hypochlorous acid. . And the aqueous solution after a process by the dilution part 53 was diluted with the pure water, and the dilution liquid was manufactured. For comparison, a conventional electrolytic unit in which the electrode surface of the electrode pair for electrolysis is parallel to the vertical direction was incorporated in an electrolysis apparatus as shown in FIG.
In an electrolysis experiment using a conventional electrolysis unit, chlorine gas does not dissolve sufficiently in an aqueous solution in an acidic range of pH 7 or lower, and even if bubbles are submerged in pure water for dilution in a dilution tank, the surface of the dilution liquid The nearby chlorine gas concentration exceeded 0.5 ppm, and in some cases it was 2 ppm or more. In the past, the production of high-concentration and low-pH hypochlorous acid by electrolysis has not been widely put into practical use. However, in the conventional method, chlorine gas is easily generated at low pH, and high-concentration liquid is efficiently produced by electrolysis. This is probably because it was difficult to generate.
On the other hand, in the electrolysis experiment using the electrolysis apparatus 15 of this experimental example as shown in FIG. 10 (a), 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. In addition, since 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.
In the electrolysis experiment using the electrolysis apparatus 15 of this experimental example as shown in FIG. 10B, the chlorine gas concentration in the vicinity of the discharge at the end of the pipe 57 for discharging the diluent was measured and found to be 0.5 ppm or less.

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. For the electrode pair 5 for electrolysis, 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.

In this experimental example, 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. When the electrode pair 5 for electrolysis is vertical, the tilt angle is 0 degree, and when 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. Yes, when the electrode pair 5 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 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. 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, 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. Specifically, when 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. In addition, when 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. When the inclination of the electrode pair 5 for electrolysis was too large, the effective chlorine concentration tended to decrease, and was approximately the same as the effective chlorine concentration at the vertical (0 degree) at about -60 degrees.
Therefore, 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). Further, 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.

As described above, in the batch type electrolytic cell 74, unlike the closed flow type electrolysis unit, 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.
At the cathode, it is considered that the electrode reaction proceeds and H ₂ is generated as in Experimental Example 1. Since the generated H ₂ is relatively difficult to dissolve, most of it becomes bubbles.
Here, unlike the closed electrolysis unit, when 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. It is thought that 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.

When the cathode side is below, 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. In the experiment, when 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.
In addition, since 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.

In the case of a closed system electrolysis unit, 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. In 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. For desorption of H ₂ is accelerated if the cathode side down, suppression and cathode surface of the cathode effective electrode area reduction of by coating effect of H ₂ is carried out supply of fresh the electrolyte. Further, since the H ₂ bubbles move to the vicinity of the anode, an aqueous solution close to the alkali near the cathode is also carried to the vicinity of the anode, so that the conversion of chlorine gas to hypochlorous acid or the like is promoted. In addition, 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. To work.
Further, since the electrolyte to be supplied to the electrolytic unit in the closed electrolysis unit is limited, the concentration of the electrolyzed substance, that is, the concentration of hypochlorous acid in this experimental example, tends to be high. When the hypochlorous acid concentration becomes too high, the electrolysis efficiency decreases. In this case, 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. However, it is considered that the increase in the concentration of hypochlorous acid in the electrolysis unit is suppressed and the electrolysis efficiency is improved.
Thus, the conditions for improving the electrolytic efficiency differ depending on the case.

As a case where the anode should be provided with the electrode pair tilted so that the anode is positioned above the cathode, (i) a closed-type electrolysis unit in which the electrode is substantially a part of the wall of the electrolytic cell or the channel. And (ii) 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 In particular, it is considered to be a structure having a means for sucking a substance generated by electrolysis and a non-electrolytic substance, or both.

As the means for forcibly supplying, 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.

In addition, (a) when performing electrolysis in which bubbles are generated from the cathode side, (b) when obtaining a substance generated on the anode side or a substance obtained by a chemical reaction thereof, (c) the outlet of the electrolysis unit is diluted. And (d) when satisfying at least one of the conditions in which the substance concentration generated by electrolysis is relatively high in the electrolysis unit, the electrode pair is inclined so that the anode is positioned above the cathode. It is considered better to provide it. Also, when multiple conditions (a) to (d) are satisfied, even when all the conditions (a) to (d) are satisfied, the anode is inclined so that the anode is positioned above the cathode. Is considered good.
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. The conversion of chlorine gas to hypochlorous acid in the dilution section is promoted, and the conversion of chlorine gas to hypochlorous acid continues in the line where dilution water flows after the dilution section. This is probably because there are many factors that promote the conversion to hypochlorous acid.

1: Housing 3: Upper electrode 4: Lower electrode 5: Electrode pair for electrolysis 6: Interelectrode flow path 7: Fluid flow path 8: Inlet 9: Outlet 10: Electrolytic unit 11: Bubble 15: Electrolyzer 16: Overlapping region when viewed from the vertical direction 17: Overlapping region when viewed from the direction perpendicular to the main surface of the lower electrode 21: Anode 22: Cathode 25: Upstream bent channel 26: Downstream bent channel 30 : 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: Solenoid valve 67: Stock solution tank 68: Pump 70: Piping unit 72: Power supply device 74: Electrolysis tank 75: Fluid to be treated 77: Wiring 100: Electrolyzer 101: Housing 103: First electrode 104: Second electrode 106: First wiring 107: Second wiring 108: Supply port 109: Discharge port 111: Housing 112: Water supply port 113: Sink Outlet 114: Switch 115: Piping 116: Solenoid valve 117: Stock solution tank 118: Pump 120: Electrolyzed water generator

Claims

With an electrolysis unit,
The electrolysis unit includes a fluid flow path to be processed, at least one pair of electrode for electrolysis, an inlet, and an outlet.
The electrode pair for electrolysis is disposed so as to be inclined with respect to the vertical direction, and includes an upper electrode and a lower electrode disposed so as to face each other,
The fluid flow path to be treated is provided such that the fluid flowing in from the inflow port flows from the lower electrode to the upper electrode flow channel between the upper electrode and the lower electrode, and flows out from the outflow port. An electrolyzer characterized by that.
The electrolysis apparatus according to claim 1, wherein the electrode pair for electrolysis is arranged so that an inclination angle with respect to a vertical direction is larger than 0 degree and smaller than 50 degrees.
2. The fluid flow path to be treated has an upstream bent flow path close to an upstream end of the interelectrode flow path or a downstream bent flow path close to a downstream end of the interelectrode flow path. Or the electrolysis apparatus of 2.
Means for forcibly supplying fluid to the fluid flow path to be treated;
The electrode pair for electrolysis is provided so that an electrode reaction in which gas is generated in the lower electrode and the upper electrode proceeds,
The electrolysis according to any one of claims 1 to 3, wherein an amount of gas generated and released to the outside at the lower electrode is substantially larger than an amount of gas generated and released to the outside at the upper electrode. apparatus.
The upper electrode is provided to be an anode,
The electrolyzer according to any one of claims 1 to 4, wherein the lower electrode is provided to be a cathode.
The electrolysis apparatus according to any one of claims 1 to 5, wherein the lower electrode has an electrode surface having a larger area than the electrode surface of the upper electrode.
A further dilution section,
The fluid is an aqueous solution;
The electrode pair for electrolysis is provided such that hypochlorite ions are generated electrochemically from a chlorine-containing compound contained in the aqueous solution,
The aqueous solution at the outlet contains hypochlorite ions of 4000 ppm or more by weight,
The dilution section is provided to generate a diluted solution of an aqueous solution containing hypochlorite ions discharged from the outlet,
The electrolysis apparatus according to any one of claims 1 to 6, wherein the dilution liquid has a pH of 7.5 or less.
The treated fluid channel is provided such that fluid is supplied to the treated fluid channel by convection,
The electrode pair for electrolysis is provided so that an electrode reaction in which gas is generated in the lower electrode and the upper electrode proceeds,
The electrolysis according to any one of claims 1 to 3, wherein an amount of gas generated and released to the outside at the upper electrode is substantially larger than an amount of gas generated and released to the outside at the lower electrode. apparatus.