JP2014098203A - Electrolyzing method and apparatus as well as electrolytic processor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To effectively inhibit, by using an inexpensive electrode for electrolysis, adhesions of impurities to the electrode for electrolysis and to extend the life of the electrode for electrolysis.SOLUTION: The provided apparatus includes: a diaphragm-free electrolytic cell 1 possessing an intake port 1a through which salt water W is taken in and a discharge port 1b through which electrolyzed water W1 obtained upon the completion of the electrolysis of the salt water W is discharged; carbon electrodes 2 having at least a paired constitution (2a, 2b) configured in opposition to one another within this electrolytic cell 1 and immersed within the salt water W provided as an electrolysis target; and an electric power supply 3 for electrolysis for impressing an electrolyzing voltage V consisting of DC components between the paired carbon electrodes 2 by designating one carbon electrode 2a (or 2b) of the paired carbon electrodes 2 as an anode and the other carbon electrode 2b (or 2a) as a cathode. The electric power supply 3 for electrolysis possesses a switch element 3b capable of switching polarities of the electrolyzing voltage V targeting the paired carbon electrodes 2 at timings determined in advance either periodically or non-periodically.

Description

  The present invention relates to an electrolysis method using a diaphragm-type electrolytic cell, and more particularly to an electrolysis method suitable for electrolyzing salt water containing impurities, an apparatus therefor, and an electrolytic treatment apparatus.

Conventionally, as this type of electrolysis method, a method of supplying electrolyzed water composed of a sodium hypochlorite solution by supplying salt water such as seawater to an electrolyzed membrane cell and electrolyzing it is already known. .
However, in this type of electrolysis method, there is a concern that the efficiency of electrolysis will be reduced if silica is deposited mainly on the anode-side electrode and hydroxide is deposited on the cathode-side electrode, which adheres to the electrode surface. Therefore, it is necessary to maintain the electrode regularly.
Therefore, as a conventional electrolysis method, for example, as shown in Patent Document 1, a hydrochloric acid solution having a concentration of 10 to 15% is used to remove deposits on electrodes of an apparatus for electrolyzing seawater by circulating seawater from below to above. Although a technique for cleaning the electrode by flowing the gas from the upper side to the lower side of the electrolyzer is already known, it does not fundamentally eliminate the adhesion of impurities to the electrode, so periodic maintenance is indispensable It is.

Moreover, as an electrode of an electrolysis apparatus, a noble metal such as platinum is generally used for an anode, and titanium or the like is generally used for a cathode. However, as shown in Patent Document 2, for example, an electrode using a carbon electrode has already been provided. Yes. In order to prevent damage to the carbon electrode and stably generate carbon dioxide and oxygen in the aqueous electrolytic bath, an electrolytic cell forming an aqueous electrolytic bath, a cathode, and an anode containing carbon And means for energizing both electrodes, generating oxygen from the anode, generating carbon dioxide with carbon and oxygen contained in the anode, and utilizing the electrolytic bath accompanied by generation of oxygen and carbon dioxide The anode containing carbon is composed of a composition of a carbonaceous material and a cured resin, and the composition is formed into a plate shape.
Furthermore, as a power source for electrolysis of an electrolysis apparatus, an electrolysis voltage composed of a direct current component is generally applied to a predetermined anode and cathode of a pair of electrodes. Some have been provided to switch the polarity of the electrodes. This is because 4-boric acid as a pH buffering agent that suppresses pH change due to electrolysis in an aqueous sodium chloride solution as electrolyzed water so that it is not necessary to use or discard the cathode side electrolyzed water for pH adjustment of the anode side electrolyzed water. In a state where the above-mentioned electrolyzed water is circulated between the first electrolyzer and the reserve tank of the electrolyzer body using sodium added, the first electrode is set as the anode side, and the electrolyzed water is set as the second electrode as the cathode side. Then, the electrolytic water is electrolyzed with the second electrode on the anode side and the first electrode on the cathode side in a state where the electrolytic water is circulated between the second electrolytic tank and the reserve tank.

JP-A-5-65683 (Example, FIG. 1) JP-A-9-195077 (Embodiment) JP 2004-305967 A (Embodiment of the Invention, FIG. 1)

  The technical problem to be solved by the present invention is an electrolysis method using an inexpensive electrolysis electrode, effectively suppressing adhesion of impurities to the electrolysis electrode, and extending the life of the electrolysis electrode, and its An apparatus and an electrolytic treatment apparatus are provided.

According to the first aspect of the present invention, when electrolyzing the salt water containing impurities, a filling step of filling the salt water, which is the subject of electrolysis, into a diaphragm-type electrolytic cell, and at least a solution to the salt water in the electrolytic cell. A first electrolysis step in which a carbon electrode having a configuration is immersed, an electrolytic voltage composed of a direct current component is applied with one carbon electrode as an anode and the other carbon electrode as a cathode, and the first electrolysis step are alternately determined in advance. And a second electrolysis step for switching and applying the polarity of the electrolysis voltage composed of a direct current component so that the one carbon electrode is a cathode and the other carbon electrode is an anode. An electrolysis method characterized by the following.
The invention according to claim 2 is an electrolysis apparatus for electrolyzing salt water containing impurities, and has an intake port for taking in the salt water and a discharge port for discharging electrolyzed water after the salt water is electrolyzed. A diaphragm-type electrolytic cell filled with the brine, at least a pair of carbon electrodes disposed opposite to the electrolytic cell and immersed in the salt water to be electrolyzed, and the carbon electrode of the pair An electrolysis power source for applying an electrolysis voltage composed of a direct current component between the paired carbon electrodes so that one carbon electrode serves as an anode and the other carbon electrode serves as a cathode, and the electrolysis power source comprises: An electrolysis apparatus comprising a switching element capable of switching a polarity of an electrolysis voltage with respect to the carbon electrode of the pair structure at a predetermined timing periodically or irregularly.

According to a third aspect of the present invention, in the electrolysis apparatus according to the second aspect, the switching element of the electrolysis power source switches the polarity of the electrolysis voltage so that the accumulated electrolysis time in each polarity is approximately the same. It is an electrolysis apparatus characterized by being.
The invention according to claim 4 is the electrolysis apparatus according to claim 2, wherein the electrolysis power source switching element switches the polarity of the electrolysis voltage when the electrolysis apparatus starts or stops operating. It is.
The invention according to claim 5 is the electrolysis apparatus according to claim 1 or 2, characterized in that the electrolytic cell has the intake port positioned below the discharge port.
The invention according to claim 6 is the electrolysis apparatus according to claim 5, wherein the electrolytic cell is located in a predetermined part of the side wall of the intake port, and the intake port is located above the intake port. The pair of carbon electrodes having a discharge port is located on the side of the side wall of the electrolytic cell opposite to the intake port and the discharge port, and at least above the intake port. It is the electrolysis apparatus characterized by being arrange | positioned.

The invention according to claim 7 is the electrolyzer according to any one of claims 2 to 6, salt water intake means for taking in salt water through the inlet of the electrolyzer of the electrolyzer, and the outlet of the electrolyzer of the electrolyzer. An electrolytic treatment apparatus comprising: treated water providing means for using the electrolytic treated water discharged through the water.
The invention according to claim 8 is the electrolytic treatment apparatus according to claim 7, which is mounted on a fishing boat, wherein the salt water intake means takes seawater as salt water into an electrolytic cell of the electrolysis apparatus, and the treated water providing means Is an electrolytic treatment apparatus characterized in that the electrolytic treatment water is used as sterilizing water for fish and shellfish that have been captured.
The invention according to claim 9 is the electrolytic treatment apparatus according to claim 7, wherein the salt water taking-in means temporarily stores the salt water, and the intake pipe for taking the salt water into the storage container; A connecting pipe connecting between the storage container and the inlet of the electrolytic cell of the electrolytic device, and the electrolytic tank of the electrolytic device via the intake pipe, the storage container and the connecting pipe A salt water is taken in, the treated water providing means is connected to a discharge port of the electrolytic cell, and a circulation pipe for circulating the electrolytic treated water discharged from the electrolytic cell in the vicinity of the inlet of the intake pipe; and the connection A branch discharge pipe provided by branching from a part of the pipe, and a flow rate adjusting means for distributing a flow rate to the branch discharge pipe and the connection pipe, and the electrolyzed water discharged from the electrolytic cell is discharged before electrolysis Of salt water intake means with salt water With recirculated to the road, an electrolysis treatment apparatus is characterized in that so as to be discharged from the branch exhaust pipe.

According to the first aspect of the present invention, there is provided an electrolysis method that uses an inexpensive electrolysis electrode, can effectively suppress adhesion of impurities to the electrolysis electrode, and can extend the life of the electrolysis electrode. Can do.
According to the second aspect of the present invention, there is provided an electrolysis apparatus that uses an inexpensive electrolysis electrode, effectively suppresses adhesion of impurities to the electrolysis electrode, and can extend the life of the electrolysis electrode. Can do.
According to the invention which concerns on Claim 3, compared with the aspect which does not have this structure, the consumption degree by the electrolysis of the carbon electrode of a pair structure can be adjusted to substantially the same grade.
According to the invention of claim 4, it is possible to more effectively prevent the adhesion of impurities to the electrode for electrolysis and to provide a balanced carbon electrode in a balanced manner as compared with an embodiment without this configuration. It can be consumed substantially evenly.
According to the invention which concerns on Claim 5, compared with the aspect which does not have this structure, the hydrogen gas generated with the treated water after electrolysis can be easily discharged | emitted from a discharge port.
According to the invention which concerns on Claim 6, in the electrolysis apparatus of the diaphragm type which takes in salt water from the side of an electrolytic cell and discharges electrolytic treatment water from the same side, the production | generation efficiency and discharge | emission efficiency of electrolytic treatment water are made favorable Can keep.
According to the invention concerning Claim 7, the electrolyzed water which electrolyzed the salt water containing an impurity can be provided for the various uses aiming at the sterilization etc.
According to the invention which concerns on Claim 8, the seafood captured with the fishing boat can be sterilized at an early stage, and the freshness of seafood can be maintained.
According to the invention which concerns on Claim 9, in the aspect which utilizes seawater directly as salt water, the electrolyzed water of desired chlorine concentration can be obtained easily, suppressing the stain | pollution | contamination by a barnacle etc. in a salt water intake path | route. .

(A) is explanatory drawing which shows the outline | summary of embodiment of the electrolysis apparatus to which this invention was applied, and an electrolysis processing apparatus using the same, (b) is the 1st electrolysis process by the electrolysis apparatus shown to (a), and 1st It is explanatory drawing which shows the electrolysis process of 2 typically. 1 is an explanatory diagram showing an overall configuration of an electrolytic treatment apparatus according to Embodiment 1. FIG. (A) is explanatory drawing which shows the structural example of the carbon electrode used in Embodiment 1, (b) is the decomposition explanatory drawing, (c) is the description which shows the deformation | transformation form of the carbon electrode used in Embodiment 1. FIG. It is explanatory drawing which shows the example of attachment structure of the carbon electrode to the electrolytic cell which concerns on Embodiment 1, an intake piping, and discharge piping. (A) is explanatory drawing which shows the structural example of the power supply for electrolysis used in Embodiment 1, (b) is explanatory drawing which shows the on-off operation state of the changeover switch shown to (a). (A) is explanatory drawing which shows the action | operation of the electrolytic treatment apparatus shown in Embodiment 1, (b) is explanatory drawing which shows a 1st electrolysis process typically, (c) is a 2nd electrolysis process typically. It is explanatory drawing shown. (A) (b) is explanatory drawing which shows the form of a respectively different deformation | transformation of the electrolysis apparatus which concerns on Embodiment 1. FIG. 6 is an explanatory view showing an electrolytic treatment apparatus according to Embodiment 2. FIG. 5 is an explanatory view showing an electrolytic treatment apparatus according to Embodiment 3. FIG. It is a graph which shows the relationship between the electrolysis current of the electrolytic device which concerns on Example 1, and the amount of chlorine production. (A) is explanatory drawing which shows the number of bacteria contained in seawater and electrolyzed water, (b) is explanatory drawing which shows the freshness maintenance effect of the fish in the washing | cleaning method by Example 3 and a comparative example, (c) is 'K value' It is explanatory drawing which shows the definition of.

Outline of Embodiment FIG. 1A is an explanatory diagram showing an outline of an embodiment of an electrolysis apparatus to which the present invention is applied.
In the figure, an electrolyzer 4 is an electrolyzer that electrolyzes salt water W containing impurities, and an intake port 1a through which the salt water W is taken in and electrolyzed water W1 after the salt water W is electrolyzed are discharged. A diaphragm-type electrolytic cell 1 having a discharge port 1b and filled with salt water W, and at least a pair of carbon electrodes 2 disposed opposite to the electrolytic cell 1 and immersed in the salt water W to be electrolyzed (For example, 2a, 2b) and one carbon electrode 2a (or 2b) of the carbon electrode 2 of this pair configuration as an anode and the other carbon electrode 2b (or 2a) as a cathode. An electrolysis power source 3 for applying an electrolysis voltage V composed of a direct current component between the electrodes 2, and the electrolysis power source 3 performs electrolysis on the paired carbon electrodes 2 at a predetermined timing periodically or irregularly. Switching element 3 whose polarity of voltage V can be switched And it has a.
And, as shown in FIGS. 1 (a) and 1 (b), the electrolysis method using the electrolysis apparatus 4 is performed when the salt water W containing impurities is electrolyzed in the diaphragm-type electrolytic cell 1 when electrolyzing the salt water W containing impurities. And a carbon electrode 2 (for example, 2a, 2b) having at least a pair configuration are immersed in the salt water W in the electrolytic cell 1, and one carbon electrode 2a is an anode, and the other carbon electrode 2b is a cathode. The first electrolysis step for applying an electrolysis voltage V composed of a direct current component and the first electrolysis step are alternately performed at predetermined timings, with one carbon electrode 2a serving as a cathode and the other carbon electrode 2b serving as a cathode. And a second electrolysis step in which the polarity of the electrolysis voltage V composed of a direct current component is switched and applied so as to be the anode.

In such technical means, the present embodiment is directed to salt water W containing impurities (mainly seawater, but not limited to seawater, salt water such as lakes and rivers with high salinity, or artificial salt water). ), And sterilized water containing sodium hypozincate (NaClO) as an electrolytic product around the anode on the premise of the diaphragm-type electrolytic cell 1.
In this example, the electrolyzer 1 may be a non-diaphragm type that has an intake port 1a for salt water W and a discharge port 1b for electrolyzed water W1 and is filled with the salt water W.
The “carbon electrode 2” means an electrode mainly composed of carbon. In this case, the “carbon electrode 2” does not need to be composed of carbon as a whole, and carbon may be used as an electrode material. For example, for other reasons (mainly durability) as in the case of a pencil lead or the like. Of course, other materials other than carbon, such as clay, silicon, and resin, may be mixed. In addition, the “carbon electrode 2” may have an aspect having the same composition as a whole, for example, an aspect in which the core is made of a conductive material other than carbon, and the periphery of the core is covered with the carbon material. Is also included.
Furthermore, since the “carbon electrode 2” needs to dissolve carbon when used as an anode, an embodiment in which the electrode surface is covered with a coating layer such as a resin is not preferable.
Furthermore, “at least the paired carbon electrodes 2” is not limited to the illustrated pair of carbon electrodes 2 but also includes a mode in which a plurality of pairs are installed.
The electrolysis power supply 3 only needs to have a power supply element 3a to which an electrolytic voltage V made of a DC component can be applied and a switching element 3b for switching the polarity of the electrolytic voltage V to be applied. The switching timing may be a timing that is determined regularly or irregularly (at the start of operation, at the end of operation, every time a predetermined operation time elapses, etc.).
Here, if the electrolytic voltage level to be applied is variably adjusted, the electrolytic current can be changed, and the chlorine concentration of the electrolytically treated water can be adjusted accordingly.

Next, the effect | action of the electrolysis method in this Embodiment is demonstrated.
In the present embodiment, when both of the paired carbon electrodes 2 are used as a cathode and an anode as in the first electrolysis process and the second electrolysis process shown in FIG. There is a concern that silicon dioxide (SiO ₂ ), which is an insulator, adheres to the surface and inhibits electrolysis, and on the cathode side, hydroxides are generated by various cations in salt water, especially hydroxides by magnesium and calcium. Since it is insoluble, there is a concern of adhering to the electrode surface.
On the anode side, since carbon is consumed due to dissolution, silicon dioxide is peeled off together with carbon at the time of consumption. On the other hand, on the cathode side, the electrode is not consumed, but hydroxide may adhere to the electrode surface. In this example, the polarity of the electrode is switched before a large amount of hydroxide is generated, so that the cathode becomes the anode. It has the effect of peeling.
In addition, the first electrolysis step and the second electrolysis step may be performed alternately at predetermined timings. However, as an implementation cycle, a large amount of hydroxide is generated on the carbon electrode 2 as the cathode. If it adheres to the electrode, there is a concern that the substantial electrolytic area when used as an anode may be narrowed. Therefore, a short period before a large amount of hydroxide adheres to the electrode surface is preferable.

Next, a typical aspect or a preferable aspect of the electrolysis apparatus 4 according to the present embodiment will be described.
In the present embodiment, a preferable aspect of the switching element 3b of the electrolysis power supply 3 is one that switches the polarity of the electrolysis voltage V so that the accumulated electrolysis time in each polarity is approximately the same.
The term "cumulative electrolysis time at each polarity is approximately the same" here is of course an aspect in which each electrolysis time that is alternately switched is approximately the same, but the electrolysis time at each operation is different, It is possible to switch periodically every predetermined number of times (1 time, 2 times, etc.), or count the operating time in each polarity, and the accumulated electrolysis time is approximately the same. It is possible to appropriately select the mode of switching so as to be.
Further, as another preferred aspect of the switching element 3b of the electrolysis power source 3, there is one that switches the polarity of the electrolysis voltage V when the electrolysis apparatus 4 is started or stopped. As in this embodiment, when the operation start time or the operation stop time is selected as the switching timing of the switching element 3b of the electrolysis power supply 3, the polarity of the electrolysis voltage V is switched every operation. No electrolytic treatment is performed over a long period of time, for example, there is little concern that hydroxide generated on the cathode side will unnecessarily adhere, and the degree of wear of the paired carbon electrodes 2 is balanced and substantially even. This is preferable.

Moreover, as a preferable aspect of the intake port 1a and the discharge port 1b of the electrolytic cell 1, the aspect in which the intake port 1a is located below the discharge port 1b is mentioned.
In this embodiment, the intake port 1a and the discharge port 1b may be disposed on any of the peripheral walls (side wall, lower wall, upper wall) of the electrolytic cell 1, but when provided on the lower wall or the upper wall, the electrolytic cell The intake pipe and the discharge pipe may be provided so as to project in the interior 1 so that there is a difference in the vertical position of the end portions (take-in port and discharge port) of each pipe.
And this aspect is effective when discharging | emitting hydrogen gas generated by electrolysis with the electrolyzed water W1. If salt water W, which is water to be treated, is taken in from above, it becomes difficult to simultaneously discharge the hydrogen gas from the discharge port 1b. Therefore, it is necessary to devise a special exhaust port for discharging the hydrogen gas. .
Furthermore, in this embodiment, when the method of taking the salt water W into the electrolytic cell 1 from the side and discharging it from the side is adopted, as shown in FIG. The carbon electrode 2 of the pair structure has an intake port 1a and a discharge port 1b positioned above the intake port 1a. The aspect arrange | positioned so that it may be located in the site | part on the opposite side of the inlet 1a and the discharge port 1b and at least upwards rather than the inlet 1a is preferable.
In this embodiment, the salt water W is taken from the side of the electrolytic cell 1 and the electrolytically treated water W1 is discharged from the same side, and the electrolytic cell 1 is taken in for efficiently discharging the electrolytically treated water W1. The positional relationship between the mouth 1a and the discharge port 1b and the arrangement position of the paired carbon electrodes 2 are specified.
Here, when at least one carbon electrode 2 (for example, 2b) is disposed at the same position as or below the intake port 1a as an arrangement position of the paired carbon electrode 2, it is used as an anode. In addition, there is a concern that the electrolytically treated water W1 generated around the electrode is difficult to discharge from the discharge port 1b, but this aspect is preferable in terms of eliminating such a concern.

Next, an electrolytic treatment apparatus using the above-described electrolytic apparatus 4 will be described.
As this type of electrolytic treatment apparatus, as shown in FIG. 1 (a), the above-described electrolysis apparatus 4, salt water intake means 5 for taking in salt water W through the intake port 1a of the electrolytic cell 1 of the electrolysis apparatus 4, There is one provided with treated water providing means 6 for using the electrolytic treated water W1 discharged through the discharge port 1b of the electrolytic cell 1 of the electrolytic device 4.
In this aspect, examples of the salt water taking-in means 5 include a pump, and the sea water may be directly pumped from the sea and injected, or for example, the salt water W stored in the tank is taken in.
The treated water providing means 6 may be a tank that temporarily stores the treated electrolytic water W1 that has been discharged, or a dish-shaped container that receives the discharged electrolytic treated water W1. In addition, it may be selected as appropriate, for example, by adding a discharge function for appropriately discharging to a tank or a dish-like container.

As a typical application example of such an electrolytic treatment apparatus, it is mounted on a fishing boat, and the salt water intake means 5 takes in seawater as salt water into the electrolytic cell 1 of the electrolysis apparatus 4, and the treated water providing means 6 performs electrolysis. What uses processing water W1 as sterilization water of the fish and shellfish which were captured is mentioned.
In this embodiment, an electrolytic treatment apparatus is incorporated in a fishing boat, and the sterilized water for washing seafood is obtained by pumping up seawater and subjecting it to electrolytic treatment.
As another typical application example of the electrolytic treatment apparatus, the salt water intake means 5 includes a storage container (not shown) that temporarily stores the salt water W, and an intake that takes the salt water W into the storage container. And a connecting pipe (not shown) for connecting the storage container and the intake port 1a of the electrolytic cell 1 of the electrolysis device 4 with the intake pipe, the storage container, and The salt water W is taken into the electrolytic cell 1 of the electrolysis apparatus 4 through the connection pipe, and the treated water providing means 6 is connected to the discharge port 1b of the electrolytic cell 1 and from the electrolytic cell 1 near the inlet of the intake pipe. A circulation pipe (not shown) for circulating the discharged electrolytic treated water W1, a branch discharge pipe (not shown) branched from a part of the connection pipe, and a flow rate for the branch discharge pipe and the connection pipe And a flow rate adjusting means (not shown) for allocating The electrolyzed water W1, together with recirculated to intake passage of water capturing means 5 with saline W before electrolysis include those to be discharged from the branch exhaust pipe.
This aspect is an aspect that is effective in an electrolytic treatment apparatus that obtains electrolytic treatment water W1 having a predetermined chlorine concentration by using, for example, seawater as the salt water W.
At this time, in the aspect in which seawater is directly taken in as the salt water W as the salt water taking-in means 5, there is a concern that a barnacle or the like may adhere to the salt water taking-in pipe and block the flow path. It is necessary to maintain the inside of the pipe. However, in this aspect, since the electrolytically treated water W1 is returned to the vicinity of the inlet of the intake pipe of the saltwater intake means 5, the electrolytically treated water W1 is again sucked into the intake pipe together with the salt water W. For this reason, the inside of intake pipe will be regularly wash | cleaned by the electrolyzed water W1, and it will be suppressed that a barnacle etc. adhere in the intake pipe. Moreover, it becomes possible to control the chlorine concentration of the electrolyzed water W1 by adjusting the electrolysis current of the electrolyzer 4, and the electrolyzed water finally drained from the branch discharge pipe has a desired chlorine concentration. It is possible to generate.

Embodiment 1
FIG. 2 is an explanatory diagram showing the overall configuration of the electrolytic treatment apparatus according to the first embodiment.
<Overall configuration of electrolytic treatment apparatus>
In the figure, an electrolytic treatment apparatus 10 is electrolyzed by an electrolysis apparatus 20 that electrolyzes salt water W, a salt water intake unit 50 that takes salt water W (seawater in this example) into the electrolysis apparatus 20, and an electrolysis apparatus 20. And a treated water discharge unit 60 for discharging the electrolyzed treated water W1.
Here, the electrolysis apparatus 20 includes a diaphragm-type electrolytic cell 21, a paired carbon electrode 30 provided in the electrolytic cell 21, and an electrolysis power source that applies an electrolytic voltage to the paired carbon electrode 30. 40.
The salt water intake unit 50 includes an intake pipe 51 that is connected to the electrolytic cell 21 in order to take in the salt water W, and a salt water W intake pipe 51 that is provided in the flow path of the intake pipe 51. And a pump 53 that is provided in a part of the intake pipe 51 and opens and closes the flow path.
Further, the treated water discharge unit 60 has a discharge pipe 61 connected to the electrolytic cell 21 for discharging the electrolytic treated water W1, and the electrolytic treated water W1 is supplied to a discharge container (not shown) via the discharge pipe 61. Are temporarily stored and used for sterilization.
Furthermore, in this example, a control panel 70 for driving the electrolyzer 20 and the salt water intake unit 50 is provided. The control panel 70 includes an operation panel 71 provided with a start switch (not shown) for driving the electrolytic treatment apparatus 10 and various switches (not shown) for setting electrolysis conditions, and this operation. A controller (for example, a predetermined control signal) to each control object (for example, the electrolysis power supply 40 of the electrolysis apparatus 20, the pumping pump 52 of the salt water intake unit 50, the valve 53, etc.) based on the input signal from the panel 71 In this example, the electrolysis power supply 40, which is an element of the electrolysis apparatus 20, is accommodated in the control panel casing.

<Electrolytic cell>
In the present embodiment, the electrolytic cell 21 is provided with a flange 23 extending in the radial direction at both ends opening edges of a cylindrical electrolytic cell body 22 made of an insulating material (for example, polyvinyl chloride, polyethylene, or polypropylene). Disk-shaped side lids 24 and 25 are fixed to the flanges 23 with stoppers 26 (see FIG. 4) via seal members (not shown) so as to close both end openings of the main body 22.
In this example, one side lid 24 of the electrolytic cell 21 is provided with an intake 27 for taking in salt water W, and the electrolytic treatment after electrolysis is performed above the intake 27 in the side lid 24. A discharge port 28 for discharging the water W1 is opened. As shown in FIG. 4, one end of the intake pipe 51 of the salt water intake unit 50 is connected to the intake port 27, and one end of the discharge pipe 61 of the treated water discharge unit 60 is connected to the discharge port 28. It is connected.
The other side lid 25 of the electrolytic cell 21 is provided with a pair of carbon electrodes 30 (specifically, 30a and 30b) in the vertical direction so as to protrude into the electrolytic cell 21 in a substantially horizontal direction.
In this example, the paired carbon electrodes 30 (30a, 30b) are disposed above the intake port 27 and below the discharge port 28.

<Carbon electrode>
In the present embodiment, as shown in FIGS. 3A and 3B, the carbon electrode 30 includes a cylindrical electrode rod 31 using carbon as an electrode material and an insulation for holding one end of the electrode rod 31. A socket 32 made of a conductive material (for example, polyvinyl chloride resin), and an electrode terminal 33 that protrudes outward from the socket 32 and passes through the socket 32 and is connected to one end of the electrode rod 31. .
In this example, the electrode rod 31 is configured by mixing clay, silicon, resin, etc. in addition to carbon as an electrode material from the viewpoint of maintaining durability. A female screw portion 311 is formed in the approximate center. The socket 32 has a bottomed U-shaped holding frame 321 into which one end of the electrode rod 31 is fitted, a mounting screw portion 322 protruding from the outside of the holding frame 321 in the direction in which the electrode rod 31 extends, The holding frame 321 and a through-hole 323 that penetrates substantially at the center of the mounting screw portion 322 are provided, and one end of the electrode rod 31 is fitted into the holding frame 321 and fixed with an adhesive or the like. Furthermore, the electrode terminal 33 is made of a mounting screw made of a conductive material (for example, made of titanium), and is screwed into the female screw portion 311 of the electrode rod 31 through the through hole 323 of the socket 32.
As shown in FIG. 4, the carbon electrode 30 (30 a, 30 b) configured in this way is fitted with the mounting screw portion 322 of the socket 32 in the mounting female screw portion 29 provided at the corresponding portion of the side cover 25. The side cover 25 is fixed. And the electrode terminal 33 of the carbon electrode 30 of a pair structure is connected to the power supply 40 for electrolysis via the conduction wire 34.
In this example, the carbon electrode 30 is configured by using the electrode rod 31 as a whole by using carbon as an electrode material. However, the present invention is not limited to this. For example, as shown in FIG. As a matter of course, the electrode rod 31 may be covered with a carbon coating layer 313 mainly composed of carbon as an electrode material around a core material 312 made of a conductive material other than carbon.

<Power supply for electrolysis>
In the present embodiment, as shown in FIG. 5A, the electrolysis power source 40 is a voltage source that applies an electrolysis voltage composed of a predetermined DC component to the paired carbon electrodes 30 (30a, 30b). 41 and a changeover switch 42 for switching the polarity of the voltage source 41.
In this example, the voltage source 41 has a voltage adjustment function so that the electrolytic voltage to be applied can be variably set.
The changeover switch 42 has four switch elements (SW1 to SW4). The switch element SW1 is interposed between the plus terminal of the voltage source 41 and one carbon electrode 30a in a pair configuration, and the switch element SW2 is interposed between the positive terminal of the voltage source 41 and the other carbon electrode 30b in the pair configuration, and the switch element SW3 is interposed between the negative terminal of the voltage source 41 and the other carbon electrode 30b in the pair configuration. A switch element SW4 is interposed between the negative terminal of the voltage source 41 and one of the paired carbon electrodes 30a. The switch elements SW1 and SW3 are turned on and off in conjunction with each other, and the switch elements SW2 and SW4 are turned on and off so as to be opposite to the on / off operation of the switch elements SW1 and SW3.

<Operation of electrolytic treatment equipment>
Next, the operation of the electrolytic treatment apparatus 10 will be described.
When the user operates the electrolytic treatment apparatus 10 now, a start switch (not shown) of the operation panel 71 of the control panel 70 may be turned on.
At this time, when the start switch of the control panel 70 is turned on, the controller 72 starts driving the pumping pump 52 of the salt water intake unit 50 and opens the valve 53 as shown in FIG. Further, the controller 72 sets SW1 and SW3 of the changeover switch 42 of the electrolysis power supply 40 to ON and sets SW2 and SW4 to OFF, as shown in, for example, the region I in FIG. 5B.
As a result, as shown in FIG. 2 and FIG. 6A, the salt water intake unit 50 enters seawater as salt water W pumped up by the pumping pump 52 into the electrolytic cell 21 through the intake pipe 51 and the intake port 27. The electrolytic treatment is carried out using one carbon electrode 30a as the anode and the other carbon electrode 30b as the cathode among the carbon electrodes 30 in the paired configuration, and as a result of the electrolytic treatment, the electrolytic treated water W1 is passed through the discharge pipe 61 of the treated water discharge unit 60. Are discharged together with hydrogen gas H ₂ which is a generated gas.
In particular, in this example, since the inlet 27 of the electrolytic cell 21 is disposed below the paired carbon electrode 30, the salt water W taken from the inlet 27 is connected to the paired carbon electrode 30. Then, after flowing at a predetermined flow velocity, the air flows toward the discharge port 28, and the discharge port 28 of the electrolytic cell 21 is disposed above the paired carbon electrode 30, so that it is generated from the anode. electrolyzed water W1 (NaClO), hydrogen gas H ₂ generated at the cathode is effectively discharged from the discharge port 28 along the flow of the fluid.
When the electrolytic treatment by the electrolytic treatment apparatus 10 is completed, a start switch (not shown) on the operation panel 71 of the control panel 70 may be turned off. In this state, the controller 72 stops driving each control target.
For this reason, in the electrolytic treatment apparatus 10, the salt water taking-in operation by the salt water taking-in unit 50 is completed, and the electrolytic treatment by the electrolytic apparatus 20 is also finished.

Next, when the user activates the electrolytic treatment apparatus 10 again, a start switch (not shown) of the operation panel 71 of the control panel 70 may be turned on.
At this time, when the start switch of the control panel 70 is turned on, the controller 72 starts driving the pumping pump 52 of the salt water intake unit 50 and opens the valve 53 as shown in FIG. Further, the controller 72 turns off SW1 and SW3 of the changeover switch 42 of the electrolysis power supply 40 and turns on SW2 and SW4, unlike the case of the previous area I, for example, as shown in the area II of FIG. 5B. Set to.
As a result, as shown in FIG. 2 and FIG. 6A, the salt water intake unit 50 enters seawater as salt water W pumped up by the pumping pump 52 into the electrolytic cell 21 through the intake pipe 51 and the intake port 27. Electrolytic treatment is performed using one carbon electrode 30a as a cathode and the other carbon electrode 30b as an anode among the carbon electrodes 30 of the paired configuration, and as a result of the electrolytic treatment, the electrolytically treated water W1 is passed through the discharge pipe 61 of the treated water discharge unit 60. Are discharged together with hydrogen gas H ₂ which is the product gas.
When the electrolytic treatment by the electrolytic treatment apparatus 10 is completed, a start switch (not shown) of the operation panel 71 of the control panel 70 may be turned off, and the controller 72 stops driving each control target.
Thereafter, each time the user operates the electrolytic treatment apparatus 10, the odd-numbered electrolytic treatment areas in the regions I, III... And the even-numbered electrolytic treatment areas in the region II. While switching the polarity of the electrolysis voltage V with respect to the carbon electrode 30 (30a, 30b), the electrolytic treatment is performed on the carbon electrode 30 having a pair structure.

Now, assuming that the electrolysis process in the odd-numbered electrolysis treatment region in FIG. 5B is the first electrolysis step, and the electrolysis step in the even-numbered electrolysis treatment region is the second electrolysis step, each electrolysis process is performed. The process is performed as shown in the schematic diagram of FIG. 6B or 6C.
-1st electrolysis process <refer FIG.6 (b)>-
In the first electrolysis step, an electrolytic voltage V is applied between the carbon electrode 30a as an anode and the other carbon electrode 30b as a cathode.
At this time, a reaction of NaCl + H ₂ O → NaClO + H ₂ occurs, chlorine Cl ₂ and oxygen O ₂ are generated around the anode, and NaClO is generated as the electrolytically treated water W1. Furthermore, since carbon (indicated by ● in the figure) dissolves in the anode, silicon (indicated by Δ in the figure) is peeled off as the carbon dissolves even if it is about to adhere.
On the other hand, hydrogen H ₂ is generated at the cathode, and hydroxides such as Mg ₂ OH ₄ and Ca ₂ OH ₄ (indicated by ◯ in the figure) are attached.

-2nd electrolysis process <refer FIG.6 (c)>-
In the second electrolysis step, an electrolytic voltage V is applied between the carbon electrode 30a as a cathode and the other carbon electrode 30b as an anode.
At this time, an electrolytic reaction substantially similar to the first electrolysis step is performed around the anode and the cathode, but the carbon electrode 30a that was the anode in the first electrolysis step acts as a cathode in the second electrolysis step, In addition, the carbon electrode 30b that was the cathode in the first electrolysis step functions as an anode in the second electrolysis step.
For this reason, since the other carbon electrode 30b acting as an anode in the second electrolysis step dissolves carbon, the hydroxide (shown by ◯ in the figure) adhered to the electrode surface in the first electrolysis step. It peels with the dissolution of carbon.
Incidentally, a hydroxide (shown by a circle in the figure) adheres to one carbon electrode 30a that acts as a cathode in the second electrolysis step, but when acting as an anode in the first electrolysis step, The hydroxide (indicated by a circle in the figure) adhering in the electrolysis step 2 is peeled off with the dissolution of carbon.

-1st, 2nd electrolysis process-
Thus, since the first electrolysis step and the second electrolysis step are performed alternately, the carbon electrode 30 (30a, 30b) of the pair structure dissolves carbon when acting as an anode. Compared with the mode in which the polarity of the electrolysis voltage V is not switched, the degree of wear of the carbon electrode 30 (30a, 30b) is substantially halved.
In particular, if the accumulated operation time obtained by accumulating the operation times of the first electrolysis step and the second electrolysis step is approximately the same, the degree of wear of the paired carbon electrode 30 can be made to be approximately the same. Accordingly, the life of the paired carbon electrode 30 can be extended accordingly.
In this example, since the polarity of the electrolysis voltage V is switched every time the electrolysis treatment apparatus 10 is operated, if each operation time is substantially constant, the cumulative operation time of the first electrolysis process and the second electrolysis process However, for example, the cumulative operating time of each electrolysis step is counted by a counter, and the difference between the cumulative operating times of both exceeds a predetermined threshold. Thus, a means for correcting so as to reduce the difference between the accumulated operation times of the two (for example, forcibly switching the operation time of the first and second electrolysis processes) is added, or regularly or irregularly Alternatively, a correction means for checking the accumulated operation time between the two and reducing the accumulated operation time difference each time may be added.
Further, in the carbon electrode 30 (30a or 30b) acting as the anode, the hydroxide adhering when employed as the cathode is peeled off together with the dissolution of the carbon, so that the hydroxide is formed on the surface of the carbon electrode 30. Does not remain attached, and the electrode action is not impaired by the attached hydroxide.

-Chlorine concentration adjustment-
Furthermore, if the level of the electrolysis voltage V is adjusted, it is possible to change the electrolysis current, and accordingly, the degree of electrolysis treatment with the carbon electrode 30 of the pair configuration, that is, the amount of chlorine generated is adjusted. It becomes possible to do. For this reason, in this aspect, electrolytically treated water having a desired chlorine concentration is formed.
-Carbon electrode life check-
Furthermore, although the lifetime of the paired carbon electrode 30 varies depending on the operating conditions of the electrolytic treatment apparatus 10, when the carbon electrode 30 is dissolved and consumed, the electrical characteristics (for example, resistance characteristics) of the carbon electrode 30 change. Therefore, if the electrical characteristics of the carbon electrode 30 corresponding to the lifetime of the carbon electrode 30 are determined in advance by measuring changes in the electrical characteristics of the carbon electrode 30 according to the degree of wear of the carbon electrode 30 in advance, the electrolysis apparatus By checking the electrical characteristics of the carbon electrode 30 incorporated into the carbon 20, it is possible to determine whether or not the carbon electrode 30 has reached the end of its life.
In this example, when the carbon electrode 30 reaches the end of its life, the electrolysis apparatus 20 can be used continuously by having the paired carbon electrode 30 replaced with a new one.

<Deformation of electrolytic cell>
In the present embodiment, the electrolytic cell 21 is a mode in which the salt water W is taken in from the side and the electrolytically treated water W1 is discharged from the side. However, the present invention is not limited to this, and is shown in FIGS. Of course, the present invention can also be applied to the modified embodiments 1-1 and 1-2 shown.
◎ Deformation form 1-1
As shown in FIG. 7A, the electrolytic cell 21 in this example has a bottomed cylindrical electrolytic cell main body 122 that opens upward and extends in the vertical direction. The top lid 123 is closed. And in the site | part away from the center of the upper cover 123 of the electrolytic cell 21, the intake piping 51 of the salt water intake unit 50 is connected in communication, and it is in the site | part located on the opposite side to the intake piping 51 among the upper lids 123. Is connected to the discharge pipe 61 of the treated water discharge unit 60. In this example, both the intake pipe 51 and the discharge pipe 61 are provided so as to protrude into the electrolytic cell 21, and the leading end opening of the intake pipe 51 functions as the intake port 27 of the electrolytic cell 21, and the discharge pipe. The front end opening 61 functions as the discharge port 28 of the electrolytic cell 21, and the discharge port 28 is positioned above the intake port 27. Further, a pair of carbon electrodes 30 (30a, 30b) are provided in symmetrical portions with the center in the region inside the upper lid 123 of the electrolytic cell 21 inside the portions where the intake pipe 51 and the discharge pipe 61 are disposed. The electrolysis power supply 40 is connected to the carbon electrode 30 of this pair configuration.
In the present embodiment, within the electrolyzer 21, water W is taken through capturing pipe 51, electrolytic treatment by the carbon electrodes 30 in the pair configuration are performed, discharged with the hydrogen gas H ₂ which electrolyzed water W1 is generated It is discharged from the pipe 61.

◎ Deformation form 1-2
As shown in FIG. 7B, the electrolytic cell 21 in this example has a bottomed cylindrical electrolytic cell main body 122 that opens upward and extends in the vertical direction. The top lid 123 is closed, and the salt water W intake port 27 is opened at the approximate center of the bottom wall of the electrolytic cell main body 122, while the electrolytic treatment water W1 discharge port 28 is opened at the approximate center of the top lid 123. It is. A pair of carbon electrodes 30 (30a, 30b) are provided in symmetrical portions of the upper lid 123 of the electrolytic cell 21 with the center interposed therebetween, and an electrolysis power source 40 is connected to the pair of carbon electrodes 30. Yes.
In this embodiment, within the electrolyzer 21, water W is taken through the inlet 27, electrolytic treatment by the carbon electrodes 30 in the pair configuration are performed, the discharge port 28 together with the hydrogen gas H ₂ which electrolyzed water W1 is generated It comes to be discharged from.

Embodiment 2
FIG. 8 shows a main part of the electrolytic treatment apparatus according to the second embodiment.
In the figure, the electrolytic treatment apparatus 10 is mounted on a fishing boat 80 that captures seafood.
The electrolytic treatment apparatus 10 includes an electrolytic apparatus 20 (specifically, an electrolytic cell 21, a paired carbon electrode 30, and a power source for electrolysis 40) substantially the same as in the first embodiment. 21 is provided with a salt water intake unit 50 (specifically, intake pipe 51, pumping pump 52, valve 53) substantially the same as in the first embodiment in which seawater as salt water W is taken in, and electrolysis from the electrolytic cell 21. A treated water discharge unit 60 that is substantially the same as that of the first embodiment in which the treated water W1 is discharged is provided.
Here, the treated water discharge unit 60 includes a discharge pipe 61 from which the electrolytic treated water W1 electrolyzed in the electrolytic tank 21 is discharged, and a washing tank 62 into which the electrolytic treated water W1 discharged from the discharge pipe 61 is poured. It is equipped with.
In the present embodiment, since the fishing boat 80 is equipped with the electrolytic treatment apparatus 10, the seawater as the salt water W is taken into the electrolytic tank 21 and electrolyzed to generate the electrolytically treated water W <b> 1, which is treated water. It is possible to sequentially pour into the cleaning tank 62 of the discharge unit 60.
At this time, since the electrolyzed water W1 has a sterilizing action, if the seafood captured in the cleaning tank 62 is washed on the spot, the seafood is immediately sterilized. For this reason, it is preferable at the point by which the freshness of seafood is maintained markedly compared with the case where it arrives at a fishing port with catching seafood.
In addition, since the electrolyzed water W1 does not contain additives and the like, even if it is discarded in seawater after washing with seafood, sodium hypochlorite (NaClO) as the electrolyzed water W1 is decomposed by sunlight or the like and To change.
2NaClO → 2Na ⁺ + 2ClO ⁻ → 2Na ⁺ + 2Cl ⁻ + O ₂
For this reason, the electrolytically treated water W1 returns to the original seawater, and the environmental load is extremely small.

Embodiment 3
FIG. 9 shows a main part of the electrolytic treatment apparatus according to the third embodiment.
In the figure, an electrolytic treatment apparatus 10 is installed along the coast, for example, and obtains electrolytically treated water W1 having a bactericidal action using seawater as salt water W.
In the present embodiment, the electrolytic treatment apparatus 10 includes an electrolysis apparatus 20, a salt water intake unit 150 that takes seawater as salt water W into the electrolysis apparatus 20, and the electrolysis apparatus 20 in substantially the same manner as in the first embodiment. And a treated water discharge unit 160 for discharging the electrolyzed electrolytically treated water W1.
In this example, the electrolysis apparatus 20 takes in seawater as salt water W from below the electrolysis tank 21 and discharges the electrolyzed water W1 from above. The electrolysis tank 21 is provided with a pair of carbon electrodes 30 and these. Is connected to an electrolysis power supply 40 to which an electrolysis voltage V can be applied.
The salt water intake unit 150 includes a tank 151 that temporarily stores sea water as the salt water W, an intake pipe 152 that takes sea water as the salt water W into the tank 151, and the tank 151 and the electrolyzer 20. A connection pipe 153 connecting between the intake port 27 of the electrolytic cell 21, a pumping pump 154 (indicated by P <b> 1 in the figure) provided in the middle of the intake pipe 152, and a circulation pump provided in the middle of the connection pipe 153 155 (indicated by P2 in the figure), and by operating the pumping pump 154 or the circulation pump 155, salt water is added to the electrolytic cell 21 of the electrolysis apparatus 20 via the intake pipe 152, the tank 151, and the connection pipe 153. It takes in seawater as W. Note that one end of the intake pipe 152 is immersed in seawater, and a dustproof filter 156 is provided at the tip.
Further, the treated water discharge unit 160 is connected to the discharge port 28 of the electrolytic cell 21 and circulates the electrolytic treated water W1 discharged from the electrolytic cell 21 in the vicinity of the inlet of the intake pipe 152, and the connection pipe 153. A branch discharge pipe 162 branched from a part of the pipe, a flow rate adjusting valve 163 that distributes the flow rate to the branch discharge pipe 162 and the connection pipe 153, and the electrolytically treated water W1 discharged from the branch discharge pipe 162 are sequentially provided. A washing tank 164 to be poured, and by operating the circulation pump 155, the electrolytically treated water W1 discharged from the electrolytic tank 21 is returned to the vicinity of the inlet of the intake pipe 152 through the circulation pipe 164, and the pump 154 In addition, by operating the circulation pump 155, the electrolyzed water W1 is taken together with the salt water W before electrolysis, the intake pipe 152, the tank 151, and the connection pipe 1 With recirculated to 3, in which so as to be discharged toward the cleaning tank 164 from the branch exhaust pipe 162.

Next, the operation of the electrolytic treatment apparatus according to this embodiment will be described.
Now, when the flow rate adjusting valve 163 is fully opened, the pumping pump 154 and the circulation pump 155 are operated and the electrolytic treatment is performed by the electrolyzer 20, the salt water intake unit 150 (tank 151, intake pipe 152, connection pipe 153) Then, seawater as salt water W is taken into the electrolytic tank 21 of the electrolysis apparatus 20, and electrolytic treatment is performed in the electrolytic tank 21, and the electrolytically treated water W 1 is taken in from the electrolytic tank 21 through the circulation pipe 161. Returned to the vicinity of the entrance.
Then, the electrolytic treatment water W <b> 1 is pumped together with the salt water W into the intake pipe 152 of the salt water intake unit 150 and is taken into the tank 151. At this time, there is a concern that marine organisms such as barnacles in seawater enter the intake pipe 152, but since the electrolytically treated water W <b> 1 having a sterilizing action flows through the intake pipe 152, a barnacle or the like is introduced into the intake pipe 152. The situation that the marine organisms adhere is suppressed.
Moreover, in order to set the chlorine concentration of the electrolytically treated water W2 to be discharged to the cleaning tank 164 to a predetermined level (for example, 10 ppm), the amount of chlorine produced is adjusted by the electrolytic treatment by the electrolytic tank 21, so that the electrolytic tank 21. Adjusting the chlorine concentration of the electrolytically treated water W1 returned to the seawater through the circulation pipe 161 from 21 to a predetermined level (for example, 100 ppm), The chlorine concentration of the mixed solution with seawater as the salt water W before electrolysis may be adjusted to the final chlorine concentration level of the electrolyzed water W2.
If the chlorine concentration level of the electrolytically treated water W2 is adjusted in this manner, the electrolytically treated water W2 can be used as cleaning water having a bactericidal action in the cleaning tank 164.

Example 1
This example embodies the electrolytic apparatus 20 used in the electrolytic treatment apparatus 10 according to the first embodiment, and shows the change in the amount of chlorine generated when the electrolytic current is changed under the following implementation conditions. It is what I have sought.
-Implementation conditions-
-Inner diameter of electrolytic cell: 154mm
・ Volume of electrolytic cell: 5585 mL
-Electrolyzer length: 300mm
-Diameter of carbon electrode: 20mm
・ Exposed length of carbon electrode: 250 mm
・ Electrolytic solution: artificial seawater (salt concentration of about 3%)
The results are shown in FIG.
According to the figure, it is understood that the amount of chlorine production tends to increase approximately proportionally as the electrolysis current increases.
For this reason, it becomes possible to variably set the chlorine generation amount by adjusting the electrolysis current, and it is possible to easily adjust the chlorine concentration of the electrolyzed water to a desired level.

Example 2
This example embodies the electrolytic apparatus 20 used in the electrolytic treatment apparatus 10 according to the first embodiment, and examines the lifetime of a paired carbon electrode under the following electrolytic conditions.
-Electrolysis conditions-
・ Electrolytic current: 20A
Electrolytic voltage polarity switching timing: every 3 hours In order to evaluate the performance of the present example, as a comparative example, the life of the paired carbon electrode was examined under electrolytic conditions in which the polarity of the electrolytic voltage was not switched.
In this example, it was confirmed that the electrolytic treatment was carried out without requiring maintenance until the cumulative operation time was about 600 hours.
Further, when the diameter change of the paired carbon electrode which reached the end of life was examined, it was confirmed that both were consumed to the same extent, and there was almost no hydroxide adhesion on any electrode surface. It was.
On the other hand, in the comparative example, when the cumulative operation time reached about 100 hours, the hydroxide was excessively attached to the cathode side, and it was difficult to perform the electrolytic treatment without maintenance. . Further, when the diameter change of the paired carbon electrode was examined, it was confirmed that the carbon electrode on the anode side was excessively consumed compared to the cathode side.

Example 3
This example embodies the electrolytic treatment apparatus according to the second embodiment, and examines the characteristics of the electrolytically treated water obtained by electrolyzing seawater and the effect of maintaining the freshness of the fish by the electrolytically treated water. .
The electrolysis conditions in this example are as follows.
・ Electrolytic voltage: 24V
・ Electrolytic current: 20A
-Seawater uptake: 20 L / min.
・ Effective chlorine concentration of electrolyzed water: 5ppm
First, as the characteristics of the used seawater and electrolytically treated water, the number of general viable bacteria and the number of halophilic bacteria per mL of unit volume were examined, and the result shown in FIG. 11 (a) was obtained.
According to the figure, it is understood that the number of bacteria in the electrolyzed water is significantly reduced compared to seawater. The electrolyzed water has a sterilizing effect on the seawater, and the electrolyzed water is generated as sterilized seawater. It is understood.

Next, after squeezing the salmon as an example of fish and shellfish, the fish surface and the salmon are washed mainly with 10 L of electrolyzed water (sterilized seawater), and the salmon immediately after washing and after washing is accommodated in a sealed container. It stored in the refrigerator kept at C, and measured K value after 12 hours. In addition, as a comparative example with respect to the present example, the surface of the carp fish and the carp were washed with 10 L of seawater instead of the electrolytically treated water, and the K value was measured under the same conditions as in the example.
The “K value” here is one index indicating the freshness of seafood, and indicates the degree of decomposition of ATP (adenosine triphosphate) in seafood. That is, as shown in FIG. 11 (b), when the seafood dies and ATP of the seafood is enzymatically degraded, with time, ADP (adenosine diphosphate) → AMP (adenosine monophosphate) ) → IMP (Inosinic acid) → HxR (Inosine), Hx (Hypoxanthine) progresses to decomposition, and HxR and Hx, which are degradation products of ATP, increase as shown in FIG. 11 (c). It is possible to determine a decrease in freshness by increasing the 'K value'. If the 'K value' is less than 20%, it is very fresh and can be used for sushi and sashimi, and if it is 20% or more and 50% or less, it can be used for heating. , 60% or more indicates unsuitable for use.
The measurement result of K value about a present Example and a comparative example is shown in FIG.11 (b).
According to the figure, it is understood that the freshness of the fish hardly decreases even after 12 hours if this example is washed with electrolytically treated water immediately after capture and refrigerated. In this regard, in the cleaning method shown in the comparative example, it is understood that the decrease in freshness starts after 12 hours.

  DESCRIPTION OF SYMBOLS 1 ... Electrolytic cell, 1a ... Intake port, 1b ... Discharge port, 2 (2a, 2b) ... Carbon electrode, 3 ... Power supply for electrolysis, 3a ... Power supply element, 3b ... Switching element, 4 ... Electrolyzer, 5 ... Salt water Intake means, 6 ... treated water providing means, V ... electrolytic voltage, W ... salt water, W1 ... electrolyzed water

Claims (9)

When electrolyzing salt water containing impurities,
A filling step of filling the salt water, which is the subject of electrolysis, into a diaphragm-type electrolytic cell;
A first electrolysis step of immersing at least a pair of carbon electrodes in salt water in the electrolytic cell, and applying an electrolysis voltage comprising a direct current component using one carbon electrode as an anode and the other carbon electrode as a cathode;
The first electrolysis step is alternately performed at a predetermined timing, and the polarity of the electrolysis voltage composed of a DC component is switched and applied so that the one carbon electrode is a cathode and the other carbon electrode is an anode. A second electrolysis step to
An electrolysis method comprising: An electrolysis apparatus for electrolyzing salt water containing impurities,
A diaphragm-type electrolytic cell having an intake port through which the salt water is taken in and a discharge port through which the electrolyzed water after the salt water is electrolyzed is discharged, and filled with the salt water;
A carbon electrode of at least a pair configuration disposed opposite to the electrolytic cell and immersed in salt water to be electrolyzed;
An electrolysis power source for applying an electrolytic voltage composed of a direct current component between the pair of carbon electrodes so that one carbon electrode of the pair of carbon electrodes serves as an anode and the other carbon electrode serves as a cathode. ,
2. The electrolysis apparatus according to claim 1, wherein the electrolysis power source includes a switching element capable of switching a polarity of an electrolysis voltage with respect to the pair of carbon electrodes at a predetermined timing periodically or irregularly. The electrolyzer according to claim 2.
The electrolysis apparatus characterized in that the switching element of the electrolysis power source switches the polarity of the electrolysis voltage so that the accumulated electrolysis times in the respective polarities are approximately the same. The electrolyzer according to claim 2.
The electrolysis apparatus characterized in that the switching element of the electrolysis power source switches the polarity of the electrolysis voltage when the electrolysis apparatus starts or stops operating. The electrolysis apparatus according to claim 1 or 2,
The electrolytic cell is characterized in that the intake port is located below the discharge port. The electrolyzer according to claim 5.
The electrolytic cell has the intake port in a predetermined part of its side peripheral wall, and the discharge port located above the intake port,
The paired carbon electrodes are disposed on the side wall of the electrolytic cell on the opposite side of the intake port and the discharge port and at least above the intake port. An electrolyzer characterized by that. An electrolyzer according to any one of claims 2 to 6,
Salt water intake means for taking in salt water through the inlet of the electrolytic cell of the electrolyzer;
Treated water providing means for using the electrolytically treated water discharged through the outlet of the electrolytic cell of the electrolyzer;
An electrolytic treatment apparatus comprising: The electrolytic treatment apparatus according to claim 7, wherein
Mounted on a fishing boat, the salt water intake means takes sea water as salt water into the electrolytic tank of the electrolysis device, and the treated water providing means uses the electrolytic treated water as sterilized water for fish and shellfish captured. An electrolytic treatment apparatus characterized by that. The electrolytic treatment apparatus according to claim 7, wherein
The salt water intake means includes a storage container that temporarily stores salt water, an intake pipe that takes salt water into the storage container, and a space between the storage container and the inlet of the electrolytic cell of the electrolysis device. Connecting pipes to be connected, and taking salt water into an electrolytic cell of the electrolysis device through the intake pipe, the storage container and the connection pipe,
The treated water providing means is branched from a part of the connection pipe, a circulation pipe connected to the discharge port of the electrolytic cell and circulating the electrolytic treated water discharged from the electrolytic cell in the vicinity of the inlet of the intake pipe. A branch discharge pipe, and a flow rate adjusting means for allocating a flow rate to the branch discharge pipe and the connection pipe, and the salt water intake means together with the salt water before electrolysis discharged from the electrolytic cell. The electrolytic treatment apparatus is characterized in that it is recirculated to the intake path and discharged from the branch discharge pipe.

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